MEANS TO INCREASE MOLECULAR WEIGHT AND REDUCE DENSITY OF ETHYLENE INTERPOLYMERS USING HOMOGENEOUS AN

专利摘要:
a continuous solution polymerization process is disclosed in which at least two catalyst formulations are used. a first homogeneous catalyst formulation is used in a first reactor to produce a first ethylene interpolymer and a first heterogeneous catalyst formulation is used in a second reactor to produce a second ethylene interpolymer. optionally a third ethylene interpolymer is formed in a third reactor. the resulting ethylene interpolymer products have desirable properties in a variety of end applications, for example in film applications. a means for increasing the molecular weight of the first ethylene interpolymer is disclosed and / or a means for increasing the temperature of the first reactor, in relation to a third homogeneous catalyst formulation. a means to reduce the weight ratio of (a-olefin / ethylene) in the first reactor is disclosed and / or to reduce the density of the first ethylene interpolymer with respect to a third homogeneous catalyst formulation.
公开号:BR112019021869A2
申请号:R112019021869-6
申请日:2018-04-17
公开日:2020-05-26
发明作者:Zhang Zengrong；Kazemi Niousha；SALOMONS Stephen；Kleczek Monika；Keshtkar Mehdi；Molloy Brian；Wang Qinyan；Zoricak Peter；Carter Charles；Wang Xiaochuan；DOBBIN Christopher；Sibtain Fazle；Taylor Kenneth；Van Asseldonk Lawrence；Khakdaman Hamidreza
申请人:Nova Chemicals (International) S.A.；
IPC主号:

专利说明:

MEANS TO INCREASE MOLECULAR WEIGHT AND REDUCE DENSITY OF ETHYLENE INTERPOLYMERS USING HOMOGENEOUS AND HETEROGENEOUS CATALYST FORMULATIONS
TECHNICAL FUNDAMENTALS
[001] Solution polymerization processes are typically carried out at temperatures that are above the melting point of the ethylene homopolymer or copolymer product. In a typical solution polymerization process, components of catalyst, solvent, monomers and hydrogen are fed under pressure to one or more reactors.
[002] For ethylene polymerization or ethylene copolymerization, reactor temperatures can vary from about 80 ° C to about 300 ° C while pressures generally range from about 3MPag to about 45MPag. The ethylene homopolymer or copolymer produced remains dissolved in the solvent under reactor conditions. The residence time of the solvent in the reactor is relatively short, for example, from about 1 second to about 20 minutes. The solution process can be operated under a wide range of process conditions that allow the production of a wide variety of ethylene polymers. After the reactor, the polymerization reaction is extinguished to prevent further polymerization, adding a catalyst deactivator and passivating it, adding an acidic decontaminant. Once passivated, the polymer solution is sent to a polymer recovery operation where the ethylene homopolymer or copolymer is separated from the process solvent, unreacted residual ethylene and optional unreacted a-olefin (s) ).
[003] There is a need to improve the continuous solution polymerization process, for example, to increase the molecular weight of the ethylene interpolymer produced at a given reactor temperature. Given a specific catalyst formulation, it is well known to those of ordinary experience that the molecular weight of
Petition 870190112009, of 11/01/2019, p. 8/168
2/156 polymer increases as the reactor temperature decreases. However, lowering the reactor temperature can be problematic when the viscosity of the solution becomes too high. As a result, in the solution polymerization process there is a need for catalyst formulations that produce high molecular weight ethylene interpolymers at high reactor temperatures. The catalyst formulations and solution polymerization processes disclosed here satisfy this need.
[004] In the solution polymerization process there is also a need for catalyst formulations that are very efficient in incorporating one or more α-olefins in a propagating macromolecular chain. In other words, for a given weight ratio of [α-olefin / ethylene] in a solution polymerization reactor, there is a need for catalyst formulations that produce lower density ethylene / α-olefin copolymers. Alternatively expressed, there is a need for catalyst formulations that produce an ethylene / a-olefin copolymer, having a specific density, in a lower (α-olefin / ethylene) ratio in the reactor feed. Such catalyst formulations efficiently use the available α-olefin and reduce the amount of α-olefin in recycling streams of the solution process.
[005] The catalyst and solution process formulations disclosed here, produce unique ethylene interpolymer products that have desirable properties in a variety of end applications, for example applications that use ethylene interpolymer films. Non-limiting examples of desirable film properties include higher film hardness, higher film break resistance, lower hexane extractables and lower sealing initiation temperature. Films prepared from the ethylene interpolymer products, disclosed herein, have these desirable properties.
SUMMARY OF THE INVENTION
Petition 870190112009, of 11/01/2019, p. 9/168
3/156
[006] One embodiment of this disclosure is an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii) optionally a third ethylene interpolymer: where the ethylene interpolymer product has a dimensionless long chain branching factor (LCBF) greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium, and; from about 0.1 ppm to about 11.4 ppm titanium.
[007] Additional embodiments of this disclosure include ethylene interpolymer products comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii) optionally a third ethylene interpolymer: where the ethylene interpolymer product has a dimensionless long chain branching factor (LCBF) greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about 0.1 ppm to about 11.4 ppm titanium, and; greater than or equal to about 0.02 terminal vinyl unsaturations per 100 carbon atoms.
[008] Other embodiments of this disclosure include ethylene interpolymer products comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii) optionally a third ethylene interpolymer: where the ethylene interpolymer product has a dimensionless long chain branching factor (LCBF) greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about 0.1 ppm to about 11.4 ppm titanium, and; greater than or equal to about 0.12 parts per million (ppm) of a total catalytic metal.
[009] The modalities of this disclosure include ethylene interpolymer products comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer, and; (iii) optionally a third ethylene interpolymer: where the ethylene interpolymer product has a Chain Branching Factor
Petition 870190112009, of 11/01/2019, p. 10/168
4/156
Dimensional Long (LCBF) greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium; from about 0.1 ppm to about 11.4 ppm titanium; greater than or equal to about 0.02 terminal vinyl unsaturations per 100 carbon atoms, and; greater than or equal to about 0.12 parts per million (ppm) of a total catalytic metal.
[010] The modalities of this disclosure include ethylene interpolymer products having a melt index of about 0.3 to about 500 dg / minute. Other embodiments include ethylene interpolymer products having a density of about 0.862 to about 0.975 g / cc. Other modalities include ethylene interpolymer products having an Mw / M _n of about 2 to about 25. The modalities include ethylene interpolymer products having a CDBbo (Composition Distribution Amplitude Index) of about 20% at about 98%.
[011] The modalities include ethylene interpolymer products containing 5 to 60% by weight of a first ethylene interpolymer, 20 to 95% by weight of a second ethylene interpolymer and 0 to 30% by weight of a third ethylene interpolymer ; where the weight% is the weight of the first, second or third optional ethylene interpolymer, individually divided by the total weight of the ethylene interpolymer product. Additional embodiments include ethylene interpolymer products where the first ethylene interpolymer has a melt index of about 0.01 to about 200 dg / minute, the second ethylene interpolymer has a melt index of about 0.3 to about 1000 dg / minute and the third ethylene interpolymer has a melt index of about 0.5 to about 2000 dg / minute. Other embodiments include ethylene interpolymer products where the first ethylene interpolymer has a density of about 0.855 g / cm ³ to about 0.975 g / cc, the second ethylene interpolymer has a density of about 0.89 g / cm ³ to about 0.975 g / cc and the third ethylene interpolymer has a density of about 0.855 g / cm ³ to about 0.975 g / cc.
Petition 870190112009, of 11/01/2019, p. 11/168
5/156
[012] The modalities include ethylene interpolymer products containing from 0 to 10 mol percent of one or more α-olefins, where α-olefins are C3 to C10 aolefins. Non-limiting examples include ethylene interpolymer products containing the following α-olefins: 1-octene, 1-hexene or a mixture of 1octene and 1-hexene.
[013] The modalities of this disclosure include a first ethylene interpolymer synthesized using at least one homogeneous catalyst formulation. Additional embodiments include the synthesis of a first ethylene interpolymer using a first homogeneous catalyst formulation. A non-limiting example of the first homogeneous catalyst formulation is a bridged metallocene catalyst formulation containing a component A defined by
Formula (I)
(I)
[014] The modalities of this disclosure include a second ethylene interpolymer synthesized using a first heterogeneous catalyst formulation. Non-limiting examples of the first heterogeneous catalyst formulation include a first in-line Ziegler-Natta catalyst formulation or a first batch Ziegler-Natta catalyst formulation.
[015] Optional modalities include the synthesis of a third ethylene interpolymer using the first heterogeneous catalyst formulation or the second heterogeneous catalyst formulation; optionally the first and second
Petition 870190112009, of 11/01/2019, p. 12/168
6/156 heterogeneous catalyst formulations are the same formulation.
[016] Other optional embodiments include the synthesis of the third ethylene interpolymer using a fifth homogeneous catalyst formulation. The fifth homogeneous catalyst formulation can be: a bridged metallocene catalyst formulation, a single site non-bridged catalyst formulation or a fourth homogeneous catalyst formulation. The fourth homogeneous catalyst formulation contains a bulky ligand-metal complex that is not a member of the chemical genera that defines: a) the bulky ligand-metal complex used in the formulation of bridged metallocene catalyst, and; b) the bulky binder-metal complex used in the formulation of a single site non-bridged catalyst.
[017] The modalities of this disclosure include ethylene interpolymer products containing <2.4 ppm of catalytic metal A, where catalytic metal A originates from the first homogeneous catalyst formulation. Non-limiting examples of metal A include titanium, zirconium and hafnium. Additional embodiments include ethylene interpolymer products containing a catalytic metal Z1 and optionally a catalytic metal Z2 and the total amount of said catalytic metal Z1 plus said catalytic metal Z2 is about 0.1 to about 11.4 parts per million; where catalytic metal Z1 originates from the first heterogeneous catalyst formulation and catalytic metal Z2 originates from the second heterogeneous catalyst formulation; optionally catalytic metal Z1 and catalytic metal Z2 are the same metal. Non-limiting examples of catalytic metals Z1 and Z2 include: titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or osmium (it being understood that metals Z1 and Z2 are independently selected from this list). Optional embodiments include an ethylene interpolymer product containing <1 ppm of a catalytic metal D; where catalytic metal D originates from said fourth homogeneous catalyst formulation. Non-limiting examples of metal D include
Petition 870190112009, of 11/01/2019, p. 13/168
7/156 titanium, zirconium and hafnium.
[018] The embodiments of the disclosed ethylene interpolymer products contain a first ethylene interpolymer having a first Mw / M _n of about 1.7 to about 2.8, a second ethylene interpolymer having a second Mw / M _n from about 2.2 to about 4.4 and an optional third ethylene interpolymer having a third Mw / Mn from about 1.7 to about 5.0.
[019] Other embodiments of ethylene interpolymer products contain a first ethylene interpolymer having a first CDBbo of about 70 to about 98%, a second ethylene interpolymer having a second CDBI of about 45 to about 98% and an optional third ethylene interpolymer having a third CDBIso of about 35 to about 98%.
[020] This disclosure includes the modality of a continuous solution polymerization process where a first and a second reactor are operated in series mode (that is, the effluent from the first reactor flows into the second reactor), a first homogeneous catalyst formulation it is used in the first reactor and a first heterogeneous catalyst formulation is used in the second reactor; optionally the first heterogeneous catalyst formulation or a second heterogeneous catalyst formulation or a fifth homogeneous catalyst formulation is used in an optional third reactor. This modality of a continuous solution polymerization process comprises: i) injecting ethylene, a process solvent, a first homogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen in a first reactor to produce a first output stream containing a first ethylene interpolymer in the process solvent; ii) pass the first outlet stream into a second reactor and inject into the second reactor, ethylene, process solvent, a first heterogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen to produce a second outlet stream containing a second
Petition 870190112009, of 11/01/2019, p. 14/168
8/156 ethylene interpolymer and the first ethylene interpolymer in the process solvent; iii) pass the second output stream in a third reactor and optionally inject in the third reactor, ethylene, process solvent, one or more α-olefins, hydrogen and one or more of the first heterogeneous catalyst formulation, a second heterogeneous catalyst formulation and a fifth homogeneous catalyst formulation to produce a third outlet stream containing an optional third ethylene interpolymer, the second ethylene interpolymer and the first ethylene interpolymer in the process solvent; iv) phase out the third outlet stream to recover an ethylene interpolymer product comprising the first ethylene interpolymer, the second ethylene interpolymer and the optional third ethylene interpolymer. The serial mode modalities of the solution process have been improved by having a lower weight ratio of [α-olefin / ethylene] in the first reactor and / or the first reactor produces a first higher molecular ethylene interpolymer. In some embodiments, the disclosed solution process had at least one weight ratio improved (reduced) to 70% [α-olefin / ethylene] as defined by the following formula
C fa - olefin ^ fa - olefin ^ j
(. ethylene) ethylene) (<_ ₇₀ „ _{/ o} ra - olefinay ethylene) J where (a-olefin / ethylene) ^A was calculated by dividing the weight of a-olefin added to the first reactor by the weight of ethylene added to the first reactor where a first ethylene interpolymer having a target density was produced by the first homogeneous catalyst formulation, and; (a-olefin / ethylene) ^c was calculated by dividing the weight of α-olefin added to the first reactor by the weight of ethylene added to the first reactor where a control ethylene interpolymer having the target density was produced by replacing the first formulation of homogeneous catalyst with a third formulation of homogeneous catalyst. In other modalities of the solution polymerization process they had at least a weight
Petition 870190112009, of 11/01/2019, p. 15/168
9/156 weighted average molecular weight of improved (highest) of 5% as defined by the following formula% Mw Enhanced = 100% x (M _W ^A -MW ^C ) / MW ^C > 5% where MvA was the weighted average molecular weight of the first ethylene interpolymer and M _w ^c was the weighted average molecular weight of a comparative ethylene interpolymer; where the comparative ethylene interpolymer was produced in the first reactor by replacing the first homogeneous catalyst formulation with the third homogeneous catalyst formulation.
[021] In another mode of the continuous solution polymerization process, the first and second reactors are operated in parallel mode, that is, the first output current (which leaves the first reactor) bypasses the second reactor and the first output current it is combined with the second output current (which leaves the second reactor) downstream of the second reactor. Parallel modes include: i) injecting ethylene, a process solvent, a first homogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen in a first reactor to produce a first outlet stream containing a first ethylene interpolymer in the process solvent; ii) injecting ethylene, process solvent, a first heterogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen in a second reactor to produce a second outlet stream containing a second ethylene interpolymer in the process solvent; iii) combining the first and second output streams to form a third output stream; iv) passing the third output stream in a third reactor and optionally injecting in the third reactor, ethylene, process solvent, one or more α-olefins, hydrogen and one or more of the first heterogeneous catalyst formulation, a second formulation of heterogeneous catalyst and a fifth formulation of homogeneous catalyst to produce a fourth outlet stream containing a third ethylene interpolymer
Petition 870190112009, of 11/01/2019, p. 16/168
10/156 optional, the second ethylene interpolymer and the first ethylene interpolymer in said process solvent; v) phase out the fourth outlet stream to recover an ethylene interpolymer product comprising the first ethylene interpolymer, the second ethylene interpolymer and the optional third ethylene interpolymer. Parallel mode modalities have been improved by having a lower weight ratio of [α-olefin / ethylene] in the first reactor and / or a first higher molecular ethylene interpolymer, as characterized by the serial mode modalities described immediately above.
[022] Additional modalities of the series and parallel solution polymerization processes include the post-reactor action of a catalyst deactivator to neutralize or deactivate the catalysts, forming a deactivated solution. In other embodiments, the solution polymerization process in series and in parallel can also include an additional step where a passivator is added to the deactivated solution, forming a passivated solution.
[023] The solution polymerization processes described above, include modalities where the first homogeneous catalyst formulation was a bridged metallocene catalyst formulation. Additional modalities included steps where the inlet temperature of the catalyst was adjusted to optimize the activity of the bridged metallocene catalyst formulation.
[024] The solution polymerization processes disclosed include the embodiment where the third homogeneous catalyst formulation was a single site non-bridged catalyst formulation.
[025] The disclosed solution polymerization processes include modalities where the first heterogeneous catalyst formulation is a Ziegler-Natta catalyst formulation prepared using an in-line process, then the ‘first in-line Ziegler-Natta catalyst formulation’. In alternative modalities the first formulation of heterogeneous catalyst is a
Petition 870190112009, of 11/01/2019, p. 17/168
11/156 Ziegler-Natta catalyst formulation prepared using a batch process, then the 'first Ziegler-Natta catalyst formulation'.
[026] Optionally, the first in-line Ziegler-Natta catalyst formulations or the first batch Ziegler-Natta catalyst formulations can be injected into the third reactor to produce the optional third ethylene interpolymer; either a second in-line Ziegler-Natta formulation or a second batch Ziegler-Natta catalyst formulation can be produced and injected into the third reactor. Optionally, a fifth formulation of homogeneous catalyst can be injected into the third reactor to produce the optional third ethylene interpolymer.
[027] Other modalities include synthesis of the solution process of an ethylene interpolymer product which includes a means to reduce, by at least 70%, the weight ratio of [α-olefin / ethylene] required to produce the first interpolymer ethylene (in the ethylene interpolymer product), where the first ethylene interpolymer has a target density; the medium involves the appropriate selection of the catalyst formulation used in the first reactor.
[028] Other modalities include the synthesis of an ethylene interpolymer product from the solution process which includes a means to increase, by at least 5%, the weighted average molecular weight (Mw) of the first ethylene interpolymer (in the interpolymer product) ethylene); the medium involves the appropriate selection of the catalyst formulation used in the first reactor.
[029] Other modalities of the present disclosure include manufactured articles; non-limiting examples of manufactured articles include flexible articles such as films and rigid articles such as containers.
[030] The modalities of the articles manufactured include a polyethylene film comprising at least one layer, where the layer comprises at least one ethylene interpolymer product disclosed here and the film has a module
Petition 870190112009, of 11/01/2019, p. 18/168
12/156 1% drying in the direction of the machine improved, as it is at least 25% improved (higher), compared to a comparative polyethylene film of the same composition but the first ethylene interpolymer in the ethylene interpolymer product is replaced with a comparative ethylene interpolymer; where the first ethylene interpolymer was synthesized with a bridged metallocene catalyst formulation and the comparative ethylene interpolymer was synthesized with a non-bridged single site catalyst formulation.
[031] Other modalities include a polyethylene film comprising at least one layer, where the layer comprises at least one ethylene interpolymer product disclosed here and the film has an improved 1% secant modulus in transverse direction, as it is at least 40 % improved (higher), compared to a comparative polyethylene film of the same composition but said first ethylene interpolymer is replaced with a comparative ethylene interpolymer; where the first ethylene interpolymer was synthesized with a bridged metallocene catalyst formulation and the comparative ethylene interpolymer was synthesized with a non-bridged single site catalyst formulation.
[032] The modalities include a polyethylene film comprising at least one layer, where the layer comprises at least one ethylene interpolymer product disclosed here and the film has improved by weight of hexane extractables, by at least 40% being improved (lower), compared to a comparative polyethylene film of the same composition but the first ethylene interpolymer was replaced with a comparative ethylene interpolymer; where the first ethylene interpolymer was synthesized with a bridged metallocene catalyst formulation and the comparative ethylene interpolymer was synthesized with a non-bridged single site catalyst formulation.
[033] Other modalities include a polyethylene film comprising at least
Petition 870190112009, of 11/01/2019, p. 19/168
13/156 minus one layer, where the layer comprises at least one ethylene interpolymer product disclosed here and the film has an Elmendorf tear strength in the direction of the improved machine, as it is at least 15% improved (higher), in compared to a comparative polyethylene film of the same composition but the first ethylene interpolymer was replaced with a comparative ethylene interpolymer; where the first ethylene interpolymer has been synthesized with a bridged metallocene catalyst formulation and the comparative ethylene interpolymer has been synthesized with a non-bridged single site catalyst formulation; where both the first ethylene interpolymer and the comparative ethylene interpolymer are synthesized in a double reactor solution process where the first and second reactors are configured in parallel.
[034] Additional modalities include a polyethylene film comprising at least one layer, where the layer comprises at least one ethylene interpolymer product disclosed here and the film has an improved sealing initiation temperature, as it is at least 5% improved ( lower), compared to a comparative polyethylene film of the same composition but said first ethylene interpolymer has been replaced with a comparative ethylene interpolymer; wherein the first ethylene interpolymer has been synthesized with a bridged metallocene catalyst formulation and the comparative ethylene interpolymer has been synthesized with a non-bridged single site catalyst formulation; where both the first ethylene interpolymer and the comparative ethylene interpolymer were synthesized in a double reactor solution process where the first and second reactors were configured in parallel.
[035] Other embodiments include a polyethylene film comprising at least one layer, where the layer comprises at least one ethylene interpolymer product and at least a second polymer. Non-limiting examples of the second polymers include ethylene polymers, propylene polymers or a
Petition 870190112009, of 11/01/2019, p. 20/168
14/156 mixture of ethylene polymers and propylene polymers.
[036] Additional modalities include a polyethylene film having a thickness of about 0.5 mil to about 10 mil. Modalities also include multilayer films comprising 2 to 11 layers, where at least one layer comprises at least one of the ethylene interpolymer products disclosed herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[037] The following Figures are presented for the purpose of illustrating selected modalities of this disclosure; being understood, that the modalities in this disclosure are not limited to the precise arrangement of or the number of, vessels shown.
[038] Figure 1 shows the determination of the Long Chain Branching Factor (LCBF). The plotted abscissa was the corrected Zero Shear Viscosity log (log (ZSVc)) and the plotted ordinate was the corrected Intrinsic Viscosity log (log (IVc)). Ethylene polymers that have no undetectable LCB or LCB fall into the reference line. Ethylene polymers having LCB deviate from the reference line and were characterized by the dimensionless long chain branching factor (LCBF). LCBF = (Sh x Sv) / 2; where Sh and Sv are factors of horizontal and vertical displacement, respectively.
[039] Figure 2 illustrates a continuous solution polymerization process where a first homogeneous catalyst formulation and an in-line heterogeneous catalyst formulation are used.
[040] Figure 3 illustrates a continuous solution polymerization process where a first homogeneous catalyst formulation and a batch heterogeneous catalyst formulation are used.
[041] Figure 4 illustrates the nomenclature used to identify various carbon atoms that give rise to signals in ¹³ C NMR spectra.
Petition 870190112009, of 11/01/2019, p. 21/168
15/156
[042] Figure 5 shows the deconvolution of the ethylene interpolymer product of Example 4 into a first, second and third ethylene interpolymer.
Definition of Terms
[043] Except in the examples or where otherwise indicated, all numbers or expressions referring to the quantities of ingredients, extrusion conditions, etc., used in the specification and claims must be understood as modified in all examples by the term "about". Consequently, unless otherwise indicated, the numerical parameters presented in the following specification and appended claims are approximations that may vary depending on the desired properties that the various modalities wish to obtain. At the very least and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in the light of the number of significant digits reported and using standard rounding techniques. The numerical values presented in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective test measurements.
[044] It should be understood that any numerical range reported here is intended to include all sub-ranges included in this. For example, a “1 to 10” range is intended to include all sub-ranges between and including the minimum reported value of 1 and the maximum reported value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. Because the numerical ranges disclosed are continuous, they include each value between the minimum and maximum values. Unless expressly stated otherwise, the various numerical ranges specified in this application are approximations.
[045] All compositional tracks expressed here are limited in total and do not exceed 100 percent (percent by volume or percent by weight) in practice.
Petition 870190112009, of 11/01/2019, p. 22/168
16/156
Where multiple components can be present in a composition, the sum of the maximum quantities of each component can exceed 100 percent, with the understanding and as those skilled in the art easily understand, that the quantities of the components actually used will be in accordance with the maximum of 100 percent.
[046] In order to form a more complete understanding of this disclosure, the following terms are defined and should be used with the attached figures and the description of the various modalities at all times.
[047] As used here, the term "monomer" refers to a small molecule that can chemically react and become chemically bound with itself or other monomers to form a polymer.
[048] As used here, the term "α-olefin" is used to describe a monomer having a linear hydrocarbon chain containing 3 to 20 carbon atoms having a double bond at one end of the chain; an equivalent term is "linear α-olefin".
[049] As used herein, the term "ethylene polymer", refers to macromolecules produced from ethylene monomers and optionally one or more additional monomers; notwithstanding the specific catalyst or specific process used to manufacture the ethylene polymer. In the polyethylene technique, the one or more additional monomers are called "comonomer (s)" and often include α-olefins. The term "homopolymer" refers to a polymer that contains only one type of monomer. Common ethylene polymers include high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (IILDPE), plastomer and elastomers . The term ethylene polymer also includes polymers produced in a high pressure polymerization process; non-limiting examples include polyethylene of
Petition 870190112009, of 11/01/2019, p. 23/168
17/156 low density (LDPE), copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and alkyl acrylate, copolymers of ethylene and acrylic acid and metal salts of ethylene and acrylic acid (commonly referred to as ionomers). The term ethylene polymer also includes block copolymers that can include 2 to 4 comonomers. The term ethylene polymer also includes combinations or mixtures, of the ethylene polymers described above.
[050] The term "ethylene interpolymer" refers to a subset of polymers within the "ethylene polymer" group that excludes polymers produced in high pressure polymerization processes; non-limiting examples of polymer produced in high pressure processes include LDPE and EVA (the latter is a copolymer of ethylene and vinyl acetate).
[051] The term "heterogeneous ethylene interpolymers" refers to a subset of polymers in the ethylene interpolymer group that is produced using a heterogeneous catalyst formulation; non-limiting examples of which include Ziegler-Natta or chromium catalysts.
[052] The term "homogeneous ethylene interpolymer" refers to a subset of polymers in the ethylene interpolymer group that is produced using homogeneous catalyst formulations. Typically, homogeneous ethylene interpolymers have narrow molecular weight distributions, for example Mw / Mn Size Exclusion Chromatography (SEC) values of less than 2.8; M _w and Mn refer to weighted and numerical average molecular weights, respectively. In contrast, the Mw / Mn of heterogeneous ethylene interpolymers is typically greater than the Mw / Mn of homogeneous ethylene interpolymers. In general, homogeneous ethylene interpolymers also have a narrow comonomer distribution, that is, each macromolecule within the molecular weight distribution has a similar comonomer content. Often, the composition distribution amplitude index “CDBI” is used to quantify how the
Petition 870190112009, of 11/01/2019, p. 24/168
18/156 comonomer is distributed within an ethylene interpolymer, as well as to differentiate ethylene interpolymers produced with different catalysts or processes. “CDBIso” is defined as the percentage of ethylene interpolymer whose composition is within 50% of the median comonomer composition; this definition is compatible with that described in U.S. Patent 5,206,075 to Exxon Chemical Patents Inc. The CDBIso of an ethylene interpolymer can be calculated from TREF (Temperature Gradient Elution Fractionation) curves; the TREF method is described in Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441 - 455. Typically the CDBIso of homogeneous ethylene interpolymers are greater than about 70%. In contrast, the CDBIso of heterogeneous ethylene interpolymers containing α-olefin is generally lower than the CDBIso of homogeneous ethylene interpolymers. A mixture of two or more homogeneous ethylene interpolymers, which differ in comonomer content, may have a CDBIso of less than 70%; in this disclosure such a mixture has been defined as a homogeneous mixture or homogeneous composition. Similarly, a mixture of two or more homogeneous ethylene interpolymers, which differ in weighted average molecular weight (Mw), can have an Mw / Mn> 2.8; in this disclosure such a mixture has been defined as a homogeneous mixture or homogeneous composition.
[053] In this disclosure, the term "homogeneous ethylene interpolymer" refers to both linear homogeneous ethylene interpolymers and substantially linear homogeneous ethylene interpolymers. In this technique, linear homogeneous ethylene interpolymers are generally considered to have no long chain branches or an undetectable amount of long chain branches; while substantially linear ethylene interpolymers are generally considered to have more than about 0.01 to about 3.0 long chain branches per 1000 carbon atoms. A long chain branch is macromolecular in nature, that is, similar in length to the
Petition 870190112009, of 11/01/2019, p. 25/168
19/156 macromolecule to which the long chain branch is attached.
[054] In this disclosure, the term homogeneous catalyst is used, for example to describe a first, a third, a fourth and a fifth formulation of a homogeneous catalyst. The term catalyst refers to the chemical compound containing the catalytic metal, which is a metal-binder complex. In this disclosure, the term 'homogeneous catalyst' is defined by the characteristics of the polymer produced by the homogeneous catalyst. Specifically, a catalyst is a homogeneous catalyst if it produces a homogeneous ethylene interpolymer that has a narrow molecular weight distribution (Mw / M _n SEC values of less than 2.8) and a narrow comonomer distribution (CDBI50> 70%). Homogeneous catalysts are well known in the art. Two subsets of the homogeneous catalyst genus include non-bridged metallocene catalysts and bridged metallocene catalysts. Non-bridged metallocene catalysts are characterized by two bulky binders attached to the catalytic metal, a non-limiting example includes bis (isopropyl-cyclopentadienyl) hafnium dichloride. In bridged metallocene catalysts the two bulky binders are covalently linked (bridged) to each other, a non-limiting example includes diphenylmethylene dichloride (cyclopentadienyl) (2,7-di-t-butylfuorenyl) hafnium; wherein the diphenylmethylene group bonds or bridges, the bulky cyclopentadienyl and fluorenyl ligands together. Two additional subsets of the homogeneous catalyst genus include single-bridged and bridged single-site catalysts. In this disclosure, single-site catalysts are characterized as having only a bulky binder attached to the catalytic metal. A non-limiting example of a single site non-bridged catalyst includes cyclopentadienyl dichloride tri (tertiary butyl) phosphinimine titanium. A non-limiting example of a single site bridged catalyst includes [C5 (CH3) 4 - Si (CH3) 2 N (tBu)] titanium dichloride, where the group -Si (CH3) 2- functions as the group of jumper.
Petition 870190112009, of 11/01/2019, p. 26/168
20/156
[055] Here, the term "polyolefin" includes polymers of ethylene and polymers of propylene; non-limiting examples of propylene polymers include isotactic, syndiotactic and atactic propylene homopolymers, random propylene copolymers containing at least one comonomer (e.g., α-olefins) and impact polypropylene copolymers or heterophasic polypropylene copolymers.
[056] The term "thermoplastic" refers to a polymer that becomes liquid when heated, will flow under pressure and solidify when cooled. Thermoplastic polymers include polymers of ethylene as well as other polymers used in the plastic industry; non-limiting examples of other polymers commonly used in film applications include barrier resins (EVOH), adhesive resins, polyethylene terephthalate (PET), polyamides and the like.
[057] As used here the term "monolayer film" refers to a film containing a single layer of one or more thermoplastics.
[058] As used here, the terms "hydrocarbyl", "hydrocarbyl radical" or "hydrocarbyl group" refer to linear, branched or cyclic, aliphatic, olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogen and carbon that are deficient in a hydrogen.
[059] As used here, an "alkyl radical" includes linear, branched and cyclic paraffin radicals that are deficient in a hydrogen radical; non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3) radicals. The term "alkenyl radical" refers to linear, branched and cyclic hydrocarbons containing at least one carbon-carbon double bond that is deficient in a hydrogen radical.
[060] As used here, the term "aryl" group includes phenyl, naphthyl, pyridyl and other radicals whose molecules have an aromatic ring structure; non-limiting examples include naphthylene, phenanthrene and anthracene. An "arylalkyl" group is an alkyl group having an aryl group pending on it; non-limiting examples include benzyl, phenethyl and tolylmethyl; an "alkylaryl" is an aryl group having one or more alkyl groups
Petition 870190112009, of 11/01/2019, p. 27/168
21/156 pending this; non-limiting examples include tolyl, xylil, mesity and cumila.
[061] As used here, the phrase "heteroatom" includes any atom except carbon and hydrogen that can be attached to carbon. A "heteroatom-containing group" is a hydrocarbon radical that contains a heteroatom and can contain one or more of the same or different heteroatoms. In one embodiment, a group containing heteroatom is a hydrocarbyl group containing 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur. Non-limiting examples of heteroatom-containing groups include radicals from imines, amines, oxides, phosphines, ethers, ketones, heterocyclic oxoazolines, oxazolines, thioethers and the like. The term "heterocyclic" refers to ring systems having a main carbon chain comprising 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur.
[062] As used here the term "unsubstituted" means that the hydrogen radicals are attached to the molecular group that follows the term unsubstituted. The term "substituted" means that the group that follows this term has one or more moieties that have replaced one or more hydrogen radicals at any position within the group; non-limiting examples of moieties include halogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1 to C1 alkyl groups, C2 to alkenyl groups C10 and combinations of these. Non-limiting examples of alkyls and substituted aryls include: acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyl radicals, acyl radicals , arylamino radicals and combinations thereof.
[063] Here the term “R1” and its superscript form “ ^R1 ” refers to a first reactor in a continuous solution polymerization process; being understood that
Petition 870190112009, of 11/01/2019, p. 28/168
22/156
R1 is distinctly different from the symbol R ¹ ; the latter is used in chemical formula, for example, representing a hydrocarbyl group. Similarly, the term "R2" and its superscript form " ^R2 " refer to a second reactor, and; the term "R3" and its superscript form " ^R3 " refer to a third reactor.
[064] As used herein, the term "oligomers" refers to a low molecular weight ethylene polymer, for example, an ethylene polymer with a weighted average molecular weight (Mw) of about 2000 to 3000 daltons. Other terms commonly used for oligomers include "wax" or "grease". As used here, the term "lighter impurities" refers to chemical compounds with relatively low boiling points that may be present in the various process vessels and streams within a continuous solution polymerization process; non-limiting examples include, methane, ethane, propane, butane, nitrogen, CO2, chloroethane, HCI, etc.
DESCRIPTION OF MODALITIES
Catalysts
[065] Catalyst formulations that are efficient in polymerizing defines are well known. In the embodiments disclosed here, at least two catalyst formulations were used in a continuous solution polymerization process. One of the catalyst formulations comprised a first homogeneous catalyst formulation that produces a first homogeneous ethylene interpolymer in a first reactor, one embodiment of the first homogeneous catalyst formulation was a bridged metallocene catalyst formulation (Formula (I)). The other catalyst formulation comprised a first heterogeneous catalyst formulation which produced a second heterogeneous ethylene interpolymer in a second reactor. Optionally a third ethylene interpolymer can be produced in a third reactor using one or more of: the first heterogeneous catalyst formulation, a second catalyst formulation
Petition 870190112009, of 11/01/2019, p. 29/168
23/156 heterogeneous and / or a fifth formulation of homogeneous catalyst. The fifth homogeneous catalyst formulation was selected from the first homogeneous catalyst formulation, a third homogeneous catalyst formulation and / or a fourth homogeneous catalyst formulation; one embodiment of the third homogeneous catalyst formulation was a single site non-bridged catalyst formulation (Formula (II)) and the fourth homogeneous catalyst formulation contains a bulky ligand-metal complex that was not a species of the defined chemical genera Formula (I) or Formula (II). In the disclosed continuous solution process, at least one homogeneous ethylene interpolymer and at least one heterogeneous ethylene interpolymer were produced and the solution mixed to produce an ethylene interpolymer product.
Bulky binder-metal complexes
Component A
[066] The present disclosure included "a first formulation of homogeneous catalyst". One embodiment of the first homogeneous catalyst formulation was "a bridged metallocene catalyst formulation" containing a bulky binder-metal complex, then "component A", represented by Formula (I).
(I)
[067] In Formula (I): non-limiting examples of M include metals from the Group
4, that is, titanium, zirconium and hafnium; non-limiting examples of G include elements
Petition 870190112009, of 11/01/2019, p. 30/168
24/156 of Group 14, carbon, silicon, germanium, tin and lead; X represents a halogen, fluorine, chlorine, bromine or iodine atom; the Re groups are independently selected from a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy radical or a C6-10 aryl oxide radical (these radicals can be linear, branched or cyclic or substituted with halogen atoms , C1-10 aikyl radicals, C1-10 alkoxy radicals, aryl or C6-10 aryloxy radicals); R1 represents a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy radical or a C6-10 aryl oxide radical; R2 and R3 are independently selected from a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy radical or a C6-10 aryl oxide radical, and; R4 and Rs are independently selected from a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy radical or a C6-10 aryl oxide radical.
[068] In the art, a term commonly used for the group X (Re) shown in Formula (I) is "starting group", that is any ligand that can be abstracted from Formula (I) forming a kind of catalyst capable of polymerize one or more sets. An equivalent term for group X (Re) is an “activable ligand”. Other non-limiting examples of the X (Re) group shown in Formula (I) include weak bases such as amines, phosphines, ethers, carboxylates and dienes. In another embodiment, the two groups Re may form part of a fused ring or ring system.
[069] Other modalities of component A include structural, optical or enantiomeric isomers (meso and racemic isomers) and mixtures of these of the structure shown in Formula (I).
[070] In this disclosure, several species of component A (Formula (I)) were denoted by the terms "component A1", "component A2" and "component A3", etc. Although not interpreted as limiting, two species of component A were used as the examples in this disclosure. Specifically: “component A1” refers to diphenylmethylene chloride (cyclopentadienyl) (2,7-di-t-butylfuorenyl) hafnium
Petition 870190112009, of 11/01/2019, p. 31/168
25/156 having the molecular formula [(2,7-tBu2Flu) Ph2C (Cp) HfCl2], and; "Component A2" refers to diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfuorenyl) hafnium dimethyl having the molecular formula [(2,7-tBu2Flu) Ph2C (Cp) HfMe2]. In this disclosure, component A1 and component A2 were used to prepare examples of the bridged metallocene catalyst formulation.
Long chain branching in ethylene interpolymer products (via Component A)
[071] In this disclosure, the first homogeneous catalyst formulation, comprising a component A, produces ethylene interpolymer products that have long chain branches, then 'LCB'.
[072] LCB is a structural phenomenon well known in polyethylenes and well known to those of ordinary skill in the art. Traditionally, there are three methods for LCB analysis, that is, nuclear magnetic resonance (NMR) spectroscopy, for example see J.C. Randall, J Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201; Triple detection SEC equipped with a DRI, a viscometer and a low angle laser light scattering detector, for example see W.W. Yau and D.R. Hill, Int. J. Polym. Anal. Charact. 1996; 2: 151; and rheology, for example see W.W. Graessley, Acc. Chem. 1977, 10, 332-3339. In this disclosure, a long chain branch is macromolecular in nature, that is, long enough to be observed in an NMR spectrum, triple detector SEC experiments or rheological experiments.
[073] A limitation with LCB analysis using NMR is that it cannot distinguish the branch length for branches equal to or longer than six carbon atoms (thus, NMR cannot be used to characterize LCB in copolymers ethylene / 1-octene, which have hexyl groups as side branches).
[074] The SEC method of triple detection measures intrinsic viscosity ([η])
Petition 870190112009, of 11/01/2019, p. 32/168
26/156 (see WW Yau, D. Gillespie, Analytical and Polymer Science, TAPPI Polymers, Laminations, and Coatings Conference Proceedings, Chicago 2000; 2: 699 or F. Beer, G. Capaccio, LJ Rose, J. Appl. Polym Sci. 1999, 73: 2807 or PM Wood-Adams, JM Dealy, AW deGroot, OD Redwine, Macromolecules 2000; 33: 7489). Referring to the intrinsic viscosity of a branched polymer ([q] b) to that of a linear unit ([η] ι) at the same molecular weight, the viscosity branch index factor g '(g' = [n] b / [q] i) was used to characterize the branch. However, both short chain branching (SCB) and long chain branching (LCB) contribute to intrinsic viscosity ([q]), an effort was made to isolate the SCB contribution to ethylene / 1-butene and ethylene / 1 copolymers -hexene but not ethylene / 1-octene copolymers (see Lue et al., US6,870,010 B1). In this disclosure, a systematic investigation was carried out to observe the impact of SCB on the Mark-Houwink K constant for three types of ethylene / 1-olefin copolymers, that is, octene, hexene and butene copolymers. After deducting the SCB contribution, an LCB Viscosity index was introduced for the characterization of ethylene / 1-olefin copolymers containing LCB. The viscosity LCB index was defined as the Mark-Houwink constant (Km) measured in 1,2,4 trichlorobenzene (TCB) at 140 ° C for the sample divided by the SCH corrected MarkHouwink constant (Kco) for copolymer of ethylene / linear 1-olefin, Eq. (1).
LCB Viscosity Index - =
Kco
[η] / Μ ° · ⁷²⁵ (391.98 — A xSCS) / 1000000
Eq. (1)
Where [q] was the intrinsic viscosity (dL / g) determined by 3D-SEC, M _v was the average viscosity molar mass (g / mol) determined using 3D-SEC; SCB was the short chain branch content (CH3 # / 1000C) determined using FTIR, and; A was a constant that depends on the α-olefin present in the ethylene / aolefin interpolymer under test, specifically, A is 2.1626, 1.9772 and 1.1398 for 1-octene, 1hexene and 1-butene respectively. In the case of an ethylene homopolymer, no correction is necessary for the Mark-Houwink constant, that is, SCB is
Petition 870190112009, of 11/01/2019, p. 33/168
27/156 zero.
[075] In the art, rheology was also an effective method to measure the amount of LCB or lack thereof, in ethylene interpolymers. Various rheological methods for quantifying LCB have been disclosed. A commonly used method was based on data of zero shear viscosity (ηο) and weighted average molar mass (Mw). The power dependence of 3.41 (ηο = KxMw ^{3 41} ) was established for monodispersed polyethylene composed only of linear chains, for example see RL Arnett and CP Thomas, J. Phys. Chem. 1980, 84, 649 - 652. An ethylene polymer with an ηο exceeding what was expected for a linear ethylene polymer, with the same Mw, was considered to contain long chain branches. However, there is a debate in the field regarding the influence of polydispersity, for example, Mw / M _n . A dependence on polydispersity has been observed in some cases (see M. Ansari et al., Rheol. Acta, 2011, 5017-27) but not in others (see TP Karjala et al., Journal of Applied Polymer Science 2011, 636 - 646 ).
[076] Another example of LCB analysis by means of rheology was based on data of zero shear viscosity (ηο) and intrinsic viscosity ([η]), for example see RN Shroff and H. Mavridis, Macromolecules 1999, 32, 8454; which is applicable for essentially linear polyethylene (ie polyethylene with very low levels of LCB). A critical limitation of this method is SCB's contribution to intrinsic viscosity. It is well known that [η] decreases with increasing SCB content.
[077] In this disclosure, a systematic investigation was carried out to observe the impact of both SCB and molar mass distribution. After deducting the contribution of both SCB and molar mass distribution (polydispersity), a Long Chain Branching Factor (LCBF) was introduced to characterize the amount of LCB in ethylene / a copolymers
Petition 870190112009, of 11/01/2019, p. 34/168
28/156 olefin, as described below.
Long Chain Branching Factor (LCBF)
[078] In this disclosure the Long Chain Branching Factor, then LCBF, was used to characterize the amount of LCB in ethylene interpolymer products. The ethylene interpolymer products disclosed were in situ mixtures of at least two ethylene interpolymers produced with at least two different catalyst formulations.
[079] Figure 1 illustrates the LCBF calculation. The solid ‘Reference Line’ shown in Figure 1 features ethylene polymers that do not contain LCB (or undetectable LCB). Ethylene polymers containing LCB deviate from this Reference Line. For example, the ethylene interpolymer products disclosed in Examples 1 to 4 (the open circles in Figure 1) deviate horizontally and vertically from the Reference Line.
[080] C LCBF calculation requires the corrected zero shear viscosity (ZSVc) of polydispersity and the corrected intrinsic viscosity of SCB (IV _C ) as fully described in the following paragraphs.
[081] The correction for the Zero Shear Viscosity, ZSVc, having poise dimensions, was performed as shown in equation Eq. (2):
i, 8389 x ) o and where ηο, the zero shear viscosity (poise), was measured by DMA as described in the ‘Test Methods’ section of this disclosure; Pd was dimensionless polydispersity (Mw / Mn) as measured using conventional SEC (see ‘Test Methods’) and 1.8389 and 2.4110 are dimensionless constants.
[082] The correction for intrinsic viscosity, IVc, having dimensions of dL / g, was performed as shown in equation Eq. (3):
IV _C = [;,] ₊ ^ xSCBxMg ' ^{725 c L / J} 1000000 ^v ' where the intrinsic viscosity [η] (dL / g) was measured using 3D-SEC (see
Petition 870190112009, of 11/01/2019, p. 35/168
29/156 'Test Methods'); SCB having dimensions of (CH3 # / 1000C) was determined using FTIR (see 'Test Methods'); M _v , the average viscosity molar mass (g / mol), was determined using 3D-SEC (see 'Test Methods'), and; A was a dimensionless constant that depends on α-olefin in the ethylene / aolefin interpolymer sample, that is, A was 2.1626, 1.9772 or 1.1398 for 1-octene, 1-hexene and 1-olefins -butene, respectively. In the case of an ethylene homopolymer, no correction is necessary for the Mark-Houwink constant, that is, SCB is zero.
[083] As shown in Figure 1, linear ethylene / α-olefin interpolymers (which do not contain LCB or contain undetectable levels of LCB) fall into the Reference Line defined by Eq. (4).
Lo # (/ 7 _C ) = 0.2100 x Log (ZSV _c ) - 0.7879 Eq. (4)
[084] Table 1A shows that the Reference Resins had Mw / Mn values ranging from 1.68 to 9.23 and contained 1-octene, 1-hexene or 1-butene α-olefins. In addition, Reference Resins included ethylene polymers produced in solution, gas phase or slurry processes with Ziegler-Natta, homogeneous and mixed (Ziegler-Natta + homogeneous) catalyst formulations.
[085] The ethylene interpolymer products, disclosed here, contain long chain branching as evidenced by Table 2 and Figure 1. More specifically, Table 2 discloses that the LCBF of Examples 1 to 4 were 0.0034, 0.0099 , 0.021 and 0.029, respectively. Examples 1 to 4 (open circles) deviate significantly from the Reference Line shown in Figure 1. Examples 1 to 4 were produced using a bridged metallocene catalyst formulation in the first reactor and an in-line Ziegler-Natta catalyst formulation in the second reactor. In contrast, as shown in Table 2, Comparatives 1, 2 had LCBF much lower than 0.00070 and 0.00068, respectively and these samples were well described by the linear Reference Line shown in Figure 1 (the symbols of X- bar), that is, Comparatives 1 and 2
Petition 870190112009, of 11/01/2019, p. 36/168
30/156 have no undetectable LCB or LCB.
[086] Comparatives 1 and 2 were produced in a pilot solution process installation using a single site non-bridged catalyst formulation in the first reactor and an in-line Ziegler-Natta catalyst formulation in the second reactor where the two reactors were operated in serial mode. Comparatives 10 and 11 (Table 2) were produced in a commercial scale solution process using a single site non-bridged catalyst formulation in the first reactor and an in-line Ziegler-Natta catalyst formulation in the second reactor ( series). Regarding Examples 1 to 4, Comparatives 10 and 11 had much lower LCBFs of 0.00023 and 0.0000658, respectively and these samples were well described by the linear Reference Line shown in Figure 1 (the symbols X).
[087] As shown in Figure 1, the LCBF calculation was based on the Horizontal Shift (Sh) and Vertical Shift (Sv) of the linear reference line, as defined by the following equations:
S _h = LogÇZSVc) - 4.7619 x LogQV ^ - 3.7519 Eq. (5)
S _v = 0.2100 x LogizVS) - LogQV ^ - 0.7879 Eq. (6).
[088] In Eq. (5) and (6), it is necessary that ZSV _C and IVc have dimensions of poise and dL / g, respectively. The Horizontal Displacement (Sh) was a displacement in ZSVc in constant Intrinsic Viscosity (IVc), if someone removes the Log function its physical meaning is apparent, this is a ratio of two Zero Shear Viscosities, the ZSVc of the sample under test in relation to to the ZSVc of a linear ethylene polymer having the same IVc. The Horizontal Shift (Sh) was dimensionless. The Vertical Displacement (Sv) was a displacement in IVc in constant Zero Shear Viscosity (ZSVc), if someone removes the Log function its physical meaning is apparent, that is, a ratio of two Intrinsic Viscosities, the IVc of an ethylene polymer linear having the same ZSVc in relation to the IVc of the sample under test.
Petition 870190112009, of 11/01/2019, p. 37/168
31/156
Vertical Displacement (Sv) was dimensionless.
[089] The dimensionless long chain branching factor (LCBF) was defined by Eq. (7):
LCBF ₌ ^ E _{Eq (7)}
[090] Given the date data in Table 2, the LCBF of the Examples and Comparatives were calculated. To be clearer, as shown in Table 2, the Sh and Sv of Example 3 were 0.442 and 0.0929, respectively, so the LCBF was 0.0205 ((0.442 x 0.0929) / 2). On the contrary, the Sh and Sv of Comparative 2 were 0.0804 and 0.0169, respectively, so the LCBF was 0.000678 ((0.0804 x 0.0169) / 2).
[091] In this disclosure, resins having no LCB (or undetectable LCB) were characterized by an LCBF of less than 0.001 (dimensionless), as evidenced by Table 1B where the reference resins had LCBF values ranging from 0.000426 to 1 , 47x10 ' ⁹ .
[092] In this disclosure, resins having LCB were characterized by an LCBF of> 0.001 (dimensionless), as evidenced by Examples 1 and 4 shown in Table 2 which had LCBF of 0.00339 and 0.0291, respectively.
[093] Table 3 summarizes the LCBF of Comparatives A to C and Comparatives D to G. It is believed that Comparatives A to C (diamond open in Figure 1) were produced in a solution process using a reactor and a formulation limited site geometry catalyst, ie AFFINITY ™ PL 1880 (three different samples (batches)). AFFINITY ™ products are ethylene / 1-octene interpolymers available from The Dow Chemical Company (Midland, Michigan, USA). It has been well documented in the art that the limited geometry catalyst produces long chain branched ethylene / 1-octene copolymers, as evidenced by the LCBF values disclosed in Table 3, that is, from 0.0396 to 0.0423. Comparatives D to G (open squares in Figure 1) are believed to have been double reactor ethylene interpolymers and double solution process series catalysts, where
Petition 870190112009, of 11/01/2019, p. 38/168
32/156 a single-site catalyst formulation of limited geometry was used in a first reactor and a batch Ziegler-Natta catalyst formulation was used in a second reactor, ie Elite® 5401G and Elite® 5100G (two different samples (lots)) and Elite® 5400G, respectively. Elite® products are ethylene / 1-octene interpolymers available from The Dow Chemical Company (Midland, Michigan, USA). As shown in Table 3, Comparatives D to G had LCBF values from 0.00803 to 0.0130.
Determination of ¹³ C NMR of long chain branching in the first ethylene interpolymer
[094] Examples of ethylene interpolymer product, disclosed here, contain a first ethylene interpolymer that was produced with a first homogeneous catalyst formulation. One embodiment of the first homogeneous catalyst formulation was a bridged metallocene catalyst formulation, this catalyst formulation produced a first long chain branched ethylene (polymer) interpolymer (LCB). Pure samples of the first ethylene interpolymer were produced using the Continuous Polymerization Unit (CPU). The CPU was fully described in the 'Continuous Polymerization Unit (CPU)' section of this disclosure. The CPU employs a reactor and a catalyst formulation was used. The CPU and the bridged metallocene catalyst formulation containing Component A [(2,7-tBu2Flu) Ph2C (Cp) HfMe2] were used to produce examples of the first ethylene interpolymer and the amount of long chain branching in this interpolymer was measured by ¹³ C NMR. Table 11 illustrates the typical CPU operation continuity for the formulation of a bridged metallocene catalyst to produce a first ethylene interpolymer at three reactor temperatures (130 ° C, 160 ° C and 190 ° C ° C) and two levels of ethylene conversion, that is, low ethylene conversion (about 75%) and high ethylene conversion (about 94%). No hydrogen was used.
Petition 870190112009, of 11/01/2019, p. 39/168
33/156
[095] Table 12 discloses the amount of LCB in examples C10 to C15, that is, pure samples of the first ethylene interpolymer, produced with the bridged metallocene catalyst formulation, as determined by ¹³ C NMR (magnetic resonance) nuclear). Examples C10 to C15 were homopolymers of ethylene produced in the CPU at three reactor temperatures (190 ° C, 160 ° C and 130 ° C), three levels of ethylene conversions, that is, about 95% by weight, about 85 % by weight and about 75% by weight and no hydrogen was used. As shown in Table 12, the amount of long chain branching in the first ethylene interpolymer ranged from 0.03 LCB / 1000C to 0.23 LCB / 1000C.
Component C
[096] The present disclosure includes "a third formulation of homogeneous catalyst". One embodiment of the third homogeneous catalyst formulation includes "a single site non-bridged catalyst formulation" containing a bulky binder-metal complex, then "component C", represented by Formula (II).
(L ^A ) aM (PI) b (Q) n (ll)
[097] In Formula (II): (L ^A ) represents a bulky binder; M represents a metal atom; PI represents a phosphinimine linker; Q represents a starting group; a is 0 or 1; b is 1 or 2; (a + b) = 2; n is 1 or 2, and; the sum of (a + b + n) is equivalent to the valence of metal M. Non-limiting examples of M in Formula (II) include Group 4 metals, titanium, zirconium and hafnium.
[098] Non-limiting examples of the bulky ligand L ^A in Formula (II) include ligands unsubstituted or substituted by cyclopentadienyl or ligands of the cyclopentadienyl type, cyclopentadienyl type ligands substituted by heteroatom and / or containing heteroatom. Additional non-limiting examples include cyclopentafenanthrene binders, indenyl unsubstituted or substituted binders, benzindenyl binders, fluorenyl unsubstituted or substituted binders,
Petition 870190112009, of 11/01/2019, p. 40/168
34/156 octahydrofluorenyl binders, cyclooctatetraendiyl binders, cyclopentacyclododecene binders, azenyl binders, azulene binders, pentalene binders, phosphoyl binders, phosphineimine, pyrrolyl binders, pirozolyl binders, and carbazoline binders, and carbazoline binders , including hydrogenated versions of these, for example tetrahydroindenyl binders. In other embodiments, L ^A can be any other binder structure capable of η-bonding to metal M, such modalities include both q ^3- bonding and q ^5- bonding to metal M. In other embodiments, L ^A can comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorus, in combination with carbon atoms to form an open, acyclic ring or a fused ring or ring system, for example, an auxiliary heterocyclopentadienyl linker. Other non-limiting modalities for L ^A include amides, phosphides, alkoxides, aryloxides, imides, carbolides, borolides, porphyrins, phthalocyanines, corrinas and other bulky polyazomacrocyclones.
[099] The phosphinimine ligand, PI, is defined by Formula (III):
(Rp) ₃ P = N - (III) in which the groups R ^p are independently selected from: a hydrogen atom; a halogen atom; C1-20 hydrocarbyl radicals that are unsubstituted or substituted with one or more halogen atoms; a C1-8 alkoxy radical; a C6-10 aryl radical; a C6-10 aryloxy radical; a starch radical; a silyl radical of the formula -Si (R ^s ) s, where the R ^s groups are independently selected from, a hydrogen atom, a C1-8 alkyl or alkoxy radical, a C6-10 aryl radical, a C6- aryloxy radical 10 or a Germanyl radical of the formula -Ge (R ^G ) s, where the R ^G groups are defined as R ^s is defined in this paragraph.
[0100] The starting group Q is any ligand that can be abstracted from Formula (II) forming a kind of catalyst capable of polymerizing one or more defines. In some embodiments, Q is a monoanonic unstable ligand having a sigma bond to M. Depending on the oxidation state of the metal, the value for n is 1
Petition 870190112009, of 11/01/2019, p. 41/168
35/156 or 2 such that Formula (II) represents a neutral bulky binder-metal complex. Non-limiting examples of Q ligands include a hydrogen atom, halogens, C1-20 hydrocarbyl radicals, C1-20 alkoxy radicals, C5-10 aryl oxide radicals; these radicals can be linear, branched or cyclic or replaced by halogen atoms, C1-10 alkyl radicals, C1-10 alkoxy radicals, C6-10 aryl radicals or aryloxy. Other non-limiting examples of Q linkers include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having 1 to 20 carbon atoms. In another embodiment, two Q linkers can form part of a fused ring or ring system.
[0101] Other modalities of component C include structural, optical or enantiomeric isomers (meso and racemic isomers) and mixtures of these from the bulky ligand-metal complex shown in Formula (II).
[0102] In this disclosure, unique chemical species of component C (Formula (II)) are denoted by the terms "component C1", "component C2" and "component C3", etc. Although not interpreted as limiting, two species of component C were used as examples in this disclosure. Specifically: "component C1" refers to cyclopentadienyl dichloride tri (tertiary butyl) phosphinimine titanium having the molecular formula [Cp [(t-Bu) 3PN] TiCl2], and; "Component C2" refers to cyclopentadienyl dichloride tri (isopropyl) phosphinimine titanium having the molecular formula [Cp [(isopropyl) 3PN] TiCl2]. In this disclosure, component C1 and component C2 were used as the source of bulky binder-metal complex to prepare two examples of the single-site non-bridged catalyst formulation.
Long chain branching in ethylene interpolymers produced with Component C
[0103] As shown in Figure 1 and Table 2, Comparative ethylene interpolymer products (Comparative 1,2, 10 and 11) produced with a homogeneous catalyst formulation containing Component C had undetectable levels of LCB,
Petition 870190112009, of 11/01/2019, p. 42/168
36/156 as evidenced by the dimensionless long chain branching factor (LCBF) of less than 0.001, for example, LCBF ranged from 0.0000658 to 0.000700.
Homogeneous catalyst formulations
[0104] In this non-limiting disclosure "Examples" of ethylene interpolymer product were prepared using a metallocene catalyst formulation bridged in a first reactor. The bridged metallocene catalyst formulation contains a component A (defined above), a component M ^A , a component B ^A and a component P ^A. Components Μ, B and P are defined below and the superscript “ ^A ” denotes the fact that the respective component was part of the catalyst formulation containing component A, that is, the bridged metallocene catalyst formulation.
[0105] In this disclosure "comparative" ethylene interpolymers were prepared using a single site non-bridged catalyst formulation in the first reactor. In other words, in Comparative Samples, the non-bridged single-site catalyst formulation replaced the bridged metallocene catalyst formulation in the first reactor. The single site non-bridged catalyst formulation contains a component C (defined above), a component M ^c , a component B ^c and a component P ^c . Components Μ, B and P are defined below and the superscript “ ^c ” denotes the fact that the respective component was part of the catalyst formulation containing component C, that is, the formulation of a single site non-bridged catalyst.
[0106] The catalyst components Μ, B and P were independently selected for each catalyst formulation. To be clearer: components M ^A and M ^c may or may not be the same chemical compound; components B ^A and B ^c may or may not be the same chemical compound, and; P ^A and P ^{c components} may or may not be the same chemical compound. In addition, the activity of the catalyst has been optimized by independently adjusting the mol ratios of the components in each
Petition 870190112009, of 11/01/2019, p. 43/168
37/156 catalyst formulation.
[0107] Components M, B and P were not particularly limited, that is, a wide variety of components can be used as described below.
[0108] Component M functioned as a co-catalyst that activated component A or component C, in a cationic complex that effectively polymerized ethylene or mixtures of ethylene and α-olefins, produced high molecular weight ethylene interpolymers. In the formulation of bridged metallocene catalyst and in the formulation of single site non-bridged catalyst the respective M component has been independently selected from a variety of compounds and those skilled in the art will understand that the modalities in this disclosure are not limited to the chemical compound specific disclosure. Suitable compounds for component M included an alumoxane co-catalyst (an equivalent term for alumoxane is aluminoxane). Although the exact structure of an alumoxane co-catalyst was uncertain, subject matter experts generally agree that it was an oligomeric species that contains repeat units of the General Formula (IV):
(R) ₂ AIO- (AI (R) -O) n-AI (R) ₂ (IV) where the R groups can be the same linear, branched or cyclic or different hydrocarbyl radicals containing 1 to 20 carbon atoms and n is from 0 to about 50. A non-limiting example of an alumoxane was methyl aluminoxane (or MMAO-7) where each R group in Formula (IV) is a methyl radical.
[0109] Component B was an ionic activator. In general, ionic activators are comprised of a cation and a bulky anion; where the latter is substantially non-coordinating.
[0110] In the formulation of bridged metallocene catalyst and in the formulation of single site non-bridged catalyst the respective component B was independently selected from a variety of compounds and those
Petition 870190112009, of 11/01/2019, p. 44/168
38/156 skilled in the art will understand that the modalities in this disclosure are not limited to the specific chemical compound disclosed. Non-limiting examples of component B were boron ionic activators which are four coordinates with four ligands attached to the boron atom. Non-limiting examples of boron ionic activators included the following Formulas (V) and (VI) shown below;
[R ⁵ ] ⁺ [B (R ⁷ ) 4] - (V) where B represented a boron atom, R ⁵ was an aromatic hydrocarbyl (eg, triphenyl methyl cation) and each R ⁷ was independently selected from phenyl radicals that have been unsubstituted or substituted with 3 to 5 substituents selected from fluorine atoms, C 1-4 alkyl radicals or alkoxy that have been unsubstituted or replaced by fluorine atoms; and a silyl radical of the formula -Si (R ⁹ ) s, where each R ⁹ was independently selected from hydrogen atoms and C 1-4 alkyl radicals, and; compounds of the formula (VI);
[(R ⁸ ) tZH] ⁺ [B (R ⁷ ) ₄ ] - (VI) where B was a boron atom, H was a hydrogen atom, Z was a nitrogen or phosphorus atom, t was 2 or 3 and R ⁸ was selected from C1-8 alkyl radicals, phenyl radicals that were unsubstituted or replaced by up to three C1-4 alkyl radicals or an R ⁸ taken together with the nitrogen atom can form an anilinium radical and R ⁷ was as defined above in Formula (VI).
[0111] In both Formula (V) and (VI), a non-limiting example of R ⁷ was a pentafluorophenyl radical. In general, boron ionic activators can be described as tetra (perfluorophenyl) boron salts; non-limiting examples include anilinium, carbon, oxon, phosphonium and sulfur of tetra (perfluorophenyl) boron with anilinium and trityl (or triphenylmethyl). Additional non-limiting examples of ionic activators included: triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (nbutil) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (otolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, pPetition 870190112009, from 11/01/2019, page 45/168
39/156 dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (ptrifluoromethylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tri (n-butyl) ammonium tetra (o-N-tolyl) boron, N, -dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) n-butylboron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron, di - (isopropyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) borohydrophenyl tetra (phenyl) boro tropilio borate, tetracispentafluorophenyl triphenylmethyl borate, benzene borate (diazonia) tetracispentafluorophenyl, tetracis (2,3,5,6-tetrafluorophenyl) tropilio borate, tetracis (2,3,5,6-tetrafluorophenyltrilylphenyl boron), (diazonia) tetracis (3,4,5-trifluorophenyl) borate, tetracis (3,4,5-trifluorophenyl) tropilium borate, benzene (diazonia) tetracis (3,4,5-trifluorophenyl) bor ato, tetracis (1,2,2trifluoroetenil) tropilio borate, tetracis (1,2,2-trifluoroetenil) triphenylmethyl borate, benzene (diazonia) tetracis (1,2,2-trifluoroetenil) borate, tetracis (2,3, 4,5 tetrafluorophenyl) tropilium borate, tetracis (2,3,4,5-tetrafluorophenyl) triphenylmethyl borate and benzene (diazonia) tetracis (2,3,4,5 tetrafluorophenyl) borate. Commercially available ionic activators included N, N-dimethylanilinium tetracispentafluorophenyl borate and triphenylmethyl tetracispentafluorophenyl borate.
[0112] Component P is an impeded phenol and is an optional component in the respective catalyst formulation. In the formulation of bridged metallocene catalyst and in the formulation of single site non-bridged catalyst the respective P component has been independently selected from a variety of compounds and those skilled in the art will understand that the modalities in this disclosure are not limited to the chemical compound specific disclosure. Non-limiting examples of hindered phenols included butylated phenolic antioxidants, butylated hydroxytoluene, 2,4-di-tertiaributyl-6-ethyl phenol, 4,4'-methylenebis (2,6-di-tertiary-butylphenol), 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene
Petition 870190112009, of 11/01/2019, p. 46/168
40/156 and octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate.
[0113] As completely described below, a first highly active homogeneous catalyst formulation or in a specific embodiment a highly active bridged metallocene catalyst formulation was produced by optimizing the quantity and mol ratios of the four components in the formulation; for example, component A1, component M ^A1 , component B ^A1 and component P ^A1 . Where highly active means a very large amount of ethylene interpolymer is produced from a very small amount of catalyst formulation. Similarly, a third highly active homogeneous catalyst formulation or a single site non-bridged catalyst formulation (comparative catalyst formulations) were produced by optimizing the quantity and mol ratios of the four components in the formulation; for example, an embodiment comprises a component C1, a component M ^C1 , a component B ^C1 and a component P ^C1 .
Heterogeneous catalyst formulations
[0114] Various heterogeneous catalyst formulations are well known to those skilled in the art, including, as non-limiting examples, Ziegler-Natta and chromium catalyst formulations. In this disclosure, a first heterogeneous catalyst formulation was used to make the Examples, as well as Comparatives, where the first heterogeneous catalyst formulation was injected into a second reactor producing the second ethylene interpolymer. In this disclosure, a second optional heterogeneous catalyst formulation can be used, where the second heterogeneous catalyst formulation can be injected into a third reactor producing an optional third ethylene interpolymer. In this disclosure, the catalytic metal in the first heterogeneous catalyst formulation was identified by the term "metal Z1"; the catalytic metal in the second heterogeneous catalyst formulation was identified by the term "metal Z2".
Petition 870190112009, of 11/01/2019, p. 47/168
41/156
[0115] In this disclosure, modalities are described where “a first in-line Ziegler-Natta catalyst formulation” and “a first batch Ziegler-Natta catalyst formulation” are used. The term "in-line" refers to the continuous synthesis of a small amount of active Ziegler-Natta catalyst and immediately injecting this catalyst into at least one continuously operating reactor, in which the catalyst polymerizes ethylene and one or more α-olefins optional to form an ethylene interpolymer. The term "batch" refers to the synthesis of a much larger amount of catalyst or pro-catalyst in one or more mixing vessels that are external or isolated from the continuously operating solution polymerization process. Once prepared, the batch ZieglerNatta catalyst formulation or batch Ziegler-Natta pro catalyst is transferred to a catalyst storage tank. The term "pro-catalyst" refers to an inactive catalyst formulation (inactive with respect to the polymerization of ethylene); the pro-catalyst is converted into an active catalyst by adding an alkyl aluminum co-catalyst. As needed, the pro-catalyst is pumped from the storage tank to at least one continuously operating reactor, in which an active catalyst polymerizes ethylene and one or more optional α-olefins to form an ethylene interpolymer. The pro-catalyst can be converted into an active catalyst in the reactor or external to the reactor.
[0116] A wide variety of chemical compounds can be used to synthesize an active Ziegler-Natta catalyst formulation. The following describes several chemical compounds that can be combined to produce an active Ziegler-Natta catalyst formulation. Those skilled in the art will understand that the modalities in this disclosure are not limited to the specific chemical compound disclosed.
[0117] An active Ziegler-Natta catalyst formulation can be formed from: a magnesium compound, a chloride compound, a metallic compound,
Petition 870190112009, of 11/01/2019, p. 48/168
42/156 is an alkyl aluminum co-catalyst and an alkyl aluminum. In this disclosure, for example in Table 4A, the term “component (v)” is equivalent to the magnesium compound, the term “component (vi)” is equivalent to the chloride compound, the term “component (vii)” is equivalent to metallic compound, the term "component (viii)" is equivalent to the alkyl aluminum co-catalyst and the term "component (ix)" is equivalent to the alkyl aluminum. As will be assessed by those skilled in the art, Ziegler-Natta catalyst formulations may contain additional components; a non-limiting example of an additional component is an electron donor, for example, amines or ethers.
[0118] A non-limiting example of a ZieglerNatta catalyst formulation active online can be prepared as follows. In the first step, a solution of a magnesium compound (component (v)) is reacted with a solution of the chloride compound (component (vi)) to form a magnesium chloride support suspended in solution. Non-limiting examples of magnesium compound include Mg (R ¹ ) 2; wherein the R ¹ groups can be the same or different, linear, branched or cyclic hydrocarbyl radicals containing 1 to 10 carbon atoms. Non-limiting examples of chloride compounds include R ² CI; wherein R ² represents a hydrogen atom or a linear, branched or cyclic hydrocarbyl radical containing 1 to 10 carbon atoms. In the first step, the magnesium compound solution can also contain an alkyl aluminum (component (ix)). Non-limiting examples of alkyl aluminum include AI (R ³ ) s, where the R ³ groups can be the same or different, linear, branched or cyclic hydrocarbyl radicals containing from 1 to 10 carbon atoms. In the second step a solution of the metallic compound (component (vii)) is added to the magnesium chloride solution and the metallic compound is supported in the magnesium chloride. Non-limiting examples of suitable metal compounds include M (X) _n or MO (X) _n ; where M represents a metal selected from Group 4 to Group 8 of the Periodic Table or mixtures of metals
Petition 870190112009, of 11/01/2019, p. 49/168
43/156 selected from Group 4 to Group 8; O represents oxygen, and; X represents chloride or bromide; n is an integer from 3 to 6 that satisfies the oxidation state of the metal. Additional non-limiting examples of suitable metal compounds include Group 4 to Group 8 metal alkyls, metal alkoxides (which can be prepared by reacting an alkyl metal with an alcohol) and metal mixed binder compounds that contain a mixture of halide binders, alkyl and alkoxide. In the third step a solution of an alkyl aluminum co-catalyst (component (viii)) is added to the metal compound supported on magnesium chloride. A wide variety of alkyl aluminum co-catalysts is suitable, as expressed by Formula (VII):
AI (R ⁴ ) P (OR ⁵ ) q (X) r (VII) where the R ⁴ groups can be the same or different, hydrocarbyl groups having from 1 to 10 carbon atoms; the OR ⁵ groups can be the same or different alkoxy or aryloxy groups where R ⁵ is a hydrocarbyl group having from 1 to 10 oxygen-bonded carbon atoms; X is chloride or bromide, and; (p + q + r) = 3, with the proviso that p is greater than 0. Non-limiting examples of commonly used alkyl aluminum co-catalysts include trimethyl aluminum, triethyl aluminum, tributyl aluminum, dimethyl aluminum methoxide, ethoxide of diethyl aluminum, aluminum dibutyl butoxide, dimethyl aluminum chloride or bromide, diethyl aluminum chloride or bromide, aluminum dibutyl chloride or bromide and ethyl aluminum dichloride or dibromide.
[0119] The process described in the paragraph above, to synthesize an in-line Ziegler-Natta catalyst formulation, can be performed in a variety of solvents; non-limiting examples of solvents include straight or branched C5 to C12 alkanes or mixtures thereof.
[0120] To produce an in-line Ziegler-Natta catalyst formulation the quantity and mol ratios of the five components, (v) to (ix), are optimized as described below.
Petition 870190112009, of 11/01/2019, p. 50/168
44/156
[0121] Additional modalities of heterogeneous catalyst formulations include formulations where the "metallic compound" is a chromium compound; non-limiting examples include silyl chromate, chromium oxide and chromocene. In some embodiments, the chromium compound is supported on a metallic oxide such as silica or alumina. Chromium-containing heterogeneous catalyst formulations can also include co-catalysts; non-limiting examples of co-catalysts include trialkylaluminum, alkylaluminoxane and dialcoxyalkylaluminum compounds and the like.
Solution polymerization process: In-line heterogeneous catalyst formulation
[0122] The disclosed continuous solution polymerization process is improved by having one or more of: 1) at least one weight ratio of [aolefin / ethylene] reduced to 70% as defined by the following formula,
C fa - olefin ^ yot - olefin ^ jl ethylene) ~ 1 ethylene) (<_ ₇₀ „ _{/ o} / g - olefinay ethylene) J where (a-olefin / ethylene) ^A is calculated by dividing the weight of a-olefin added to the first reactor by the weight of ethylene added to the first reactor, wherein a first ethylene interpolymer is produced having "a target density" using a first homogeneous catalyst formulation, and; (a-olefin / ethylene) ^c is calculated by dividing the weight of α-olefin added to the first reactor by the weight of ethylene added to the first reactor, in which a control ethylene interpolymer having the target density is produced by replacing the first homogeneous catalyst formulation with a third homogeneous catalyst formulation and / or; 2) the first ethylene interpolymer with at least 5% improved weighted average molecular weight as defined by the following formula% Improved Mw = 100% x (M _W ^A -M ^C ) / MW ^C > 5% where M _W ^A is a weighted average molecular weight of the first interpolymer
Petition 870190112009, of 11/01/2019, p. 51/168
45/156 ethylene and M _w ^c is a weighted average molecular weight of a comparative ethylene interpolymer; wherein said comparative ethylene interpolymer is produced in the first reactor by replacing the first homogeneous catalyst formulation with the third homogeneous catalyst formulation.
[0123] Modalities of the improved continuous solution polymerization process are shown in Figure 2. Figure 2 should not be interpreted as limiting, it being understood that modalities are not limited to the precise arrangement or the number of vessels shown.
[0124] In a continuous solution polymerization process modality, process solvent, monomer (s) and a catalyst formulation are continuously fed to a reactor in which the desired ethylene interpolymer is formed in solution. In Figure 2, process solvent 1, ethylene 2 and optional q-olefin 3 are combined to produce the feed stream from reactor RF1 flowing into reactor 11a. In Figure 2, optional chains or optional modalities are denoted with dotted lines. It is not particularly important that the supply current of the combined reactor RF1 is formed; that is, reactor supply currents can be combined in all possible combinations, including a mode where currents 1 to 3 are independently injected into reactor 11a. Optionally hydrogen can be injected into reactor 11a via stream 4; hydrogen can be added to control (reduce) the molecular weight of the first ethylene interpolymer produced in reactor 11a. The reactor 11a is continuously agitated by shaking the assembly 11b which includes an external motor to the reactor and an agitator inside the reactor. In the art, such a reactor is often called a CSTR (Continuously Stirred Tank Reactor).
[0125] A first homogeneous catalyst formulation is injected into reactor 11a via stream 5e. One embodiment of the first homogeneous catalyst formulation is a metallocene catalyst formulation bound in
Petition 870190112009, of 11/01/2019, p. 52/168
46/156 bridge. The bridged metallocene catalyst formulation (described above) was used in reactor 11a to produce all Examples in this disclosure. In contrast, a third formulation of homogeneous catalyst was used in reactor 11a to produce all Comparatives in this disclosure. As described above, one embodiment of the third homogeneous catalyst formulation was a single site non-bridged catalyst formulation.
[0126] Referring to Figures 2 and 3, the bridged metallocene catalyst formulation was prepared by combining: stream 5a, containing component P dissolved in a catalyst component solvent; stream 5b, containing component M dissolved in a catalyst component solvent; stream 5c, containing component A dissolved in a catalyst component solvent, and; stream 5d, containing component B dissolved in a catalyst component solvent. The bridged metallocene catalyst formulation was then injected into reactor 11a via process stream 5e. Any combination of the streams used to prepare and release the bridged metallocene catalyst formulation can be heated or cooled, i.e., streams 5a to 5e. The "inlet temperature of catalyst R1", defined as the temperature of the solution containing the bridged metallocene catalyst formulation (current 5e) before injection into reactor 11a, was controlled. In some cases the upper temperature limit at the inlet temperature of catalyst R1 may be about 180 ° C, in other cases about 160 ° C and in other cases about 150 ° C, and; in some cases the lower temperature limit at the inlet temperature of catalyst R1 may be about 80 ° C, in other cases 100 ° C and in other cases about 120 ° C. In still other cases the upper temperature limit at the inlet temperature of catalyst R1 can be about 70 ° C, in other cases about 60 ° C and in other cases about 50 ° C, and; in some cases the lower temperature limit at the inlet temperature of catalyst R1
Petition 870190112009, of 11/01/2019, p. 53/168
47/156 can be about 0 ° C, in other cases 10 ° C and in other cases about 20 ° C.
[0127] Each catalyst component was dissolved in a catalyst component solvent. The catalyst component solvent used for each catalyst component can be the same or different. Catalyst component solvents are selected such that the combination of catalyst components does not produce a precipitate in any process stream; for example, precipitation of a catalyst component in stream 5e. The optimization of the catalyst formulations is described below.
[0128] Reactor 11a produces a first output stream, stream 11c, containing the first ethylene interpolymer dissolved in the process solvent, as well as unreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen (if present) ), first homogeneous active catalyst, deactivated catalyst, residual catalyst components and other impurities (if present). Melt index ranges and density ranges of the first ethylene interpolymer produced are described below.
[0129] The continuous solution polymerization process shown in Figures 2 and 3 includes two modes where reactors 11 a and 12a can be operated in series or parallel modes. In series mode 100% of the current 11c (the first output current) passes through the flow controller 11d forming the current 11e that enters the reactor 12a. On the contrary, in parallel mode 100% of the current 11c passes through the flow controller 11f forming the current 11g. Current 11g bypasses reactor 12a and is combined with current 12c (the second output current) to form current 12d (the third output current).
[0130] Fresh reactor supply chains are injected into reactor 12a; process solvent 6, ethylene 7 and optional α-olefin 8 are combined to produce the RF2 reactor supply current. It is not important that the RF2 current is
Petition 870190112009, of 11/01/2019, p. 54/168
Formed 48/156; that is, reactor supply currents can be combined in all possible combinations, including independently injecting each current into the reactor. Optionally hydrogen can be injected into reactor 12a via stream 9 to control (reduce) the molecular weight of the second ethylene interpolymer. The reactor 12a is continuously agitated by shaking the assembly 12b which includes an external motor to the reactor and an agitator inside the reactor.
[0131] A first heterogeneous catalyst formulation was injected into reactor 12a via stream 10f, one embodiment of the first heterogeneous catalyst formulation is a first in-line Ziegler-Natta catalyst formulation and a second ethylene interpolymer was formed in reactor 12a. The components comprising the first in-line Ziegler-Natta catalyst formulation are introduced through streams 10a, 10b, 10c and 10d. A first heterogeneous catalyst assembly, defined by the channels and flow controllers associated with currents 10a to 10h, is operated as described below. The first heterogeneous catalyst assembly produces a first highly active in-line Ziegler-Natta catalyst formulation optimizing the following molar ratios: (aluminum alkyl) / (magnesium compound) or (ix) / (v); (chloride compound) / (magnesium compound) or (vi) / (v); (alkyl aluminum co-catalyst) / (metallic compound) or (viii) / (vii), and; (aluminum alkyl) / (metallic compound) or (ix) / (vii); as well as the time these compounds have to react and balance.
[0132] Stream 10a (stream S1 in the claims) contains a binary mixture of a magnesium compound, component (v) and an alkyl aluminum, component (ix), in the process solvent. The upper limit on the molar ratio of (alkyl aluminum) / (magnesium compound) in stream 10a can be about 70, in some cases about 50 and in other cases about 30. The lower limit on the molar ratio of (alkyl aluminum) ) / (magnesium compound) can be about 3.0, in some cases about 5.0 and in other cases about 10. Current 10b (current S2 in
Petition 870190112009, of 11/01/2019, p. 55/168
49/156 claims) contains a solution of a chloride compound, component (vi), in the process solvent. Stream 10b is combined with stream 10a and the mixture of streams 10a and 10b produces a magnesium chloride catalyst support. To produce a first highly active in-line Ziegler-Natta catalyst (highly active in olefin polymerization), the molar ratio of (chloride compound) / (magnesium compound) is optimized. The upper limit in the molar ratio of (chloride compound) / (magnesium compound) can be about 4, in some cases about 3.5 and in other cases about 3.0. The lower limit in the molar ratio of (chloride compound) / (magnesium compound) can be about 1.0, in some cases about 1.5 and in other cases about 1.9. The time between the addition of the chloride compound and the addition of the metallic compound (component (vii)) via stream 10c (stream S3 in the claims) is controlled; then HllT-1 (the first Retention Time). HllT-1 is the time for currents 10a (current S1 in claims) and 10b (current S2 in claims) to balance and form a magnesium chloride support. The upper limit in HllT-1 can be about 70 seconds, in some cases about 60 seconds and in other cases about 50 seconds. The lower limit in HllT-1 can be about 5 seconds, in some cases about 10 seconds and in other cases about 20 seconds. HUT1 is controlled by adjusting the channel length between the current injection port 10b and the current injection port 10c, as well as controlling the flow rates of currents 10a and 10b. The time between the addition of component (vii) and the addition of the alkyl aluminum co-catalyst, component (viii), via stream 10d (stream S4 in the claims) is controlled; then HllT-2 (the second Retention Time). HllT-2 is the time for the magnesium chloride support and current 10c to react and balance. The upper limit in HllT-2 can be about 50 seconds, in some cases about 35 seconds and in other cases about 25 seconds. The lower limit on HllT-2 can be about 2 seconds, in some
Petition 870190112009, of 11/01/2019, p. 56/168
50/156 cases about 6 seconds and in other cases about 10 seconds. HllT-2 is controlled by adjusting the channel length between the current injection port 10c and the current injection port 10d, as well as controlling the flow rates of the currents 10a, 10b and 10c. The amount of the added aluminum aluminum co-catalyst is optimized to produce an efficient catalyst; this is accomplished by adjusting the molar ratio of (alkyl aluminum co-catalyst) / (metallic compound) or molar ratio of (viii) / (vii). The upper limit on the (aluminum aluminum co-catalyst) / (metal compound) molar ratio can be about 10, in some cases about 7.5 and in other cases about 6.0. The lower limit in the molar ratio of (alkyl aluminum co-catalyst) / (metallic compound) can be 0, in some cases about 1.0 and in other cases about 2.0. In addition, the time between the addition of the alkyl aluminum co-catalyst (current S4 in the claims) and the injection of the in-line Ziegler-Natta catalyst formulation into reactor 12a is controlled; then HllT-3 (the third Retention Time). HllT-3 is the time for current 10d to mix and balance to form the first in-line Ziegler Natta catalyst formulation. The upper limit in HllT-3 can be about 15 seconds, in some cases about 10 seconds and in other cases about 8 seconds. The lower limit in HUT-3 can be about 0.5 seconds, in some cases about 1 second and in other cases about 2 seconds. HUT-3 is controlled by adjusting the length of the channel between the current injection port 10d and the catalyst injection port in the reactor 12a and controlling the flow rates of the currents 10a to 10d. As shown in Figure 2, optionally, 100% current 10d, the alkyl aluminum co-catalyst, can be injected directly into reactor 12a via the current 10h. Optionally, a portion of the current 10d can be injected directly into the reactor 12a via the current 10h and the remaining portion of the current 10d injected into the reactor 12a via the current 10f.
[0133] As previously indicated, an equivalent term for reactor 12a is
Petition 870190112009, of 11/01/2019, p. 57/168
51/156 "R2". The amount of the first heterogeneous in-line catalyst formulation added to R2 is expressed as the parts-per-million (ppm) of metallic compound (component (vii)) in the reactor solution, then “R2 (vii) (ppm)” . The upper limit in R2 (vii) (ppm) can be about 10 ppm, in some cases about 8 ppm and in other cases about 6 ppm. The lower limit in R2 (vii) (ppm) in some cases can be about 0.5 ppm, in other cases about 1 ppm and in other cases about 2 ppm. The molar ratio of (alkyl aluminum) / (metallic compound) in reactor 12a or the molar ratio of (ix) / (vii) is also controlled. The upper limit in the molar ratio of (alkyl aluminum) / (metallic compound) in the reactor can be about 2, in some cases about 1.5 and in other cases about 1.0. The lower limit in the molar ratio of (alkyl aluminum) / (metallic compound) can be about 0.05, in some cases about 0.075 and in other cases about 0.1.
[0134] Any combination of the streams used to prepare and release the first heterogeneous catalyst formulation in line with R2 can be heated or cooled, ie streams 10a to 10am (including 10g stream (optional R3 release) which is discussed below ); in some cases, the upper temperature limit of currents 10a to 10g can be about 90 ° C, in other cases about 80 ° C and in other cases about 70 ° C and; in some cases the lower temperature limit can be around 20 ° C; in other cases about 35 ° C and in other cases about 50 ° C.
[0135] The injection of the first heterogeneous catalyst formulation in reactor 12a produces a second ethylene interpolymer and a second output stream 12c.
[0136] If reactors 11a and 12a are operated in a serial mode, the second output stream 12c contains the second ethylene interpolymer and the first ethylene interpolymer dissolved in the process solvent; as well as unreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen (if present),
Petition 870190112009, of 11/01/2019, p. 58/168
52/156 active catalysts, deactivated catalysts, catalyst components and other impurities (if present). Optionally the second output current 12c is deactivated by adding a catalyst deactivator A from the catalyst deactivator tank 18A forming a deactivated solution A, current 12e; in this case, Figure 2 defaults to a dual reactor solution process. If the second output current 12c is not deactivated the second output current enters the tubular reactor 17. Catalyst deactivator A is discussed below.
[0137] If reactors 11a and 12a are operated in parallel mode, the second output stream 12c contains the second ethylene interpolymer dissolved in the process solvent. The second output stream 12c is combined with the stream 11g to form a third output stream 12d, the last containing the second ethylene interpolymer and the first ethylene interpolymer dissolved in the process solvent; as well as unreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen (if present), active catalyst, deactivated catalyst, catalyst components and other impurities (if present). Optionally, the third output current 12d is deactivated by adding catalyst deactivator A from catalyst deactivator tank 18A forming the deactivated solution A, current 12e; in this case, Figure 2 defaults to a dual reactor solution process. If the third output current 12d is not deactivated the third output current 12d enters the tubular reactor 17.
[0138] The term "tubular reactor" aims to convey its conventional meaning, that is, a simple tube; where the length / diameter ratio (L / D) is at least 10/1. Optionally, one or more of the following reactor feed streams can be injected into the tubular reactor 17; process solvent 13, ethylene 14 and a-olefin 15. As shown in Figure 2, currents 13, 14 and 15 can be combined to form the feed stream of the RF3 reactor and the latter is injected into the reactor 17. Not particularly important that the RF3 current is
Petition 870190112009, of 11/01/2019, p. 59/168
Formed 53/156; that is, reactor supply currents can be combined in all possible combinations. Optionally hydrogen can be injected into reactor 17 via stream 16. Optionally, the first in-line ZieglerNatta catalyst formulation can be injected into reactor 17 via catalyst stream 10g; that is, a portion of this catalyst formulation enters reactor 12a through stream 10f and the remainder enters reactor 17 through stream 10g.
[0139] Figure 2 shows an additional modality where the reactor 17 is supplied with a second heterogeneous catalyst formulation produced in a second heterogeneous catalyst assembly. The second heterogeneous catalyst assembly refers to the combination of channels and flow controllers that include currents 34a to 34e and 34h. The chemical composition of the first and second heterogeneous catalyst formulations can be the same or different. In the case of a Ziegler-Natta catalyst, the second heterogeneous catalyst assembly produces a second in-line Ziegler-Natta catalyst formulation. For example, the catalyst components ((v) to (ix)), mol ratios and retention times may differ in the first and second heterogeneous catalyst assemblies. Regarding the first heterogeneous catalyst assembly, the second heterogeneous catalyst assembly is operated in a similar manner, that is, the second heterogeneous catalyst assembly generates a high activity catalyst optimizing the retention times and the following molar ratios: (aluminum alkyl) / (magnesium compound), (chloride compound) / (magnesium compound), (alkyl aluminum co-catalyst / (metallic compound and (aluminum alkyl) / (metallic compound). To be clear: a stream 34a contains a binary mixture of magnesium compound (component (v)) and alkyl aluminum (component (ix)) in the process solvent; stream 34b contains a chloride compound (component (vi)) in the process solvent; stream 34c contains a metallic compound (component (vii)) in the process solvent, and stream 34d contains an alkyl co-catalyst
Petition 870190112009, of 11/01/2019, p. 60/168
54/156 aluminum (component (viii)) in the process solvent. Once prepared, the second in-line Ziegler-Natta catalyst is injected into reactor 17 via stream 34e; optionally, additional aluminum alkyl co-catalyst is injected into reactor 17 via stream 34h. As shown in Figure 2, optionally, 100% of the current 34d, the alkyl aluminum co-catalyst, can be injected directly into the reactor 17 via the current 34h. Optionally, a portion of the current 34d can be injected directly into the reactor 17 via the current 34h and the remaining portion of the current 34d injected into the reactor 17 via the current 34e. In Figure 2, the first or second heterogeneous catalyst assembly supplies 100% of the catalyst to the reactor 17. Any combination of the streams comprising the second heterogeneous catalyst assembly can be heated or cooled, that is, currents 34a to 34e and 34h; in some cases the upper temperature limit of currents 34a to 34e and 34h can be about 90 ° C, in other cases about 80 ° C and in other cases about 70 ° C and; in some cases the lower temperature limit can be around 20 ° C; in other cases about 35 ° C and in other cases about 50 ° C.
[0140] Although not shown in Figure 2, an additional modality includes the injection of the first homogeneous catalyst formulation in the tubular reactor 17. An option to perform this modality would be to divide the current 5e, that is, a portion of the current 5e is injected into the reactor 11a and the remainder is injected into reactor 17 (not shown in Figure 2). Another option (not shown in Figure 2) would be to build a second assembly of homogeneous catalyst, that is, a replica of channels and flow controllers 5a to 5e that injects a first formulation of essentially equivalent homogeneous catalyst (for example, containing component A ) directly in reactor 17.
[0141] An additional modality (not shown in Figure 2) includes the use of the second homogeneous catalyst assembly to inject a fifth formulation of
Petition 870190112009, of 11/01/2019, p. 61/168
55/156 homogeneous catalyst in the tubular reactor 17. The fifth homogeneous catalyst formulation can be the first homogeneous catalyst formulation, the third homogeneous catalyst formulation or a fourth homogeneous catalyst formulation.
[0142] In reactor 17 a third ethylene interpolymer may or may not be formed. A third ethylene interpolymer will not form if catalyst deactivator A is added upstream of reactor 17 via catalyst deactivator tank 18A. A third ethylene interpolymer will be formed if catalyst deactivator B is added downstream of reactor 17 via catalyst deactivator tank 18B.
[0143] The optional third ethylene interpolymer produced in reactor 17 can be formed using a variety of operational modes; with the proviso that catalyst deactivator A is not added upstream of reactor 17. Non-limiting examples of operational modes include: (a) residual ethylene, optional residual α-olefin and residual active catalyst entering reactor 17 react to form the optional third ethylene interpolymer, or; (b) fresh process solvent 13, fresh ethylene 14 and optionally fresh α-olefin 15 are added to reactor 17 and the residual active catalyst entering the reactor 17 forms the optional third ethylene interpolymer, or; (c) the inline Ziegler-Natta catalyst formulation is added to reactor 17 via stream 10g or the second inline Ziegler-Natta catalyst formulation is added to reactor 17 via stream 34e to polymerize residual ethylene and α- optional residual olefin to form the optional third ethylene interpolymer (optionally, 100% of the alkyl aluminum co-catalyst can be added to reactor 17 via stream 34h or a portion of the alkyl aluminum co-catalyst can be added to reactor 17 through stream 10g or 34h and the remaining portion added via stream 34h) and / or; (d) fresh process solvent 13, ethylene 14, a
Petition 870190112009, of 11/01/2019, p. 62/168
56/156 optional olefin 15 and a fifth homogeneous catalyst formulation (not shown in Figure 2) are added to reactor 17 to form the optional third ethylene interpolymer. Optionally fresh hydrogen 16 can be added to reduce the molecular weight of the optional third ethylene interpolymer.
[0144] In series mode, Reactor 17 produces a third output stream 17b containing the first ethylene interpolymer, the second ethylene interpolymer and optionally a third ethylene interpolymer. As shown in Figure 2, catalyst deactivator B can be added to the third output stream 17b via catalyst deactivator tank 18B producing a deactivated solution B, stream 19; with the proviso that catalyst deactivator B is not added if catalyst deactivator A was added upstream of reactor 17. Deactivated solution B may also contain unreacted ethylene, optional unreacted a-olefin, optional unreacted hydrogen and impurities if present. As indicated above, if catalyst deactivator A was added, deactivated solution A (current 12e) exits tubular reactor 17 as shown in Figure 2.
[0145] In parallel operation, reactor 17 produces a fourth output stream 17b containing the first ethylene interpolymer, the second ethylene interpolymer and optionally a third ethylene interpolymer. As indicated above, in parallel mode, current 12d is the third output current. As shown in Figure 2, in parallel mode, catalyst deactivator B is added to the fourth output stream 17b via catalyst deactivator tank 18B producing a deactivated solution B, current 19; with the proviso that catalyst deactivator B is not added if catalyst deactivator A is added upstream of reactor 17.
[0146] In Figure 2, the deactivated solution A (current 12e) or B (current 19) passes through the pressure reducing device 20, heat exchanger 21 and a passivator is added through the tank 22 forming a solution
Petition 870190112009, of 11/01/2019, p. 63/168
57/156 passivated 23; the passivator is described below. The passivated solution passes through the pressure reducing device 24 and enters a first vapor / liquid separator 25. Then, “V / L” is equivalent to vapor / liquid. Two streams are formed in the first V / L separator: a first bottom stream 27 comprising a solution that is rich in ethylene interpolymers and also contains residual ethylene, optional residual α-olefins and catalyst residues, and; a first gas suspended stream 26 comprising ethylene, process solvent, optional α-olefins, optional hydrogen, oligomers and lighter impurities if present.
[0147] The first bottom stream enters a second V / L separator 28. In the second V / L separator two streams are formed: a second bottom stream 30 comprising a solution that is richer in ethylene interpolymer and more poor in process solvent in relation to the first bottom stream 27, and; a second gas suspended stream 29 comprising process solvent, optional α-olefins, ethylene, oligomers and lighter impurities if present.
[0148] The second bottom stream 30 flows in a third V / L separator 31. In the third V / L separator two streams are formed: a product stream 33 comprising an ethylene interpolymer product, deactivated catalyst residues and less than 5% by weight of residual solvent from the process, and; a third gas suspended stream 32 comprised essentially of process solvent, optional α-olefins and lighter impurities if present.
[0149] Product stream 33 proceeds to polymer recovery operations. Non-limiting examples of polymer recovery operations include one or more of a gear pump, single-screw extruder or double-screw extruder that forces the fused ethylene interpolymer product through a pelletizer. A devolatilization extruder can be used to remove
Petition 870190112009, of 11/01/2019, p. 64/168
58/156 small amounts of residual process solvent and optional q-olefin, if present. Once pelletized, the solidified ethylene interpolymer product is typically dried and transported to a product silo.
[0150] The first, second and third gas suspended streams shown in Figure 2 (streams 26, 29 and 32, respectively) are sent to a distillation column where solvent, ethylene and optional q-olefin are separated for recycling, or; the first, second and third suspended gas streams are recycled to the reactors, or; a portion of the first, second and third suspended gas streams are recycled to the reactors and the remaining portion is sent to a distillation column.
Solution polymerization process: Formulation of heterogeneous batch catalyst
[0151] Additional modalities of the improved continuous solution polymerization process are shown in Figure 3. Again, Figure 3 should not be interpreted as limiting, it being understood that the modalities are not limited to the precise arrangement or the number of vessels shown .
[0152] In Figure 3, a first assembly of heterogeneous batch catalyst (vessels and currents 60a to 60h) and a second assembly of heterogeneous batch catalyst (vessels and currents 90a to 90f) are shown. For the sake of clarity and to avoid any confusion, many of the vessels and chains shown in Figure 3 are equivalent to the respective vessels and chains shown in Figure 2; equivalence is indicated through the use of a compatible vessel or chain label, ie number. For the avoidance of doubt, referring to Figure 3, the process solvent is injected into the CSTR 11a reactor, CSTR 12a reactor and tubular reactor 17 via currents 1, 6 and 13. Ethylene is injected into the reactors 11a, 12a and 17 through currents 2, 7 and 14. Optional q-olefin is injected into reactors 11a, 12a and 17 through currents 3, 8 and 15. Optional hydrogen is injected
Petition 870190112009, of 11/01/2019, p. 65/168
59/156 in reactors 11a, 12a and 17 using streams 4, 9 and 16. A first homogeneous catalyst formulation is injected into reactor 11a, producing the first ethylene interpolymer. Homogeneous catalyst component currents (5a to 5e) have been described above. A batch Ziegler-Natta catalyst formulation or batch Ziegler-Natta pro-catalyst is injected into reactor 12a via stream 60e and the second ethylene interpolymer is formed. Reactors 11a and 12a shown in Figure 3 can be operated in series or parallel modes, as described in Figure 2 above.
[0153] Processes for preparing heterogeneous batch pro-catalysts and batch Ziegler-Natta pro-catalysts are well known to those skilled in the art. A non-limiting formulation useful in the disclosed polymerization process can be prepared as follows. A batch ZieglerNatta pro-catalyst can be prepared by sequentially adding the following components to a stirred mixing vessel: (a) a solution of a magnesium compound (an equivalent term for the magnesium compound is "component (v)"); (b) a solution of a chloride compound (an equivalent term for the chloride compound is "component (vi)"; (c) optionally a solution of an alkyl aluminum halide, and; (d) a solution of a compound metallic (an equivalent term for the metallic compound is “component (vii)”). Non-limiting, suitable examples of alkyl aluminum halides are defined by the formula (R ⁶ ) vAIXs-v; where the R ⁶ groups can be the same or different hydrocarbyl group having 1 to 10 carbon atoms, X represents chloride or bromide, and; v is 1 or 2. Suitable non-limiting examples of the magnesium compound, the chloride compound and the metal compound have been described earlier suitable solvents within which to prepare the pro-catalyst include linear or branched C5 to C12 alkanes or mixtures thereof.Mixing times and mixing temperatures can be used in each of steps (a) to (d). upper limit at
Petition 870190112009, of 11/01/2019, p. 66/168
60/156 mixture for steps (a) to (d) can in some cases be 160 ° C, in other cases 130 ° C and in other cases 100 ° C. The lower limit on mixing temperatures for steps (a) to (d) in some cases may be 10 ° C, in other cases 20 ° C and in other cases 30 ° C. The upper limit in mixing time for steps (a) to (d) in some cases may be 6 hours, in other cases 3 hours and in other cases 1 hour. The lower limit in mixing times for steps (a) to (d) in some cases can be 1 minute, in other cases 10 minutes and in other cases 30 minutes.
[0154] Batch Ziegler-Natta pro-catalyst can have several ratios in mol of catalyst component. The upper limit in the molar ratio of (chloride compound) / (magnesium compound) in some cases may be about 3, in other cases about 2.7 and in other cases about 2.5; the lower limit in some cases may be about 2.0, in other cases about 2.1 and in other cases about 2.2. The upper limit in the molar ratio of (magnesium compound) / (metallic compound) in some cases may be about 10, in other cases about 9 and in other cases about 8; the lower limit in some cases may be about 5, in other cases about 6 and in other cases about 7. The upper limit in the molar ratio of (aluminum alkyl halide) / (magnesium compound) in some cases may be about 0.5, in other cases about 0.4 and in other cases about 0.3; the lower limit in some cases may be 0, in other cases about 0.1 and in other cases about 0.2. A batch active Ziegler-Natta catalyst formulation is formed when the pro-catalyst is combined with an alkyl aluminum co-catalyst. Suitable co-catalysts have been described earlier in this disclosure. The pro-catalyst can be activated external to the reactor or in the reactor; in the latter case, the pro-catalyst and an appropriate amount of alkyl aluminum co-catalyst are independently injected R2 and optionally R3.
[0155] Once the Ziegler-Natta pro-catalyst in batch is prepared, it is pumped into the pro-catalyst storage tank 60a shown in Figure
Petition 870190112009, of 11/01/2019, p. 67/168
61/156
3. Tank 60a may or may not be agitated. The storage tank 60c contains an alkyl aluminum co-catalyst; non-limiting examples of suitable alkyl aluminum co-catalysts have been described earlier in this disclosure. A Ziegler Natta catalyst formulation stream in batch 60e, which is efficient in converting defines to polyolefins, is formed by combining the Ziegler Natta procatalyst stream in batch 60b with the 60d aluminum alkyl co-catalyst stream. Current 60e is injected into reactor 12a where the second ethylene interpolymer is formed. Operationally, the following options can be used: (a) 100% of the alkyl aluminum co-catalyst can be injected into the reactor 12a through the 60g stream, that is, the batch Ziegler-Natta pro-catalyst is injected into the reactor 12a through current 60e, or; (b) a portion of the alkyl aluminum co-catalyst is injected into reactor 12a via stream 60g and the remainder passes through stream 60d where it combines with stream 60b to form the batch formulation of Ziegler-Natta catalyst injected into reactor 12a through current 60e.
[0156] Additional optional modalities, where a heterogeneous batch catalyst formulation is used, are shown in Figure 3 where: (a) a batch Ziegler-Natta procatalyst is injected into the tubular reactor 17 via current 60f, or; (b) a batch Ziegler-Natta catalyst formulation is injected into the tubular reactor 17 via stream 60f. In the case of option (a), 100% of the aluminum aluminum co-catalyst is injected directly into reactor 17 through the current 60h. An additional embodiment exists where a portion of the alkyl aluminum co-catalyst flows through stream 60f and the remaining portion flows through stream 60h. Any combination of tanks or chains 60a to 60h can be heated or cooled.
[0157] Figure 3 includes additional modalities where a second batch heterogeneous catalyst assembly, which is defined by vessels and currents 90a to
Petition 870190112009, of 11/01/2019, p. 68/168
62/156
90f, can be used to optionally inject a second batch Ziegler-Natta catalyst formulation or a second batch Ziegler-Natta pro catalyst in reactor 17. Once the second batch Ziegler-Natta pro catalyst is prepared it is pumped into the tank pro-catalyst storage tank 90a shown in Figure 3. Tank 90a may or may not be agitated. The storage tank 90c contains an alkyl aluminum co-catalyst. A stream of Ziegler Natta catalyst formulation in batch 90e, which is efficient in converting definites to polyolefins, is formed by combining the second Ziegler Natta procatalyst stream in batch 90b (stream S6 in the claims) with the co-catalyst stream of alkyl aluminum 90d (optionally chain S4 in the claims). The current 90e is optionally injected into reactor 17, in which an optional third ethylene interpolymer can be formed. Figure 3 includes additional modalities where: (a) the batch Ziegler-Natta pro-catalyst is injected directly into reactor 17 via current 90e and the pro-catalyst is activated into reactor 17 by injecting 100% of the co-catalyst of aluminum directly in reactor 17 through the current 90f, or; (b) a portion of the aluminum co-catalyst can flow through stream 90e with the remaining portion flowing through stream 90f. Any combination of tanks or chains 90a to 90f can be heated or cooled.
[0158] Although not shown in Figure 3, an additional modality includes the injection of the first homogeneous catalyst formulation in the tubular reactor 17. An option to carry out this modality would be to divide the current 5e, ie a portion of the current 5e is injected into the reactor 11a and the remaining portion is injected into reactor 17 (tubing not shown in Figure 3). Another option (not shown in Figure 3) would be to build a second assembly of homogeneous catalyst that injects a first formulation of essentially equivalent homogeneous catalyst (for example, containing component A) directly into the reactor 17.
Petition 870190112009, of 11/01/2019, p. 69/168
63/156
[0159] An additional embodiment (not shown in Figure 3) includes the use of a second homogeneous catalyst assembly to inject a third or fifth homogeneous catalyst formulation into the tubular reactor 17. The fifth homogeneous catalyst formulation may be the first formulation of homogeneous catalyst, the third homogeneous catalyst formulation or a fourth homogeneous catalyst formulation.
[0160] The time between the addition of the aluminum aluminum co-catalyst and the batch injection of the Ziegler-Natta catalyst formulation in reactor 12a is controlled; then HUT-4 (the fourth Retention Time). Referring to Figure 3, HllT-4 is the time for current 60d (current S4 in the claims) to mix and balance with current 60b (pro-catalyst Ziegler-Natta in batch) to form the batch catalyst formulation Ziegler Natta before injection into reactor 12a via current 60e. Optionally, HUT-4 is the time for current 60d to mix and balance with current 60b to form the batch Ziegler-Natta catalyst formulation prior to injection into optional third reactor 17 via current 60f, or; HUT-4 is the time for current 90d to mix and equilibrate with current 90b to form the batch Ziegler-Natta catalyst formulation prior to injection into reactor 17 via current 90e. The upper limit in HUT-4 can be about 300 seconds, in some cases about 200 seconds and in other cases about 100 seconds. The lower limit in HUT-4 can be about 0.1 seconds, in some cases about 1 second and in other cases about 10 seconds.
[0161] The amount of batch Ziegler-Natta pro-catalyst produced and / or the size of the pro-catalyst storage tank 60a or 90a are not particularly important with respect to this disclosure. However, a greater amount of pro-catalyst produced allows someone to operate the continuous solution polymerization facility for a longer period of time (before renewing the pro-catalyst): the upper limit in this time in some cases may be
Petition 870190112009, of 11/01/2019, p. 70/168
64/156 about 3 months, in other cases about 2 months and in other cases about 1 month; the lower limit in this time in some cases can be about 1 day, in other cases about 1 week and in other cases about 2 weeks.
[0162] The amount of batch Ziegler-Natta pro-catalyst or batch Ziegler-Natta catalyst formulation added to reactor 12a is expressed as “R2 (vii) (ppm)”, ie parts-per-million (ppm) ) of metallic compound (component (vii)) in the reactor solution. The upper limit in R2 (vii) (ppm) can be about 10 ppm, in some cases about 8 ppm and in other cases about 6 ppm. The lower limit in R2 (vii) (ppm) can be about 0.5 ppm, in some cases about 1 ppm and in other cases about 2 ppm. The amount of the alkyl aluminum cocatalyst added to the reactor 12a is optimized to produce an efficient catalyst; this is accomplished by adjusting the molar ratio of (alkyl aluminum co-catalyst) / (metallic compound). The upper limit on the (aluminum aluminum cocatalyst) / (metallic compound) molar ratio can be about 10, in some cases about 8.0 and in other cases about 6.0. The lower limit on the (aluminum aluminum co-catalyst) / (metallic compound) molar ratio can be 0.5, in some cases about 0.75 and in other cases about 1.
[0163] Referring to Figure 3, where the heterogeneous catalyst formulation is a batch Ziegler-Natta catalyst formulation, a third ethylene interpolymer may or may not be formed. A third ethylene interpolymer will not form if catalyst deactivator A is added upstream of reactor 17 via catalyst deactivator tank 18A. A third ethylene interpolymer will be formed if catalyst deactivator B is added downstream of reactor 17 via catalyst deactivator tank 18B.
[0164] The optional third ethylene interpolymer produced in reactor 17 can be formed using a variety of operational modes; with the proviso that catalyst deactivator A is not added upstream of reactor 17. Examples
Petition 870190112009, of 11/01/2019, p. 71/168
65/156 non-limiting operational modes include: (a) residual ethylene, optional residual α-olefin and residual active catalyst entering reactor 17 react to form the optional third ethylene interpolymer, or; (b) fresh process solvent 13, fresh ethylene 14 and optionally fresh α-olefin 15 are added to reactor 17 and the residual active catalyst entering the reactor 17 forms the optional third ethylene interpolymer, or; (c) the first batch (or pro-catalyst) Ziegler-Natta catalyst formulation is added to reactor 17 via stream 10g or the second batch (or procatalyst) Ziegler-Natta catalyst formulation is added to reactor 17 intermediate 34e to polymerize residual ethylene and optional residual α-olefin to form the optional third ethylene interpolymer and / or; (d) fresh process solvent 13, ethylene 14, optional α-olefin 15 and a fifth homogeneous catalyst formulation (not shown in Figure 3) are added to reactor 17 to form the optional third ethylene interpolymer; where the fifth homogeneous catalyst formulation can be the first homogeneous catalyst formulation, the third homogeneous catalyst or the fourth homogeneous catalyst formulation. In this disclosure, the fourth homogeneous catalyst formulation contains a bulky metal-ligand complex that is not a member of the chemical genres defined by Formula (I) or Formula (II). Optionally fresh hydrogen 16 can be added to reduce the molecular weight of the optional third ethylene interpolymer.
[0165] As shown in Figure 3, the first batch Ziegler-Natta catalyst formulation can be deactivated upstream of reactor 17 by adding catalyst deactivator A via deactivator tank 18A to form a deactivated solution A (current 12e), or; the first batch Ziegler-Natta catalyst formulation and optionally the second batch Ziegler-Natta catalyst formulation can be deactivated downstream of reactor 17 by adding catalyst deactivator B via the deactivator tank
Petition 870190112009, of 11/01/2019, p. 72/168
66/156
18B to form a deactivated solution B (current 19), or; the first batch formulation of Ziegler-Natta catalyst and optionally the fifth formulation of homogeneous catalyst can be deactivated downstream of reactor 17 by adding catalyst deactivator B to form deactivated solution B.
[0166] The deactivated solution A or B then passes through the pressure reducing device 20, heat exchange 21 and a passivator can be added through the tank 22 forming the passivated solution 23. The vessels (24, 25, 28 and 31) and current (26, 27, 29, 39, 32 and 33) remnants and process conditions have been previously described. The ethylene interpolymer product stream 33 proceeds to recover the polymer. The first, second and third gas suspended streams shown in Figure 3 (streams 26, 29 and 32, respectively) are sent to a distillation column where solvent, ethylene and optional α-olefin are separated for later use, or; the first, second and third suspended gas streams are recycled to the reactors, or; a portion of the first, second and third gas suspended streams is recycled to the reactors and the remaining portion is sent to a distillation column.
Comparatives
[0167] In this disclosure comparative ethylene interpolymer samples were produced by replacing the first homogeneous catalyst formulation (used in the first reactor (R1)) with a third homogeneous catalyst formulation. One embodiment of the first homogeneous catalyst formulation was a bridged metallocene catalyst formulation containing component A (represented by Formula (I)) and one embodiment of the third homogeneous catalyst formulation was a single site non-bonded catalyst formulation containing component C (represented by Formula (II)), as completely described above.
[0168] To be clearer, referring to Figures 2 and 3, the third formulation
Petition 870190112009, of 11/01/2019, p. 73/168
67/156 of homogeneous catalyst or the single-site non-bridged catalyst formulation was prepared by combining: stream 5a, containing component P dissolved in a catalyst component solvent; stream 5b, containing component M dissolved in a catalyst component solvent; stream 5c, containing component C dissolved in a catalyst component solvent, and; stream 5d, containing component B dissolved in a catalyst component solvent. The third homogeneous catalyst formulation was then injected into reactor 11a via process stream 5e producing a first comparative ethylene interpolymer in reactor 11a. The "inlet temperature of catalyst R1" was controlled. In the case of a single-site non-bridged catalyst formulation, the upper temperature limit at the inlet temperature of catalyst R1 may be about 70 ° C, in other cases about 60 ° C and in other cases about 50 ° C, and; in some cases the lower temperature limit at the inlet temperature of the catalyst R1 can be about 0 ° C, in other cases about 10 ° C and in other cases about 20 ° C. The same catalyst component solvents were used to prepare both the first and the third homogeneous catalyst formulations.
[0169] For all the comparative ethylene interpolymer products disclosed, the in-line Ziegler-Natta catalyst formulation (described above) was injected into reactor 12a (R2), in which the second ethylene interpolymer was formed. Comparative ethylene interpolymer products were a mixture of in situ solution: 1) of the first comparative ethylene interpolymer (produced with the third homogeneous catalyst formulation); 2) the second ethylene interpolymer, and; 3) optionally of the third ethylene interpolymer.
Optimization of homogeneous catalyst formulations
[0170] Referring to the bridged metallocene catalyst formulation, a highly active formulation was produced optimizing the proportion of
Petition 870190112009, of 11/01/2019, p. 74/168
68/156 each of the four catalyst components: component A, component M, component B and component P. The term “highly active” means that the catalyst formulation is very efficient in converting defines to polyolefins. In practice, the aim of optimization is to maximize the following ratio: (pounds of ethylene interpolymer product produced) / (pounds of catalyst consumed). The amount of the bulky binder-metal complex, component A, added to R1 was expressed as the parts per million (ppm) of component A in the total mass of the solution in R1. The upper limit on ppm of component A can be about 5, in some cases about 3 and in other cases about 2. The lower limit on ppm of component A can be about 0.02, in some cases about 0 , 05 and in other cases about 0.1.
[0171] The proportion of catalyst component B, the ionic activator, added to R1 was optimized by controlling the molar ratio of (ionic activator) / (component A), ([B] / [A]), in the solution of R1. The upper limit on R1 ([B] / [A]) can be about 10, in some cases about 5 and in other cases about 2. The lower limit on R1 ([B] / [A]) can be about 0.3, in some cases about 0.5 and in other cases about 1.0. The proportion of catalyst component M was optimized by controlling the molar ratio of (alumoxane) / (component A), ([M] / [A]), in the R1 solution. The alumoxane co-catalyst was generally added in a molar excess over component A. The upper limit in R1 ([M] / [A]), can be around 300, in some cases around 200 and in other cases about 100. The lower limit in R1 ([M] / [A]), can be about 1, in some cases about 10 and in other cases about 30. The addition of catalyst component P (the prevented phenol ) R1 is optional. If added, the proportion of component P was optimized by controlling the molar ratio of (hindered phenol) / (alumoxane), ([P] / [M]) in R1. The upper limit in R1 ([P] / [M]) can be about 1, in some cases about 0.75 and in other cases about 0.5. The lower limit in R1 ([P] / [M]) can be 0.0, in some cases
Petition 870190112009, of 11/01/2019, p. 75/168
69/156 cases about 0.1 and in other cases about 0.2.
[0172] Similarly, in the case of the third homogeneous catalyst formulation (used to synthesize the Comparative Examples) a highly active formulation was produced by optimizing the proportion of each of the four catalyst components: component C, component M, component B and component P. The componentes, B and P catalyst components were independently selected for the third homogeneous catalyst formulation, and; the catalyst components Μ, B and P were independently selected for the first homogeneous catalyst formulation. To be more clear, the components Μ, B and P in the third homogeneous catalyst formulation can be the same chemical compound or a different chemical compound, which was used to formulate the first homogeneous catalyst formulation.
[0173] The amount of the binder and bulky metal complex, component C, added to R1 is expressed as the parts per million (ppm) of component C in the total mass of the solution in R1. The upper limit on R1 ppm of component C can be about 5, in some cases about 3 and in other cases about 2. The lower limit on R1 ppm of component C can be about 0.02, in some cases about 0.05 and in other cases about 0.1. The proportion of catalyst component B, the ionic activator, added to R1 was optimized by controlling the molar ratio of (ionic activator) / (bulky ligand-metal complex), ([B] / [C]), in the solution of R1. The upper limit in R1 ([B] / [C]) can be around 10, in some cases around 5 and in other cases around 2. The lower limit in R1 ([B] / [C]) can be about 0.3, in some cases about 0.5 and in other cases about 1.0. The proportion of catalyst component M was optimized by controlling the molar ratio of (alumoxane) / (binder-bulky metal complex), ([M] / [C]), in the R1 solution. The alumoxane cocatalyst was generally added in a molar excess over the bulky binder-metal complex. The upper limit in the molar ratio of ([M] / [C])
Petition 870190112009, of 11/01/2019, p. 76/168
70/156 can be about 1000, in some cases about 500 and in other cases about 200. The lower limit in the molar ratio of ([M] / [C]) can be about 1, in some cases about 10 and in other cases about 30. The addition of catalyst component P to R1 is optional. If added, the proportion of component P was optimized by controlling the molar ratio of (hindered phenol) / (alumoxane), ([P] / [M]), in R1. The upper limit on the molar ratio of R1 ([P] / [M]) can be about 1.0, in some cases about 0.75 and in other cases about 0.5. The lower limit on the molar ratio of R1 ([P] / [M]) can be 0.0, in some cases about 0.1 and in other cases about 0.2.
Additional solution polymerization process parameters
[0174] In the modalities of the continuous solution processes shown in Figures 2 and 3 a variety of solvents can be used as the process solvent; non-limiting examples include linear, branched or cyclic C5 to C12 alkanes. Non-limiting examples of α-olefins include 1-propene, 1-butene, 1-pentene, 1-hexene and 1-octene. Suitable catalyst component solvents include aliphatic and aromatic hydrocarbons. Non-limiting examples of aliphatic catalyst component solvents include linear, branched or cyclic C5-12 aliphatic hydrocarbons, for example, pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, hydrogenated naphtha or combinations thereof. Non-limiting examples of aromatic catalyst component solvents include benzene, toluene (methylbenzene), ethylbenzene, o-xylene (1,2dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene) , mixtures of xylene isomers, hemelitene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixtures of isomers of trimethylbenzene, pre-henitene ( 1,2,3,4-tetramethylbenzene), durene (1,2,3,5tetramethylbenzene), mixtures of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene and combinations thereof.
[0175] It is well known to individuals experienced in the art that currents of
Petition 870190112009, of 11/01/2019, p. 77/168
71/156 reactor feed (solvent, monomer, α-olefin, hydrogen, catalyst formulation, etc.) must be essentially free of catalyst deactivation poisons; non-limiting examples of poisons include micro-quantities of oxygenates such as water, fatty acids, alcohols, ketones and aldehydes. Such poisons were removed from reactor feed streams using standard purification practices; non-limiting examples include molecular sieve beds, alumina beds and oxygen removal catalysts for the purification of solvents, ethylene and aolefins, etc.
[0176] Referring to the first and second reactors in Figures 2 and 3 any combination of the CSTR reactor supply currents can be heated or cooled: more specifically, currents 1 to 4 (reactor 11a) and currents 6 to 9 (reactor 12a). The upper limit on the reactor supply current temperatures can be about 90 ° C; in other cases about 80 ° C and in other cases about 70 ° C. The lower limit on the reactor supply current temperatures can be about 0 ° C; in other cases about 10 ° C and in other cases about 20 ° C.
[0177] Any combination of the currents supplying the tubular reactor can be heated or cooled; specifically, currents 13 to 16 in Figures 2 and 3. In some cases, tubular reactor feed streams are tempered, that is, the tubular reactor feed streams are heated to at least above room temperature. The upper temperature limit in the tubular reactor supply chains is in some cases about 200 ° C, in other cases about 170 ° C and in other cases about 140 ° C; the lower temperature limit in the tubular reactor supply chains is in some cases about 60 ° C, in other cases about 90 ° C and in other cases about 120 ° C; with the proviso that the temperature of the tubular reactor feed streams is lower than the temperature of the process stream entering the tubular reactor.
Petition 870190112009, of 11/01/2019, p. 78/168
72/156
[0178] In the modalities shown in Figures 2 and 3 the operating temperatures of the solution polymerization reactors (vessels 11a (R1) and 12a (R2)) can vary over a wide range. For example, the upper limit on reactor temperatures in some cases may be about 300 ° C, in other cases about 280 ° C and in other cases about 260 ° C; and the lower limit in some cases can be about 80 ° C, in other cases about 100 ° C and in other cases about 125 ° C. The second reactor, reactor 12a (R2), is operated at a higher temperature than the first reactor 11a (R1). The maximum temperature difference between these two reactors (T ^R2 - T ^R1 ) in some cases is about 120 ° C, in other cases about 100 ° C and in other cases about 80 ° C; the minimum (T ^R2 - T ^R1 ) in some cases is about 1 ° C, in other cases about 5 ° C and in other cases about 10 ° C. The optional tubular reactor, reactor 17 (R3), can be operated in some cases at about 100 ° C higher than R2; in other cases about 60 ° C higher than R2, still in other cases about 10 ° C higher than R2 and in alternative cases 0 ° C higher, this is the same temperature as R2. The temperature inside the optional R3 may increase along its length. The maximum temperature difference between the R3 inlet and outlet in some cases is around 100 ° C, in other cases around 60 ° C and in other cases around 40 ° C. The minimum temperature difference between the R3 inlet and outlet in some cases can be 0 ° C, in other cases about 3 ° C and in other cases about 10 ° C. In some cases R3 is operated in an adiabatic form and in other cases R3 is heated.
[0179] The pressure in the polymerization reactors must be high enough to maintain the polymerization solution as a single phase solution and to provide the upstream pressure to force the polymer solution from the reactors through a heat exchanger and in operations polymer recovery. Referring to the modalities shown in Figures 2 and 3, the operating pressure of the solution polymerization reactors can vary over a wide range. For example, the limit
Petition 870190112009, of 11/01/2019, p. 79/168
73/156 higher in the reactor pressure in some cases can be around 45 MPag, in other cases about 30 MPag and still in other cases about 20 MPag; and the lower limit in some cases can be about 3 MPag, in some additional cases about 5 MPag and still in other cases about 7 MPag.
[0180] Referring to the modalities shown in Figures 2 and 3, before entering the first V / L separator, the passivated solution (current 23) can have a maximum temperature in some cases of around 300 ° C, in others about 290 ° C and in other cases about 280 ° C; the minimum temperature can be in some cases about 150 ° C, in other cases about 200 ° C and in other cases about 220 ° C. Immediately before entering the first V / L separator, the passivated solution may in some cases have a maximum pressure of about 40 MPag, in other cases about 25 MPag and in some cases about 15 MPag; the minimum pressure in some cases can be about 1.5 MPag, in other cases about 5 MPag and in other cases about 6 MPag.
[0181] The first V / L separator (vessel 25 in Figures 2 and 3) can be operated over a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the first V / L separator in some cases can be about 300 ° C, in other cases about 285 ° C and in other cases about 270 ° C; the minimum operating temperature in some cases may be about 100 ° C, in other cases about 140 ° C and in other cases 170 ° C. The maximum operating pressure of the first V / L separator in some cases can be about 20 MPag, in other cases about 10 MPag and still in other cases about 5 MPag; the minimum operating pressure in some cases can be about 1 MPag, in other cases about 2 MPag and in other cases about 3 MPag.
[0182] The second V / L separator (vessel 28 in Figures 2 and 3) can be operated over a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the second V / L separator in some cases
Petition 870190112009, of 11/01/2019, p. 80/168
74/156 can be about 300 ° C, in other cases about 250 ° C and in other cases about 200 ° C; the minimum operating temperature in some cases can be about 100 ° C, in other cases about 125 ° C and in other cases about 150 ° C. The maximum operating pressure of the second V / L separator in some cases can be about 1000 kPag, in other cases about 900 kPag and still in other cases about 800kPag; the minimum operating pressure in some cases can be about 10 kPag, in other cases about 20 kPag and in other cases about 30 kPag.
[0183] The third V / L separator (vessel 31 in Figures 2 and 3) can be operated over a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the third V / L separator in some cases may be about 300 ° C, in other cases about 250 ° C and in other cases about 200 ° C; the minimum operating temperature in some cases can be about 100 ° C, in other cases about 125 ° C and in other cases about 150 ° C. The maximum operating pressure of the third V / L separator in some cases can be about 500 kPag, in other cases about 150 kPag and in other cases about 100 kPag; the minimum operating pressure in some cases may be about 1 kPag, in other cases about 10 kPag and in other cases 25 about kPag.
[0184] Modalities of the continuous solution polymerization process shown in Figures 2 and 3 show three V / L separators. However, continuous solution polymerization modalities may include configurations comprising at least one V / L separator.
[0185] The ethylene interpolymer product produced in the continuous solution polymerization process can be recovered using conventional devolatilization systems that are well known to those skilled in the art, non-limiting examples include instant devolatilization systems and
Petition 870190112009, of 11/01/2019, p. 81/168
75/156 devolatilization extruders.
[0186] Any shape or design of reactor can be used for reactor 11 a (R1) and reactor 12a (R2) in Figures 2 and 3; non-limiting examples include tank-like, cylindrical, spherical, unsteady or agitated vessels, as well as tubular or recirculating reactors. On a commercial scale, the maximum volume of R1 in some cases may be about 20,000 gallons (about 75,710 L), in other cases about 10,000 gallons (about 37,850 L) and still in other cases about 5,000 gallons (about 18,930 L) L). On a commercial scale the minimum volume of R1 in some cases can be around 100 gallons (about 379 L), in other cases about 500 gallons (about 1,893 L) and in other cases around 1,000 gallons (about 3,785 L). On pilot installation scales, reactor volumes are typically much smaller, for example the volume of R1 on a pilot scale may be less than about 2 gallons (less than about 7.6 L). In this disclosure the reactor volume R2 was expressed as a percentage of the reactor volume R1. The upper limit on the volume of R2 in some cases may be about 600% of R1, in other cases about 400% of R1 and in other cases about 200% of R1. For clarity, if the volume of R1 is 5,000 gallons and R2 is 200% the volume of R1, then R2 has a volume of 10,000 gallons. The lower limit on the volume of R2 in some cases may be about 50% of R1, in other cases about 100% of R1 and in other cases about 150% of R1. In the case of Continuously Stirred Tank Reactors the agitation rate can vary over a wide range; in some cases from about 10 rpm to about 2000 rpm, in other cases from about 100 to about 1500 rpm and still in other cases from about 200 to about 1300 rpm. In this disclosure the volume of R3, the tubular reactor, was expressed as a percentage of the volume of reactor R2. The upper limit on the volume of R3 in some cases may be about 500% of R2, in other cases about 300% of R2 and in other cases about 100% of R2. The lower limit on the volume of R3 in some cases can be around 3
Petition 870190112009, of 11/01/2019, p. 82/168
76/156% of R2, in other cases about 10% of R2 and in other cases about 50% of R2.
[0187] The "average reactor residence time", a parameter commonly used in the chemical engineering technique, is defined by the first moment of the residence time distribution in the reactor; the residence time distribution in the reactor is a probability distribution function that describes the amount of time that a fluid element spends inside the reactor. The average reactor residence time can vary widely depending on process flow rates and mix, design and capacity of the reactor. The upper limit on the average reactor residence time of the solution in R1 in some cases can be about 600 seconds, in other cases about 360 seconds and in other cases about 180 seconds. The lower limit on the average reactor residence time of the solution in R1 in some cases can be about 10 seconds, in other cases about 20 seconds and in other cases about 40 seconds. The upper limit on the average reactor residence time of the solution in R2 in some cases can be about 720 seconds, in other cases about 480 seconds and in other cases about 240 seconds. The lower limit on the average reactor residence time of the solution in R2 in some cases can be about 10 seconds, in other cases about 30 seconds and in other cases about 60 seconds. The upper limit on the average reactor residence time of the solution in R3 in some cases can be about 600 seconds, in other cases about 360 seconds and in other cases about 180 seconds. The lower limit on the average reactor residence time of the solution in R3 in some cases can be about 1 second, in other cases about 5 seconds and in other cases about 10 seconds.
[0188] Optionally, additional reactors (for example, CSTRs, circulating or tubular, etc.) can be added to the modalities of the process
Petition 870190112009, of 11/01/2019, p. 83/168
77/156 continuous solution polymerization shown in Figures 2 and 3. In this disclosure, the number of reactors was not particularly important; with the proviso that the continuous solution polymerization process comprises at least two reactors that use at least one first homogeneous catalyst formulation and at least one heterogeneous catalyst formulation.
[0189] In operating the continuous solution polymerization process modalities shown in Figures 2 and 3 the total amount of ethylene supplied to the process can be portioned or divided between the three reactors R1, R2 and R3. This operational variable was referred to as the Ethylene Division (ES), that is "ES ^R1 ", "ES ^R2 " and "ES ^R3 " refer to the percentage by weight of ethylene injected into R1, R2 and R3, respectively; with the proviso that ES ^R1 + ES ^R2 + ES ^R3 = 100%. This was accomplished by adjusting the flow rates of ethylene in the following streams: stream 2 (R1), stream 7 (R2) and stream 14 (R3). The upper limit in ES ^R1 in some cases is around 60%, in other cases around 55% and in other cases around 50%; the lower limit in ES ^R1 in some cases is about 5%, in other cases about 8% and in other cases about 10%. The upper limit in ES ^R2 in some cases is about 95%, in other cases about 92% and in other cases about 90%; the lower limit in ES ^R2 in some cases is about 20%, in other cases about 30% and in other cases about 40%. The upper limit in ES ^R3 in some cases is around 30%, in other cases around 25% and in other cases around 20%; the lower limit in ES ^R3 in some cases is 0%, in other cases about 5% and in other cases about 10%.
[0190] In operating the modalities of the continuous solution polymerization process shown in Figures 2 and 3, the ethylene concentration in each reactor was also controlled. The ethylene concentration in reactor 1, then EC ^R1 , is defined as the weight of ethylene in reactor 1 divided by the total weight of everything added to reactor 1; EC ^R2 and EC ^R3 are defined similarly. Ethylene concentrations in
Petition 870190112009, of 11/01/2019, p. 84/168
78/156 reactors (EC ^R1 or EC ^R2 or EC ^R3 ) in some cases can vary from about 7 weight percent (% by weight) to about 25 weight percent, in other cases from about 8 weight percent at about 20% by weight and in still other cases from about 9% by weight to about 17% by weight.
[0191] In operating the modalities of the continuous solution polymerization process shown in Figures 2 and 3 the total amount of ethylene converted in each reactor was monitored. The term "Q ^R1 " refers to the percentage of ethylene added to R1 that has been converted to an ethylene interpolymer by the catalyst formulation. Similarly, Q ^R2 and Q ^R3 represent the percentage of ethylene added to R2 and R3 that was converted to ethylene interpolymer in the respective reactor. Ethylene conversions can vary significantly depending on a variety of process conditions, for example, catalyst concentration, catalyst formulation, impurities and poisons. The upper limit in both Q ^R1 and Q ^R2 in some cases is about 99%, in other cases about 95% and in other cases about 90%; the lower limit in both Q ^R1 and Q ^R2 in some cases is about 65%, in other cases about 70% and in other cases about 75%. The upper limit in Q ^R3 in some cases is about 99%, in other cases about 95% and in other cases about 90%; the lower limit in Q ^R3 in some cases is 0%, in other cases about 5% and in other cases about 10%. The term "Q ^T " represents the conversion of total or global ethylene through the installation of polymerization of entire continuous solution; ie Q ^T = 100 x [weight of ethylene in the interpolymer product] / ([weight of ethylene in the interpolymer product] + [weight of unreacted ethylene]). The upper limit in Q ^{T is} in some cases about 99%, in other cases about 95% and in other cases about 90%; the lower limit in Q ^T in some cases is about 75%, in other cases about 80% and in other cases about 85%.
[0192] Optionally, α-olefin can be added to the process
Petition 870190112009, of 11/01/2019, p. 85/168
79/156 continuous solution polymerization. If added, α-olefin can be provided or divided between R1, R2 and R3. This operational variable was referred to as the Comonomer Division (CS), that is, “CS ^R1 ”, “CS ^R2 ” and “CS ^R3 ” refer to the weight percentage of α-olefin comonomer that is injected into R1, R2 and R3, respectively; with the proviso that CS ^R1 + CS ^R2 + CS ^R3 = 100%. This is accomplished by adjusting the flow rates of q-olefin in the following currents: current 3 (R1), current 8 (R2) and current 15 (R3). The upper limit in CS ^R1 in some cases is 100% (ie 100% of the q-olefin is injected into R1), in other cases about 95% and in other cases about 90%. The lower limit in CS ^R1 in some cases is 0% (ethylene homopolymer produced in R1), in other cases about 5% and in other cases about 10%. The upper limit in CS ^R2 in some cases is about 100% (ie 100% of the q-olefin is injected into reactor 2), in other cases about 95% and in other cases about 90%. The lower limit in CS ^{R2 is} in some cases 0%, in other cases about 5% and in other cases about 10%. The upper limit in CS ^R3 in some cases is 100%, in other cases about 95% and in other cases about 90%. The lower limit in CS ^R3 in some cases is 0%, in other cases about 5% and in other cases about 10%.
First ethylene interpolymer
[0193] The first ethylene interpolymer was synthesized using the first homogeneous catalyst formulation. One embodiment of the first homogeneous catalyst formulation was a bridged metallocene catalyst formulation. Referring to the modalities shown in Figures 2 and 3, if the optional q-olefin was not added to reactor 1 (R1), then the ethylene interpolymer produced in R1 was an ethylene homopolymer. If a q-olefin is added, the following weight ratio was a parameter to control the density of the first ethylene interpolymer: (((q-olefin) / (ethylene)) ^R1 . The upper limit on ((aolefin) / (ethylene)) ^R1 can be about 3; in other cases about 2 and in still others
Petition 870190112009, of 11/01/2019, p. 86/168
80/156 cases about 1. The lower limit in ((a-olefin) / (ethylene)) ^R1 can be 0; in other cases about 0.25 and in other cases about 0.5. Then, the symbol “o ¹ ” refers to the density of the first ethylene interpolymer produced in R1. The upper limit in o ¹ can be about 0.975 g / cm ³ ; in some cases about 0.965 g / cm ³ and; in other cases about 0.955 g / cm ³ . The lower limit at o ¹ can be about 0.855 g / cm ³ , in some cases about 0.865 g / cm ³ , and; in other cases about 0.875 g / cm ³ .
[0194] Methods for determining the CDBIso (composition distribution branch index) of an ethylene interpolymer are well known to those skilled in the art. CDBIso, expressed as a percentage, was defined as the percentage of the ethylene interpolymer whose comonomer composition is within 50% of the median comonomer composition. It is also well known to those skilled in the art that the CDBIso of ethylene interpolymers produced with homogeneous catalyst formulations is higher than the CDBIso of ethylene interpolymers containing α-olefin produced with heterogeneous catalyst formulations. The upper limit on the CDBIso of the first ethylene interpolymer (produced with a homogeneous catalyst formulation) can be about 98%, in other cases about 95% and in other cases about 90%. The lower limit on the CDBIso of the first ethylene interpolymer can be about 70%, in other cases about 75% and in other cases about 80%.
[0195] As is well known to those skilled in the art, the Mw / Mn of ethylene interpolymers produced with homogeneous catalyst formulations is lower in relation to ethylene interpolymers produced with heterogeneous catalyst formulations. Thus, in the disclosed modalities, the first ethylene interpolymer had a lower Mw / Mn compared to the second ethylene interpolymer; where the second ethylene interpolymer was produced with a formulation
Petition 870190112009, of 11/01/2019, p. 87/168
81/156 of heterogeneous catalyst. The upper limit in Mw / Mn of the first ethylene interpolymer can be about 2.8, in other cases about 2.5 and in other cases about 2.2. The lower limit on the Mw / M _n of the first ethylene interpolymer can be about 1.7, in other cases about 1.8 and in other cases about 1.9.
[0196] The first ethylene interpolymer, produced with the bridged metallocene catalyst formulation, contains long chain branching characterized by the LCBF disclosed here. The upper limit in the LCBF of the first ethylene interpolymer can be about 0.5, in other cases about 0.4 and in other cases about 0.3 (dimensionless). The lower limit in the LCBF of the first ethylene interpolymer can be about 0.001, in other cases about 0.0015 and in other cases about 0.002 (dimensionless).
[0197] The first ethylene interpolymer contained catalyst residues that reflect the chemical composition of the first homogeneous catalyst formulation. Those skilled in the art will understand that catalyst residues are typically quantified by parts per million of metal in the first ethylene interpolymer, where the metal originates from the metal in catalyst component A (Formula (I)); then this metal will be referred to as “metal A”. As reported earlier in this disclosure, non-limiting examples of metal A include Group 4 metals, titanium, zirconium and hafnium. The upper limit on ppm of metal A in the first ethylene interpolymer can be about 3.0 ppm, in other cases about 2.0 ppm and still in other cases about 1.5 ppm. The lower limit on ppm of metal A in the first ethylene interpolymer can be about 0.03 ppm, in other cases about 0.09 ppm and still in other cases about 0.15 ppm.
[0198] The amount of hydrogen added to R1 can vary over a wide range allowing the continuous solution process to produce first ethylene interpolymers that differ greatly in melt index, then I2 ¹ (melt index was measured at 190 ° C using a 2.16 kg load following the
Petition 870190112009, of 11/01/2019, p. 88/168
82/156 procedures outlined in ASTM D1238). This was done by adjusting the hydrogen flow rate in stream 4 (as shown in Figures 2 and 3). The amount of hydrogen added to R1 was expressed as the parts-per-million (ppm) of hydrogen in R1 in relation to the total mass in the R1 reactor; then H2 ^R1 (ppm). In some cases H2 ^R1 (ppm) varies from about 100 ppm to 0 ppm, in other cases from about 50 ppm to 0 ppm, in alternative cases from about 20 ppm to 0 ppm and in other cases from about 2 ppm to 0 ppm. The upper limit in I2 ¹ can be about 200 dg / min, in some cases about 100 dg / min; in other cases about 50 dg / min, and; in still other cases about 1 dg / min. The lower limit in I2 ¹ can be about 0.01 dg / min, in some cases about 0.05 dg / min; in other cases about 0.1 dg / min, and; in still other cases about 0.5 dg / min.
[0199] The upper limit on the percentage by weight (% by weight) of the first ethylene interpolymer in the ethylene interpolymer product can be about 60% by weight, in other cases around 55% by weight and still in other cases about 50% by weight. The lower limit in weight% of the first ethylene interpolymer in the ethylene interpolymer product can be about 5% by weight; in other cases about 8% by weight and in other cases about 10% by weight.
Second ethylene interpolymer
[0200] Referring to the modalities shown in Figure 2, if optional c-olefin was not added to reactor 12a (R2) via fresh c-olefin current 8 or transported from reactor 11a (R1) in current 11e (in mode series), then the ethylene interpolymer produced in reactor 12a (R2) was an ethylene homopolymer. If an optional c-olefin is present in R2, the following weight ratio was a parameter to control the density of the second ethylene interpolymer produced in R2: (((c-olefin) / (ethylene)) ^R2 . The upper limit on ((c-olefin) / (ethylene)) ^R2 can be about 3; in other cases about 2 and still in other cases about 1. The lower limit in ((c-olefin) / (ethylene)) ^R2 can be 0; in other cases about 0.25 and still
Petition 870190112009, of 11/01/2019, p. 89/168
83/156 in other cases about 0.5. Then, the symbol “o ² ” refers to the density of the ethylene interpolymer produced in R2. The upper limit in o ² can be about 0.975 g / cm ³ ; in some cases about 0.965 g / cm ³ and; in other cases about 0.955 g / cm ³ Depending on the heterogeneous catalyst formulation used, the lower limit at o ² can be about 0.89 g / cm ³ , in some cases about 0.90 g / cm ³ , and ; in other cases about 0.91 g / cm ³ . The ranges disclosed in this paragraph also apply to the modalities shown in Figure 3.
[0201] A heterogeneous catalyst formulation was used to produce the second ethylene interpolymer. If the second ethylene interpolymer contains an α-olefin, the CDBIso of the second ethylene interpolymer was lower compared to the CDBIso of the first ethylene interpolymer that was produced with the first homogeneous catalyst formulation. In one embodiment of this disclosure, the upper limit in the CDBIso of the second ethylene interpolymer (which contains an α-olefin) can be about 70%, in other cases about 65% and in other cases about 60%. In one embodiment of this disclosure, the lower limit on the CDBIso of the second ethylene interpolymer (which contains an α-olefin) may be about 45%, in other cases about 50% and in other cases about 55%. If an aolefin is not added to the continuous solution polymerization process, the second ethylene interpolymer was an ethylene homopolymer. In the case of a homopolymer, which does not contain α-olefin, a person can still measure a CDBIso using TREF. In the case of a homopolymer, the upper limit on the CDBIso of the second ethylene interpolymer can be about 98%, in other cases about 96% and still in other cases about 95%, and; the lower limit on CDBIso can be around 88%, in other cases around 89% and in other cases around 90%. It is well known to those skilled in the art that as the α-olefin content in the second ethylene interpolymer approaches zero, there is a smooth transition between the reported CDBIso limits for the second ethylene interpolymers (which contain
Petition 870190112009, of 11/01/2019, p. 90/168
84/156 an α-olefin) and the CDBIso limits reported for the second ethylene interpolymers which are ethylene homopolymers.
[0202] The Mw / Mn of the second ethylene interpolymer was higher than the Mw / Mn of the first ethylene interpolymer. The upper limit in Mw / M _n of the second ethylene interpolymer can be about 4.4, in other cases about 4.2 and in other cases about 4.0. The lower limit in Mw / Mn of the second ethylene interpolymer can be about 2.2. M _w / M _n 's of 2.2 were observed when the melting index of the second ethylene interpolymer is high or when the melting index of the ethylene interpolymer product is high, for example, greater than 10 g / 10 minutes. In other cases, the lower limit on the Mw / Mn of the second ethylene interpolymer may be about 2.4 and in still other cases about 2.6.
[0203] The second ethylene interpolymer, produced with the first heterogeneous catalyst formulation, was characterized by an undetectable level of long chain branching, i.e., LCBF of <0.001 (dimensionless).
[0204] The second ethylene interpolymer contains catalyst residues that reflect the chemical composition of the first or second heterogeneous catalyst formulation. The first heterogeneous catalyst formulation contains ‘catalytic ZT metal. The second heterogeneous catalyst formulation contains catalytic 'Z2 metal'. The efficiency of the first heterogeneous catalyst formulation can be quantified by measuring the parts per million of metal Z1 or metal Z2 in the second ethylene interpolymer, where metal Z1 originates from the first component (vii) in the first heterogeneous catalyst formulation or metal Z2 originates from the second component (vii) in the second heterogeneous catalyst formulation. Non-limiting examples of metal Z1 and metal Z2 include metals selected from Group 4 to Group 8 of the Periodic Table or mixtures of metals selected from Group 4 to Group 8. The upper limit in ppm of Z1 metal or Z2 metal in the second ethylene interpolymer can be about 12 ppm, in other cases about 10 ppm and still in other cases
Petition 870190112009, of 11/01/2019, p. 91/168
85/156 about 8 ppm. The lower limit in ppm of metal Z1 or metal Z2 in the second ethylene interpolymer can be about 0.5 ppm, in other cases about 1 ppm and in still other cases about 3 ppm.
[0205] Referring to the modalities shown in Figures 2 and 3, the amount of hydrogen added to R2 can vary over a wide range that allows the continuous solution process to produce second ethylene interpolymers that differ greatly in melt index, in then I2 ² This is accomplished by adjusting the flow rate of hydrogen in stream 9. The amount of hydrogen added was expressed as the parts-per-million (ppm) of hydrogen in R2 relative to the total mass in reactor R2; then H2 ^R2 (ppm). In some cases H2 ^R2 (ppm) ranges from about 50 ppm to 0 ppm, in some cases from about 25 ppm to 0 ppm, in other cases from about 10 to 0 and in other cases from about 2 ppm to 0 ppm. The upper limit in I2 ² can be about 1000 dg / min; in some cases about 750 dg / min; in other cases about 500 dg / min, and; in still other cases about 200 dg / min. The lower limit in I2 ² can be about 0.3 dg / min, in some cases about 0.4 dg / min, in other cases about 0.5 dg / min, and; in still other cases about 0.6 dg / min.
[0206] The upper limit on the percentage by weight (% by weight) of the second ethylene interpolymer in the ethylene interpolymer product can be about 95% by weight, in other cases about 92% by weight and still in other cases about 90% by weight. The lower limit in weight% of the second ethylene interpolymer in the ethylene interpolymer product can be about 20% by weight; in other cases about 30% by weight and in other cases about 40% by weight.
Third Ethylene Interpolymer
[0207] Optionally, the disclosed ethylene interpolymer products contain a third ethylene interpolymer. Referring to the modalities shown in Figure 2, a third ethylene interpolymer was not produced in reactor 17 (R3) if
Petition 870190112009, of 11/01/2019, p. 92/168
Catalyst deactivator A was added upstream of reactor 17 via catalyst deactivator tank 18A. If catalyst deactivator A was not added and optional α-olefin was not added to reactor 17 via fresh α-olefin current 15 or carried from reactor 12a (R2) in current 12c (serial mode) or current 12d (mode parallel) so the ethylene interpolymer produced in reactor 17 was an ethylene homopolymer. If catalyst deactivator A was not added and optional α-olefin was present in R3, the following weight ratio was a parameter that determined the density of the third ethylene interpolymer: (((aolefin) / (ethylene)) ^R3 . The upper limit on ((a-olefin) / (ethylene)) ^R3 can be about 3; in other cases about 2 and still in other cases about 1. The lower limit in ((a-olefin) / (ethylene)) ^R3 can be 0; in other cases about 0.25 and in other cases about 0.5. Then, the symbol “o ³ ” refers to the density of the ethylene interpolymer produced in R3. The upper limit in o ³ can be about 0.975 g / cm ³ ; in some cases about 0.965 g / cm ³ and; in other cases about 0.955 g / cm ³ . Depending on the catalyst formulations used in R3, the lower limit on o ³ can be about 0.855 g / cm ³ , in some cases about 0.865 g / cm ³ , and; in other cases about 0.875 g / cm ³ . The ranges disclosed in this paragraph also apply to the modalities shown in Figure 3.
[0208] Optionally, one or more of the following homogeneous or heterogeneous catalyst formulations can be injected into R3: the first homogeneous catalyst formulation, the first heterogeneous catalyst formulation, the second homogeneous catalyst formulation, the third homogeneous catalyst formulation the fifth formulation of homogeneous catalyst. If the first homogeneous catalyst formulation is used, comprising the bridged metallocene catalyst formulation, the third ethylene interpolymer contains metal A. The upper limit in ppm of metal A in the third ethylene interpolymer can be about 3.0 ppm, in other cases about 2.0 ppm and in other cases
Petition 870190112009, of 11/01/2019, p. 93/168
87/156 about 1.5 ppm. The lower limit on ppm of metal A in the third ethylene interpolymer can be about 0.03 ppm, in other cases about 0.09 ppm and still in other cases about 0.15 ppm. If the first heterogeneous catalyst formulation is used, the third ethylene interpolymer contains metal Z1. The upper limit on ppm of metal Z1 in the third ethylene interpolymer can be about 12 ppm, in other cases about 10 ppm and still in other cases about 8 ppm. The lower limit in ppm of metal Z1 in the third ethylene interpolymer can be about 0.5 ppm, in other cases about 1 ppm and still in other cases about 3 ppm. If the second heterogeneous catalyst formulation is used, the third ethylene interpolymer contains metal Z2. The upper limit in ppm of metal Z2 in the third ethylene interpolymer can be about 12 ppm, in other cases about 10 ppm and in other cases about 8 ppm. The lower limit in ppm of metal Z2 in the third ethylene interpolymer can be about 0.5 ppm, in other cases about 1 ppm and in other cases about 3 ppm. If the third homogeneous catalyst formulation is used, comprising the single site non-bridged catalyst formulation, the third ethylene interpolymer contains metal C. The upper limit on ppm of metal C in the third ethylene interpolymer can be about 3 , 0 ppm, in other cases about 2.0 ppm and in other cases about 1.5 ppm. The lower limit on ppm of metal C in the third ethylene interpolymer can be about 0.03 ppm, in other cases about 0.09 ppm and still in other cases about 0.15 ppm. If the fifth homogeneous catalyst formulation is used, comprising a bulky binder-metal complex that is not a member of the genera defined by Formulas (I) or (II) the third ethylene interpolymer contains metal D. The upper limit in ppm of metal D in the third ethylene interpolymer can be about 3.0 ppm, in other cases about 2.0 ppm and still in other cases about 1.5 ppm. The lower limit on ppm of metal D in the third ethylene interpolymer can be about 0.03 ppm, in other cases about 0.09 ppm and still
Petition 870190112009, of 11/01/2019, p. 94/168
88/156 other cases about 0.15 ppm.
[0209] The upper limit in the CDBIso of the optional third ethylene interpolymer (containing an α-olefin) can be about 98%, in other cases about 95% and in other cases about 90%. The lower limit on the CDBIso of the optional third ethylene interpolymer can be about 35%, in other cases about 40% and in other cases about 45%.
[0210] The upper limit in Mw / M _n of the optional third ethylene interpolymer can be about 5.0, in other cases about 4.8 and in other cases about 4.5. The lower limit in Mw / M _n of the optional third ethylene interpolymer can be about 1.7, in other cases about 1.8 and in other cases about 1.9.
[0211] Referring to the modalities shown in Figures 2 and 3, optional hydrogen can be added to the tubular reactor (R3) via stream 16. The amount of hydrogen added to R3 can vary over a wide range. Adjusting the amount of hydrogen in R3, then H2 ^R3 (ppm), allows the continuous solution process to produce optional third ethylene interpolymers that differ widely in melt index, then I2 ³ The amount of optional hydrogen added to R3 varies from about 50 ppm to 0 ppm, in some cases from about 25 ppm to 0 ppm, in other cases from about 10 to 0 and still in other cases from about 2 ppm to 0 ppm. The upper limit in I2 ³ can be about 2000 dg / min; in some cases about 1500 dg / min; in other cases about 1000 dg / min, and; in still other cases about 500 dg / min. The lower limit in I2 ³ can be about 0.5 dg / min, in some cases about 0.6 dg / min, in other cases about 0.7 dg / min, and; in still other cases about 0.8 dg / min.
[0212] The upper limit on the percentage by weight (% by weight) of the optional third ethylene interpolymer in the ethylene interpolymer product can be about 30% by weight, in other cases around 25% by weight and still in other cases about 20% by weight. The lower limit on the weight% of the third interpolymer of
Petition 870190112009, of 11/01/2019, p. 95/168
89/156 optional ethylene in the ethylene interpolymer product can be 0% by weight; in other cases about 5% by weight and in other cases about 10% by weight.
Ethylene interpolymer product
[0213] The upper limit on the density of the ethylene interpolymer product (p ^f ) can be about 0.975 g / cm ³ ; in some cases about 0.965 g / cm ³ and; in other cases about 0.955 g / cm ³ . The lower limit on the density of the ethylene interpolymer product can be about 0.862 g / cm ³ , in some cases about 0.872 g / cm ³ , and; in other cases about 0.882 g / cm ³ .
[0214] The upper limit on the CDBIso of the ethylene interpolymer product can be about 97%, in other cases about 90% and still in other cases about 85%. An ethylene interpolymer product with a 97% CDBIso can result if an α-olefin is not added to the continuous solution polymerization process; in this case, the ethylene interpolymer product is an ethylene homopolymer. The lower limit on the CDBIso of an ethylene interpolymer product can be about 20%, in other cases about 40% and in other cases about 60%.
[0215] The upper limit in Mw / Mn of the ethylene interpolymer product may be about 25, in other cases about 15 and in other cases about 9. The lower limit in Mw / Mn of the ethylene interpolymer product it may be 2.0, in other cases about 2.2 and in other cases about 2.4.
[0216] The catalyst residues in the ethylene interpolymer product reflect the chemical compositions of: the first homogeneous catalyst formulation used in R1; the first heterogeneous catalyst formulation used in R2, and; optionally one or more catalyst formulations used in R3. Catalyst residues were quantified by measuring parts per million catalytic metal in ethylene interpolymer products using Neutron Activation Analysis (N.A.A.). As shown in Table 5, the interpolymer product
Petition 870190112009, of 11/01/2019, p. 96/168
90/156 ethylene Example 3 contained 0.541 ppm hafnium and 4.24 ppm titanium. As shown in Table 4A, Example 3 was produced with reactors 1 and 2 operating in parallel mode, a bridged metallocene catalyst formulation containing hafnium (Hf) was injected into reactor 1 and a first Ziegler-Natta catalyst formulation. in line containing titanium (Ti) was injected in reactor 2 (catalysts were not injected in reactor 3). In addition, in Example 3, Hf originated from CpF-2 (the diphenylmethylene (cyclopentadienyl) (2,7-di-t-butiIfuorenyl) hafnium dimethyl [(2,7tBu2Flu) Ph2C (Cp) HfMe2] component A (Formula (I))) and Ti originated from the TiCk species of component (vii). Example 3 had a residual catalyst Hf / Ti ratio of 0.128 (0.541 ppm Hf / 4.24 ppm Ti).
[0217] As shown in Table 5, Comparative 1 contained 0.0 ppm of hafnium and 6.10 ppm of titanium, thus a residual catalyst Hf / Ti ratio of 0.0. As shown in Table 4A, Comparative 1 was produced with reactors 1 and 2 operating in series mode, a single-site non-bridged catalyst formulation (containing Ti) was injected into reactor 1 and a first Ziegler- In-line Natta (containing Ti) was injected into reactor 2 (catalysts were not injected into reactor 3). In Comparative 1, the sources of Ti were: PIC-1 (the cyclopentadienyl dichloride tri (tertiary butyl) phosphinimine titanium [Cp [(tBu) sPN] TiCl2] component C (Formula (II))) and the species of Component TiCk (vü).
[0218] As shown in Table 5, the ethylene interpolymer product from Example 4 contained 0.502 ppm Hf and 8.45 ppm Ti and the residual catalyst Hf / Ti ratio was 0.059. As shown in Table 4A, Example 4 was produced with reactors 1 and 2 operating in series mode, a bridged metallocene catalyst formulation containing Hf (CpF-1) was injected into reactor 1 and a first Ziegler catalyst formulation -Natta in line containing Ti (TiCk) was injected in reactor 2 (catalysts were not injected in reactor 3).
Petition 870190112009, of 11/01/2019, p. 97/168
91/156
[0219] Comparative 10 contained 0.0 ppm Hf and 6.8 ppm Ti and the residual catalyst Hf / Ti ratio was 0.0. Comparative 10 was produced using the single site non-bridged catalyst formulation in reactor 1 and the first in-line Ziegler-Natta catalyst formulation in reactor 2. Comparative 10 was an ethylene / 1-octene process polymer commercially available solution produced by NOVA Chemicals Corporation (Calgary, Alberta, Canada) code SURPASS® SPs116-C02.
[0220] The upper limit in ppm of metal A in the ethylene interpolymer product was determined by maximizing the weight fraction (ie 0.60) of the first ethylene interpolymer, minimizing the weight fraction (ie 0 , 20) of the second ethylene interpolymer and the remaining weight fraction (ie 0.20) was the third ethylene interpolymer produced with catalytic metal A. Specifically, the upper limit in ppm of metal A in the ethylene interpolymer product was 2.4 ppm: i.e. ((0.6 x 3 ppm) + (0.2 x 3 ppm)); where 3 ppm is the upper limit in ppm of metal A in the first and third ethylene interpolymers. In other cases, the upper limit in ppm of metal A in the ethylene interpolymer product was 2 ppm and in still other cases 1.5 ppm. The lower limit in ppm of metal A in the ethylene interpolymer product was determined by minimizing the weight fraction (ie 0.05) of the first ethylene interpolymer and maximizing the weight fraction (ie 0.95) of the second ethylene interpolymer. Specifically, the lower limit on ppm of metal A in the ethylene interpolymer product was 0.0015 ppm: that is (0.05 x 0.03 ppm), where 0.03 ppm was the lower limit of metal A on the first interpolymer of ethylene. In other cases, the lower limit on ppm of metal A in the ethylene interpolymer product was 0.0025 ppm and in still other cases 0.0035 ppm.
[0221] The upper limit in ppm of metal Z1 in the ethylene interpolymer product was determined by maximizing the weight fraction (ie 0.95) of the second ethylene interpolymer, ie 11.4 ppm (0.95 x 12 ppm), where 12 ppm was the limit
Petition 870190112009, of 11/01/2019, p. 98/168
92/156 higher in ppm of metal Z1 in the second ethylene interpolymer. In other cases, the upper limit on the amount of Z1 metal in the ethylene interpolymer product was 10 ppm and in other cases 8 ppm. The lower limit in ppm of metal Z1 in the ethylene interpolymer product was determined by minimizing the weight fraction (ie 0.20) of the second ethylene interpolymer, ie 0.1 ppm (0.20 x 0.5 ppm), where 0.5 ppm was the lower limit in ppm of metal Z1 in the second ethylene interpolymer. In other cases, the lower limit on the ppm of metal Z1 in the ethylene interpolymer product was 0.15 ppm and in still other cases 0.2 ppm.
[0222] The upper limit in ppm of metal Z2 in the ethylene interpolymer product was determined by maximizing the weight fraction (ie 0.30) of the third ethylene interpolymer, ie 3.6 ppm (0.30 x 12 ppm), where 12 ppm was the upper limit in ppm of metal Z2 in the third ethylene interpolymer. In other cases, the upper limit on the amount of Z2 metal in the ethylene interpolymer product was 3 ppm and in still other cases 2.4 ppm.
[0223] The lower limit in ppm of metal Z2 in the ethylene interpolymer product was determined by minimizing the weight fraction (ie 0.0) of the third ethylene interpolymer, ie 0.0 ppm (0.0 x 0.5 ppm), where 0.5 ppm was the lower limit in the ppm of metal Z2 in the third ethylene interpolymer. In other cases where the ethylene interpolymer product contains a small fraction of the third ethylene interpolymer the lower limit in ppm of metal Z1 in the ethylene interpolymer product may be 0.025 ppm and in other cases 0.05 ppm, that is 5 and 10% of the third ethylene interpolymer, respectively.
[0224] The upper limit in ppm of metal C or metal D in the ethylene interpolymer product was determined by maximizing the weight fraction (ie 0.30) of the third ethylene interpolymer, ie 0.9 ppm ( 0.3 x 3 ppm), where 3 ppm is the upper limit in ppm of metal C or metal D, in the third ethylene interpolymer. In other cases, the upper limit in ppm of metal C or metal D, in the product of
Petition 870190112009, of 11/01/2019, p. 99/168
93/156 ethylene interpolymer was 0.7 ppm and still in other cases 0.5 ppm. The lower limit in ppm of metal C or metal D in the ethylene interpolymer product was determined by minimizing the weight fraction (ie 0.0) of the third ethylene interpolymer, ie 0.0 ppm (0.0 x 0.03 ppm), where 0.03 ppm was the lower limit in ppm of metal C or metal D, in the third ethylene interpolymer. In other cases when the ethylene interpolymer product contains a small fraction of the third ethylene interpolymer the lower limit in ppm of metal C or metal D, in the ethylene interpolymer product it can be 0.0015 ppm or 0.003 ppm, that is 5 and 10% of the third ethylene interpolymer, respectively.
[0225] The ratio of hafnium to titanium (Hf / Ti) in the ethylene interpolymer product can vary from 24 to 0.00013, as determined by Neutron Activation Analysis. An Hf / Ti ratio of 24 can result in the case of an ethylene interpolymer product containing 80% by weight of the first and a third ethylene interpolymer containing 3 ppm of Hf (upper limit) and 20% by weight of an second ethylene interpolymer containing 0.5 ppm Ti (lower limit). A Hf / Ti ratio of 0.00013 can result in the case of an ethylene interpolymer product containing 5% by weight of a first ethylene interpolymer containing 0.03 ppm Hf (lower limit) and 95% by weight of a second ethylene interpolymer containing 12 ppm Ti (upper limit).
[0226] The upper limit on the total amount of catalytic metal (metals A and Z1 and optionally metals Z2, C and D) in the ethylene interpolymer product can be 11.6 ppm, in other cases 10 ppm and still in other cases 8 ppm. The lower limit on the total amount of catalytic metal in the ethylene interpolymer product can be 0.12 ppm, in other cases 0.15 ppm and still in other cases 0.2 ppm.
[0227] Modalities of the ethylene interpolymer products disclosed here have lower catalyst residues compared to the polyethylene polymers described in US 6,277,931. Higher catalyst residues in U.S. 6,277,931
Petition 870190112009, of 11/01/2019, p. 100/168
94/156 increase the complexity of the continuous solution polymerization process; an example of increased complexity includes additional purification steps to remove catalyst residues from the polymer. In contrast, in the present disclosure, catalyst residues are not removed.
[0228] The upper limit on the melt index of the ethylene interpolymer product can be about 500 dg / min, in some cases about 400 dg / min; in other cases about 300 dg / min, and; in still other cases about 200 dg / min. The lower limit on the melt index of the ethylene interpolymer product can be about 0.3 dg / min, in some cases about 0.4 dg / min; in other cases about 0.5 dg / min, and; in still other cases about 0.6 dg / min.
Catalyst deactivation
[0229] In the continuous polymerization processes described in this disclosure, the polymerization is terminated by adding a catalyst deactivator. Modalities in Figures 2 and 3 show the catalyst deactivation taking place: (a) upstream of the tubular reactor by adding a catalyst deactivator A from the catalyst deactivator tank 18A, or; (b) downstream of the tubular reactor by adding a catalyst deactivator B from the catalyst deactivator tank 18B. Catalyst deactivator tanks 18A and 18B may contain pure catalyst deactivator (100%), a catalyst deactivator solution in a solvent, or a catalyst deactivator slurry in a solvent. The chemical composition of catalyst deactivator A and B can be the same or different. Non-limiting examples of suitable solvents include straight or branched C5 to C12 alkanes. In this disclosure, how the catalyst deactivator is added is not particularly important. Once added, the catalyst deactivator substantially for the polymerization reaction by changing the species of active catalyst to inactive forms. Suitable deactivators are well known in the art, non-limiting examples include: amines (e.g., Pat.
Petition 870190112009, of 11/01/2019, p. 101/168
95/156 of the USA I P 4,803,259 to Zboril et al.); alkali or alkaline earth metal salts of carboxylic acid (e.g., U.S. Pat. hP 4,105,609 to Machan et al.); water (for example, U.S. Pat. No. 4,731,438 to Bernier et al.); hydrotalcites, alcohols and carboxylic acids (for example, U.S. Pat. No. 4,379,882 to Miyata); or a combination thereof (U.S. Pat. 6,180,730 to Sibtain etal.). In this disclosure the quantification of the added catalyst deactivator was determined by the following molar ratio of catalyst deactivator: 0.3 <(catalyst deactivator) / ((total catalytic metal) + (aluminum aluminum co-catalyst) + (aluminum alkyl) ) <2.0; where the catalytic metal is the total mol of (metal A + metal Z1 + any optional catalytic metals added to the third reactor). The upper limit on the catalyst deactivator molar ratio can be about 2, in some cases about 1.5 and in other cases about 0.75. The lower limit on the molar ratio of catalyst deactivator can be about 0.3, in some cases about 0.35 and in other cases about 0.4. In general, the catalyst deactivator is added in a minimal amount such that the catalyst is deactivated and the polymerization reaction is extinguished.
Solution passivation
[0230] Referring to the modalities shown in Figures 2 and 3; before entering the first V / L separator, an acid passivator or discount is added to the deactivated solution A or B to form a passivated solution, that is, passivated solution stream 23. The passivator tank 22 may contain pure passivator ( 100%), a passivator solution in a solvent or a passivator slurry in a solvent. Non-limiting examples of suitable solvents include straight or branched C5 to C12 alkanes. In this disclosure, how the passivator is added is not particularly important. Suitable passivators are well known in the art, non-limiting examples include alkali or alkaline earth metal salts of carboxylic acids or hydrotalcites. The amount of passivator
Petition 870190112009, of 11/01/2019, p. 102/168
96/156 added can vary over a wide range. In this disclosure the amount of passivator added was determined by the total mole of chloride compounds added to the solution process, that is the chloride compound "compound (vi)" plus the metallic compound "compound (vii)". Optionally, a first and second chloride compound and a first and second metal compound can be used, that is, to form the first and second heterogeneous catalyst formulations; in this case, the amount of passivator added is determined by the total mol of all chloride-containing compounds. The upper limit on the (passivator) / (total chloride) molar ratio can be 15, in some cases 13 and in other cases 11. The lower limit on the (passivator) / (total chloride) molar ratio can be around 5, in some cases about 7 and in other cases about 9. In general, the passivator is added in the minimum amount to substantially passivate the deactivated solution.
Flexible articles manufactured
[0231] The ethylene interpolymer products disclosed here can be converted into manufactured flexible articles such as monolayer or multilayer films. Non-limiting examples of processes for preparing such films include blow molded film processes, double bubble processes, triple bubble processes, fused film processes, stripping processes and machine-oriented orientation (MDO) processes.
[0232] In the blow molded film extrusion process, an extruder heats, melts, mixes and loads a thermoplastic or thermoplastic mixture. Once melted, the thermoplastic is forced through an annular mold to produce a thermoplastic tube. In the case of co-extrusion, multiple extruders are used to produce a multilayer thermoplastic tube. The temperature of the extrusion process is mainly determined by the thermoplastic or thermoplastic mixture being processed, for example the melting temperature or
Petition 870190112009, of 11/01/2019, p. 103/168
97/156 glass transition temperature of the thermoplastic and the desired melt viscosity. In the case of polyolefins, typical extrusion temperatures are 330 ° F to 550 ° F (166 ° C to 288 ° C). At the exit of the annular mold, the thermoplastic tube is inflated with air, cooled, solidified and collected through a pair of narrowing rollers. Due to inflation with air, the tube increases in diameter forming a bubble of desired size. Due to the pulling action of the nip rollers, the bubble is stretched towards the machine. Thus, the bubble is stretched in two directions: the transverse direction (TD) where the inflated air increases the diameter of the bubble; and the machine direction (MD) where the nip rollers stretch the bubble. As a result, the physical properties of blow molded films are typically anisotropic, that is, the physical properties differ in the directions of MD and TD; for example, the tensile and tear strength properties of the film typically differ in MD and TD. In some prior art documents, the terms "transverse direction" or "CD" are used; these terms are equivalent to the terms “transversal direction” or “TD” used in this disclosure. In the blow molded film process, air is also blow molded on the outer circumference of the bubble to cool the thermoplastic as it exits the annular mold. The final width of the film is determined by controlling the inflated air or the internal pressure of the bubble; in other words, increasing or decreasing the bubble diameter. The thickness of the film is mainly controlled by increasing or decreasing the speed of the nip rollers to control the flow rate. After exiting the nip rollers, the bubble or tube is collapsed and can be notched in the direction of the machine thus creating the lamination. Each sheet can be wrapped in a roll of film. Each roll can also be slotted to create the film of the desired width. Each roll of film is further processed into a variety of consumer products as described below.
[0233] The molten film process is similar in that a single or multiple extruder can be used; however, the various thermoplastic materials are measured
Petition 870190112009, of 11/01/2019, p. 104/168
98/156 in a flat mold and extruded into a monolayer or multilayer sheet, instead of a tube. In the molten film process, the extruded sheet is solidified on a cooling roll.
[0234] In the double bubble process a first blow molded film bubble is formed and cooled, then the first bubble is heated and re-inflated to form a second blow molded film bubble, which is subsequently cooled. The ethylene interpolymer products, disclosed herein, are also suitable for the triple blow molded bubble process. Additional film conversion processes, suitable for the disclosed ethylene interpolymer products, include processes that involve a machine-oriented orientation step (MDO); for example, blowing a film, tempering the film and then subjecting the film tube or film sheet to an MDO process at any stretch ratio. In addition, the ethylene interpolymer film products disclosed here are suitable for use in stripping processes as well as other processes that introduce biaxial orientation.
[0235] Depending on the final application, the disclosed ethylene interpolymer products can be converted into films that span a wide range of thicknesses. Non-limiting examples include, films for food packaging where thicknesses can vary from about 0.5 mil (13 pm) to about 4 mil (102 pm), and; in heavy duty bag applications the film thickness can vary from about 2 mil (51 μ) to about 10 mil (254 pm).
[0236] The monolayer, in monolayer film, may contain more than one ethylene interpolymer product and / or one or more additional polymers; non-limiting examples of additional polymers include ethylene polymers and propylene polymers. The lower limit on the weight percentage of the ethylene interpolymer product in a monolayer film can be about 3% by weight, in other cases about 10% by weight and still in other cases about 30% by weight.
Petition 870190112009, of 11/01/2019, p. 105/168
99/156 weight. The upper limit on the weight percentage of the ethylene interpolymer product in the monolayer film can be 100% by weight, in other cases about 90% by weight and in still other cases about 70% by weight.
[0237] The ethylene interpolymer products disclosed here can also be used in one or more layers of a multilayer film; non-limiting examples of multilayer films include three, five, seven, nine, eleven or more layers. The ethylene interpolymer products disclosed are also suitable for use in processes using micro-overlay molds and / or feed blocks, such processes can produce films having many layers, non-limiting examples include 10 to 10,000 layers. The thickness of a specific layer (containing the ethylene interpolymer product) within a multilayer film can be about 5%, in other cases about 15% and still in other cases about 30% of the film thickness total multiple layers. In other embodiments, the thickness of a specific layer (containing the ethylene interpolymer product) within a multilayer film can be about 95%, in other cases about 80% and in other cases about 65% of the total multilayer film thickness. Each individual layer of a multilayer film can contain more than one additional ethylene interpolymer product and / or thermoplastics.
[0238] Additional modalities include laminations and coatings, in which monolayer or multilayer films containing the disclosed ethylene interpolymer products are either laminated by extrusion or adhesive laminated or coated by extrusion. In extrusion inhalation or adhesive inhalation, two or more substrates are bonded together with a thermoplastic or an adhesive, respectively. In extrusion coating, a thermoplastic is applied to the surface of a substrate. These processes are well known to those skilled in the art. Often, adhesive inaction or extrusion inaction is used
Petition 870190112009, of 11/01/2019, p. 106/168
100/156 for connecting dissimilar materials, non-limiting examples include the connection of a paper network to a thermoplastic network or the connection of a network containing aluminum foil to a thermoplastic network or the connection of two thermoplastic networks that are chemically incompatible, for example , the connection of a network containing ethylene interpolymer product to a network of polyester or polyamide. Before lamination, the mesh containing the disclosed ethylene interpolymer product (s) may be monolayer or multilayer. Before lamination, individual nets can be treated on the surface to improve bonding, a non-limiting example of a surface treatment is corona treatment. A primary mesh or film can be laminated on its upper surface, its lower surface or both its upper and lower surfaces with a secondary mesh. A secondary network and a tertiary network can be rolled into the primary network; in which the secondary and tertiary networks differ in chemical composition. As non-limiting examples, secondary or tertiary networks may include; polyamide, polyester and polypropylene or networks containing layers of barrier resin such as EVOH. Such networks may also contain a vapor deposited barrier layer; for example a thin layer of silicon oxide (SiOx) or aluminum oxide (AlOx). Multilayer networks (or films) can contain three, five, seven, nine, eleven or more layers.
[0239] The ethylene interpolymer products disclosed here can be used in a wide range of articles manufactured comprising one or more films (monolayer or multilayer). Non-limiting examples of such manufactured articles include: films for food packaging (fresh and frozen foods, liquids and granular foods), bags that remain upright, sterilizable packaging and box packaging; barrier films (oxygen, moisture, aroma, oil, etc.) and modified atmosphere packaging; light and heavy duty heat-shrink films and shrink wrap, comparison heat-shrink film, film
Petition 870190112009, of 11/01/2019, p. 107/168
101/156 heat shrink pallet, heat shrink bags, heat shrink wrap and heat shrink caps; light and heavy duty stretch films, manual stretch wrap, machine stretch wrap and stretch hood films; high purity films; heavy-duty bags; household wrapping, reel films and sandwich bags; industrial and institutional films, garbage bags, tin liners, magazine wrap, newspaper bags, tote bags, correspondence bags and envelopes, bubble wrap, carpet film, furniture bags, clothing bags, coin bags automotive panel films; medical applications such as gowns, drapes and surgical clothing; construction films and inaction, asphalt films, insulating bags, masking film, film and landscaping bags; geomembrane linings for municipal waste disposal and extraction applications; batch inclusion bags; agricultural films, decomposing plant material film and greenhouse films; stock packaging, self-service bags, store bags, shopping bags, transport bags and t-shirt bags; oriented films, machine-oriented films (MDO), biaxially oriented films and functional film layers in oriented polypropylene (OPP) films, for example, sealing and / or resistant layers. Additional manufactured articles comprising one or more films containing at least one ethylene interpolymer product include laminates and / or multilayer films; sealants and bonding layers in multilayer films and composites; laminations with paper; laminates of aluminum foil or laminates containing vacuum-deposited aluminum; polyamide laminates; polyester laminates; extrusion-coated laminates, and; hot melt adhesive formulations. The manufactured articles summarized in this paragraph contain at least one film (monolayer or multilayer) comprising at least one embodiment of the disclosed ethylene interpolymer products.
[0240] The desired physical properties of the film (monolayer or
Petition 870190112009, of 11/01/2019, p. 108/168
102/156 multiple layers) typically depend on the application of interest. Non-limiting examples of desirable film properties include: optical properties (gloss, haze and clarity), perforation, Elmendorf rupture, modulus (secant modulus at 1% and 2%), tensile properties (yield strength, tear strength, elongation at break, toughness, etc.), heat sealing properties (heat sealing initiation temperature, SIT and heat bonding). Specific hot-glue and heat-sealing properties are desired in high-speed vertical and horizontal form-fill-seal processes that load and seal a commercial product (liquid, solid, paste, part, etc.) in a similar package at pocket.
[0241] In addition to the desired physical properties of film, it is desired that the disclosed ethylene interpolymer products are easy to process film lines. Those skilled in the art often use the term "processability" to differentiate polymers with improved processability from polymers with inferior processability. A measure commonly used to quantify processability is extrusion pressure; more specifically, a polymer with improved processability has a lower extrusion pressure (in a blow-molded or molten film extrusion line) compared to a polymer with less processability.
[0242] The films used in the manufactured articles described in this section may optionally include, depending on their intended use, additives and adjuvants. Non-limiting examples of additives and adjuvants include, anti-blocking agents, antioxidants, thermal stabilizers, gliding agents, processing aids, anti-static additives, dyes, dyes, fillers, light stabilizers, light absorbers, lubricants, pigments , plasticizers, nucleating agents and combinations thereof.
Rigid manufactured articles
Petition 870190112009, of 11/01/2019, p. 109/168
103/156
[0243] The processes disclosed here are also capable of making ethylene interpolymer products that have a useful combination of desirable physical properties in manufactured rigid articles. Non-limiting examples of rigid items include: delicacy containers, margarine buckets, beverage cups and product trays; domestic and industrial containers, glasses, bottles, buckets, crates, tanks, drums, large glasses, lids, industrial volume containers, industrial vessels, material handling containers, bottle cap liners, bottle caps, hinge closures; toys, playground equipment, recreational equipment, boats, naval and safety equipment; wire and cable applications such as power cables, cables and communication channels; flexible tubing and hoses; pipe applications including both pressurized pipe and non-pressurized pipe markets, for example, natural gas distribution, water pipelines, internal piping, rainwater piping, sanitary sewer pipe, corrugated pipes and channels; foamed articles made of foamed foil or bread foam; military packaging (equipment and ready meals); personal care packaging, diapers and sanitary products; cosmetic, pharmaceutical and medical packaging, and; body floor liners, pallets and automotive mat. The manufactured rigid articles summarized in this paragraph contain one or more of the ethylene interpolymer products disclosed herein or a mixture of at least one of the ethylene interpolymer products disclosed here with at least one other thermoplastic.
[0244] Such manufactured rigid articles can be manufactured using the following non-limiting processes: injection molding, compression molding, blow molding, rotational molding, profile extrusion, tube extrusion, sheet thermoforming and foaming using agents chemical or physical blowing agents.
[0245] The desired physical properties of rigid articles manufactured
Petition 870190112009, of 11/01/2019, p. 110/168
104/156 depend on the application of interest. Non-limiting examples of desired properties include: flexural module (1% and 2% secant module); tensile toughness; resistance to cracking by environmental fatigue (ESCR); resistance to slow crack growth (PENT); abrasion resistance; shore hardness; deflection temperature under load; softening point of VICAT; resistance to the impact of IZOD; resistance to the impact of ARM; resistance to Charpy's impact, and; color (whiteness and / or yellowness index).
[0246] The manufactured rigid articles described in this section may optionally include, depending on their intended use, additives and adjuvants. Non-limiting examples of additives and adjuvants include, antioxidants, glidants, processing aids, anti-static additives, dyes, dyes, fillers, thermal stabilizers, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleation and combinations thereof.
Test Methods
[0247] Before the test, each specimen was conditioned for at least 24 hours at 23 ± 2 ° C and 50 ± 10% relative humidity and the subsequent test was conducted at 23 ± 2 ° C and 50 ± 10% relative humidity . Here, the term “ASTM conditions” refers to a laboratory that is maintained at 23 ± 2 ° C and 50 ± 10% relative humidity; and specimens to be tested were conditioned for at least 24 hours in this laboratory before testing. ASTM refers to the American Society for Testing and Materials.
Density
[0248] Product densities of ethylene interpolymer were determined using ASTM D792-13 (November 1, 2013).
melting index
[0249] The melting index of the ethylene interpolymer product has been determined
Petition 870190112009, of 11/01/2019, p. 111/168
105/156 using ASTM D1238 (August 1, 2013). The fusion indices, I2, Ιβ, I10 and I21 were measured at 190 ° C., Using weights of 2.16 kg, 6.48 kg, 10 kg and one of 21.6 kg respectively. Here, the term “stress exponent” or its acronym “S.Ex”., Is defined by the following relationship:
S.Ex. = log ( ₁₆ / l2) / log (6480/2160) where le and I2 are the melt flow rates measured at 190 ° C using loads of 6.48 kg and 2.16 kg, respectively .
Conventional size exclusion chromatography (SEC)
[0250] Sample solutions of ethylene interpolymer (polymer) product (1 to 3 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150 ° C in an oven. An antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Polymer solutions were subjected to chromatography at 140 ° C in a PL 220 high temperature chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with a differential refractive index (DRI) as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect the GPC columns from oxidative degradation. The sample injection volume was 200 pL. The GPC columns were calibrated with polystyrene standards of narrow distribution. Molecular weights of polystyrene were converted to molecular weights of polyethylene using the Mark-Houwink equation, as described in the standard test method ASTM D6474-12 (December 2012). The raw GPC data was processed with Cirrus GPC software, to produce molar mass averages (M _n , Mw, Mz) and molar mass distribution (for example, Polydispersity, Mw / Mn). In the polyethylene technique, a commonly used term that is equivalent to SEC is GPC, ie Gel Permeation Chromatography.
Petition 870190112009, of 11/01/2019, p. 112/168
106/156
Triple detection size exclusion chromatography (3D-SEC)
[0251] Sample solutions of ethylene interpolymer (polymer) product (1 to 3 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150 ° C in an oven. An antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were subjected to chromatography at 140 ° C in a PL 220 high temperature chromatography unit equipped with a differential refractive index (DRI) detector, a double angle light scattering detector (15 and 90 degrees) and a differential viscometer. The SEC columns used were four Shodex columns (HT803, HT804, HT805 and HT806) or four ALS or BLS PL Mixed columns. TCB was the mobile phase with a flow rate of 1.0 mL / minute, BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sample injection volume was 200 pL. The raw SEC data were processed with the Cirrus GPC software, to produce absolute molar masses and intrinsic viscosity ([η]). The term “absolute” molar mass was used to distinguish absolute molar masses determined by 3D-SEC from molar masses determined by conventional SEC. The average viscosity molar mass (M _v ) determined by 3D-SEC was used in the calculations to determine the Long Chain Branching Factor (LCBF).
GPC-FTIR
[0252] Ethylene interpolymer (polymer) product solutions (2 to 4 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and spinning on a wheel for 4 hours at 150 ° C in an oven. The antioxidant 2,6-ditherc-butyl-4-methylphenol (BHT) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were subjected to chromatography at 140 ° C in a
Petition 870190112009, of 11/01/2019, p. 113/168
107/156 Waters GPC 150C chromatography equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with an FTIR spectrometer and an FTIR flow heated via cell connected with the chromatography unit via a heated transfer line as the detection system. BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sample injection volume was 300 pL. The raw FTIR spectra were processed with the OPUS FTIR software and the polymer concentration and methyl content were calculated in real time with the Chemometric Software (PLS technique) associated with OPUS. Then the polymer concentration and the methyl content were acquired and corrected to a reference value with the Cirrus GPC software. SEC columns were calibrated with narrow distribution polystyrene standards. The molecular weights of polystyrene were converted to molecular weights of polyethylene using the Mark-Houwink equation, as described in the standard test method ASTM D6474. The comonomer content was calculated based on the polymer concentration and methyl content predicted by the PLS technique as described in Paul J. DesLauriers, Polymer 43, pages 159 - 170 (2002); incorporated herein by reference.
[0253] The GPC-FTIR method measures the total methyl content, which includes the methyl groups located at the ends of each macromolecular chain, ie final methyl groups. Thus, the raw GPC-FTIR data must be corrected by subtracting the contribution of final methyl groups. To be more clear, the raw GPC-FTIR data overestimate the amount of short chain branching (SCB) and this overestimation increases as the molecular weight (M) decreases. In this disclosure, raw GPC-FTIR data was corrected using the 2-methyl correction. At a given molecular weight (Μ), the number of final methyl groups (Ne) was calculated using the following equation; Ne = 28000 / M and Ne (dependent on M) was subtracted from the data
Petition 870190112009, of 11/01/2019, p. 114/168
108/156 crude GPC-FTIR to produce the GPC-FTIR data from SCB / 1000C (2-Methyl corrected).
composition distribution branch index (CDBI)
[0254] The "composition distribution branch index", then CDBI, of the Examples and Comparative Examples disclosed were measured using a CRYSTAF / TREF 200+ unit equipped with an IR detector, then the CTREF. The acronym "TREF" refers to Fractionation by Temperature Gradient Elution. CTREF was supplied by PolymerChAR S.A. (Valencia Technology Park, Gustave Eiffel, 8, Paterna, E-46980 Valencia, Spain). CTREF was operated in the TREF mode, which generates the chemical composition of the polymer sample as a function of the elution temperature, the Co / Ho ratio (Copolymer / Homopolymer ratio) and CDBI (the Distribution Amplitude index of Composition), ie CDBIso and CDBI25. A polymer sample (80 to 100 mg) was placed in the CTREF reactor vessel. The reactor vessel was filled with 35 ml of 1,2,4trichlorobenzene (TCB) and the polymer was dissolved by heating the solution at 150 ° C for 2 hours. An aliquot (1.5 mL) of the solution was then loaded onto the CTREF column which was packed with stainless steel beads. The column, loaded with sample, was allowed to stabilize at 110 ° C for 45 minutes. The polymer was then crystallized from the solution, inside the column, reducing the temperature to 30 ° C at a cooling rate of 0.09 ° C / minute. The column was then equilibrated for 30 minutes at 30 ° C. The crystallized polymer was then eluted from the column with TCB flowing through the column at 0.75 ml / minute, while the column was slowly heated from 30 ° C to 120 ° C at a heating rate of 0.25 ° C / minute. The raw CTREF data was processed using the Polymer ChAR software, an Excel spreadsheet and in-house developed CTREF software. CDBI50 was defined as the percentage of polymer whose composition is within 50% of the median comonomer composition; CDBI50 was calculated from the cure of
Petition 870190112009, of 11/01/2019, p. 115/168
109/156 composition distribution and the normalized cumulative integral of the composition distribution curve, as described in United States Patent 5,376,439. Those skilled in the art will understand that a calibration curve is necessary to convert a CTREF elution temperature to the comonomer content, that is, the amount of comonomer in the ethylene / aolefin polymer fraction that elutes at a specific temperature. The generation of such calibration curves is described in the prior art, for example, Wild, etal., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441 - 455: hereby fully incorporated by reference. CDBI25 as calculated in a similar manner; CDBI25 is defined as the percentage of polymer whose composition is 25% of the median comonomer composition. At the end of each sample run, the CTREF column was cleaned for 30 minutes; specifically, with the CTREF column temperature at 160 ° C, TCB flowed (0.5 mL / minute) through the column for 30 minutes. CTREF deconvolutions were performed to determine the amount of branching (BrF (# C6 / 1000C)) and density of the first ethylene interpolymer using the following equations: BrF (# Ce / 1000C) = 74.29 - 0.7598 (T ^p ctref), where T ^p ctref is the peak elution temperature of the first ethylene interpolymer in the CTREF and BrF chromatogram (#C ₆ / 1000C) = 9341.8 (p ¹ ) ² - 17766 (p ¹ ) + 8446, 8, where p ¹ was the density of the first ethylene interpolymer. The BrF (# Ce / 1000C) and the density of the second ethylene interpolymer were determined using combination rules, given the global BrF (# Ce / 1000C) and the density of the ethylene interpolymer product. BrF (# Ce / 1000C) and the density of the second and third ethylene interpolymer were considered to be the same.
Neutron activation (Elemental Analysis)
[0255] Neutron Activation Analysis, then N.A.A., was used to determine catalyst residues in ethylene interpolymer products as follows. One radiation bottle (composed of ultrapure polyethylene, 7 mL volume
Petition 870190112009, of 11/01/2019, p. 116/168
110/156 internal) was filled with a sample of ethylene interpolymer product and the sample weight was recorded. Using a pneumatic transfer system, the sample was placed inside a SLOWPOKE ™ nuclear reactor (Atomic Energy of Canada Limited, Ottawa, Ontario, Canada) and irradiated for 30 to 600 seconds to short half-life elements (for example, Ti, V, Al, Mg and Cl) or 3 to 5 hours for long half-life elements (for example, Zr, Hf, Cr, Fe and Ni). The average thermal neutron flux inside the reactor was 5x10 ¹¹ / cm ² / s. After irradiation, the samples were removed from the reactor and aged, allowing radioactivity to decay; short half-life elements were aged for 300 seconds or long half-life elements were aged for several days. After aging, the sample's gamma-ray spectrum was recorded using a germanium semiconductor gamma-ray detector (Ortec model GEM55185, Advanced Measurement Technology Inc., Oak Ridge, TN, USA) and a multi-channel analyzer (Ortec model DSPEC Pro). The quantity of each element in the sample was calculated from the gamma ray spectrum and recorded in parts per million in relation to the total weight of the sample of ethylene interpolymer product. The NAA system was calibrated with Specpure standards (solutions at 1000 ppm of the desired element (greater than 99% purity)). One mL of solutions (elements of interest) was pipetted over a 15 mm x 800 mm rectangular paper filter and air dried. The filter paper was then placed in a 1.4 ml polyethylene irradiation flask and analyzed by the NAA system. Standards are used to determine the sensitivity of the NAA procedure (in counts / pg).
Unsaturation
[0256] The number of unsaturated groups, ie double bonds, in an ethylene interpolymer product was determined according to ASTM D3124-98 (vinylidene unsaturation, published in March 2011) and ASTM D6248-98 (establishment of vinyl and trans, published in July 2012). A product sample
Petition 870190112009, of 11/01/2019, p. 117/168
111/156 ethylene interpolymer was: a) first subjected to carbon disulfide extraction to remove additives that may interfere with the analysis; b) the sample (pellet, film or granular form) was compressed on a plate of uniform thickness (0.5 mm), and; c) the plate was analyzed by FTIR.
Comonomer content: Fourier transform infrared spectroscopy (FTIR)
[0257] The amount of comonomer in an ethylene interpolymer product was determined by FTIR and reported as the short chain branch content (SCB) having CH3 # / 1000C dimensions (number of methyl branches per 1000 carbon atoms) . This test was completed according to ASTM D6645-01 (2001), using a compression-molded polymer plate and a Thermo-Nicolet 750 Magna-IR Spectrophotometer. The polymer plate was prepared using a compression molding device (Wabash-Genesis Series press) according to ASTM D4703-16 (April 2016).
Dynamic mechanical analysis (DMA)
[0258] Oscillatory shear measurements under small strain ranges were performed to obtain linear viscoelastic functions at 190 ° C under N2 atmosphere, at a strain range of 10% and in a frequency range of 0.02 - 126 rad / s on 5 points per group of ten. Frequency scanning experiments were carried out with a DHR3 TA Instruments voltage-controlled rheometer using coniform plate geometry with a coniform angle of 5 ^o , a truncation of 137 pm and a diameter of 25 mm. In this experiment, a sinusoidal deformation wave was applied and the stress response was analyzed in terms of linear viscoelastic functions. The viscosity rate η the zero shear (ηο) based on the DMA frequency scan results was predicted by the Ellis model (see RB Bird et al. “Dynamics of Polymer Liquids. Volume 1: Fluid Mechanics” Wiley-lnterscience Publications (1987) p, 228) or
Petition 870190112009, of 11/01/2019, p. 118/168
112/156 Carreau-Yasuda model (see K. Yasuda (1979) PhD Thesis, IT Cambridge). In this disclosure, the LCBF (Long Chain Branching Factor) was determined using ο ηο determined by DMA.
Fluency test
[0259] Creep measurements were performed by an Anton Paar MCR 501 rheometer at 190 ° C using 25 mm parallel plate geometry under N2 atmosphere. In this experiment, a circular compression-molded plate with a thickness of 1.8 mm was placed between the preheated upper and lower measurement fixtures and allowed to come into thermal equilibrium. The upper plate was then decreased to 50 pm above the 1.5 mm test interval size. At this point, the excess material was removed and the upper fixation was decreased to the size of the measuring range. A waiting time of 10 min after loading the sample and adjusting was applied for residual stresses that cause the deformation to fluctuate. In the creep experiment, the shear stress was increased instantly from 0 to 20 Pa and the strain was recorded versus time. The sample continued to deform under the constant shear stress and eventually reached a constant stress rate. Creep data has been reported in terms of creep compliance (/ (t)) that has the reciprocal module units. The inversion of the slope / (t) in the constant creep regime was used to calculate the viscosity at the zero shear rate based on the linear regression of the data points in the last 10% time window of the creep experiment.
[0260] In order to determine if the sample was degraded during the creep test, frequency sweep experiments under small strain range (10%) were performed before and after the creep stage in a frequency range of 0.1 - 100 rad / s. The difference between the magnitude of complex viscosity at 0.1 rad / s before and after the creep stage was used as a
Petition 870190112009, of 11/01/2019, p. 119/168
113/156 thermal degradation indicator. The difference must be less than 5% to consider the zero shear rate viscosity determined by acceptable creep.
[0261] Creep experiments confirmed that the Reference Line, shown in Figure 1, for linear ethylene interpolymers was also valid if the ηο determined by creep was used instead of the ηο determined by DMA. In this disclosure, the LCBF (Long Chain Branching Factor) was determined using ο ηο determined by DMA. To be absolutely clear, the zero shear viscosity (ZSV [oise]) data reported in Tables 1A, 2 and 3 were measured using DMA.
¹³ C nuclear magnetic resonance (NMR)
[0262] Between 0.21 and 0.30 g of the polymer sample was weighed in 10 mM NMR tubes. The sample was then dissolved with deuterated ortho-dichlorobenzene (ODCB-d4) and heated to 125 ° C; a heat gun was used to assist the mixing process. ¹³ C NMR spectra (24000 scans per spectrum) were collected on a 400 MHz Bruker AVANCE III HD NMR spectrometer fitted with a 10 mm PABBO probe head maintained at 125 ° C. Replacement chemicals were referred to the polymer main chain resonance, which was assigned a value of 30.0 ppm. ¹³ C spectra were processed using exponential multiplication with a line widening factor (LB) of 1.0 Hz. They were also processed using Gaussian multiplication with LB = -0.5 Hz and GB = 0.2 to enhance resolution .
[0263] Short chain branching was calculated using the isolated method, where the integral area of single peaks at that branch length is compared to the total integral (standard practice for branches up to and including C5). Quantitative data for carbons C1, C2, C3, C4, (C6 + LCB) and Saturated Endings (Term. Sat.) were presented in Table 12, all values reported per 1000
Petition 870190112009, of 11/01/2019, p. 120/168
114/156 total carbon atoms, data accuracy was ± 0.03 branches / 1000C. Any values of 0.03 branches / 1000C or less were considered beyond the ability to quantify and were marked with a 'D' to indicate that a peak was detected but not quantified in Table 12.
[0264] Figure 4 illustrates a long chain branched macromolecule on the left side and a C6 branched macromolecule on the right side and the nomenclature used to identify each carbon atom. Carbon peaks at the branch point (CH (l) and CH (6), 38.2 ppm), as well as the carbon peaks 1 Bi_ / 1 Be, 2Bi72Be and 3Bi_ / 3Be (at 14.1, 22.9 and 32.2 ppm, respectively) are together in the spectrum. In addition, the ends of an LCB are functionally equivalent to the ends of macromolecular chains. In ethylene-octene copolymers there was separation between peaks 2Be and 3Be and peaks 2s & 3s at the ends of the chain. In order to deconvolve the contributions of C6 and LCB to the peak branching point (38.2 ppm), the spectra were reprocessed using a Gaussian function (as opposed to an exponential function), specifically LB = -0.5 and GB = 0.2. The net effect of this reprocessing was to 'balance' some signal / noise (Y / N) for further resolution without negatively impacting the peak integration, that is, quantification of the respective carbons. Using this technique, the values for C6, LCB and saturated termini were obtained using the following method: 1) the values for (C6 + LCB) peak at 38.2 ppm and the two peaks of (LCB + term, sat.) at 32.2 and 22.9 ppm they were calculated from the 'standard' spectrum; 2) these three peak regions in the Gaussian reprocessed spectra (ie 38.2, 32.2 and 22.9 ppm) were integrated to obtain a ratio for each carbon within the respective peak; 3) these ratios were converted to a value per 1000 carbons, normalizing to the respective integrated area measured in step 1); 4) the saturated terms were the average of those of the 2s & 3s peaks; 5) the C6 value was estimated from the integrals of the small peaks on the extreme left of these three regions, and; 6) the LCB value was estimated from the
Petition 870190112009, of 11/01/2019, p. 121/168
115/156 peak at 38.2 ppm.
Film perforation
[0265] The puncture resistance of the film was determined using Method A of ASTM D1709-09 (May 1, 2009). In this disclosure the drill test used a 1.5 inch (38 mm) diameter hemispherical head dart.
Film punch
[0266] “Punch” of the film, the energy (J / mm) required to break the film was determined using ASTM D5748-95 (originally adopted in 1995, re-approved in 2012).
Film lubrication punch
[0267] The “lubrication punch” test was performed as follows: the energy (J / mm) to puncture a film sample was determined using a 0.75 inch (1.9 pear) fluorocarbon-coated probe cm) in diameter running at 10 inches per minute (25.4 cm / minute). ASTM conditions were used. Before specimens were present, the probe head was manually lubricated with Muko Lubricating Jelly to reduce friction. Muko Lubricating Jelly is a water-soluble personal lubricant available from Cardinal Health Inc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. The probe was mounted on an Instron Model 5 SL Universal Testing Machine and a 1000 N load cell as used. Film samples (1.0 mil (25 pm) thick, 5.5 inches (14 cm) wide and 6 inches (15 cm) long) were mounted on the Instron and punctured.
Film pull
[0268] The following tensile properties of the film were determined using ASTM D882-12 (August 1, 2012): tensile strength (MPa), tensile strength (%), tensile strength limit (MPa), tensile elongation in elasticity (%) and toughness of the film or total energy to break
Petition 870190112009, of 11/01/2019, p. 122/168
116/156 (ft lb / in ³ ). The tensile properties were measured both in the machine direction (MD) and in the transversal direction (TD) of the blow molded films.
Film drying module
[0269] The drying module is a measure of the film's hardness. The secant modulus is the slope of a line drawn between two points on the strain-strain curve, that is, the secant line. The first point on the stress-strain curve is the origin, that is, the point that corresponds to the origin (the point of zero percent strain and zero stress), and; the second point on the stress-strain curve is the point that corresponds to a 1% strain; given these two points, the 1% secant modulus is calculated and expressed in terms of force per unit area (MPa). The 2% secant modulus is calculated similarly. This method is used to calculate the modulus of the film because the polyethylene stress-strain ratio does not follow Hook's rule; that is, the stress-strain behavior of polyethylene is nonlinear due to its viscoelastic nature. Drying modules were measured using a conventional Instron tensile tester equipped with a 200 Ibf load cell. Strips of monolayer film samples were cut to test with the following dimensions: 14 inches long, 1 inch wide and 1 mil thick; ensuring that there was no notch or cut at the edges of the samples. Film samples were cut both in the machine (MD) and transverse (TD) directions and tested. ASTM conditions were used to condition the samples. The thickness of each film was exactly measured with a portable micrometer and entered along with the sample name in the Instron software. Samples were loaded onto Instron with a 10-inch adhesion separation and collected at a rate of 1 inch / min generating the strain-strain curve. The 1% and 2% secant module was calculated using the Instron software.
Puncture-film breakage
Petition 870190112009, of 11/01/2019, p. 123/168
117/156
[0270] Puncture-propagation break strength of blow-molded film was determined using ASTM D2582-09 (May 1, 2009). This test measures the resistance of a blow molded film to tearing or, more precisely, to the dynamic punch and the spread of this punch resulting in a break. The resistance to rupture by puncture-propagation was measured in the machine direction (MD) and in the transversal direction (TD) of the blow molded films.
Elmendorf break from the movie
[0271] The breaking performance of the film was determined by ASTM D192209 (May 1, 2009); an equivalent term for the rupture is "Elmendorf rupture". The rupture of the film was measured both in the machine direction (MD) and in the transversal direction (TD) of the blow molded films.
Film optics
[0272] The optical properties of the film were measured as follows: Blurring, ASTM D1003-13 (15 November 2013), and; Brightness ASTM D245713 (April 1, 2013).
Impact of film Dynatup
[0273] The instrumented impact test was performed on a machine called a Dynatup Impact Tester purchased from Illinois Test Works Inc., Santa Barbara, CA, USA; those skilled in the art often call this test the Dynatup impact test. The test was completed according to the following procedure. Test samples are prepared by quoting strips about 5 inches (12.7 cm) wide and about 6 inches (15.2 cm) long from a roll of blow-molded film; the film was about 1 mil thick. Before testing, the thickness of each sample was exactly measured with a portable micrometer and recorded. ASTM conditions were used. Test samples were mounted on the 9250 Dynatup Impact drop tower / testing machine using the pneumatic clamp. Dynatup tup # 1, 0.5 inch (1.3 cm) in diameter,
Petition 870190112009, of 11/01/2019, p. 124/168
118/156 was connected to the crosshead using the supplied Allen screw. Before testing, the crosshead is raised to a height such that the film's impact speed is 10.9 ± 0.1 ft / s. A weight was added to the crosshead such that: 1) the deceleration or acceleration of the crosshead was no more than 20% from the beginning of the test at the peak load point and 2) the hammer must penetrate through the specimen. If the hammer does not penetrate through the film, additional weight is added to the crosshead to increase the wedge speed. During each test, the Dynatup Impulse Data Acquisition System software collected the experimental data (load (Ib) versus time). At least 5 film samples are tested and the software reports the following average values: “Maximum Dynatup Load (Max) (Ib)”, the highest load measured during the impact test; “Total Dynatup Energy (ft-lb)”, the area under the load curve from the beginning of the test to the end of the test (sample puncture), and; “Total Dynatup Energy at Max Load (ft-lb)”, the area under the load curve from the start of the test to the maximum load point.
Hot film bonding
[0274] In this disclosure, the "Hot Bonding Test" was carried out as follows, using ASTM conditions. Hot glue data was generated using a J&B Hot Glue Tester which is commercially available from Jbi Hot Tack, Geloeslaan 30, B-3630 Maamechelen, Belgium. In the hot bond test, the strength of a polyolefin seal to polyolefin is measured immediately after heat sealing two film samples together (the two film samples were cut from the same 2.0 mil film roll (51 pm ) thick), that is, when the polyolefin macromolecules that comprise the film are in a semi-molten state. This test simulates the heat sealing of polyethylene films on automatic high-speed packaging machines, for example, filling and sealing equipment, in vertical or horizontal form. The following parameters were used in the J&B Hot Glue Test: film specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; sealing pressure
Petition 870190112009, of 11/01/2019, p. 125/168
119/156 of the film, 0.27 N / mm ² ; delay time, 0.5 seconds; peeling speed of the film, 7.9 in / second (200 mm / second); test temperature range, 203 ° F to 293 ° F (95 ° C to 145 ° C); temperature increments, 9 ° F (5 ° C); and five film samples were tested at each temperature increase to calculate the average values at each temperature. The following data were recorded for the Example films and Comparative Example films released: o “Start of Bonding @ 1.0 N (° C)”, the temperature at which a hot bond strength of 1N was observed (average of 5 film samples); “Max hot bond strength (N)” means the maximum hot bond strength (average of 5 film samples) over the test temperature range, and; “Temperature - Hot bonding max. (° C) ”, the temperature at which the maximum hot bond strength was observed.
Resistance to heat sealing of the film
[0275] In this disclosure, the "Heat Seal Resistance Test" was carried out as follows. ASTM conditions were used. Heat-seal data was generated using a conventional Instron Tensile Tester. In this test, two film samples are sealed over a temperature range (the two film samples were cut from the same 2.0 mil (51 pm) thick film roll). The following parameters were used in the Heat Seal Resistance Test: film specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; film sealing pressure, 40 psi (0.28 N / mm ² ); temperature range, 212 ° F to 302 ° F (100 ° C to 150 ° C) and temperature increase, 9 ° F (5 ° C). After aging for at least 24 hours under ASTM conditions, the sealing resistance was determined using the following tensile parameters: pull speed (crosshead), 12 inches / min (2.54 cm / min); pull direction, 90 ° to the seal, and; 5 film samples were tested at each temperature increase. The sealing initiation temperature, then SIT, is defined as the temperature required to form a commercially viable seal; a stamp
Petition 870190112009, of 11/01/2019, p. 126/168
120/156 commercially viable has a sealing resistance of 2.0 Ib per inch of seal (8.8 N per 25.4 mm seal).
Hexane extractables from film
[0276] Hexane extractables were determined according to the Code of Federal Registration 21 CFR §177.1520 For (c) 3.1 and 3.2; wherein the amount of extractable hexane material in a film is determined gravimetrically. Elaborating, 2.5 grams of monolayer film of 3.5 thousand (89 pm) were placed in a stainless steel basket, the film and the basket were weighed (w '), while in the basket the film was: extracted with n -hexane at 49.5 ° C for two hours; dried at 80 ° C in a vacuum oven for 2 hours; cooled in a desiccator for 30 minutes, and; heavy (w ^f ). The percentage of weight loss is the percentage of hexane extractables (w ^C6 ): w ^C6 = 100 x (w'-w ^f ) / w '.
Examples
Pilot installation polymerizations
[0277] The following examples are presented for the purpose of illustrating the selected modalities of this disclosure, it being understood that the examples presented below do not limit the claims presented.
[0278] The disclosed modalities of the ethylene interpolymer products were prepared in a pilot solution of continuous solution operated both in series mode and in parallel mode as fully described below. Comparative ethylene interpolymer products were also prepared at the same pilot plant.
Serial polymerization
[0279] The Examples in series mode (Example 1, 2, 4) of ethylene interpolymer products and Comparatives 1 and 2 in series mode shown in Tables 4A to 4C were produced using an R1 pressure of about 14 MPa at about 18 MPa; R2 was operated at a lower pressure to facilitate flow
Petition 870190112009, of 11/01/2019, p. 127/168
121/156 continuous from R1 to R2. The first output current in series mode of R1 flows directly into R2. Both CSTR’s were stirred to provide conditions where the reactor’s contents were well mixed. The process was operated continuously by feeding fresh process solvent, ethylene, 1-octene and hydrogen to the reactors. Methylpentane was used as the process solvent (a commercial mixture of methylpentane isomers). The volume of the first CSTR reactor (R1) was 3.2 gallons (12 L), the volume of the second CSTR reactor (R2) was 5.8 gallons (22 L) and the volume of the tubular reactor (R3) was 0 , 58 gallons (2.2 L).
[0280] The following components were used to prepare the first homogeneous catalyst formulation, a bridged metallocene catalyst formulation comprising: a component A, diphenylmethylene (cyclopentadienyl) chloride (2,7-di-t-butylfuorenyl) hafnium [(2,7tBu2Flu) Ph2C (Cp) HfCl2] (abbreviated CpF-1) or diphenylmethylene- (cyclopentadienyl) (2,7-dit-butylfuorenyl) hafnium dimethyl, [(2,7-tBu2Flu) Ph2C (Cp) HfMe2] (abbreviated CpF-2); component M, methylaluminoxane (MMAO-07); component B, trityl tetracis (pentafluoro-phenyl) borate, and; component P, 2,6-di-tert-butyl-4-ethylphenol. As shown in Table 4A, CpF-1 was used to produce Example 1 and CpF-2 was used to produce Examples 2 to 4. To prepare the bridged metallocene catalyst formulation the following catalyst component solvents were used : methylpentane for components M and P, and; xylene for components A and B.
[0281] Comparative ethylene interpolymer products were prepared using the third homogeneous catalyst formulation. In comparative ethylene interpolymer products, the third homogeneous catalyst formulation replaces the first homogeneous catalyst formulation. One embodiment of the third homogeneous catalyst formulation was a single site non-bridged catalyst formulation comprising: component C, dichloride
Petition 870190112009, of 11/01/2019, p. 128/168
122/156 cyclopentadienyl tri (tertiary butyl) phosphinimine titanium [Cp [(t-Bu) 3PN] TiCl2] (abbreviated PIC-1) or cyclopentadienyl tri (isopropyl) phosphinimine dichloride titanium [Cp [(isopropyl) 3PN] TiCl2] ( abbreviated PIC-2); component M, methylaluminoxane (MMAO-07); component B, trityl tetracis (pentafluoro-phenyl) borate, and; component P, 2,6-di-tert-butyl-4-ethylphenol. As shown in Table 4A, PIC-1 was used to produce Comparative 1 and PIC-2 was used to produce Comparative 2. To prepare the non-bridged single site catalyst formulation the following catalyst component solvents were used : methylpentane for components M and P, and; xylene for components A and B.
[0282] The amount of CpF-1 or CpF-2 added to reactor 1 (R1) is shown in Table 4A, for example, “R1 catalyst (ppm)” was 0.872 ppm of CpF1 in the case of Example 1. of the first homogeneous catalyst formulation was optimized by adjusting the mol ratios of the catalyst components and the inlet temperature of the catalyst R1. As shown in Table 4A, the optimized mol ratios were: ([M] / [A]), that is [(MMAO-07) / (CpF-1)]; ([P] /] M]), i.e. [(2,6-di-tert-butyl-4-ethylphenol) / (MMAO-07)], and; ([B] / [A]), i.e. [(trityl tetracis (pentafluoro-phenyl) borate) / (CpF-1)]. To be more clear, in Example 1 (Table 4A), the mol ratios in R1 were: ([M] / [A]) = 74; ([P] / [M]) = 0.2, and; ([B] / [A]) = 1.2. As shown in Table 4C, the inlet temperature of the catalyst in the bridged metallocene catalyst formulation was: about 143 ° C in the case of CpF-1, and; about 21 to about 31 ° C in the case of CpF-2.
[0283] In Comparatives the amount of PIC-1 or PIC-2 added to reactor 1 (R1) is shown in Table 4A, for example, “R1 catalyst (ppm)” was 0.10 ppm of PIC-1 in the case de Comparativo 1. The efficiency of the third homogeneous catalyst formulation was optimized by adjusting the mol ratios of the catalyst components and the inlet temperature of the catalyst R1. As shown in Table 4A, the optimized mol ratios were: ([M] / [C]), that is (MMAO-07) / (PIC-1); ([P] / [M]),
Petition 870190112009, of 11/01/2019, p. 129/168
123/156 i.e. (2,6-di-tert-butyl-4-ethylphenol) / (MMAO-07), and; ([B] / [C]), i.e. (trityl tetracis (pentafluoro-phenyl) borate) / (PIC-1). To be more clear, as shown in Table 4A, in Comparative 1 the mol ratios in R1 were: ([M] / [C]) = 100; ([P] / [M]) = 0.0, and; ([B] / [C]) = 1.1. As shown in Table 4C, the inlet temperature of the catalyst in the single-bridged catalyst formulation was about 21 to about 30 ° C.
[0284] In both Examples and Comparatives, a first heterogeneous catalyst formulation was injected into the second reactor (R2), specifically a first in-line Ziegler-Natta catalyst formulation. The first in-line Ziegler-Natta catalyst formulation was prepared using the following components: component (v), butyl ethyl magnesium; component (vi), tertiary butyl chloride; component (vii), titanium tetrachloride; component (viii), diethyl aluminum ethoxide, and; component (ix), triethyl aluminum. Methylpentane was used as the catalyst component solvent. The first in-line ZieglerNatta catalyst formulation was prepared using the following steps. In step one, a solution of triethylaluminium and dibutylmagnesium, having a molar ratio of ((dibutylmagnesium) / ((triethylalumina)) of 20 was combined with a solution of tertiary butyl chloride and allowed to react for about 30 seconds (HllT- 1); in step two, a titanium tetrachloride solution was added to the mixture formed in step one and allowed to react for about 14 seconds (HllT-2), and in step three, the mixture formed in step two was left at reactor for an additional 3 seconds (HllT-3) before injection into R2 The in-line Ziegler-Natta catalyst formulation was formed in R2 by injecting a solution of diethyl aluminum ethoxide into R2. The amount of titanium tetrachloride added to reactor 2 (R2) is shown in Table 4A, ie "R2 (vii) (ppm)"; to be more clear, in Example 1 the solution in R2 contained 7.28 ppm of TiCk The efficiency of the first formulation of in-line Ziegler-Natta catalyst has been optimized by adjusting the molar ratios of the
Petition 870190112009, of 11/01/2019, p. 130/168
124/156 catalyst, specifically: ([vi] / [v]), i.e. (tertiary butyl chloride) / (butyl ethyl magnesium); ([viii] / [vii]), i.e. (diethyl aluminum ethoxide) / (titanium tetrachloride), and; ([ix] / [vii]), that is (aluminum triethyl) / (titanium tetrachloride). To be more clear, in Example 1 (Table 4A) the mol ratios in R2 were: ([vi]) / [v]) = 1.87; ([viii] / [vii]) = 1.35, and; ([ix] / [vii]) = 0.35. Referring to Figure 2, in both Examples and Comparatives, 100% of diethyl aluminum ethoxide in stream 10d, component (viii), was added to reactor 12a via stream 10h.
[0285] The average residence time of the solvent in a reactor is mainly influenced by the amount of solvent flowing through each reactor and the total amount of solvent flowing through the solution process, the following are representative or typical values for the Examples and Comparisons shown in Tables 4A to 4C: average reactor dwell times were: about 61 seconds in R1, about 73 seconds in R2, about 7.3 seconds for a R3 volume of 0.58 gallons (2, 2 L).
[0286] Polymerization in the continuous solution polymerization process was terminated by adding a catalyst deactivator to the third output stream that leaves the tubular reactor (R3). The catalyst deactivator used was octanoic acid (caprylic acid), commercially available from P&G Chemicals, Cincinnati, OH, USA The catalyst deactivator was added such that the moles of added fatty acid were 50% of the total molar amount of hafnium, titanium and aluminum added to the polymerization process; to be clear, the moles of added octanoic acid = 0.5 x (moles of hafnium + moles of titanium + moles of aluminum); this mol ratio was consistently used in both Examples and Comparatives.
[0287] A two-stage devolatilization process was used to recover the ethylene interpolymer product from the process solvent, that is, two vapor / liquid separators were used and the second bottom stream (from
Petition 870190112009, of 11/01/2019, p. 131/168
125/156 second V / L separator) was passed through a gear pump / pelletizer combination. DHT-4V (hydrotalcite), supplied by Kyowa Chemical Industry Co. LTD, Tokyo, Japan was used as an acid passivator or decontaminant in the continuous solution process. A DHT-4V slurry in process solvent was added before the first V / L separator. The molar amount of DHT-4V added was 10 times higher than the molar amount of tertiary butyl chloride and titanium tetrachloride added to the solution process.
[0288] Before pelletizing the ethylene interpolymer product was stabilized by adding 500 ppm Irganox 1076 (a primary antioxidant) and 500 ppm Irgafos 168 (a secondary antioxidant), based on the weight of the ethylene interpolymer product. Antioxidants were dissolved in the process solvent and added between the first and second V / L separators.
[0289] Tables 4A to 4C disclose additional process parameters, for example, ethylene and 1-octene divisions between reactors and reactor temperatures and ethylene conversions, etc. In Tables 4A to 4C the targeted ethylene interpolymer product was about 1.0 melt index (b) (as measured according to ASTM D1239, 2.16 kg load, 190 ° C) and about 0.917 g / cm ³ (as measured according to ASTM D792).
Parallel polymerization
[0290] The pilot installation described above has been reconfigured to operate in parallel mode. The first output current in parallel mode (exiting the first reactor) bypasses the second reactor and the first output current is combined with the second output current (exiting the second reactor) downstream of the second reactor. To be clearer, Figure 2 illustrates the parallel operation where: the first output current 11g (dotted line) bypasses the second reactor 12a, currents 11g and 12c (second output current from the reactor 12a) are combined to form a third output current 12d, and; the third output current flows in the tubular reactor 17.
Petition 870190112009, of 11/01/2019, p. 132/168
126/156
As shown in Tables 4A to 4C, Example 3 is an embodiment of an ethylene interpolymer product synthesized using the parallel mode of operation. The optimization of the catalyst and additional process parameters for Example 3, for example, ethylene and 1-octene divisions between the reactors and reactor temperatures and ethylene conversions, etc., are summarized in Tables 4A-4C.
[0291] Given the continuous solution polymerization conditions shown in Table 4A to Table 4C, the resulting ethylene interpolymer products produced are summarized in Table 5. Table 5 also includes the following commercially available products: Comparative 10 and Comparative 11 are commercially available ethylene / 1-octene solution process polymers produced by NOVA Chemicals Company (Calgary, Alberta, Canada) SURPASS® SPs116-C03 and SURPASS® VPsK914-A01, respectively, both of these products were produced using the catalyst formulation of single non-bridged site in reactor 1 and in-line Ziegler-Natta catalyst formulation in reactor 2. As shown in Table 5, the results of the Neutron Activation Analysis disclose catalyst residues in Examples 3 to 4 and Comparatives 1, 2, 10 and 11.
[0292] Table 6 compares the physical attributes of Example 4 with Comparative 1. Fractions by weight, molecular weights (M _n , M _w and Mw / Mn), branch (# C6 / 1000C), CDBbo, density, index melting points and long chain branching factor (LDBF) of the first ethylene interpolymer, second ethylene interpolymer, third ethylene interpolymer and the ethylene interpolymer product are disclosed. The results in Table 6 were generated by deconvolution of the SEC and CTREF curves of Example 4 and Comparative 1 in their respective components. Graphically, Figure 5 illustrates the deconvolution of the experimentally measured SEC of Example 4 into three components, that is, the first, second and third ethylene interpolymer. In example 4, the first ethylene interpolymer having a density of 0.8943 g / cm ³ was produced using a weight ratio of ((1
Petition 870190112009, of 11/01/2019, p. 133/168
127/156 octene) / (ethylene)) ^R1 of 0.41. In contrast, in Comparative 1 the density of the first ethylene interpolymer having a density of 0.9112 g / cm ³ was produced using a weight ratio of ((1-octene) / (ethylene)) ^R1 of 0.66. Although Example 4 was produced with a 40% lower octene / ethylene ratio, compared to Comparative 1, the first ethylene interpolymer in Example 2 was of lower density. Both of these trends shown by Example 4 using the bridged metallocene catalyst formulation, i.e., a lower (octene / ethylene) ratio and a lower density are advantageous over Comparative 1 using the catalyst formulation. single site not bridged. Table 6 also discloses a Δρ, (p ² - p ¹ ) or [(the density of the second ethylene interpolymer) - (the density of the first ethylene interpolymer)], was higher in Example 4 compared to Comparative 1. Specifically, Δρ was 0.0481 and 0.0087 g / cm ³ for example 4 and Comparative 1, respectively. Higher p's are advantageous in various end-use applications. In Figure 5: the molecular weight distribution of the first ethylene interpolymer was considered similar to a Flory distribution; the molecular weight distribution of the second ethylene interpolymer (produced with the Ziegler-Natta catalyst formulation in a multi-site line), having an Mw / Mn of 3.09, was adjusted using four Flory distributions; the molecular weight distribution of the third ethylene interpolymer was considered to be the same as the second ethylene interpolymer. The weight percentage of the third ethylene interpolymer was considered to be 5%.
[0293] As shown in Table 6, the weighted average molecular weights (Mw) of the first ethylene interpolymers in Example 4 and Comparative 1 were 126,051 and 137,984, respectively. The lowest Mw of the first ethylene interpolymer in Example 4 reflects the fact that reactor 1 contained 5.35 ppm of hydrogen; on the contrary, in Comparative 1 the first ethylene interpolymer was synthesized using 0.6 ppm of hydrogen in reactor 1. Those of ordinary experience are aware
Petition 870190112009, of 11/01/2019, p. 134/168
128/156 of the fact that hydrogen is used to control Mw (or melt index) in olefin polymerization, that is, hydrogen is very effective in stopping the spread of macromolecules. In addition, given Table 6, those of ordinary experience would have recognized the higher molecular weight capacity of the bridged metallocene catalyst compared to the single-site non-bridged catalyst. Elaborating, in relation to Comparative 1, the amount of hydrogen used to synthesize the first ethylene interpolymer in Example 4 was an order of magnitude higher and the M _w 's differed by only 8.6%. In addition, Example 4 was produced at a higher reactor temperature (141 ° C), compared to Comparative 1 (135 ° C). These trends of higher hydrogen concentration and higher reactor temperature for the formulation of bridged metallocene catalyst, compared to the formulation of single site non-bridged catalyst, demonstrate the higher molecular weight capacity of the previous one.
Blow-molded films: Ethylene interpolymer products
[0294] Blow molded monolayer films were produced in a 2.5 inch (6.45 cm) diameter, 24/1 L / D (barrel length / barrel diameter) Gloucester extruder equipped with: barrier thread; a low pressure mold 4 inches (10.16 cm) in diameter with a mold range of 35 mil (0.089 cm), and; a Western Polymero Air ring. Blow molded films, 1.0 mil (25 pm) thick, were produced at a constant productivity rate of 100 Ib / h (45.4 kg / h) by adjusting the speed of the extruder thread, and; the height of the freezing line was maintained around 16 inches (40.64 cm) by adjusting the cooling air. Processing conditions for blow molded film for Examples 3 and 4 and Comparatives 10 and 11 are disclosed in Table 7. Blow molded monolayer film was also produced at 2.0 mil (51 pm) and 3.5 mil (89 pm) to determine the seal initiation temperature (SIT) and hexane extractables, respectively. Processing aid,
Petition 870190112009, of 11/01/2019, p. 135/168
129/156 encapsulated in a main polyethylene batch, it was added to all resins before the film extrusion; the processing aid added was Dynamar FX 5920A (commercially available from The 3M Company, St. Paul, MN, USA).
[0295] As shown in Table 7, in blow molded film processes, Examples 3 and 4 have improved processability over Comparatives 10 and 11, that is, lower extrusion pressures and lower extruder electrical absorption. This improvement in processability was evident even though Examples 3 and 4, had lower melting rates than equivalents, compared to Comparatives 10 and 11. Improved processability is desirable to the film converter because improved processability means higher production rates, for example, an increase in pounds of film produced per hour or feet (meters) of film produced per hour.
[0296] As shown in Table 8A, in relation to Comparatives 10 and 11, blow molded films produced from Examples 3 and 4 can be advantageously used in any film application where improved hexane extractables from film are desired, for example , in food packaging applications. The hexane extractables of a blow molded film prepared from Example 3 were: 48% lower than Comparative 10, and; 44% lower than Comparative 11. The hexane extractables of a blow molded film prepared from Example 4 were: 62% lower than Comparative 10, and; 59% lower than Comparative 11.
[0297] As shown in Table 8A, the sealing initiation temperature (SIT) of the film prepared from Example 3 (parallel solution process) was 83.0 ° C; which has been improved (this is 14% lower) compared to Comparative 10 SIT of 96.9 ° C. Compared to Comparative 11, having a SIT of 88.1 ° C, the film produced from Example 3 has been improved by 6% (lower in SIT). Lower SIT’s are desirable in food packaging applications, for example
Petition 870190112009, of 11/01/2019, p. 136/168
130/156 example, high speed vertical form-fill-seal food packaging lines.
[0298] As shown in Table 8A, the Elmendorf tear strength in the machine direction of the film prepared from Example 3 (parallel solution process) was 321 g; that is, it improved in relation to Elmendorf's breaking strength of the film of Comparatives 10 and 11 of 270 and 277 g, respectively; improvement percentages were 19 and 16%, respectively. Higher Elmendorf tear strengths are desirable in a myriad of film applications, for example, bags for consumer food and packaging have bags and liners for industrial transport. Similarly, Elmendorf's breaking strength in the transverse direction of the film prepared from Example 3 (parallel solution process) was 670 g; that is, it improved in relation to Elmendorf's breaking strengths of the film in the transversal direction of Comparatives 10 and 11 of 541 and 533 g, respectively; improvement percentages were 24 and 26%, respectively.
[0299] As shown in Table 8B, in relation to Comparatives 10 and 11, blow molded films produced from Examples 3 and 4 can be advantageously used in film application where higher film modules are desired. One of the desirable characteristics of taller film modules is the ability to reduce film thickness, reduce film thickness contributes to source reduction, sustainability and reduces overall costs. The 1% secant modulus in the machine direction of Example 3 (222 MPa) has been improved by 39% (higher) compared to Comparative 10 (160 MPa) and improved by 54% compared to Comparative 11 (144 MPa), and; the 1% secant modulus in the transverse direction of Example 3 (251 MPa) has been improved by 52% and 72% over Comparative 10 (165 MPa) and Comparative 11 (146 MPa), respectively. Similarly, the 1% secant modulus in the machine direction of Example 4 (207 MPa) has been improved by 29% (higher) compared to Comparative 10 and improved by 44% compared to
Petition 870190112009, of 11/01/2019, p. 137/168
131/156
Comparative 11 e; the 1% secant modulus in the transverse direction of Example 4 (236) has been improved by 43% and 62% over Comparative 10 and 11, respectively. This same trend was also evident in the 2% secant module. Specifically, the secant modulus at 2% in the machine direction of Example 3 (187 MPa) has been improved by 34% (higher) over Comparative 10 (140 MPa) and improved by 52% over Comparative 11 (123 MPa ), and; the secant modulus at 2% in the transverse direction of Example 3 (210 MPa) was improved by 48% and 69% over Comparative 10 (142 MPa) and Comparative 11 (124 MPa), respectively. Similarly, the 2% secant modulus in the machine direction of Example 4 (174 MPa) has been improved by 24% (higher) over Comparative 10 and improved by 41% over Comparative 11 e; the secant modulus at 2% in the transverse direction of Example 4 (199 MPa) has been improved by 40% and 60% over Comparatives 10 and 11, respectively.
[0300] Table 8B also shows the improved (higher) tensile strength limit for the films in Examples 3 and 4, compared to the films in Comparatives 10 and 11. Higher yield limits reduce the tendency of a loaded package. to elasticity, to deform or distort under its own weight. The tensile strength limit in the machine direction of a blow molded film prepared from Example 3 was 10.0 MPa, which was improved by 19% (higher) over Comparative 10 (8.4MPa) and 30 Higher% compared to Comparative 11 (7.7 MPa) and the limit of tensile strength in the transversal direction was improved by 26% and 48% in relation to Comparative 10 (8.6 MPa) and Comparative 11 (7.3 MPa), respectively. The tensile strength limit in the machine direction of a blow molded film prepared from Example 4 was 9.8 MPa, which was improved by 17% (higher) compared to Comparative 10 and 27% higher compared to to Comparative 11 and the tensile strength limit in the transversal direction was improved by 24% and 47% in relation to Comparative 10
Petition 870190112009, of 11/01/2019, p. 138/168
132/156 and 11, respectively.
Continuous Polymerization Unit (CPU)
Comparison of catalyst formulations in a reactor
[0301] Small scale continuous solution polymerizations were carried out in a Continuous Polymerization Unit, then CPU. The purpose of these experiments was to directly compare the performance of the bridged metallocene catalyst formulation (containing component A, CpF-1) with the single-site non-bridged catalyst formulation (containing component C, PIC-1) in a polymerization reactor.
[0302] The single CPU reactor was a 71.5 mL continuously stirred CSTR, polymerizations were conducted at 130 ° C, 160 ° C or 190 ° C and the reactor pressure was about 10.5 MPa. The CPU included a 20 mL upstream mixing chamber that was operated at a temperature that was 5 ° C lower than the downstream polymerization reactor. The upstream mixing chamber was used to preheat ethylene, optional α-olefin and a portion of the process solvent. Catalyst feeds and the remaining solvent were added directly to the polymerization reactor as a continuous process. The total flow rate for the polymerization reactor was kept constant at 27 mL / minute. The components of the bridged metallocene catalyst formulation (component A, component M, component B and component P) were added directly to the polymerization reactor to maintain the continuous polymerization process. More specifically: component A and component B were pre-mixed in xylene and injected directly into the reactor, and; component M and optionally component P were premixed in the process solvent and injected directly into the reactor. In the comparative experiments, the components of the non-bridged single site catalyst formulation (component C, component M, component B and component P) were added directly to the polymerization reactor for
Petition 870190112009, of 11/01/2019, p. 139/168
133/156 keep the polymerization process continuous. More specifically: component C and component B were pre-mixed in xylene and injected directly into the reactor, and; component M and optionally component P were premixed in the process solvent and injected directly into the reactor. In the examples, component A used was CpF-1 [(2,7-tBu2Flu) Ph2C (Cp) HfCl2]. In comparisons, component C used was PIC-1 ([Cp [(t-Bu) 3PN] TiCl2]). The components M, B and P were methylaluminoxane (MMAO-07), trityl tetracis (pentafluoro-phenyl) borate and 2,6-di-tert-butyl4-ethylphenol, respectively. During the injection, the catalyst was activated in situ (in the polymerization reactor) in the presence of ethylene comonomer and optional α-olefin. Component M was added such that the molar ratio of ([M] / [A]) or ([M] / [C]) was about 80; component B was added such that the molar ratio of ([M] / [A]) or ([M] / [C]) was about 1.0, and; component P was added such that the molar ratio of ([P] / [M]) was about 0.4.
[0303] Ethylene was supplied to the reactor by a calibrated thermal mass flow meter and was dissolved in the reaction solvent before the polymerization reactor. Optional comonomer (1-octene) was pre-mixed with ethylene before entering the polymerization reactor, the weight ratio of (1-octene) / (ethylene) ranged from 0 to about 6.0. Ethylene was fed to the reactor such that the concentration of ethylene in the reactor varied from about 7 to about 15% by weight; where% by weight is the weight of ethylene divided by the total weight of the reactor contents. The internal reaction temperature was monitored by a thermocouple in the polymerization medium and was controlled at the target set point at ± 0.5 ° C. Solvent, monomer and comonomer streams were all purified by the CPU systems before entering the reactor.
[0304] The conversion of ethylene, Q ^cpu , that is, the fraction of converted ethylene was determined by line gas chromatography (GC) and polymerization activity, K _p ^cpu , having dimensions of [L / (mmol min)] was defined as:
- Q ^cpu tfCPU _ () CPU (________ ^v ___________ λ ^p ^ [catalyst] x HUT ^CPU
Petition 870190112009, of 11/01/2019, p. 140/168
134/156 where HUT ^cpu a reciprocal spatial velocity (Retention Time) in the polymerization reactor having dimensions of minutes (min), and; [catalyst] was the concentration of catalyst in the polymerization reactor expressed in mmol / L of titanium or hafnium. In some CPU experiments, Q ^cpu was kept constant around 90% and HUT ^cpu was kept constant over 2.5 minutes. In other CPU experiments, Q ^cpu ranged from about 75 to about 95%. Downstream of the reactor, the pressure was reduced to atmospheric pressure. The polymeric product was recovered as a slurry in the process solvent and subsequently dried by evaporation in a vacuum oven before characterization.
[0305] At a polymerization temperature of 130 ° C, the CPU conditions were adjusted to synthesize ethylene interpolymers at approximately constant melt index and density; specifically, a first ethylene interpolymer synthesized with the bridged metallocene catalyst formulation and a comparative ethylene interpolymer produced with the non-bridged single site catalyst formulation. As shown by each row in Table 9A, at a reactor temperature of 130 ° C, the bridged metallocene catalyst formulation produced an improved (higher) weighted average molecular weight (Mw ^A ) compared to the comparative formulation of single site non-bridged catalyst (M _w ^c ). The percentage of improvement in Mw was at least 5% as calculated using the following formula:
% of Improved Mw = 100% x (M _W ^A -MW ^C ) / MW ^C
[0306] Similarly, at a polymerization temperature of 160 ° C, each row in Table 9B shows that the bridged metallocene catalyst formulation produced an improved (higher) weighted average molecular weight (M _W ^A ), in relation to the formulation of single-site catalyst not bridged comparatively (M _w ^c ). The percentage of improvement in Mw was at least 10%.
[0307] As shown in Table 10A, at a polymerization temperature
Petition 870190112009, of 11/01/2019, p. 141/168
135/156 of 130 ° C, the weight ratio of (α-olefin / ethylene) in the reactor had to be adjusted such that ethylene interpolymers were produced having a target density. More specifically, (a-olefin / ethylene) ^A was necessary to synthesize a first ethylene interpolymer, having a target density, using the bridged metallocene catalyst formulation. In contrast, (a-olefin / ethylene) ^c was necessary to synthesize a control ethylene interpolymer, having the target density, using the single-site non-bridged catalyst formulation. As shown by each row in Table 10A, at 130 ° C, the bridged metallocene catalyst formulation allows the operation of the continuous solution polymerization process at an improved (reduced) weight ratio (α-olefin / ethylene) , in relation to the formulation of a single site catalyst not bound to a control bridge. The percentage reduction in the weight ratio of (α-olefin / ethylene) was at least 70% as calculated using the following formula:
C fa - olefin ^ fa - olefin ^ jl ethylene) ~ 1 ethylene) _£ _ _70% ra - olefinay I ethylene) J
[0308] Similarly, at a polymerization temperature of 160 ° C, each row of Table 10B shows that the bridged metallocene catalyst formulation allows the operation of the continuous solution polymerization process at a weight ratio of (α- olefin / ethylene) improved (reduced), in relation to the formulation of single-site catalyst not bound in control bridge. In Table 10B, the percentage reduction in the weight ratio of (α-olefin / ethylene) was at least -70%.
[0309] CPU experiments were also conducted to collect samples of the first ethylene interpolymer, produced with the bridged metallocene catalyst formulation, for characterization, specifically, ¹³ C NMR analysis to quantify the long chain branching (LCB ). Table 11 summarizes the typical CPU process conditions at three reactor temperatures (130, 160 and
Petition 870190112009, of 11/01/2019, p. 142/168
136/156
190 ° C) and two levels of ethylene conversion (about 75% by weight and about 95% by weight). Polymer characterization data (first ethylene interpolymer produced with the bridged metallocene catalyst formulation) are summarized in Table 12. As shown in Table 12, the amount of long chain branching (LCB) in the ethylene interpolymer synthesized using the formulation of bridged metallocene catalyst ranged from 0.03 to 0.23 LCB per 1000 carbon atoms.
TABLE 1A
Reference Resins (Linear Ethylene Polymers) Containing Levels
Undetectable Chain Branching Long ( LCB) Reference Resins Mv(g / mol) [η](dL / g) M _w / Mn THE SCBD CH ₃ # / 1000C ZSV (poise) Resin 1 1.06E + 05 1,672 2.14 1.9772 10.5 7.81 E + 04 Resin 2 1.11E + 05 1,687 2.00 1.9772 11.2 7.94E + 04 Resin 3 1.06E + 05 1.603 1.94 1.9772 15.9 7.28E + 04 Resin 4 1.07E + 05 1,681 1.91 1.9772 11.0 8.23E + 04 Resin 5 7.00E + 04 1,192 2.11 1.9772 13.7 1.66E + 04 Resin 6 9.59E + 04 1,497 1.88 1.9772 12.6 5.73E + 04 Resin 7 1.04E + 05 1,592 1.85 1.9772 12.8 6.60E + 04 Resin 8 5.09E + 04 0.981 2.72 2.1626 0.0 6.42E + 03 Resin 9 5.27E + 04 0.964 2.81 2.1626 0.0 6.42E + 03 Resin 10 1.06E + 05 1,663 1.89 1.1398 13.3 7.69E + 04 Resin 11 1.10E + 05 1,669 1.81 1.1398 19.3 7.31 E + 04 Resin 12 1.07E + 05 1.606 1.80 1.1398 27.8 6.99E + 04 Resin 13 6.66E + 04 1,113 1.68 2.1626 17.8 1.39E + 04 Resin 14 6.62E + 04 1,092 1.76 2.1626 21.4 1.45E + 04 Resin 15 6.83E + 04 1,085 1.70 2.1626 25.3 1.44E + 04
Petition 870190112009, of 11/01/2019, p. 143/168
137/156
Resin 16 7.66E + 04 1,362 2.51 2.1626 4.0 3.24E + 04 Resin 17 6.96E + 04 1,166 2.53 2.1626 13.9 2.09E + 04 Resin 18 6.66E + 04 1,134 2.54 2.1626 13.8 1.86E + 04 Resin 19 5.81 E + 04 1,079 2.44 2.1626 5.8 1.10E + 04 Resin 20 7.85E + 04 1,369 2.32 2.1626 3.7 3.34E + 04 Resin 21 6.31 E + 04 1,181 2.26 2.1626 4.3 1.61 E + 04 Resin 22 7.08E + 04 1,277 2.53 2.1626 3.6 2.58E + 04 Resin 23 9.91 E + 04 1.539 3.09 2.1626 14.0 8.94E + 04 Resin 24 1.16E + 05 1,668 3.19 2.1626 13.3 1.32E + 05 Resin 25 1.12E + 05 1,689 2.71 2.1626 12.8 1.38E + 05 Resin 26 1.14E + 05 1,690 3.37 2.1626 8.0 1.48E + 05 Resin 27 9.55E + 04 1,495 3.44 2.1626 13.8 8.91 E + 04 Resin 28 1.00E + 05 1.547 3.33 2.1626 14.1 9.61 E + 04 Resin 29 1.07E + 05 1,565 3.52 2.1626 13.0 1.12E + 05 Resin 30 1.04E + 05 1.525 3.73 2.1626 13.4 1.10E + 05 Resin 31 1.10E + 05 1,669 3.38 2.1626 8.7 1.26E + 05 Resin 32 1.09E + 05 1.539 3.42 2.1626 13.4 1.07E + 05 Resin 33 8.04E + 04 1,474 5.29 2.1626 1.7 7.60E + 04 Resin 34 8.12E + 04 1,410 7.64 2.1626 0.9 9.11 E + 04 Resin 35 7.56E + 04 1,349 9.23 2.1626 1.0 9.62E + 04 Resin 36 7.34E + 04 1,339 8.95 2.1626 1.1 1.00E + 05 Resin 37 1.01 E + 05 1.527 3.76 2.1626 13.3 1.11 E + 05
TABLE 1B
Long Chain Branching Factor (LCBF) of Reference Resins (Linear Ethylene Polymers) Containing Undetectable Long Chain Branching Levels (LCB)
Petition 870190112009, of 11/01/2019, p. 144/168
138/156
Resins Log ZSVc Log IVc Sh Sv LCBF Reference (log (poise)) log (dL / g) (adimenssional) (adimenssional) (adimenssional) Resin 1 4.87E + 00 2.46E-01 -5.77E-02 -1.21 E-02 3.49E-04 Resin 2 4.90E + 00 2.52E-01 -5.39E-02 -1.13E-02 3.05E-04 Resin 3 4.87E + 00 2.41 E-01 -2.46E-02 -5.16E-03 6.33E-05 Resin 4 4.93E + 00 2.50E-01 -9.46E-03 -1.99E-03 9.41 E-06 Resin 5 4.20E + 00 1.07E-01 -6.37E-02 -1.34E-02 4.26E-04 Resin 6 4.78E + 00 2.04E-01 5.83E-02 1.22E-02 3.57E-04 Resin 7 4.85E + 00 2.31 E-01 -1.73E-03 -3.65E-04 3.16E-07 Resin 8 3.69E + 00 -8.43E-03 -2.17 E-02 -4.55E-03 4.93E-05 Resin 9 3.68E + 00 -1.58E-02 1.21E-04 2.44E-05 1.47E-09 Resin 10 4.91 E + 00 2.38E-01 2.19E-02 4.60E-03 5.04E-05 Resin 11 4.90E + 00 2.48E-01 -2.96E-02 -6.21 E-03 9.17E-05 Resin 12 4.88E + 00 2.42E-01 -1.99E-02 -4.19E-03 4.17E-05 Resin 13 4.21 E + 00 9.14E-02 2.36E-02 4.96E-03 5.86E-05 Resin 14 4.21 E + 00 9.22E-02 1.89E-02 3.97E-03 3.75E-05 Resin 15 4.22E + 00 1.00E-01 -9.82E-03 -2.06E-03 1.01E-05 Resin 16 4.42E + 00 1.44E-01 -1.23E-02 -2.59E-03 1.60E-05 Resin 17 4.23E + 00 1.01 E-01 -4.64E-03 -9.75E-04 2.26E-06 Resin 18 4.18E + 00 8.91 E-02 1.66E-03 3.47E-04 2.87E-07 Resin 19 3.97E + 00 4.73E-02 -1.09E-02 -2.29E-03 1.25E-05 Resin 20 4.47E + 00 1.45E-01 2.28E-02 4.78E-03 5.44E-05 Resin 21 4.16E + 00 8.23E-02 1.78E-02 3.73E-03 3.31 E-05 Resin 22 4.32E + 00 1.15E-01 2.45E-02 5.14E-03 6.30E-05 Resin 23 4.78E + 00 2.22E-01 -2.25E-02 -4.73E-03 5.31 E-05 Resin 24 4.94E + 00 2.56E-01 -3.13E-02 -6.57E-03 1.03E-04 Resin 25 5.02E + 00 2.59E-01 3.91 E-02 8.21 E-03 1.60E-04
Petition 870190112009, of 11/01/2019, p. 145/168
139/156
Resin 26 4.97E + 00 2.48E-01 3.94E-02 8.27E-03 1.63E-04 Resin 27 4.74E + 00 2.09E-01 -2.83E-03 -5.95E-04 8.42E-07 Resin 28 4.79E + 00 2.24E-01 -3.13E-02 -6.57E-03 1.03E-04 Resin 29 4.83E + 00 2.28E-01 -2.96E-03 -6.22E-04 9.20E-07 Resin 30 4.80E + 00 2.18E-01 1.47E-02 3.08E-03 2.26E-05 Resin 31 4.90E + 00 2.44E-01 -1.40E-02 -2.94E-03 2.06E-05 Resin 32 4.82E + 00 2.23E-01 1.27E-02 2.66E-03 1.69E-05 Resin 33 4.51 E + 00 1.72E-01 -6.37E-02 -1.34E-02 4.26E-04 Resin 34 4.45E + 00 1.52E-01 -2.68E-02 -5.62E-03 7.52E-05 Resin 35 4.40E + 00 1.33E-01 1.55E-02 3.26E-03 2.53E-05 Resin 36 4.43E + 00 1.30E-01 5.82E-02 1.22E-02 3.55E-04 Resin 37 4.80E + 00 2.17E-01 1.77E-02 3.71 E-03 3.28E-05
TABLE 2
Long Chain Branching Factor (LCBF) of Ethylene Interpolymer Product of Examples 1 to 4 compared to Comparatives 1,2, 10 and 11
Example1 Example 2 Example 3 Example 4 Comp.1 Comp.2 Comp.10 Comp.11 Mv (g / mol) 9.64E + 04 9.60E + 04 1.02E + 05 1.04E + 05 9.84E + 04 1.04E + 05 9.90E + 04 1.11E + 05 [η] (dL / g) 1,432 1,426 1,410 1,433 1.515 1,557 1,494 1,565 Mw / Mn 3.03 2.40 2.23 2.99 3.09 2.59 3.70 2.51 THE 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 SCB (CH ₃ # / 1000C) 15.3 15.8 19.8 16.7 14.1 14.7 15.6 18.1 ZSV (poise) 1.05E + 05 1.14E + 05 1.58E + 05 2.47E + 05 1.06E + 05 1.05E + 05 9.09E + 04 1.03E + 05 Log ZSVc(log (poise)) 4.86E + 00 4.99E + 00 5.16E + 00 5.24E + 00 4.86E + 00 4.92E + 00 4.72E + 00 4.93E + 00 Log IVc(log (dL / g)) __________ 1.95E-01 1.95E-01 2.02E-01 2.02E-01 2.15E-01 2.29E-01 2.14E-01 2.41E-01
Petition 870190112009, of 11/01/2019, p. 146/168
140/156
Example1 Example 2 Example 3 Example 4 Comp.1 Comp.2 Comp.10 Comp.11 Sh(dimensionless) 1.80E-01 3.08E-01 4.42E-01 5.27E-01 8.16E-02 8.04E-02 -4.61 E-02 2.50E-02 Sv(dimensionless) 3.77E-02 6.46E-02 9.29E-02 1.11E-01 1.71 E-02 1.69E-02 -9.67E-03 5.26E-03 LCBF(dimensionless) 3.39E-03 9.94E-03 2.05E-02 2.91 E-02 7.00E-04 6.78E-04 2.23E-04 6.58E-05
TABLE 3
Long Chain Branching Factor (LCBF) of Ethylene Polymers
Comparatives: Comparatives A to C and Comparatives D to G_______________________
Comp. THE Comp. B Comp. Ç Comp. D Comp. AND Comp. F Comp. G Mv (g / mol) 8.79E + 04 8.94E + 04 8.70E + 04 9.75E + 04 1.02E + 05 1.04E + 05 9.76E + 04 [η] (dL / g) 1,300 1,314 1.293 1,441 1,488 1.507 1,448 Mw / Mn 1.88 1.80 1.89 3.04 2.85 2.79 2.89 THE 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 2.1626 SCB (CH ₃ # / 1000C) 23.2 23.3 23.4 14.2 13.7 14.1 15.1 ZSV (poise) 1.51E + 05 1.51E + 05 1.53E + 05 1.56E + 05 1.43E + 05 1.55E + 05 1.35E + 05 Log ZSVc (log (poise)) 5.20E + 00 5.22E + 00 5.21 E + 00 5.03E + 00 5.02E + 00 5.06E + 00 4.99E + 00 Log IVc (log (dL / g)) 1.74E-01 1.79E-01 1.72E-01 1.95E-01 2.08E-01 2.15E-01 2.00E-01 Sh (adimenssional) 6.22E-01 6.14E-01 6.35E-01 3.51 E-01 2.76E-01 2.90E-01 2.87E-01 Sv (adimenssional) 1.31 E-01 1.29E-01 1.33E-01 7.38E-02 5.81 E-02 6.09E-02 6.03E-02 LCBF (adimenssional) 4.06E-02 3.96E-02 4.23E-02 1.30E-02 8.03E-03 8.83E-03 8.65E-03 Ti (ppm) 0.33 ± 0.01 ^a 1.5 2.2 2.2 2.0 Hf (ppm) B B B B B Internal 0.006 0.006 0.006 0.004 0.004 0.004 0.004
Petition 870190112009, of 11/01/2019, p. 147/168
141/156
Comp. THE Comp. B Comp. Ç Comp. D Comp. AND Comp. F Comp. G Inscriptions / 100C Side chainInscriptions / 100C 0.001 0.025 0.025 0.002 0.003 0.002 0.004 TerminalInscriptions / 100C 0.008 0.007 0.007 0.025 0.020 0.021 0.03
^the AFFINITY average (3 samples, but not Comp. A to C); through
Neutron Activation Analysis (NAA) ^b undetectable through Neutron Activation Analysis
TABLE 4A
Continuous Solution Process Catalyst parameters for
Examples 1 to 4 and Comparatives 1 a2 Process parameter Example1 Example2 Example3 Example 4 Comp.1 Comp.2 Reactor mode Series Series Parallel Series Series Series Catalyst from R1 ^to CpF-1 CpF-2 CpF-2 CpF-2 PIC-1 PIC-2 (component A or component C) (THE) (THE) (THE) (THE) (Ç) (Ç) R2 ^b catalyst ZN ZN ZN ZN ZN ZN R1 catalyst (ppm) 0.872 0.262 0.380 0.380 0.100 0.280 Mole ratio of R1 ([M ^C ] / [A]) or R1 ([M] / [C]) 74 64 48 64.2 100 40 mol ratio of R1 ([P ^d ] / [M]) 0.20 0.16 0.15 0.16 0 0.50 mol ratio of R1 ([B ^and ] / [A]) or R1 ([B] / [C]) 1.20 1.20 1.36 1.20 1.10 1.23 R2 (vii) (ppm) 7.28 3.85 7.24 5.16 4.00 7.50 mol ratio R2 (vi) / (v) 1.87 2.07 2.07 2.07 2.04 1.80 mol ratio R2 (viii) / (vii) 1.35 1.35 1.35 1.35 1.35 1.35
Petition 870190112009, of 11/01/2019, p. 148/168
142/156
mol ratio R2 (ix) / (vii) 0.35 0.35 0.35 0.35 0.35 0.35 Prod Rate, (kg / h) 78.2 74.8 61.5 72.0 88.2 76.7
^a Catalysts: CpF-1 = [(2,7-tBu2Flu) Ph ₂ C (Cp) HfCl2]: CpF-2 = [(2,7tBu ₂ Flu) Ph ₂ C (Cp) HfMe ₂ ]; PIC-1 = [Cp [(t-Bu) ₃ PN] TiCI ₂ ], and; PIC-2 [Cp [(isopropyl) ₃ PN] TiCI ₂ ].
^b Ziegler-Natta in-line catalyst formulation ^c methylaluminoxane (MMAO-7) ^d 2,6-di-tert-butyl ~ 4-ethylphenol ^and trityl tetracis (pentafluoro-phenyl) borate TABLE 4B
Continuous Solution Process Catalyst parameters for
Examples 1 to 4 and Comparatives 1 a2 Process parameter Example1 Example2 Example3 Example 4 Comp.1 Comp.2 Volume of R3 (L) 2.2 2.2 2.2 2.2 2.2 2.2 ES ^R1 (%) 40.0 40.0 60.0 50.0 40.0 40.0 ES ^R2 (%) 60.0 60.0 40.0 50.0 60.0 60.0 ES ^R3 (%) 0.0 ο, ο ο, ο ο, ο ο, ο 0.0 ethylene concentration of R1 (% by weight) 11.8 12.1 11.1 9.80 10.3 8.30 ethylene concentration of R2 (% by weight) 13.6 13.2 13.2 13.8 15.4 13.5 ethylene concentration of R3 (% by weight) 13.6 13.2 ΝΑ 13.8 15.4 13.5 ((1-octene) / (ethylene)) ^R1 (w / w) 0.40 0.40 0.48 0.41 1.76 1.11 ((1-octene) / (ethylene)) ^R2 (w / w) 0.67 0.52 ο, ο 0.201 ο, ο 0.0 (1-octene / ethylene) 0.56 0.47 0.29 0.31 0.66 0.40
Petition 870190112009, of 11/01/2019, p. 149/168
143/156
Process parameter Example1 Example 2 Example3 Example 4 Comp.1 Comp.2 (w / w) (total) OS ^R1 (%) 28 34 100 67 100 100 OS ^R2 (%) 72 66 0.0 33 0.0 0.0 OS ^R3 (%) 0 0 0 0 0 0 H2 ^R1 (ppm) 8.00 8.00 6.82 5.35 0.20 0.60 H2 ^R2 (ppm) 1.00 0.50 2.78 18.00 3.70 1.00 H2 ^R3 (ppm) 0 0 0 0 0 0
TABLE 4C
Continuous Solution Process Catalyst parameters for
Examples 1 to 4 and Comparatives to 2
Process parameter Example1 Example 2 Example3 Example 4 Comp.1 Comp.2 total solution rate of R1 (kg / h) 276.6 261.8 352.0 387.3 360.5 341.6 total R2 solution rate (kg / h) 323.4 338.2 198.0 162.7 239.5 183.4 solution rate of R3 (kg / h) 0.0 0 0 0 0 0 Total solution rate (kg / h) 600 600 550 550 600 525 R1 power input temp(° C) 30 30 30 30 30 30 R2 power input temp(° C) 30 30 50 50 30 40 R3 power input temp(° C) AT 130 130 130 130 130 R1 catalyst inlet temp(° C) 143 31 24 21 21 30 R2 catalyst input temp 38 38 38 38 38 38
Petition 870190112009, of 11/01/2019, p. 150/168
144/156
(° C) Average temp of R1 (° C) 164.0 164.0 154.7 141.1 141.0 135.3 R2 average temp (° C) 190.3 185.0 205.7 197.7 206.0 196.1 R3 output temp (° C) 194.7 189.3 181.6 197.4 208.0 196.6 Q ^R1 (%) 80.0 80.0 80.0 80.0 78.2 91.0 Q ^R2 (%) 80.0 80.0 95.0 81.7 80.0 83.8 Q (R2 ₊ R3) (O _{/ o} ) 83.5 83.0 AT 84.6 80.8 86.1 Q ^R3 (%) 2.4 2.0 AT 1.7 4.0 1.5 Q ^T (%) 88.7 88.4 89.9 90.8 93.4 91.1
TABLE 5
Physical properties of Examples and Comparisons
Physical property Example1 Example 2 Example3 Example 4 Comp.1 Comp.2 Comp.10 Comp.11 Density (g / cc) 0.9178 0.9170 0.9177 0.9170 0.9169 0.9163 0.9156 0.9124 melting index, I2(dg / min) 1.07 0.99 0.92 0.70 0.88 0.85 0.95 0.92 Exponent of stress 1.33 1.32 1.38 1.40 1.23 1.25 1.23 1.24 I10 / I2 7.96 7.85 8.56 8.94 7.10 7.20 7.17 at MFR, I21 / I2 27.5 26.4 29.8 34.8 23.4 22.8 24.7 23.3 SEC, Mw 100119 100544 93315 106261 109444 99158 112007 107517 SEC, Mw / Mn 3.03 2.40 2.23 2.99 3.09 2.59 3.38 2.51 SEC, Mz / Mw 2.66 2.09 1.73 2.05 2.16 2.54 2.59 2.14 CDBI50 38.4 37.3 57.0 49.8 74.8 31.1 70.4 59.7 Freq. branching(C6 / 1000C) 15.3 15.8 19.8 16.7 14.1 14.7 15.6 18.1 Comonomermol% 3.1 3.2 4.0 3.3 2.8 2.9 3.1 3.6
Petition 870190112009, of 11/01/2019, p. 151/168
145/156
Physical property Example1 Example2 Example3 Example 4 Comp.1 Comp.2 Comp.10 Comp.11 Ti (ppm) at at 4.24 8.45 6.1 7.1 ^to 6.8 ^b Hf (ppm) at at 0.541 0.502 0.0 0.0 ^to 0.0 ^b Al (ppm) at at 160 187 97 120 ^to 79 ^b Mg (ppm) at at 327 389 199 247 ^a 173 ^b Cl (ppm) at at 69.5 120 99 91 ^a 92 ^b Internallnsaturation / 100C 0.006 0.005 0.005 0.004 0.008 0.008 ^a at 0.008 Chain unsaturationlateral / 100C 0.005 0.005 0.004 0.004 0.005 0.004 ^a at 0.003 UnsaturationTerminal / 100C 0.029 0.030 0.025 0.049 0.044 0.045 ^a at 0.029
^the average of 21 samples, with similar melting index and density, produced in the pilot solution installation.
^b average of ethylene interpolymer products produced in a commercial facility.
TABLE 6
Physical Attributes of the First, Second and Third Ethylene Interpolymers in Example 4, compared to Comparative 1_____________________________
Example 4 Physical attribute Reactor 11- Interpoli Reactor 222 Interpoli Reactor 332 Interpoli Example 4 Percentage by weight (%) 51.5 43.5 5% 100 Mn 64729 23029 23029 35536 Mw 126051 71144 71144 106261 Polydispersity (M _w / M _n ) 1.95 3.09 3.09 2.99
Petition 870190112009, of 11/01/2019, p. 152/168
146/156
BrF (#C ₆ / 1000C) 30.0 ^to 2.58 9 2.58 16.7 CDBI50 (%) (range) 90 60 60 49.8 Density (g / cm ³ ) 0.8943 ^b 0.9424 ^f 0.9424 0.9170 melting index (dg / min) 0.19 ^c 4.30 ^c 4.30 0.70 LCBF (adimenssional) 0.0565 ^d and and 0.0291 Comparative 1 Physical attribute Reactor 11- Interpoli Reactor 222 Interpoli Reactor 332 Interpoli Comparative 1 Percentage by weight (%) 35 60 5% 100 Mn 70678 24482 24482 35419 Mw 137984 76220 76220 109444 Polydispersity (Mw / M _n ) 1.95 3.11 3.11 3.09 BrF (#C ₆ / 1000C) 14.8 ^a 13.7 9 13.7 14.1 CDBI50 (%) (range) 85 60 60 74.8 Density (g / cm ³ ) 0.9112 ^b 0.9200 ^f 0.9200 0.9169 melting index (dg / min) 0.12 ^c 3.27 ^c 3.27 0.88 LCBF (adimenssional) and and and 0.0007
^a BrF (#C ₆ / 1000C) = 120.32807 - 2.1677891 (T ^p ctref) +0.011 8658 (T ^p ctref) ² '°. ^oo O22 (T ^p ctref) ³ where T ^p ctref is the temperature peak elution of the first ethylene interpolymer in the CTREF chromatogram.
^b BrF (#C ₆ / 1000C) = 9341.8 (p ¹ ) ² -17766 (p ¹ ) + 8446.8, where p ¹ was the density of the first ethylene interpolymer.
^c melting index (b, dg / min) = 5000 [1 + (5.7e-5 x Mw) ²⁰ ] ⁽⁽ '' ⁴ ' ⁵ ' ^{1) / 20)} + 1.0e-6 where Mw is Mw each portion of a MWD with a weight defined by one (fraction by weight * sigmoid function); where the sigmoid function = 1 / (1 + exp (- (logMw -4,2) / 0.55)) ^d 0.0582 = LCBF ^{Example 4} / (wt ^R1 fr), where wt ^R1 fr is the fraction by weight of the first ethylene interpolymer in Example 4.
Petition 870190112009, of 11/01/2019, p. 153/168
147/156 ^and LCBF <0.0001 (undetectable LCB levels) ^f density of the second and third ethylene interpolymer provided the combination rule in specific linear volume ep ¹ , p ^f and fractions in weight ^g BrF (# C6 / 1000C) of the second and third ethylene interpolymer provided a rule for combining linear BrF and fractions by weight
TABLE 7
Processing Conditions for Blow Molded Film Targeting 1.0 mil
(25 μΓη) of Film and Productivity Rate of 1 00 lb / h Processing parameter Units Example3 Example 4 Comp.10 Comp.11 Density (g / cm ³ ) 0.9177 0.9170 0.9156 0.9124 melting index, I2 (dg / min) 0.92 0.70 0.95 0.92 Processing aid PPm 800 (FX5920A) ¹ 800(FX5920A) 800(FX5920A) 800(FX5920A) Productivity (Ibs / h) Ib / h 100 100 100 100 Melting temperature ° F 430 434 430 430 Extruder Pressure psi 3820 3925 4145 4488 Extruder Current Amp 36.2 36 40 40 Extruder Voltage Volt 188 190 190 204 Thread Speed Rpm 39 40 40 43 Nip rollvelocity ft / min 131 131 130 130 Freezing line height In 16 16 16 16 Specific Productivity IbZ (hrpm) 2.6 2.5 2.5 2.3 Specific Power lb / (hamp) 2.8 2.8 2.5 2.5 Specific Energy W / lb / h 68.1 69.0 76.0 81.6
Petition 870190112009, of 11/01/2019, p. 154/168
148/156 ¹ FX5920 Fluoroelastomeric Processing Aid Mix Available from 3M
Company, St. Paul, MN, U.S.A.
TABLE 8A
Physical Properties of the Blow Molded Film of Examples and Comparatives; 1.0 Mil (25 μΜ) film thickness unless otherwise noted
Physical property Units Method Example3 Example 4 Comp.10 Comp.11 Density (g / cm ³ ) ASTM D792 0.9177 0.9170 0.9156 0.9124 melting index, I2 (dg / min) ASTM D1238 0.92 0.70 0.95 0.92 Film thickness thousand Micrometer 1.0 1.0 1.0 1.0 Hexane extractables from film ^a % inWeight 21 CFR §177.1520 0.45 0.33 0.87 0.81 SIT @ 4.4N / 13mm ^b ° C Internally 83 102.3 96.9 88.1 Break MD g / thousand ASTM D1922 321 189 270 277 Break TD g / thousand ASTM D1922 670 462 541 533 Drilling g / thousand ASTM D1709Method A 404 569 695 770 Lubrication punch J / mm Internally 66 68 95 91 45 ° brightnessASTM D2457 41 57 78 79 Haze % ASTM D1003 16.1 8.6 5 4.1
^a = 3.5 thousand film (89 pm) ^b = 2.0 thousand film (51 pm)
TABLE 8B
Physical Properties of the Blow Molded Film of Examples and Comparatives; Film thickness 1.0 mil (25 pm) unless otherwise noted
Petition 870190112009, of 11/01/2019, p. 155/168
149/156
Physical property Units Method Example3 Example 4 Comp.10 Comp.11 Density (g / cm ³ ) ASTM D792 0.9177 0.9170 0.9156 0.9124 melting index, I2 (dg / min) ASTMD1238 0.92 0.70 0.95 0.92 Film thickness thousand Micrometer 1.0 1.0 1.0 1.0 Sec Module at 1% MD MPa ASTM D882 222 207 160 144 Sec Module at 1% TD MPa ASTM D882 251 236 165 146 Sec Module at 2% MD MPa ASTM D882 187 174 140 123 Sec Module at 2% TD MPa ASTM D882 210 199 142 124 MD tensile strength MPa ASTM D882 39.3 34.2 35.2 57.3 TD tensile strength MPa ASTM D882 39.5 34.1 51.6 47 Elongation at break MD % ASTM D882 531 461 499 639 Elongation at break TD % ASTM D882 748 618 869 803 Tensile strength limitMD MPa ASTM D882 10.0 9.8 8.4 7.7 Tensile strength limitTD MPa ASTM D882 10.8 10.7 8.6 7.3 Along, by tensile in elasticityMD % ASTM D882 9 10 10 10 Along, traction in TD elasticity % ASTM D882 9 10 10 10
TABLE 9A
Enhanced SEC Weighted Average Molecular Weight (%) (Mw) at a Reactor Temperature of 130 ° C and 90% Ethylene Conversion for the Bridged Metallocene Catalyst Formulation over the Single Site Catalyst Formulation Not Bridged
Petition 870190112009, of 11/01/2019, p. 156/168
150/156
% by weight of 1octene in ethylene interpolymers Bridged metallocene catalyst formulation Formulation of single-site non-bridged catalyst % Mw Improved (see ³ ) ComponentTHE Mw ^A (see ¹ ) ComponentÇ Mw ^c (see ² ) 0.1 CpF-1 520658 PIC-1 493848 5.4 2.5 CpF-1 216926 PIC-1 165308 31 5.0 CpF-1 179652 PIC-1 130600 38 7.5 CpF-1 160892 PIC-1 113782 41 10.0 CpF-1 148783 PIC-1 103179 44 12.5 CpF-1 140021 PIC-1 95641 46 15.0 CpF-1 133246 PIC-1 89892 48 17.5 CpF-1 127775 PIC-1 85302 50 20.0 CpF-1 123217 PIC-1 81516 51 22.5 CpF-1 119332 PIC-1 78316 52 25.0 CpF-1 115961 PIC-1 75560 53 27.5 CpF-1 112994 PIC-1 73151 54 30.0 CpF-1 110351 PIC-1 71019 55 32.5 CpF-1 107974 PIC-1 69112 56 35.0 CpF-1 105820 PIC-1 67392 57 37.5 CpF-1 103852 PIC-1 65830 58 40.0 CpF-1 102045 PIC-1 64401 58 42.5 CpF-1 100376 PIC-1 63087 59 45.0 CpF-1 98828 PIC-1 61873 60
¹ MW ^A = 278325 χ (Octene ^{% in} ρθ5 °) -θ.272 · onc | _e (Octene ^{% by weight} ) is the% by weight of octene in the ethylene / 1-octene interpolymer ² Mw ^c = 225732 x (Octene ^{% in} P ^eso ) - ⁰ · ³⁴⁰
Petition 870190112009, of 11/01/2019, p. 157/168
151/156 ³ 100% x (Mw ^A -Mw ^c ) / Mw ^c
TABLE 9B
Enhanced SEC weighted average molecular weight (%) percent (Mw) at a reactor temperature of 160 ° C and 90% ethylene conversion for the bridged metallocene catalyst formulation relative to the single site catalyst formulation not bridged__________________________________
% by weight of 1octene in ethylene interpolymers Bridged metallocene catalyst formulation Formulation of single-site non-bridged catalyst % Mw Improved (see ³ ) Component A Mw ^A (see ¹ ) Component C Mw ^c (see ² ) 0.1 CpF-1 293273 PIC-1 248166 18 2.5 CpF-1 130734 PIC-1 91198 43 5.0 CpF-1 109858 PIC-1 73513 49 7.5 CpF-1 99227 PIC-1 64804 53 10.0 CpF-1 92315 PIC-1 59257 56 12.5 CpF-1 87287 PIC-1 55285 58 15.0 CpF-1 83382 PIC-1 52237 60 17.5 CpF-1 80217 PIC-1 49792 61 20.0 CpF-1 77573 PIC-1 47766 62 22.5 CpF-1 75314 PIC-1 46048 64 25.0 CpF-1 73348 PIC-1 44564 65 27.5 CpF-1 71614 PIC-1 43262 66 30.0 CpF-1 70067 PIC-1 42107 66 32.5 CpF-1 68673 PIC-1 41072 67 35.0 CpF-1 67408 PIC-1 40136 68 37.5 CpF-1 66251 PIC-1 39284 69
Petition 870190112009, of 11/01/2019, p. 158/168
152/156
40.0 CpF-1 65186 PIC-1 38504 69 42.5 CpF-1 64202 PIC-1 37784 70 45.0 CpF-1 63287 PIC-1 37119 70
M _W ^A = 164540 x (Octene ^{% weight} ) - ⁰ '²⁵¹; where (Octene ^{% by weight} ) is the% by weight of octene in the ethylene / 1-octene interpolymer ² Mw ^c = 121267 x (Octene ^{% weight} ) - ⁰ ' ^{311 3} 100% x (M _W ^A - Mw ^c ) / Mw ^c
TABLE 10A
Percentage (%) of improvement (reduction) in the weight ratio of (aolefin / ethylene) in the reactor feed, for the formulation of bridged metallocene catalyst in relation to the formulation of single site non-bridged catalyst, to produce ethylene interpolymers at the densities shown (Reactor temperature 130 ° C and about 90% ethylene conversion) ________
% by weight of 1octene in ethylene interpolymers Bridged metallocene catalyst formulation Formulation of single-site non-bridged catalyst % (α-olefin / ethylene) ratio reduced (see ³ ) ComponentTHE (a-olefin / ethylene) ^A (see ¹ ) ComponentÇ (a-olefin / ethylene) ^c (see ² ) 0.0 CpF-1 0.000 PIC-1 0.00 at 2.5 CpF-1 0.0075 PIC-1 0.174 -96% 5.0 CpF-1 0.045 PIC-1 0.422 -89% 7.5 CpF-1 0.088 PIC-1 0.690 -87% 10.0 CpF-1 0.136 PIC-1 0.980 -86% 12.5 CpF-1 0.188 PIC-1 1.29 -85% 15.0 CpF-1 0.246 PIC-1 1.62 -85% 17.5 CpF-1 0.309 PIC-1 1.98 -84%
Petition 870190112009, of 11/01/2019, p. 159/168
153/156
20.0 CpF-1 0.377 PIC-1 2.35 -84% 22.5 CpF-1 0.449 PIC-1 2.75 -84% 25.0 CpF-1 0.527 PIC-1 3.17 -83% 27.5 CpF-1 0.610 PIC-1 3.60 -83% 30.0 CpF-1 0.698 PIC-1 4.06 -83% 32.5 CpF-1 0.790 PIC-1 4.55 -83% 35.0 CpF-1 0.888 PIC-1 5.05 -82% 37.5 CpF-1 0.991 PIC-1 5.57 -82% 40.0 CpF-1 1.10 PIC-1 6.12 -82% 42.5 CpF-1 1.21 PIC-1 6.68 -82% 45.0 CpF-1 1.33 PIC-1 7.27 -82%
¹ (α-olefin / ethylene) ^A = 0.0004 x (Octene ^{% by weight} ) ² + 0.0121 x (Octene ^{% by weight} ) - 0.0253; where (Octene ^{% by weight} ) is the% by weight of octene in the ethylene / 1 octene ² (a-olefin / ethylene) interpolymer ^c = 0.0017 x (Octene ^{% by weight} ) ² + 0.0862 x (Octene ^{% by weight} ) -0.0517 ³ 100% x ((a-olefin / ethylene) ^A - (a-olefin / ethylene) ^c ) / (a-olefin / ethylene) ^c
TABLE 10B
Percentage (%) of improvement (reduction) in the weight ratio of (aolefin / ethylene) in the reactor feed, for the formulation of bridged metallocene catalyst in relation to the formulation of single site non-bridged catalyst, to produce ethylene interpolymers at the densities shown (reactor temperature 160 ° C and about 90% ethylene conversion)
Petition 870190112009, of 11/01/2019, p. 160/168
154/156
% by weight of 1octene in ethylene interpolymers Catalyst formulationbridge-linked metallocene Formulation of single-site non-bridged catalyst % (α-olefin / ethylene) ratio reduced (see ³ ) ComponentTHE (a-olefin / ethylene) ^A (see ¹ ) ComponentÇ (a-olefin / ethylene) ^c (see ² ) 0.0 CpF-1 0.00 PIC-1 0.00 at 2.5 CpF-1 0.0078 PIC-1 0.183 -96% 5.0 CpF-1 0.031 PIC-1 0.407 -92% 7.5 CpF-1 0.066 PIC-1 0.653 -90% 10.0 CpF-1 0.112 PIC-1 0.920 -88% 12.5 CpF-1 0.170 PIC-1 1.21 -86% 15.0 CpF-1 0.238 PIC-1 1.52 -84% 17.5 CpF-1 0.318 PIC-1 1.85 -83% 20.0 CpF-1 0.409 PIC-1 2.20 -81% 22.5 CpF-1 0.512 PIC-1 2.57 -80% 25.0 CpF-1 0.625 PIC-1 2.97 -79% 27.5 CpF-1 0.750 PIC-1 3.39 -78% 30.0 CpF-1 0.886 PIC-1 3.82 -77% 32.5 CpF-1 1.03 PIC-1 4.28 -76% 35.0 CpF-1 1.19 PIC-1 4.76 -75% 37.5 CpF-1 1.36 PIC-1 5.26 -74% 40.0 CpF-1 1.54 PIC-1 5.78 -73% 42.5 CpF-1 1.74 PIC-1 6.33 -73% 45.0 CpF-1 1.94 PIC-1 6.89 -72%
¹ (α-olefin / ethylene) ^A = 0.0009 x (Octene ^{% by weight} ) ² + 0.0027 x (Octene ^{% by weight} )
- 0.0046; where (Octene ^{% by weight} ) is the% by weight of octene in the ethylene interpolymer / 1 Petition 870190112009, of 11/01/2019, p. 161/168
155/156 octene ² (a-olefin / ethylene) ^c = 0.0017 x (Octene ^{% by weight} ) ² + 0.0771 x (Octene ^{% by weight} )
- 0.0208 ³ 100% x ((α-olefin / ethylene) ¹ - (a-olefin / ethylene) ^w / (a-olefin / ethylene) ^c
TABLE 11
Continuous solution phase of CPU, a reactor, homopolymerization of ethylene using the bridged metallocene catalyst formulation
Temp, Polymerization (° C) 130 160 190 Sample code ExampleC1 ExampleC2 ExampleC3 ExampleC4 ExampleC5 ExampleC6 Component A ¹ Concentration in the reactor [mM / L] 0.15 0.47 0.19 0.82 0.22 0.93 mol ratio of ([M] / [A]) 100 100 100 100 100 100 mol ratio of ([P] / [M]) 0.40 0.40 0.40 0.40 0.40 0.40 mol ratio ([B] / [A]) 1.20 1.20 1.20 1.20 1.20 1.20 HUT ^CPU (min) 119 119 109 109 99 99 Q ^cpu (%) 74.5 94.2 74.9 94.4 75.5 94.8 K _P ^CPU (L / (mMmin) 12731 22328 11727 15704 13116 17761
¹ CpF-2 = [(2,7-tBu2Flu) Ph2C (Cp) HfMe ₂ ]
TABLE 12
Long-chain branching (LCB) determined by 13C NMR on the first ethylene interpolymer (ethylene homopolymer) produced using the ^1- bridged metallocene catalyst formulation on the CPU ___________________________
Sample ExampleC10 ExampleC11 ExampleC12 ExampleC13 ExampleC14 ExampleC15 Temp, CPU Reactor 190 190 160 160 130 130
Petition 870190112009, of 11/01/2019, p. 162/168
156/156
(° C) Conversion of ethylene fromCPU (% by weight) 95.6 85.3 95.0 75.3 93.6 85.1 Output of [ethylene] of (% by weight) 0.62 2.10 0.57 2.80 0.53 1.23 ¹³ C LCB / 1000C 0.23 0.09 0.09 0.03 0.07 0.03 GPC Mw (g / mol) 46337 93368 107818 255097 234744 305005 Pd (Mw / Mn) 1.88 1.88 1.85 1.9 2.02 2.29 ¹³ C-NMR, C1 / 1000C 2.37 1.68 1.64 0.98 0.94 0.73 ¹³ C-NMR, C2 / 1000C 0.2 0.14 0.17 0.10 0.12 0.09 ¹³ C-NMR, C3 / 1000C 0.08 0.05 0.05 D ² D D ¹³ C-NMR, C4 / 1000C 0.07 0.05 0.05 D D D ¹³ C-NMR, (C6 + LCB) / 1000C 0.3 0.12 0.12 D 0.07 D ¹³ C-NMR, Term. Sat./1000C 1.1 0.52 0.47 0.22 0.23 0.21 M _n (g / mol) 24640 49615 58131 118329 116035 133001 Mz (g / mol) 73219 152320 176254 383637 447833 567658 I2 (dg / min) 16.6 at 0.15 at at at I21 (dg / min) 380 at 10 0.54 0.53 0.12 I21 / I2 22.9 at 66.1 at at at
¹ Component A = [(2,7-tBu2Flu) Ph2C (Cp) HfMe2]
D = detectable but not quantifiable
INDUSTRIAL APPLICABILITY
[0310] The ethylene interpolymer products disclosed here have industrial applicability in a wide range of manufactured articles; non-limiting examples include flexible packaging films and rigid molded articles.

权利要求:
Claims (198)
[1]
1. Ethylene interpolymer product, CHARACTERIZED by the fact that it comprises:
(i) a first ethylene interpolymer;
(ii) a second ethylene interpolymer, and;
(iii) optionally a third ethylene interpolymer;
wherein said ethylene interpolymer product has a long chain branching factor, LCBF, dimensionless greater than or equal to about 0.001;
wherein said ethylene interpolymer product has from about 0.0015 ppm to about 2.4 ppm hafnium, and;
wherein said ethylene interpolymer product has from about 0.1 ppm to about 11.4 ppm titanium.
[2]
2. Ethylene interpolymer product, according to claim 1, CHARACTERIZED by the fact that it further comprises one or more of the following:
(i) greater than or equal to about 0.02 terminal vinyl unsaturations per 100 carbon atoms;
(ii) greater than or equal to about 0.12 parts per million (ppm) of a total catalytic metal.
[3]
3. Ethylene interpolymer product, according to claim 1, CHARACTERIZED by the fact that it has a melting index of about 0.3 to about 500 dg / minute; where the melt index is measured according to ASTM D1238 (2.16 kg load and 190 ° C).
[4]
4. Ethylene interpolymer product, according to claim 1, CHARACTERIZED by the fact that it has a density of about 0.862 to about 0.975 g / cc; wherein the density is measured according to ASTM D792.
[5]
5. Ethylene interpolymer product, according to claim 1, CHARACTERIZED by the fact that it has an M _w / M _n of about 2 to about 25.
Petition 870190105193, of 10/17/2019, p. 17/77
2/60
[6]
6. Ethylene interpolymer product, according to claim 1, CHARACTERIZED by the fact that it has a CDBIso of about 20% to about 98%.
[7]
7. Ethylene interpolymer product according to claim 1, CHARACTERIZED by the fact that (i) said first ethylene interpolymer is from about 5 to about 60 weight percent of said ethylene interpolymer product;
(ii) said second ethylene interpolymer is from about 20 to about 95 weight percent of said ethylene interpolymer product, and;
(iii) optionally said third ethylene interpolymer is from about 0 to about 30 weight percent of said ethylene interpolymer product;
wherein the weight percentage is the weight of said first, said second or said optional third ethylene interpolymer, individually divided by the weight of said ethylene interpolymer product.
[8]
8. Ethylene interpolymer product, according to claim 1, CHARACTERIZED by the fact that (i) said first ethylene interpolymer has a melting index of about 0.01 to about 200 dg / minute;
(ii) said second ethylene interpolymer has a melt index of about 0.3 to about 1000 dg / minute, and;
(iii) optionally said third ethylene interpolymer has a melt index of about 0.5 to about 2000 dg / minute;
where the melt index is measured according to ASTM D1238 (2.16 kg load and 190 ° C).
[9]
9. Ethylene interpolymer product, according to claim 1, CHARACTERIZED by the fact that (i) said first ethylene interpolymer has a density of about
Petition 870190105193, of 10/17/2019, p. 18/77
3/60
0.855 g / cm ³ to about 0.975 g / cc;
(ii) said second ethylene interpolymer has a density of about 0.89 g / cm ³ to about 0.975 g / cc, and;
(iii) optionally said third ethylene interpolymer has a density of about 0.855 g / cm ³ to about 0.975 g / cc;
wherein the density is measured according to ASTM D792.
[10]
10. Ethylene interpolymer product, according to claim 1, CHARACTERIZED by the fact that it is manufactured using a solution polymerization process.
[11]
11. Ethylene interpolymer product according to claim 1, CHARACTERIZED by the fact that it also comprises from 0 to about 10 mol percent of one or more α-olefins.
[12]
12. Ethylene interpolymer product according to claim 11, CHARACTERIZED by the fact that said one or more α-olefins are C3 to C10 a-olefins.
[13]
13. Ethylene interpolymer product according to claim 11, CHARACTERIZED by the fact that said one or more α-olefins are 1-hexene, 1-octene or a mixture of 1-hexene and 1-octene.
[14]
14. Ethylene interpolymer product according to claim 1, CHARACTERIZED by the fact that said first ethylene interpolymer is produced using at least one homogeneous catalyst formulation.
[15]
15. Ethylene interpolymer product according to claim 13, CHARACTERIZED by the fact that said first ethylene interpolymer is produced using a first homogeneous catalyst formulation.
[16]
16. Ethylene interpolymer product according to claim 15, CHARACTERIZED by the fact that said first homogeneous catalyst formulation is a bridged metallocene catalyst formulation.
Petition 870190105193, of 10/17/2019, p. 19/77
4/60
[17]
17. Ethylene interpolymer product according to claim 16, CHARACTERIZED by the fact that said formulation of bridged metallocene catalyst comprises a component A defined by Formula (I)

[18]
18. Ethylene interpolymer product according to claim 17, CHARACTERIZED by the fact that said second ethylene interpolymer is produced using a first heterogeneous catalyst formulation.
[19]
19. Ethylene interpolymer product according to claim 18, CHARACTERIZED by the fact that said optional third ethylene interpolymer is
Petition 870190105193, of 10/17/2019, p. 20/77
5/60 produced using said first heterogeneous catalyst formulation or a second heterogeneous catalyst formulation.
[20]
20. Ethylene interpolymer product according to claim 19, CHARACTERIZED by the fact that said first and said second heterogeneous catalyst formulations are a first and a second in-line Ziegler-Natta catalyst formulation; optionally, said first and said second in-line Ziegler-Natta catalyst formulations are the same formulation.
[21]
21. Ethylene interpolymer product according to claim 19, CHARACTERIZED by the fact that said first and said second heterogeneous catalyst formulations are a first and a second batch Ziegler-Natta catalyst formulation; optionally, said first and said second batch Ziegler-Natta catalyst formulations are the same formulation.
[22]
22. Ethylene interpolymer product according to claim 18, CHARACTERIZED by the fact that said optional third ethylene interpolymer is produced using a fifth homogeneous catalyst formulation.
[23]
23. Ethylene interpolymer product according to claim 22, CHARACTERIZED by the fact that said fifth formulation of homogeneous catalyst is said formulation of bridged metallocene catalyst, a third formulation of homogeneous catalyst or a fourth formulation of homogeneous catalyst.
[24]
24. Ethylene interpolymer product according to claim 23, CHARACTERIZED by the fact that said third homogeneous catalyst formulation is a single-site non-bridged catalyst formulation comprising a component C defined by Formula (II) ( L ^A ) aM (PI) b (Q) n (ll) where M is a metal selected from titanium, hafnium and zirconium;
L ^A is selected from the group consisting of unsubstituted cyclopentadienyl,
Petition 870190105193, of 10/17/2019, p. 21/77
6/60 substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; PI is a phosphinimine linker; Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1 -10 hydrocarbyl radical, a C1 -10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or replaced by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, a starch radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals or a phosphide radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals; where a is 1; b is 1; n is 1 or 2; and (a + b + n) is equivalent to the valence of metal M.
[25]
25. Ethylene interpolymer product according to claim 24, CHARACTERIZED by the fact that said fourth homogeneous catalyst formulation comprises a bulky metal-binder complex that is not a member of the chemical genera defined by Formula (I) or Formula (II).
[26]
26. Ethylene interpolymer product according to claim 16, CHARACTERIZED by the fact that said ethylene interpolymer product contains <2.4 ppm of catalytic metal A, wherein said catalytic metal A originates from said bridged metallocene catalyst formulation.
[27]
27. Ethylene interpolymer product according to claim 26; CHARACTERIZED by the fact that said catalytic metal A is hafnium.
[28]
28. Ethylene interpolymer product according to claim 19, CHARACTERIZED by the fact that said ethylene interpolymer product contains a catalytic metal Z1 and optionally a catalytic metal Z2 and the total amount of said catalytic metal Z1 plus said catalytic metal Z2 is about 0.1 to about 12 parts per million; wherein said catalytic metal Z1 originates from said first heterogeneous catalyst formulation and said catalytic metal Z2 originates from said second heterogeneous catalyst formulation; optionally said catalytic metal
Petition 870190105193, of 10/17/2019, p. 22/77
7/60
Z1 and said catalytic metal Z2 are the same metal.
[29]
29. Ethylene interpolymer product according to claim 28; CHARACTERIZED by the fact that said catalytic metal Z1 and said catalytic metal Z2, are independently selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or osmium .
[30]
30. Ethylene interpolymer product according to claim 28; CHARACTERIZED by the fact that said catalytic metal Z1 and said catalytic metal Z2, are independently selected from titanium, zirconium, hafnium, vanadium or chromium.
[31]
31. Ethylene interpolymer product according to claim 22, CHARACTERIZED by the fact that said ethylene interpolymer product contains <0.9 ppm of a catalytic metal D; wherein said catalytic metal D originates from said fourth homogeneous catalyst formulation.
[32]
32. Ethylene interpolymer product according to claim 31; CHARACTERIZED by the fact that said catalytic metal D is titanium, zirconium or hafnium.
[33]
33. Ethylene interpolymer product according to claim 1, CHARACTERIZED by the fact that said first ethylene interpolymer has a first M _w / M _n of about 1.7 to about 2.8, said second ethylene interpolymer has a second M _w / M _n of about 2.2 to about 4.4 and said optional third ethylene interpolymer has a third M _w / M _n of about 1.7 to about 5, 0.
[34]
34. Ethylene interpolymer product according to claim 33, CHARACTERIZED by the fact that said first M _w / M _n is lower than said second M _w / M _n .
[35]
35. Ethylene interpolymer product, according to claim 1, CHARACTERIZED by the fact that said first ethylene interpolymer has a
Petition 870190105193, of 10/17/2019, p. 23/77
8/60 first CDBho of about 70 to about 98%, said second ethylene interpolymer has a second CDBIso of about 45 to about 98% and said optional third ethylene interpolymer has a third CDBIso of about 35 about 98%.
[36]
36. Ethylene interpolymer product according to claim 35; CHARACTERIZED by the fact that said first CDBIso is higher than said second CDBIso.
[37]
37. Continuous solution polymerization process, CHARACTERIZED by the fact that it comprises:
i) injecting ethylene, a process solvent, a first homogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen in a first reactor to produce a first outlet stream containing a first ethylene interpolymer in said process solvent;
ii) passing said first outlet stream into a second reactor and injecting said second reactor, ethylene, said process solvent, a first heterogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen to produce a second stream outlet containing a second ethylene interpolymer and said first ethylene interpolymer in said process solvent;
iii) passing said second outlet stream into a third reactor and optionally injecting said third reactor, ethylene, process solvent, one or more aolefins, hydrogen and one or more of said first heterogeneous catalyst formulation, a second catalyst formulation heterogeneous and / or a fifth homogeneous catalyst formulation to produce a third outlet stream containing an optional third ethylene interpolymer, said second ethylene interpolymer and said first ethylene interpolymer in said process solvent;
Petition 870190105193, of 10/17/2019, p. 24/77
Iv) phase out said third outlet stream to recover an ethylene interpolymer product comprising said first ethylene interpolymer, said second ethylene interpolymer and said optional third ethylene interpolymer;
wherein, said continuous solution polymerization process is improved by having one or more of the following:
(a) at least one weight ratio of [α-olefin / ethylene] reduced to 70% as defined by the following formula% a - ethylene olefin
Reduced = 100x
AC α - olefin _ / a - olefin ethylene J ethylene J (a - olefin ^c ethylene)
-70% where (a-olefin / ethylene) ^A is calculated by dividing the weight of said a-olefin added to said first reactor by the weight of said ethylene added to said first reactor, wherein said first ethylene interpolymer having a target density is produced by said first homogeneous catalyst formulation, and; (a-olefin / ethylene) ^c is calculated by dividing the weight of said α-olefin added to said first reactor by the weight of said ethylene added to said first reactor, wherein a control ethylene interpolymer having said target density is produced by replacing said first homogeneous catalyst formulation with a third homogeneous catalyst formulation;
(b) at least one weighted average molecular weight improved to 5% as defined by the following formula% improved Mw = 100% x (Mw ^A -Mw ^c ) / Mw ^c > 5% where Mw ^A is a weighted average molecular weight said first ethylene interpolymer and M _w ^c is a weighted average molecular weight of a comparative ethylene interpolymer; wherein said comparative ethylene interpolymer is produced in said first reactor by replacing said first homogeneous catalyst formulation with said third homogeneous catalyst formulation.
Petition 870190105193, of 10/17/2019, p. 25/77
10/60
[38]
38. Process, according to claim 37, CHARACTERIZED by the fact that it further comprises:
a) optionally adding a catalyst deactivator A to said second output stream, downstream of said second reactor, forming a deactivated solution A;
b) adding a catalyst deactivator B to said third output stream, downstream of said third reactor, forming a deactivated solution B; with the proviso that step b) is skipped if said catalyst deactivator A is added in step a);
c) phase off said deactivated solution A or B to recover said ethylene interpolymer product.
[39]
39. Process, according to claim 38, CHARACTERIZED by the fact that it further comprises:
d) adding a passivator to said deactivated solution A or B forming a passivated solution, and;
e) phase out said passivated solution to recover said ethylene interpolymer product.
[40]
40. Process according to claim 39, CHARACTERIZED by the fact that said first homogeneous catalyst formulation is a bridged metallocene catalyst formulation comprising:
(a) a component A defined by Formula (I)
Petition 870190105193, of 10/17/2019, p. 26/77
11/60

[41]
41. Process according to claim 40, CHARACTERIZED by the fact that it has the following molar ratios in said first reactor: a molar ratio of said component B to 0 said component A from about 0.3: 1 to about 10 : 1; a molar ratio of said component M to 0 said component A of about 1: 1 to
Petition 870190105193, of 10/17/2019, p. 27/77
12/60 about 300: 1, and; a molar ratio of said optional component P to said component M is from 0.0: 1 to about 1: 1.
[42]
42. Process according to claim 41, CHARACTERIZED by the fact that component M is methylalumoxane (MMAO-7).
[43]
43. Process according to claim 41, CHARACTERIZED by the fact that component B is trityl tetracis (pentafluoro-phenyl) borate.
[44]
44. Process according to claim 41, CHARACTERIZED by the fact that component P is 2,6-di-tert-butyl-4-ethylphenol.
[45]
45. Process according to claim 41, CHARACTERIZED by the fact that it further comprises the injection of said bridged metallocene catalyst formulation in said first reactor at a catalyst inlet temperature of about 20 ° C at about 70 ° C; optionally, said Meo component and said P component can be deleted from said bridged metallocene catalyst formulation and replaced with a component J defined by the formula AI (R ¹ ) n (OR ² ) _o , where the groups (R ¹ ) can be the same or different hydrocarbyl groups having from 1 to 10 carbon atoms; the groups (OR ² ) can be the same or different alkoxy or aryloxy groups, where R ² is a hydrocarbyl group having from 1 to 10 oxygen-bonded carbon atoms, and; (n + o) = 3, with the proviso that n is greater than 0.
[46]
46. Process according to claim 41, CHARACTERIZED by the fact that it further comprises the injection of said bridged metallocene catalyst formulation in said first reactor at a catalyst inlet temperature of about 80 ° C at about 180 ° C.
[47]
47. Process according to claim 39, CHARACTERIZED by the fact that said third homogeneous catalyst formulation is a single site non-bridged catalyst formulation comprising:
a) a component C defined in Formula (II)
Petition 870190105193, of 10/17/2019, p. 28/77
13/60 (L ^A ) aM (PI) b (Q) n (ll) where M is a metal selected from titanium, hafnium and zirconium;
L ^A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; PI is a phosphinimine linker; Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1 -10 hydrocarbyl radical, a C1 -10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or replaced by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, a starch radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals or a phosphide radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals;
where a is 1; b is 1; n is 1 or 2, and (a + b + n) is equivalent to the valence of metal M;
b) an M component, comprising an alumoxane co-catalyst;
c) a component B, comprising a boron ionic activator, and;
d) optionally, a component P, comprising a hindered phenol.
[48]
48. Process according to claim 47, CHARACTERIZED by the fact that it has the following molar ratios in said first reactor: a molar ratio of said component B to said component C from about 0.3: 1 to about 10 : 1; a molar ratio of said component M to said component C from about 1: 1 to about 1000: 1, and; a molar ratio of said optional component P to said component M is from 0.0: 1 to about 1: 1.
[49]
49. Process according to claim 48, CHARACTERIZED by the fact that component M is methylalumoxane (MMAO-7).
[50]
50. Process according to claim 48, characterized by the fact that component B is trityl tetracis (pentafluoro-phenyl) borate.
Petition 870190105193, of 10/17/2019, p. 29/77
14/60
[51]
51. Process according to claim 48, CHARACTERIZED by the fact that component P is 2,6-di-tert-butyl-4-ethylphenol.
[52]
52. Process according to claim 48, CHARACTERIZED by the fact that it further comprises the injection of said formulation of a single site non-bridged catalyst in said first reactor at a catalyst inlet temperature of about 20 ° C at about 70 ° C; optionally, said component Meo and said component P can be deleted from said formulation of single site non-bridged catalyst and replaced with a component J defined by the formula AI (R ¹ ) n (OR ² ) _o , in which the groups ( R ¹ ) can be the same or different hydrocarbyl groups having from 1 to 10 carbon atoms; the groups (OR ² ) can be the same or different alkoxy or aryloxy groups, where R ² is a hydrocarbyl group having from 1 to 10 oxygen-bonded carbon atoms, and; (n + o) = 3, with the proviso that n is greater than 0.
[53]
53. Process according to claim 39, CHARACTERIZED by the fact that said fifth homogeneous catalyst formulation is said first homogeneous catalyst formulation, said third homogeneous catalyst formulation or fourth fourth homogeneous catalyst formulation.
[54]
54. Process according to claim 53, CHARACTERIZED by the fact that said first homogeneous catalyst formulation is a bridged metallocene catalyst formulation containing a component A defined by Formula (I)
Petition 870190105193, of 10/17/2019, p. 30/77
15/60

[55]
55. Process according to claim 54, CHARACTERIZED by the fact that said third homogeneous catalyst formulation is a single site non-bridged catalyst formulation comprising a component C defined by Formula (II) (L ^A ) aM (PI) b (Q) n (ll) where M is a metal selected from titanium, hafnium and zirconium;
L ^A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, fluorenyl
Petition 870190105193, of 10/17/2019, p. 31/77
16/60 unsubstituted and fluorenyl substituted; PI is a phosphinimine linker; Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1 -10 hydrocarbyl radical, a C1 -10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or further substituted by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, a starch radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals or a phosphide radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals, and;
where a is 1; b is 1; n is 1 or 2; and (a + b + n) is equivalent to the valence of metal M.
[56]
56. Process according to claim 55, CHARACTERIZED by the fact that said fourth homogeneous catalyst formulation comprises a bulky metal-binder complex that is not a member of the chemical genres defined by Formula (I) or Formula (II) ;

[57]
57. Process according to claim 39, CHARACTERIZED by the fact that said first and said second heterogeneous catalyst formulations are a first and a second in-line Ziegler-Natta catalyst formulation; optionally, said first and said second in-line Ziegler-Natta catalyst formulations are the same formulation.
[58]
58. Process according to claim 57, CHARACTERIZED by the fact that said first online Ziegler-Natta catalyst formulation is formed in an online process comprising:
Petition 870190105193, of 10/17/2019, p. 33/77
18/60
i) forming a first product mixture in a first heterogeneous catalyst assembly by combining a current S1 and a current S2 and allowing said first product mixture to equilibrate for a HUT-1 of seconds; wherein said S1 stream comprises a magnesium compound and an alkyl aluminum in said process solvent and said S2 stream comprises a chloride compound in said process solvent;
ii) forming a second product mixture in said first heterogeneous catalyst assembly by combining said first product mixture with an S3 stream and allowing said second product mixture to equilibrate for a HUT-2 of seconds; wherein said stream S3 comprises a metallic compound in said process solvent;
iii) forming said first Ziegler-Natta catalyst formulation in line in said first heterogeneous catalyst assembly by combining said second product mixture with an S4 stream and allowing said first Ziegler-Natta catalyst formulation in line equilibrate for a HUT-3 of seconds before injection into said second reactor and optional injection into said third reactor, wherein said stream S4 comprises an alkyl aluminum co-catalyst in said process solvent;
iv) optionally, step iii) is skipped and said first in line Ziegler-Natta catalyst formulation is formed within said second reactor and optionally within said third reactor; wherein, said second product mixture is balanced by an additional HUT-3 of seconds and injected into said second reactor and optionally into said third reactor, and said current S4 is independently injected into said second reactor and optionally into said third reactor , and;
v) optionally, said second in-line Ziegler-Natta catalyst formulation is formed by conducting steps i) to iii) in a second heterogeneous catalyst assembly, wherein said second Ziegler-Natta catalyst formulation
Petition 870190105193, of 10/17/2019, p. 34/77
19/60 in line is injected into said third reactor or optionally step iii) is skipped and said second Ziegler-Natta catalyst formulation in line is formed within said third reactor by balancing said second product mixture by a HUT -3 additional seconds and independently injecting said second product mixture and said current S4 into said third reactor.
[59]
59. Process, according to claim 58, CHARACTERIZED by the fact that said HUT-1 is from about 5 seconds to about 70 seconds, said HUT-2 is from about 2 seconds to about 50 seconds and said HUT-3 is about 0.5 to about 15 seconds; wherein said first Ziegler-Natta catalyst formulation, said second Ziegler-Natta catalyst formulation and said second product mixture are injected at a catalyst inlet temperature of about 20 ° C to about 70 ° C.
[60]
60. Process, according to claim 58, CHARACTERIZED by the fact that;
i) said magnesium compound is defined by the formula Mg (R ¹ ) 2, wherein the R ¹ groups can be the same or different;
ii) said alkyl aluminum is defined by the formula AI (R ³ ) 3, wherein the R ³ groups can be the same or different;
iii) said chloride compound is defined by the formula R ² CI;
iv) said metallic compound is defined by the formulas M (X) _n or MO (X) _n , where M represents titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium or mixtures thereof, O represents oxygen, X represents chloride or bromide and n is an integer that satisfies the oxidation state of metal M, and;
v) said alkyl aluminum co-catalyst is defined by the formula AI (R ⁴ ) _p (OR ⁵ ) q (X) r, in which the R ⁴ groups can be the same or different, the OR ⁵ groups can be the same or different and (p + q + r) = 3, with the proviso that p
Petition 870190105193, of 10/17/2019, p. 35/77
20/60 is greater than 0;
wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent hydrocarbyl groups having from 1 to 10 carbon atoms; optionally R ² can be a hydrogen atom.
[61]
61. Process according to claim 60, CHARACTERIZED by the fact that M in said metallic compound is titanium, zirconium, hafnium, vanadium, chromium or mixtures thereof.
[62]
62. Process according to claim 60, CHARACTERIZED by the fact that a molar ratio of said aluminum alkyl to said magnesium compound in said second and optionally in said third reactor is about 3.0: 1 to about 70: 1; a molar ratio of said chloride compound to said magnesium compound in said second and optionally in said third reactor is from about 1.0: 1 to about 4.0: 1; a molar ratio of said aluminum aluminum co-catalyst to said metal compound in said second and optionally in said third reactor is about 0: 1a to about 10: 1, and; a molar ratio of said alkyl aluminum to said metallic compound in said second and optionally in said third reactor is from about 0.05: 1 to about 2: 1.
[63]
63. Process according to claim 39, CHARACTERIZED by the fact that said first and said second heterogeneous catalyst formulations are a first and a second batch Ziegler-Natta catalyst formulation; optionally, said first and said second batch ZieglerNatta catalyst formulations are the same formulation.
[64]
64. Process according to claim 63, CHARACTERIZED by the fact that said first and said second batch Ziegler-Natta catalyst formulations are formed in a batch process comprising:
i) forming said first batch of Ziegler-Natta catalyst formulation by combining a current S5 and chain S4 and injecting said first batch formulation of Ziegler-Natta catalyst into said second reactor, wherein said second reactor
Petition 870190105193, of 10/17/2019, p. 36/77
Stream S4 comprises an alkyl aluminum co-catalyst in said process solvent and stream S5 comprises a first batch Ziegler-Natta pro-catalyst in said process solvent;
ii) optionally forming said second batch formulation of Ziegler-Natta catalyst by combining a stream S6 and said stream S4 and optionally injecting said second formulation of catalyst Ziegler-Natta in batch in said third reactor, wherein said stream S6 comprises a second batch Ziegler-Natta pro-catalyst in said process solvent;
iii) optionally, steps i) and ii) are skipped and said first batch Ziegler-Natta catalyst formulation and said second optional batch Ziegler-Natta catalyst formulation are formed within said reactors; wherein, said current S5 is injected into said second reactor and optionally said current S6 is injected into said third reactor and said current S4 is independently injected into said second reactor and optionally into said third reactor;
iv) optionally said second batch Ziegler-Natta catalyst formulation is formed by combining said chain S5 and said chain S4 and optionally injecting said second batch formulation of Ziegler-Natta catalyst into said third reactor; or said second batch Ziegler-Natta catalyst formulation is formed within said third reactor independently by injecting said current S5 and said current S4 into said third reactor;
wherein, said first and second Ziegler-Natta catalyst formulations and said streams S4, S5 and S6 are independently injected at a temperature of about 20 ° C to about 70 ° C.
[65]
65. Process according to claim 64, CHARACTERIZED by the fact that said alkyl aluminum co-catalyst is defined by the formula AI (R ⁴ ) _p (OR ⁵ ) q (X) r, in which the groups R ⁴ can be the same or different, the OR ⁵ groups can be the same or different and (p + q + r) = 3, with the proviso that p
Petition 870190105193, of 10/17/2019, p. 37/77
22/60 is greater than 0; wherein R ⁴ and R ⁵ represent hydrocarbyl groups having from 1 to 10 carbon atoms.
[66]
66. Process according to claim 64, CHARACTERIZED by the fact that said first and second batch Ziegler-Natta pro-catalysts comprise:
i) a magnesium compound defined by the formula Mg (R ¹ ) 2, in which the R ¹ groups can be the same or different;
ii) a chloride compound defined by the formula R ² CI;
iii) optionally an alkyl aluminum halide defined by the formula (R ⁶ ) _V AIX3 _v ; wherein the R ⁶ groups can be the same or different, X represents chloride or bromide, and v is 1 or 2.
iv) a metallic compound defined by the formulas M (X) _n or MO (X) _n , where M represents titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium or mixtures thereof, O represents oxygen, X represents chloride or bromide and n is an integer that satisfies the oxidation state of metal M, and;
wherein R ¹ , R ² and R ⁶ represent hydrocarbyl groups having from 1 to 10 carbon atoms; optionally R ² can be a hydrogen atom.
[67]
67. Process according to claim 66, CHARACTERIZED by the fact that M in said metallic compound represents titanium, zirconium, hafnium, vanadium, chromium or mixtures thereof.
[68]
68. Process according to claim 66, CHARACTERIZED by the fact that a molar ratio of said chloride compound to said magnesium compound in said batch Ziegler-Natta pro-catalyst is about 2: 1 to about 3: 1; wherein a molar ratio of said magnesium compound to said metal compound in said pro-catalyst is 5: 1 to about 10: 1; in which a molar ratio
Petition 870190105193, of 10/17/2019, p. 38/77
23/60 of said alkyl aluminum halide for said magnesium compound in said pro-catalyst is from about 0: 1 to about 0.5: 1, and; wherein a molar ratio of said aluminum aluminum cocatalyst to said metal compound in said pro-catalyst is from about 0.5: 1 to about 10: 1.
[69]
69. Process according to claim 39, CHARACTERIZED by the fact that said process solvent is one or more C5 to C12 alkanes.
[70]
70. Process according to claim 39, CHARACTERIZED by the fact that said first, second and third reactors operate at a temperature of about 80 ° C to about 300 ° C and a pressure of about 3 MPag at about 45 MPag.
[71]
71. Process according to claim 39, CHARACTERIZED by the fact that said process solvent in said first reactor has an average reactor residence time of about 10 seconds to about 600 seconds and said process solvent in said second reactor has an average reactor dwell time of about 10 seconds to about 720 seconds.
[72]
72. Process according to claim 39, CHARACTERIZED by the fact that a reactor temperature difference (T ^R2 - T ^R1 ) varies from about 1 ° C to about 120 ° C; where T ^R2 is the temperature of the solution in said second reactor and T ^R1 is the temperature of the solution in said first reactor.
[73]
73. Process according to claim 39, CHARACTERIZED by the fact that said one or more optional α-olefins are C3 to C10 α-olefins.
[74]
74. Process according to claim 39, CHARACTERIZED by the fact that said optional α-olefin is 1-hexene or 1-octene or a mixture of 1-hexene and 1-octene.
[75]
75. Ethylene interpolymer product, CHARACTERIZED by the fact that it is produced according to the process according to claim 39.
[76]
76. Ethylene interpolymer product, CHARACTERIZED by the fact that it is
Petition 870190105193, of 10/17/2019, p. 39/77
24/60 produced using a continuous solution polymerization process comprising:
(i) from about 5 weight percent to about 60 weight percent of a first ethylene interpolymer having a melt index of about 0.01 g / 10 minutes to about 200 g / 10 minutes and a target density from about 0.855 g / cm ³ to about 0.975 g / cm ³ ;
(ii) from about 20 weight percent to about 95 weight percent of a second ethylene interpolymer having a melt index of about 0.3 g / 10 minutes to about 1000 g / 10 minutes and a density from about 0.89 g / cm ³ to about 0.975 g / cm ³ ;
(iii) optionally from about 0 weight percent to about 30 weight percent of a third ethylene interpolymer having a melt index of about
0.5 g / 10 minutes at about 2000 g / 10 minutes and a density from about 0.855 g / cm ³ to about 0.975 g / cm ³ , and;
(iv) a means to reduce by at least -70% a weight ratio of [aolefin / ethylene] required to produce said first ethylene interpolymer having said target density, wherein the reduction in said weight ratio of [a -olefin / ethylene] is defined by the following formula% a - ethylene olefin
Reduced = 100x
AC α - olefin _ / g - olefin ethylene J ethylene J (a - olefin ^c ethylene)
-70% where (g-olefin / ethylene) ^A is calculated by dividing the weight of one or more olefins added to a first reactor by the weight of ethylene added to said first reactor, wherein said first ethylene interpolymer having said target density is produced using a bridged metallocene catalyst formulation, and; (c-olefin / ethylene) ^c is calculated by dividing the weight of said one or more oolefins added to said first reactor by the weight of said ethylene added to the
Petition 870190105193, of 10/17/2019, p. 40/77
Said first reactor, wherein a control ethylene interpolymer having said target density is produced by replacing said bridged metallocene catalyst formulation with a non-bridged single site catalyst formulation;
wherein said ethylene interpolymer product is CHARACTERIZED to have a melt index of about 0.3 g / 10 minutes to about 500 g / 10 minutes, a density of about 0.862 g / cm ³ to about 0.975 g / cm ³ , an M _w / M _n of about 2 to about 25 and a CDBIso of about 20% to about 98%; a long chain branching factor, LCBF, dimensionless greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium and from about 0.1 ppm to about 11.4 ppm of titanium;
where the melt index is measured according to ASTM D1238 (2.16 kg load and 190 ° C), the density is measured according to ASTM D792 and the weight percentage is the weight of said first, said second or said optional third ethylene polymer, individually divided by the weight of said ethylene interpolymer product.
[77]
77. Ethylene interpolymer product according to claim 76, CHARACTERIZED by the fact that said second ethylene interpolymer is produced by a first heterogeneous catalyst formulation, optionally said third ethylene interpolymer is produced by said first formulation of heterogeneous catalyst or a second heterogeneous catalyst formulation.
[78]
78. Ethylene interpolymer product according to claim 77, CHARACTERIZED by the fact that said first and said heterogeneous catalyst formulations are a first and a second in-line Ziegler-Natta catalyst formulation; optionally, said first and said second in-line Ziegler-Natta catalyst formulations are the same formulation.
[79]
79. Ethylene interpolymer product according to claim 77,
Petition 870190105193, of 10/17/2019, p. 41/77
26/60
CHARACTERIZED by the fact that said first and said second heterogeneous catalyst formulations are a first and a second batch Ziegler-Natta catalyst formulation; optionally, said first and said second batch Ziegler-Natta catalyst formulations are the same formulation.
[80]
80. Ethylene interpolymer product according to claim 77, CHARACTERIZED by the fact that said third ethylene interpolymer is produced using a fifth homogeneous catalyst formulation.
[81]
81. Ethylene interpolymer product according to claim 80, CHARACTERIZED by the fact that said fifth homogeneous catalyst formulation is said bridged metallocene catalyst formulation, said unalloyed single site catalyst formulation bridge or a fourth formulation of homogeneous catalyst.
[82]
82. Ethylene interpolymer product according to claim 81, CHARACTERIZED by the fact that said bridged metallocene catalyst formulation comprises a component A defined by Formula (I)

[83]
83. Ethylene interpolymer product, according to claim 82, CHARACTERIZED by the fact that said formulation of single site non-bridged catalyst comprises a component C defined by Formula (II) (L ^A ) aM (PI) b (Q) n (ll) where M is a metal selected from titanium, hafnium and zirconium;
L ^A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; PI is a phosphinimine linker; Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1 -10 hydrocarbyl radical, a C1 -10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or replaced by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, a starch radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals or a phosphide radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals; where a is 1; b is 1; n is 1 or 2; and (a + b + n) is equivalent to the valence of metal M.
[84]
84. Ethylene interpolymer product according to claim 83, CHARACTERIZED by the fact that said fourth homogeneous catalyst formulation comprises a bulky metal-binder complex that is not a member of the chemical genera defined by Formula (I) or Formula (II).
Petition 870190105193, of 10/17/2019, p. 43/77
28/60
[85]
85. Ethylene interpolymer product according to claim 82, CHARACTERIZED by the fact that said ethylene interpolymer product contains <2.4 ppm of catalytic metal A, wherein said catalytic metal A originates from said bridged metallocene catalyst formulation.
[86]
86. Ethylene interpolymer product according to claim 85; CHARACTERIZED by the fact that said catalytic metal A is hafnium.
[87]
87. Ethylene interpolymer product according to claim 77, CHARACTERIZED by the fact that said ethylene interpolymer product contains a catalytic metal Z1 and optionally a catalytic metal Z2 and the total amount of said catalytic metal Z1 plus said catalytic metal Z2 is about 0.1 to about 12 parts per million; wherein said catalytic metal Z1 originates from said first heterogeneous catalyst formulation and said catalytic metal Z2 originates from said second heterogeneous catalyst formulation; optionally said catalytic metal Z1 and said catalytic metal Z2 are the same metal.
[88]
88. Ethylene interpolymer product according to claim 87; CHARACTERIZED by the fact that said catalytic metal Z1 and said catalytic metal Z2, are independently selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or osmium .
[89]
89. Ethylene interpolymer product according to claim 87; CHARACTERIZED by the fact that said catalytic metal Z1 and said catalytic metal Z2, are independently selected from titanium, zirconium, hafnium, vanadium or chromium.
[90]
90. Ethylene interpolymer product according to claim 81, CHARACTERIZED by the fact that said ethylene interpolymer product contains <0.9 ppm of a catalytic metal D; wherein said catalytic metal D originates from said fourth homogeneous catalyst formulation.
Petition 870190105193, of 10/17/2019, p. 44/77
29/60
[91]
91. Ethylene interpolymer product according to claim 90; CHARACTERIZED by the fact that said catalytic metal D is titanium, zirconium or hafnium.
[92]
92. Ethylene interpolymer product according to claim 76, CHARACTERIZED by the fact that said first ethylene interpolymer has a first M _w / M _n of about 1.7 to about 2.8, said second ethylene interpolymer has a second M _w / M _n of about 2.2 to about 4.4 and said optional third ethylene interpolymer has a third M _w / M _n of about 1.7 to about 5, 0.
[93]
93. Ethylene interpolymer product according to claim 92, CHARACTERIZED by the fact that said first M _w / M _n is lower than said second M _w / M _n .
[94]
94. Ethylene interpolymer product, according to claim 76, CHARACTERIZED by the fact that said first ethylene interpolymer has a first CDBIso of about 70 to about 98%, said second ethylene interpolymer has a second CDBIso from about 45 to about 98% and said optional third ethylene interpolymer has a third CDBIso of about 35 to about 98%.
[95]
95. Ethylene interpolymer product, according to claim 94, CHARACTERIZED by the fact that said first CDBIso is higher than said second CDBIso.
[96]
96. Polyethylene film, CHARACTERIZED by the fact that it comprises at least one layer, wherein said layer comprises at least one ethylene interpolymer product comprising:
(i) a first ethylene interpolymer;
(ii) a second ethylene interpolymer, and;
(iii) optionally a third ethylene interpolymer;
Petition 870190105193, of 10/17/2019, p. 45/77
30/60 wherein said ethylene interpolymer product has a long chain branching factor, LCBF, dimensionless greater than or equal to about 0.001;
wherein said ethylene interpolymer product has from about 0.0015 ppm to about 2.4 ppm hafnium, and;
wherein said ethylene interpolymer product has from about 0.1 ppm to about 11.4 ppm titanium.
[97]
97. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said ethylene interpolymer product further comprises one or more of the following:
(i) more than or equal to about 0.02 terminal vinyl unsaturations per 100 carbon atoms;
(ii) more than or equal to about 0.12 parts per million (ppm) of a total catalytic metal.
[98]
98. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said ethylene interpolymer product has a melt index of about 0.3 to about 500 dg / minute; where the melt index is measured according to ASTM D1238 (2.16 kg load and 190 ° C).
[99]
99. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said ethylene interpolymer product has a density of about 0.862 to about 0.975 g / cc; wherein the density is measured according to ASTM D792.
[100]
100. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said ethylene interpolymer product has an Mw / Mn of about 2 to about 25.
[101]
101. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said ethylene interpolymer product has a CDBho of about 20% to about 98%.
Petition 870190105193, of 10/17/2019, p. 46/77
31/60
[102]
102. Polyethylene film, according to claim 96, CHARACTERIZED by the fact that
i) said first ethylene interpolymer is from about 5 to about 60 weight percent of said ethylene interpolymer product;
(ii) said second ethylene interpolymer is from about 20 to about 95 weight percent of said ethylene interpolymer product, and;
(iii) optionally said third ethylene interpolymer is from about 0 to about 30 weight percent of said ethylene interpolymer product;
wherein the weight percentage is the weight of said first, said second or said optional third ethylene interpolymer, individually divided by the weight of said ethylene interpolymer product.
[103]
103. Polyethylene film according to claim 96, CHARACTERIZED by the fact that (i) said first ethylene interpolymer has a melt index of about 0.01 to about 200 dg / minute;
(ii) said second ethylene interpolymer has a melt index of about 0.3 to about 1000 dg / minute, and;
(iii) optionally said third ethylene interpolymer has a melt index of about 0.5 to about 2000 dg / minute;
where the melt index is measured according to ASTM D1238 (2.16 kg load and 190 ° C).
[104]
104. Polyethylene film according to claim 96, CHARACTERIZED by the fact that (i) said first ethylene interpolymer has a density of about 0.855 g / cm ³ to about 0.975 g / cc;
(ii) said second ethylene interpolymer has a density of about 0.89 g / cm ³ to about 0.975 g / cc, and;
Petition 870190105193, of 10/17/2019, p. 47/77
(Iii) optionally said third ethylene interpolymer has a density of about 0.855 g / cm ³ to about 0.975 g / cc;
wherein the density is measured according to ASTM D792.
[105]
105. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said ethylene interpolymer product is manufactured using a solution polymerization process.
[106]
106. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said ethylene interpolymer product further comprises from 0 to about 10 mol percent of one or more α-olefins.
[107]
107. Polyethylene film according to claim 106, CHARACTERIZED by the fact that said one or more α-olefins are C3aC10 a-olefins.
[108]
108. Polyethylene film according to claim 106, CHARACTERIZED by the fact that said one or more α-olefins are 1-hexene, 1-octene or a mixture of 1-hexene and 1-octene.
[109]
109. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said first ethylene interpolymer is produced using at least one homogeneous catalyst formulation.
[110]
110. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said first ethylene interpolymer is produced using a first homogeneous catalyst formulation.
[111]
111. Polyethylene film according to claim 110, CHARACTERIZED by the fact that said first homogeneous catalyst formulation is a bridged metallocene catalyst formulation.
[112]
112. Polyethylene film according to claim 111, CHARACTERIZED by the fact that said bridged metallocene catalyst formulation comprises a component A defined by Formula (I)
Petition 870190105193, of 10/17/2019, p. 48/77
33/60

[113]
113. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said second ethylene interpolymer is produced using a first heterogeneous catalyst formulation; optionally, said third ethylene interpolymer is produced using said first heterogeneous catalyst formulation or a second heterogeneous catalyst formulation.
[114]
114. Polyethylene film according to claim 113, CHARACTERIZED by the fact that said first and said second heterogeneous catalyst formulations are a first and a second catalyst formulation
Petition 870190105193, of 10/17/2019, p. 49/77
34/60
Ziegler-Natta online; optionally, said first and said second in-line Ziegler-Natta catalyst formulations are the same formulation.
[115]
115. Polyethylene film according to claim 113, CHARACTERIZED by the fact that said first and said heterogeneous catalyst formulations are a first and a second batch Ziegler-Natta catalyst formulation; optionally, said first and said second batch Ziegler-Natta catalyst formulations are the same formulation.
[116]
116. Polyethylene film according to claim 112, CHARACTERIZED by the fact that said third ethylene interpolymer is produced using a fifth formulation of homogeneous catalyst.
[117]
117. Polyethylene film according to claim 116, CHARACTERIZED by the fact that said fifth homogeneous catalyst formulation is said bridged metallocene catalyst formulation, a third homogeneous catalyst formulation or fourth homogeneous catalyst formulation .
[118]
118. Polyethylene film according to claim 117, CHARACTERIZED by the fact that said third homogeneous catalyst formulation is a single site non-bridged catalyst formulation comprising a component C defined by Formula (II) (L ^A ) aM (PI) b (Q) n (ll) where M is a metal selected from titanium, hafnium and zirconium;
L ^A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; PI is a phosphinimine linker; Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1 -10 hydrocarbyl radical, a C1 -10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals can
Petition 870190105193, of 10/17/2019, p. 50/77
35/60 be unsubstituted or replaced by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, a starch radical that is unsubstituted or substituted by up to two C1-8 alkyl radicals or a phosphide radical that is unsubstituted or substituted by up to two C1-8 alkyl radicals; where a is 1; b is 1; n is 1 or 2; and (a + b + n) is equivalent to the valence of metal M.
[119]
119. Polyethylene film according to claim 118, CHARACTERIZED by the fact that said fourth homogeneous catalyst formulation comprises a bulky metal-binder complex that is not a member of the chemical genres defined by Formula (I) or Formula ( II).
[120]
120. Polyethylene film according to claim 111, CHARACTERIZED by the fact that said ethylene interpolymer product contains <2.4 ppm of catalytic metal A, wherein said catalytic metal A originates from said formulation bridged metallocene catalyst.
[121]
121. Polyethylene film according to claim 120;
CHARACTERIZED by the fact that said catalytic metal A is hafnium.
[122]
122. Polyethylene film according to claim 113,
CHARACTERIZED by the fact that said ethylene interpolymer product contains a catalytic metal Z1 and optionally a catalytic metal Z2 and the total amount of said catalytic metal Z1 plus said catalytic metal Z2 is from about 0.1 to about 12 parts per million; wherein said catalytic metal Z1 originates from said first heterogeneous catalyst formulation and said catalytic metal Z2 originates from said second heterogeneous catalyst formulation; optionally said catalytic metal Z1 and said catalytic metal Z2 are the same metal.
[123]
123. Polyethylene film according to claim 122; CHARACTERIZED by the fact that said catalytic metal Z1 and said catalytic metal Z2, are independently selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or
Petition 870190105193, of 10/17/2019, p. 51/77
36/60 os.
[124]
124. Polyethylene film according to claim 122; CHARACTERIZED by the fact that said catalytic metal Z1 and said catalytic metal Z2, are independently selected from titanium, zirconium, hafnium, vanadium or chromium.
[125]
125. Polyethylene film according to claim 116, CHARACTERIZED by the fact that said ethylene interpolymer product contains <0.9 ppm of a catalytic metal D; wherein said catalytic metal D originates from said fourth homogeneous catalyst formulation.
[126]
126. Polyethylene film according to claim 125; CHARACTERIZED by the fact that said catalytic metal D is titanium, zirconium or hafnium.
[127]
127. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said first ethylene interpolymer has a first M _w / M _n of about 1.7 to about 2.8, said second interpolymer of ethylene has a second M _w / M _n from about 2.2 to about 4.4 and said optional third ethylene interpolymer has a third M _w / M _n from about 1.7 to about 5.0.
[128]
128. Polyethylene film according to claim 127, CHARACTERIZED by the fact that said first M _w / M _n is lower than said second M w / M _n .
[129]
129. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said first ethylene interpolymer has a first CDBIso of about 70 to about 98%, said second ethylene interpolymer has a second CDBIso of about from 45 to about 98% and said optional third ethylene interpolymer has a third CDBIso of about 35 to about 98%.
[130]
130. Polyethylene film according to claim 129;
Petition 870190105193, of 10/17/2019, p. 52/77
37/60
CHARACTERIZED by the fact that said first CDBI50 is higher than said second CDBIso.
[131]
131. Polyethylene film according to claim 96, CHARACTERIZED by the fact that a drying module in the machine direction measured at 1% tension is at least 25% higher and a drying module in the transversal direction measured at 1% tension tension is at least 40% higher; with respect to a comparative polyethylene film of the same composition but said first ethylene interpolymer in said ethylene interpolymer product is replaced with a comparative ethylene interpolymer; wherein said first ethylene interpolymer is produced with a bridged metallocene catalyst formulation and said comparative ethylene interpolymer is produced with a non-bridged single site catalyst formulation; where the drying module has been determined according to ASTM D882.
[132]
132. Polyethylene film according to claim 96, CHARACTERIZED by the fact that a drying module in the machine direction measured at 2% tension is at least 20% higher and a drying module in the transversal direction measured at 2% tension tension is at least 40% higher; with respect to a comparative polyethylene film of the same composition but said first ethylene interpolymer in said ethylene interpolymer product is replaced with a comparative ethylene interpolymer; wherein said first ethylene interpolymer is produced with a bridged metallocene catalyst formulation and said comparative ethylene interpolymer is produced with a non-bridged single site catalyst formulation; where the drying module has been determined according to ASTM D882 ..
[133]
133. Polyethylene film according to claim 96, CHARACTERIZED by the fact that one% by weight of hexane extractable is better
Petition 870190105193, of 10/17/2019, p. 53/77
38/60 because it is at least 40% lower than a comparative polyethylene film of the same composition, but said first ethylene interpolymer in said ethylene interpolymer product is replaced with a comparative ethylene interpolymer; wherein said first ethylene interpolymer is produced with a bridged metallocene catalyst formulation and said comparative ethylene interpolymer is produced with a non-bridged single site catalyst formulation; where the% by weight of hexane extractables was determined according to the Code of Federal Registration 21 CFR §117.1520 For (c) 3.1 and 3.2.
[134]
134. Polyethylene film, according to claim 96, CHARACTERIZED by the fact that an Elmendorf tear resistance in the machine direction is improved, since it is at least 15% higher, compared to a comparative polyethylene film of the same composition but said first ethylene interpolymer in said ethylene interpolymer product is replaced with a comparative ethylene interpolymer; wherein said first ethylene interpolymer is produced with a bridged metallocene catalyst formulation and said comparative ethylene interpolymer is produced with a non-bridged single site catalyst formulation; wherein both said first ethylene interpolymer and said comparative ethylene interpolymer are produced in a double reactor solution process, in which a first reactor and a second reactor are configured in parallel; where the Elmendorf rupture was determined according to ASTM D1922 - 09.
[135]
135. Polyethylene film according to claim 96, CHARACTERIZED by the fact that a sealing initiation temperature is improved, as it is at least 5% lower, than a comparative polyethylene film of the same composition but said first ethylene interpolymer in said ethylene interpolymer product is replaced with a comparative ethylene interpolymer; wherein said first ethylene interpolymer is produced with a
Petition 870190105193, of 10/17/2019, p. 54/77
39/60 bridged metallocene catalyst formulation and said comparative ethylene interpolymer is produced with a non-bridged single site catalyst formulation; wherein both said first ethylene interpolymer and said comparative ethylene interpolymer are produced in a double reactor solution process, in which a first reactor and a second reactor are configured in parallel.
[136]
136. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said layer further comprises at least a second polymer.
[137]
137. Polyethylene film according to claim 136, CHARACTERIZED by the fact that said second polymer is an ethylene polymer, a propylene polymer or a mixture of said ethylene polymer and said propylene polymer.
[138]
138. Polyethylene film, according to claim 96, CHARACTERIZED by the fact that said film has a thickness of about 0.5 thousand to about 10 thousand.
[139]
139. Polyethylene film according to claim 96, CHARACTERIZED by the fact that said film comprises from 2 to 11 layers, wherein at least one layer comprises said ethylene interpolymer product.
[140]
140. Continuous solution polymerization process, CHARACTERIZED by the fact that it comprises:
i) injecting ethylene, a process solvent, a first homogeneous catalyst formulation, optionally one or more α-olefins and optionally hydrogen in a first reactor to produce a first outlet stream containing a first ethylene interpolymer in said process solvent;
ii) injecting ethylene, said process solvent, a first formulation of ca
Petition 870190105193, of 10/17/2019, p. 55/77
40/60 heterogeneous talisator, optionally one or more α-olefins and optionally hydrogen in a second reactor to produce a second outlet stream containing a second ethylene interpolymer in said process solvent;
iii) combining said first and said second output streams to form a third output stream;
iv) passing said third output stream into a third reactor and optionally injecting said process solvent, ethylene, said process solvent, one or more α-olefins, hydrogen and one or more of said first heterogeneous catalyst formulation, a second heterogeneous catalyst formulation and / or a fifth homogeneous catalyst formulation to produce a fourth outlet stream containing an optional third ethylene interpolymer, said second ethylene interpolymer and said first ethylene interpolymer in said process solvent;
v) phasing said fourth outlet stream to recover an ethylene interpolymer product comprising said first ethylene interpolymer, said second ethylene interpolymer and said optional third ethylene interpolymer;
wherein, said continuous solution polymerization process is improved by having one or more of the following:
(a) at least one weight ratio of [α-olefin / ethylene] reduced to 70% as defined by the following formula i / a - olefin _ / a - olefin A [a - olefin] 1 ethylene J ethylene / __ _n ,% of --------- Reduced = 100 x <----------------- -------><- 70% ethylene / g - olefinav v ethylene) J where (a-olefin / ethylene) ^A is calculated by dividing the weight of said a-olefin added to said first reactor by the weight of said ethylene added to said first reactor, where said first ethylene interpolymer having a target density is produced by said first homogeneous catalyst formulation, and; (a-olefin / ethylene) ^c is calculated by dividing the weight of said α-olefin added to said first
Petition 870190105193, of 10/17/2019, p. 56/77
41/60 reactor by the weight of said ethylene added to said first reactor, wherein a control ethylene interpolymer having said target density is produced by replacing said first homogeneous catalyst formulation with a third homogeneous catalyst formulation;
(b) at least one weighted average molecular weight improved to 5% as defined by the following formula% improved Mw = 100% x (M _w ^A -Mw ^c ) / M _w ^c > 5% where Mw ^A is a molecular weight weighted average of said first ethylene interpolymer and M _w ^c is a weighted average molecular weight of a comparative ethylene interpolymer; wherein said comparative ethylene interpolymer is produced in said first reactor by replacing said first homogeneous catalyst formulation with said third homogeneous catalyst formulation.
[141]
141. Process, according to claim 140, CHARACTERIZED by the fact that it further comprises:
a) optionally adding a catalyst deactivator A to said third output stream, downstream of said first and said second reactor, forming a deactivated solution A;
b) adding a catalyst deactivator B to said fourth output stream, downstream of said third reactor, forming a deactivated solution B; with the proviso that step b) is skipped if said catalyst deactivator A is added in step a);
c) phase off said deactivated solution A or B to recover said ethylene interpolymer product.
[142]
142. Process, according to claim 141, CHARACTERIZED by the fact that it further comprises:
d) adding a passivator to said deactivated solution A or B forming a passivated solution, and;
Petition 870190105193, of 10/17/2019, p. 57/77
42/60
e) phase out said passivated solution to recover said ethylene interpolymer product.
[143]
143. Process according to claim 142, CHARACTERIZED by the fact that said first homogeneous catalyst formulation is a bridged metallocene catalyst formulation comprising:
(a) a component A defined by Formula (I)

[144]
144. Process according to claim 143, CHARACTERIZED by the fact that it has the following molar ratios in said first reactor: a molar ratio of said component B to said component A from about 0.3: 1 to about 10 :1; a molar ratio of said component M to said component A from about 1: 1 to about 300: 1, and; a molar ratio of said optional component P to said component M is from 0.0: 1 to about 1: 1.
[145]
145. Process according to claim 144, characterized by the fact that component M is methylalumoxane (MMAO-7).
[146]
146. Process according to claim 144, CHARACTERIZED by the fact that component B is trityl tetracis (pentafluoro-phenyl) borate.
[147]
147. Process according to claim 144, CHARACTERIZED by the fact that component P is 2,6-di-tert-butyl-4-ethylphenol.
[148]
148. Process according to claim 144, CHARACTERIZED by the fact that it further comprises the injection of said bridged metallocene catalyst formulation in said first reactor at a catalyst inlet temperature of about 20 ° C at about 70 ° C; optionally said component M and said component P can be deleted from said bridged metallocene catalyst formulation and replaced with a component J defined by the formula AI (R ¹ ) _n (OR ² ) o, wherein the groups ( R ¹ ) can be the same or different hydrocarbyl groups having from 1 to 10 carbon atoms; the groups (OR ² ) can be the same or different alkoxy or aryloxy groups, where R ² is a hydrocarbyl group having from 1 to 10 oxygen-bonded carbon atoms, and; (n + o) = 3, with the proviso that n is greater than 0.
[149]
149. Process according to claim 144, CHARACTERIZED by the fact that it further comprises the injection of said metal catalyst formulation
Petition 870190105193, of 10/17/2019, p. 59/77
44/60 bridged scene in said first reactor at a catalyst inlet temperature of about 80 ° C to about 180 ° C.
[150]
150. Process according to claim 142, CHARACTERIZED by the fact that said third homogeneous catalyst formulation is a single site non-bridged catalyst formulation comprising:
a) a component C defined in Formula (II) (L ^A ) aM (PI) b (Q) n (ll) where M is a metal selected from titanium, hafnium and zirconium;
L ^A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; PI is a phosphinimine linker; Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1 -10 hydrocarbyl radical, a C1 -10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or replaced by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, a starch radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals or a phosphide radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals;
where a is 1; b is 1; n is 1 or 2, and (a + b + n) is equivalent to the valence of metal M;
b) an M component, comprising an alumoxane co-catalyst;
c) a component B, comprising a boron ionic activator, and;
d) optionally, a component P, comprising a hindered phenol.
[151]
151. Process according to claim 150, CHARACTERIZED by the fact that it has the following molar ratios in said first reactor: a molar ratio of said component B to said component C from about 0.3: 1 to about 10 :1; a molar ratio of said component M to said component C of about 1: 1 to
Petition 870190105193, of 10/17/2019, p. 60/77
45/60 about 1000: 1, and; a molar ratio of said optional component P to said component M is from 0.0: 1 to about 1: 1.
[152]
152. Process according to claim 151, CHARACTERIZED by the fact that component M is methylalumoxane (MMAO-7).
[153]
153. Process according to claim 151, characterized by the fact that component B is trityl tetrads (pentafluoro-phenyl) borate.
[154]
154. Process according to claim 151, CHARACTERIZED by the fact that component P is 2,6-di-tert-butyl-4-ethylphenol.
[155]
155. Process according to claim 151, CHARACTERIZED by the fact that it further comprises the injection of said formulation of single site non-bridged catalyst in said first reactor at a catalyst inlet temperature of about 20 ° C at about 70 ° C; optionally, said component M and said component P can be deleted from said formulation of single site non-bridged catalyst and replaced with a component J defined by the formula AI (R ¹ ) n (OR ² ) o, where the groups (R ¹ ) can be the same or different hydrocarbyl groups having from 1 to 10 carbon atoms; the groups (OR ² ) can be the same or different alkoxy or aryloxy groups, where R ² is a hydrocarbyl group having from 1 to 10 oxygen-bonded carbon atoms, and; (n + o) = 3, with the proviso that n is greater than 0 ..
[156]
156. Process according to claim 142, CHARACTERIZED by the fact that said fifth homogeneous catalyst formulation is said first homogeneous catalyst formulation, said third homogeneous catalyst formulation or fourth homogeneous catalyst formulation.
[157]
157. Process according to claim 156, CHARACTERIZED by the fact that said first homogeneous catalyst formulation is a bridged metallocene catalyst formulation containing a component A defined by Formula (I)
Petition 870190105193, of 10/17/2019, p. 61/77
46/60

[158]
158. Process according to claim 157, CHARACTERIZED by the fact that said third homogeneous catalyst formulation is a single site non-bridged catalyst formulation comprising a component C defined by Formula (II) (L ^A ) aM (PI) b (Q) n (ll) where M is a metal selected from titanium, hafnium and zirconium;
L ^A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, fluorenyl
Petition 870190105193, of 10/17/2019, p. 62/77
47/60 unsubstituted and substituted fluorenyl; PI is a phosphinimine linker; Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1 -10 hydrocarbyl radical, a C1 -10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or further substituted by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, a starch radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals or a phosphide radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals, and;
where a is 1; b is 1; n is 1 or 2; and (a + b + n) is equivalent to the valence of metal M.
[159]
159. Process according to claim 158, CHARACTERIZED by the fact that said fourth homogeneous catalyst formulation comprises a bulky metal-binder complex that is not a member of the chemical genres defined by Formula (I) or Formula (II) ;

[160]
160. Process according to claim 142, CHARACTERIZED by the fact that said first and said second heterogeneous catalyst formulations are a first and a second in-line Ziegler-Natta catalyst formulation; optionally, said first and said second ZieglerNatta online catalyst formulations are the same formulation.
[161]
161. Process according to claim 160, CHARACTERIZED by the fact that said first online Ziegler-Natta catalyst formulation is formed in an online process comprising:
Petition 870190105193, of 10/17/2019, p. 64/77
49/60
i) forming a first product mixture in a first heterogeneous catalyst assembly by combining a current S1 and a current S2 and allowing said first product mixture to equilibrate for a HUT-1 of seconds; wherein said S1 stream comprises a magnesium compound and an alkyl aluminum in said process solvent and said S2 stream comprises a chloride compound in said process solvent;
ii) forming a second product mixture in said first heterogeneous catalyst assembly by combining said first product mixture with an S3 stream and allowing said second product mixture to equilibrate for a HUT-2 of seconds; wherein said stream S3 comprises a metallic compound in said process solvent;
iii) forming said first Ziegler-Natta catalyst formulation in line in said first heterogeneous catalyst assembly by combining said second product mixture with an S4 stream and allowing said first Ziegler-Natta catalyst formulation in line equilibrate for a HUT-3 of seconds before injection into said second reactor and optional injection into said third reactor, wherein said stream S4 comprises an alkyl aluminum co-catalyst in said process solvent;
iv) optionally, step iii) is skipped and said first in line Ziegler-Natta catalyst formulation is formed within said second reactor and optionally within said third reactor; wherein, said second product mixture is balanced by an additional HUT-3 of seconds and injected into said second reactor and optionally into said third reactor, and said current S4 is independently injected into said second reactor and optionally into said third reactor , and;
v) optionally, said second in-line Ziegler-Natta catalyst formulation is formed by conducting steps i) to iii) in a second heterogeneous catalyst assembly, wherein said second Ziegler-Natta catalyst formulation
Petition 870190105193, of 10/17/2019, p. 65/77
50/60 in line is injected into said third reactor or optionally step iii) is skipped and said second Ziegler-Natta catalyst formulation in line is formed within said third reactor by balancing said second product mixture by a HUT -3 additional seconds and independently injecting said second product mixture and said current S4 into said third reactor.
[162]
162. Process according to claim 161, CHARACTERIZED by the fact that said HUT-1 is about 5 seconds to about 70 seconds, said HUT-2 is about 2 seconds to about 50 seconds and said HUT-3 is about 0.5 to about 15 seconds; wherein said first Ziegler-Natta catalyst formulation, said second Ziegler-Natta catalyst formulation and said second product mixture are injected at a catalyst inlet temperature of about 20 ° C to about 70 ° C.
[163]
163. Process according to claim 161, CHARACTERIZED by the fact that;
i) said magnesium compound is defined by the formula Mg (R ¹ ) 2, wherein the R ¹ groups can be the same or different;
ii) said alkyl aluminum is defined by the formula AI (R ³ ) 3, wherein the R ³ groups can be the same or different;
iii) said chloride compound is defined by the formula R ² CI;
iv) said metallic compound is defined by the formulas M (X) _n or MO (X) _n , where M represents titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium or mixtures thereof, O represents oxygen, X represents chloride or bromide and n is an integer that satisfies the oxidation state of metal M, and;
v) said alkyl aluminum co-catalyst is defined by the formula AI (R ⁴ ) _p (OR ⁵ ) q (X) r, in which the R ⁴ groups can be the same or different, the OR ⁵ groups can be the same or different and (p + q + r) = 3, with the proviso that p
Petition 870190105193, of 10/17/2019, p. 66/77
51/60 is greater than 0;
wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent hydrocarbyl groups having from 1 to 10 carbon atoms; optionally R ² can be a hydrogen atom.
[164]
164. Process according to claim 163, CHARACTERIZED by the fact that M in said metallic compound is titanium, zirconium, hafnium, vanadium, chromium or mixtures thereof.
[165]
165. Process according to claim 163, CHARACTERIZED by the fact that a molar ratio of said aluminum alkyl to said magnesium compound in said second and optionally in said third reactor is about 3.0: 1 to about 70: 1; a molar ratio of said chloride compound to said magnesium compound in said second and optionally in said third reactor is from about 1.0: 1 to about 4.0: 1; a molar ratio of said alkyl aluminum co-catalyst to said metal compound in said second and optionally in said third reactor is from about 0: 1 to about 10: 1, and; a molar ratio of said alkyl aluminum to said metallic compound in said second and optionally in said third reactor is from about 0.05: 1 to about 2: 1.
[166]
166. Process according to claim 142, CHARACTERIZED by the fact that said first and said second heterogeneous catalyst formulations are a first and a second batch Ziegler-Natta catalyst formulation; optionally, said first and said second batch Ziegler-Natta catalyst formulations are the same formulation.
[167]
167. Process according to claim 166, CHARACTERIZED by the fact that said first and said second batch Ziegler-Natta catalyst formulations are formed in a batch process comprising:
i) forming said first batch of Ziegler-Natta catalyst formulation by combining a current S5 and chain S4 and injecting said first batch formulation of Ziegler-Natta catalyst into said second reactor, wherein said second reactor
Petition 870190105193, of 10/17/2019, p. 67/77
52/60 stream S4 comprises an alkyl aluminum co-catalyst in said process solvent and stream S5 comprises a first batch Ziegler-Natta pro-catalyst in said process solvent;
ii) optionally forming said second batch formulation of Ziegler-Natta catalyst by combining a stream S6 and said stream S4 and optionally injecting said second formulation of catalyst Ziegler-Natta in batch in said third reactor, wherein said stream S6 comprises a second batch Ziegler-Natta pro-catalyst in said process solvent;
iii) optionally, steps i) and ii) are skipped and said first batch Ziegler-Natta catalyst formulation and said second optional batch Ziegler-Natta catalyst formulation are formed within said reactors; wherein, said current S5 is injected into said second reactor and optionally said current S6 is injected into said third reactor and said current S4 is independently injected into said second reactor and optionally into said third reactor;
iv) optionally said second batch Ziegler-Natta catalyst formulation is formed by combining said chain S5 and said chain S4 and optionally injecting said second batch formulation of Ziegler-Natta catalyst into said third reactor; or said second batch Ziegler-Natta catalyst formulation is formed within said third reactor independently by injecting said current S5 and said current S4 into said third reactor;
wherein, said first and second Ziegler-Natta catalyst formulations and said streams S4, S5 and S6 are independently injected at a temperature of about 20 ° C to about 70 ° C.
[168]
168. Process according to claim 167, CHARACTERIZED by the fact that said aluminum aluminum co-catalyst is defined by the formula AI (R ⁴ ) _p (OR ⁵ ) q (X) r, in which the groups R ⁴ can be the same or different, the OR ⁵ groups can be the same or different and (p + q + r) = 3, with the proviso that p
Petition 870190105193, of 10/17/2019, p. 68/77
53/60 is greater than 0; wherein R ⁴ and R ⁵ represent hydrocarbyl groups having from 1 to 10 carbon atoms.
[169]
169. Process according to claim 167, CHARACTERIZED by the fact that said first and second batch Ziegler-Natta pro-catalysts comprise:
i) a magnesium compound defined by the formula Mg (R ¹ ) 2, in which the R ¹ groups can be the same or different;
ii) a chloride compound defined by the formula R ² CI;
iii) optionally an alkyl aluminum halide defined by the formula (R ⁶ ) _V AIX3 _v ; wherein the R ⁶ groups can be the same or different, X represents chloride or bromide, and v is 1 or 2.
iv) a metallic compound defined by the formulas M (X) _n or MO (X) _n , where M represents titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium or mixtures thereof, O represents oxygen, X represents chloride or bromide and n is an integer that satisfies the oxidation state of metal M, and;
wherein R ¹ , R ² and R ⁶ represent hydrocarbyl groups having from 1 to 10 carbon atoms; optionally R ² can be a hydrogen atom.
[170]
170. Process according to claim 169, CHARACTERIZED by the fact that M in said metallic compound represents titanium, zirconium, hafnium, vanadium, chromium or mixtures thereof.
[171]
171. Process according to claim 169, CHARACTERIZED by the fact that a molar ratio of said chloride compound to said magnesium compound in said batch Ziegler-Natta pro-catalyst is about 2: 1 to about 3: 1; wherein a molar ratio of said magnesium compound to said metal compound in said pro-catalyst is 5: 1 to about 10: 1; in which a molar ratio
Petition 870190105193, of 10/17/2019, p. 69/77
54/60 of said alkyl aluminum halide for said magnesium compound in said pro-catalyst is from about 0: 1 to about 0.5: 1, and; wherein a molar ratio of said aluminum aluminum cocatalyst to said metal compound in said pro-catalyst is from about 0.5: 1 to about 10: 1.
[172]
172. Process according to claim 142, CHARACTERIZED by the fact that said process solvent is one or more C5 to C12 alkanes.
[173]
173. Process according to claim 142, CHARACTERIZED by the fact that said first, second and third reactors operate at a temperature of about 80 ° C to about 300 ° C and a pressure of about 3 MPag at about 45 MPag.
[174]
174. Process according to claim 142, CHARACTERIZED by the fact that said process solvent in said first reactor has an average reactor residence time of about 10 seconds to about 600 seconds and said process solvent in said second reactor has an average reactor dwell time of about 10 seconds to about 720 seconds.
[175]
175. Process according to claim 142, CHARACTERIZED by the fact that a reactor temperature difference (T ^R2 - T ^R1 ) varies from about 1 ° C to about 120 ° C; where T ^R2 is the temperature of the solution in said second reactor and T ^R1 is the temperature of the solution in said first reactor.
[176]
176. Process according to claim 142, CHARACTERIZED by the fact that said one or more optional α-olefins are C3 to C10 α-olefins.
[177]
177. Process according to claim 142, CHARACTERIZED by the fact that said optional α-olefin is 1-hexene or 1-octene or a mixture of 1hexene and 1-octene.
[178]
178. Ethylene interpolymer product, CHARACTERIZED by the fact that it is produced according to the process according to claim 142.
[179]
179. Ethylene interpolymer product, CHARACTERIZED by the fact that it is
Petition 870190105193, of 10/17/2019, p. 70/77
55/60 produced using a continuous solution polymerization process comprising:
(i) from about 5 weight percent to about 60 weight percent of a first ethylene interpolymer having a melt index of about 0.01 g / 10 minutes to about 200 g / 10 minutes and a target density from about 0.855 g / cm ³ to about 0.975 g / cm ³ ;
(ii) from about 20 weight percent to about 95 weight percent of a second ethylene interpolymer having a melt index of about 0.3 g / 10 minutes to about 1000 g / 10 minutes and a density from about 0.89 g / cm ³ to about 0.975 g / cm ³ ;
(iii) optionally from about 0 weight percent to about 30 weight percent of a third ethylene interpolymer having a melt index of about 0.5 g / 10 minutes to about 2000 g / 10 minutes and a density of about 0.89 g / cm ³ to about 0.975 g / cm ³ , and;
(iv) a means to improve by at least 5% a weighted average molecular weight (Mw), where the% Mw improved is defined by the following formula% Mw Improved = 100% x (M _w ^A -Mw ^c ) / M _w ^c > 5% where M _W ^A is a weighted average molecular weight of said first ethylene interpolymer produced using a bridged metallocene catalyst formulation in a first reactor, and; M _w ^c is a weighted average molecular weight of a comparative ethylene interpolymer having said target density produced by replacing said bridged metallocene catalyst formulation in said first reactor with a non-bridged single site catalyst formulation ;
wherein said ethylene interpolymer product is CHARACTERIZED to have a melt index of about 0.3 g / 10 minutes to about 500 g / 10 minutes, a density of about 0.862 g / cm ³ to about 0.975 g / cm ³ , an M _w / M _n of about
Petition 870190105193, of 10/17/2019, p. 71/77
56/60 from 2 to about 25 and a CDBIso of about 20% to about 98%; a long chain branching factor, LCBF, dimensionless greater than or equal to about 0.001; from about 0.0015 ppm to about 2.4 ppm of hafnium and from about 0.1 ppm to about 11.4 ppm of titanium;
where the melt index is measured according to ASTM D1238 (2.16 kg load and 190 ° C), the density is measured according to ASTM D792 and the weight percentage is the weight of said first, said second or said optional third ethylene polymer, individually divided by the weight of said ethylene interpolymer product.
[180]
180. Ethylene interpolymer product according to claim 179, CHARACTERIZED by the fact that said second ethylene interpolymer is produced by a first heterogeneous catalyst formulation, optionally said third ethylene interpolymer is produced by said first formulation of ethylene heterogeneous catalyst or a second heterogeneous catalyst formulation.
[181]
181. Ethylene interpolymer product according to claim 180, CHARACTERIZED by the fact that said first and said second heterogeneous catalyst formulations are a first and a second in-line Ziegler-Natta catalyst formulation; optionally, said first and said second in-line Ziegler-Natta catalyst formulations are the same formulation.
[182]
182. Ethylene interpolymer product according to claim 180, CHARACTERIZED by the fact that said first and said heterogeneous catalyst formulations are a first and a second batch Ziegler-Natta catalyst formulation; optionally, said first and said second batch Ziegler-Natta catalyst formulations are the same formulation.
[183]
183. Ethylene interpolymer product according to claim 180, CHARACTERIZED by the fact that said third ethylene interpolymer is produced using a fifth formulation of homogeneous catalyst.
Petition 870190105193, of 10/17/2019, p. 72/77
57/60
[184]
184. Ethylene interpolymer product according to claim 183, CHARACTERIZED by the fact that said fifth formulation of homogeneous catalyst is said formulation of bridged metallocene catalyst, said formulation of single site catalyst not bound in bridge or a fourth formulation of homogeneous catalyst.
[185]
185. Ethylene interpolymer product according to claim 184, CHARACTERIZED by the fact that said bridged metallocene catalyst formulation comprises a component A defined by Formula (I)

[186]
186. Ethylene interpolymer product according to claim 185, CHARACTERIZED by the fact that said formulation of single-site non-bridged catalyst comprises a component C defined by Formula (II) (L ^A ) aM (PI) b (Q) n (ll) where M is a metal selected from titanium, hafnium and zirconium;
L ^A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; PI is a phosphinimine linker; Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1 -10 hydrocarbyl radical, a C1 -10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or replaced by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, a starch radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals or a phosphide radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals; where a is 1; b is 1; n is 1 or 2; and (a + b + n) is equivalent to the valence of metal M.
[187]
187. Ethylene interpolymer product according to claim 186, CHARACTERIZED by the fact that said fourth homogeneous catalyst formulation comprises a bulky metal-binder complex that is not a member of the chemical genera defined by Formula (I) or Formula (II).
[188]
188. Ethylene interpolymer product according to claim 185, CHARACTERIZED by the fact that said ethylene interpolymer product contains <2.4 ppm of a catalytic metal A, wherein said catalytic metal A originates from said bridged metallocene catalyst formulation.
[189]
189. Ethylene interpolymer product according to claim 188; CHARACTERIZED by the fact that said catalytic metal A is hafnium.
[190]
190. Ethylene interpolymer product according to claim 180,
Petition 870190105193, of 10/17/2019, p. 74/77
59/60
CHARACTERIZED by the fact that said ethylene interpolymer product contains a catalytic metal Z1 and optionally a catalytic metal Z2 and the total amount of said catalytic metal Z1 plus said catalytic metal Z2 is from about 0.1 to about 12 parts per million; wherein said catalytic metal Z1 originates from said first heterogeneous catalyst formulation and said catalytic metal Z2 originates from said second heterogeneous catalyst formulation; optionally said catalytic metal Z1 and said catalytic metal Z2 are the same metal.
[191]
191. Ethylene interpolymer product according to claim 190; CHARACTERIZED by the fact that said catalytic metal Z1 and said catalytic metal Z2, are independently selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or osmium .
[192]
192. Ethylene interpolymer product according to claim 190; CHARACTERIZED by the fact that said catalytic metal Z1 and said catalytic metal Z2, are independently selected from titanium, zirconium, hafnium, vanadium or chromium.
[193]
193. Ethylene interpolymer product according to claim 184, CHARACTERIZED by the fact that said ethylene interpolymer product contains <0.9 ppm of a catalytic metal D; wherein said catalytic metal D originates from said fourth homogeneous catalyst formulation.
[194]
194. Ethylene interpolymer product according to claim 193; CHARACTERIZED by the fact that said catalytic metal D is titanium, zirconium or hafnium.
[195]
195. Ethylene interpolymer product according to claim 179, CHARACTERIZED by the fact that said first ethylene interpolymer has a first M _w / M _n of about 1.7 to about 2.8, said second ethylene interpolymer has a second M _w / M _n of about 2.2 to about 4.4 and said third interpolymer
Petition 870190105193, of 10/17/2019, p. 75/77
60/60 optional ethylene has a third M _w / M _n of about 1.7 to about 5.0.
[196]
196. Ethylene interpolymer product according to claim 195, CHARACTERIZED by the fact that said first M _w / M _n is lower than said second M _w / M _n .
[197]
197. Ethylene interpolymer product according to claim 179, CHARACTERIZED by the fact that said first ethylene interpolymer has a first CDBIso of about 70 to about 98%, said second ethylene interpolymer has a second CDBIso from about 45 to about 98% and said optional third ethylene interpolymer has a third CDBIso of about 35 to about 98%.
[198]
198. Ethylene interpolymer product according to claim 197, CHARACTERIZED by the fact that said first CDBIso is higher than said second CDBIso.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112019021869A2|2020-05-26|MEANS TO INCREASE MOLECULAR WEIGHT AND REDUCE DENSITY OF ETHYLENE INTERPOLYMERS USING HOMOGENEOUS AND HETEROGENEOUS CATALYST FORMULATIONS

---

KR102259584B1|2021-06-03|Means for increasing molecular weight and decreasing density of ethylene interpolymers using mixed homogeneous catalyst formulations

---

US20210221929A1|2021-07-22|Ethylene interpolymer products and films

---

US20200325258A1|2020-10-15|Manufacturing ethlene interpolymer products at higher production rate

---

CA2964565A1|2018-10-19|Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations

---

CA2964598A1|2018-10-19|Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing mixed homogeneous catalyst formulations

---

KR102365847B1|2022-02-23|Preparation of Ethylene Interpolymer Products at High Production Rates

---

KR102365853B1|2022-02-24|Improved Process for Making Ethylene Interpolymer Products

---

JP7030975B2|2022-03-07|Improved process for producing ethylene interpolymer products

---

JP6995199B2|2022-02-04|Production of ethylene interpolymer products at higher production rates

---

JP7030976B2|2022-03-07|Ethylene interpolymer products and films

---

US20200224013A1|2020-07-16|Ethylene interpolymer products and films

同族专利:

---

公开号 | 公开日

---

AR111477A1|2019-07-17|

---

CN111194327A|2020-05-22|

---

JP2020517779A|2020-06-18|

---

CL2019002999A1|2020-02-07|

---

WO2018193375A1|2018-10-25|

---

JP6944539B2|2021-10-06|

---

US20180305531A1|2018-10-25|

---

AU2018254004A1|2019-10-31|

---

US20200325317A1|2020-10-15|

---

PE20191771A1|2019-12-17|

---

US20200056025A1|2020-02-20|

---

KR102259586B1|2021-06-03|

---

US11111368B2|2021-09-07|

---

AU2018254004B2|2021-01-21|

---

US10442920B2|2019-10-15|

---

AU2018254004B9|2021-02-18|

---

US10738183B2|2020-08-11|

---

KR20190137157A|2019-12-10|

---

EP3612575A1|2020-02-26|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

FR2302305B1|1975-02-28|1978-12-29|Charbonnages Ste Chimique|

---

JPS6328102B2|1980-11-12|1988-06-07|Kyowa Kagaku Kogyo Kk|

---

GB8610126D0|1986-04-25|1986-05-29|Du Pont Canada|Isopropanolamines|

---

US4731438A|1986-12-30|1988-03-15|Union Carbide Corporation|Water treatment method for resin in a purge vessel|

---

US5198401A|1987-01-30|1993-03-30|Exxon Chemical Patents Inc.|Ionic metallocene catalyst compositions|

---

US5382630A|1988-09-30|1995-01-17|Exxon Chemical Patents Inc.|Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distribution|

---

US5382631A|1988-09-30|1995-01-17|Exxon Chemical Patents Inc.|Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions|

---

US5387568A|1989-10-30|1995-02-07|Fina Technology, Inc.|Preparation of metallocene catalysts for polymerization of olefins|

---

US5519091A|1990-02-13|1996-05-21|Mitsui Petrochemical Industries, Ltd.|Method for the preparation of ethylene polymer compositions|

---

US5571880A|1991-05-09|1996-11-05|Phillips Petroleum Company|Organometallic fluorenyl compounds and use thereof in an alpha-olefin polymerization process|

---

US5525695A|1991-10-15|1996-06-11|The Dow Chemical Company|Elastic linear interpolymers|

---

US6316549B1|1991-10-15|2001-11-13|The Dow Chemical Company|Ethylene polymer fiber made from ethylene polymer blends|

---

US5674342A|1991-10-15|1997-10-07|The Dow Chemical Company|High drawdown extrusion composition and process|

---

US5278272A|1991-10-15|1994-01-11|The Dow Chemical Company|Elastic substantialy linear olefin polymers|

---

US5677383A|1991-10-15|1997-10-14|The Dow Chemical Company|Fabricated articles made from ethylene polymer blends|

---

US5847053A|1991-10-15|1998-12-08|The Dow Chemical Company|Ethylene polymer film made from ethylene polymer blends|

---

KR100478377B1|1996-11-13|2005-03-23|다우 글로벌 테크놀로지스 인크.|Shrink Film Having Balanced Properties or Improved Toughness and Methods of Making the Same|

---

US5206075A|1991-12-19|1993-04-27|Exxon Chemical Patents Inc.|Sealable polyolefin films containing very low density ethylene copolymers|

---

DE69211569T2|1991-12-30|1997-01-23|Dow Chemical Co|ETHYLENE INTERPOLYMER POLYMERIZATION|

---

US5530065A|1992-01-07|1996-06-25|Exxon Chemical Patents Inc.|Heat sealable films and articles made therefrom|

---

AT148905T|1992-09-16|1997-02-15|Exxon Chemical Patents Inc|SOFT FILMS WITH IMPROVED PHYSICAL PROPERTIES|

---

US6448341B1|1993-01-29|2002-09-10|The Dow Chemical Company|Ethylene interpolymer blend compositions|

---

BR9405715A|1993-01-29|1995-11-28|Dow Chemical Co|Process for preparing an ethylene / a-olefin interpolymer composition and ethylene / a-olefin interpolymer composition|

---

US6313240B1|1993-02-22|2001-11-06|Tosoh Corporation|Process for producing ethylene/α-olefin copolymer|

---

CN1085227C|1993-04-28|2002-05-22|陶氏化学公司|Fabricated articles made from ethylene polymer blends|

---

US5408004A|1993-08-17|1995-04-18|The Dow Chemical Company|Polyolefin blends and their solid state processing|

---

US5773106A|1994-10-21|1998-06-30|The Dow Chemical Company|Polyolefin compositions exhibiting heat resistivity, low hexane-extractives and controlled modulus|

---

US7153909B2|1994-11-17|2006-12-26|Dow Global Technologies Inc.|High density ethylene homopolymers and blend compositions|

---

US5767208A|1995-10-20|1998-06-16|Exxon Chemical Patents Inc.|High temperature olefin polymerization process|

---

EP0889912B1|1996-03-27|2000-07-12|The Dow Chemical Company|Highly soluble olefin polymerization catalyst activator|

---

JPH09309926A|1996-05-17|1997-12-02|Dow Chem Co:The|Production of ethylene copolymer|

---

US6812289B2|1996-12-12|2004-11-02|Dow Global Technologies Inc.|Cast stretch film of interpolymer compositions|

---

US6486284B1|1997-08-15|2002-11-26|Dow Global Technologies Inc.|Films produced from substantially linear homogeneous olefin polymer compositions|

---

US6416833B1|1997-08-22|2002-07-09|Dupont Canada Inc.|Interpolymer film pouch|

---

US6441116B1|1997-09-03|2002-08-27|Idemitsu Kosan Co., Ltd.|Ethylenic copolymer, composition containing said copolymer, and ethylenic copolymer film|

---

JP2003517487A|1997-09-19|2003-05-27|ザダウケミカルカンパニー|Ethylene interpolymer compositions exhibiting narrow MWD with optimized composition, methods of making the same, and articles made therefrom|

---

EP0905151A1|1997-09-27|1999-03-31|Fina Research S.A.|Production of polyethylene having a broad molecular weight distribution|

---

US6242545B1|1997-12-08|2001-06-05|Univation Technologies|Polymerization catalyst systems comprising substituted hafinocenes|

---

GB9800245D0|1998-01-07|1998-03-04|Bp Chem Int Ltd|Novel polymers|

---

CA2227674C|1998-01-21|2007-04-24|Stephen John Brown|Catalyst deactivation|

---

DE69907785T2|1998-03-09|2004-02-12|Basell Poliolefine Italia S.P.A.|Multi-stage process for olefin polymerization|

---

AU2738599A|1998-03-12|1999-09-27|Bp Chemicals Limited|Polymerisation catalysts|

---

GB9806407D0|1998-03-25|1998-05-20|Bp Chem Int Ltd|Novel polymer compositions|

---

DE19833858C2|1998-07-28|2000-06-08|Elenac Gmbh|Low-odor polyethylene blends|

---

CA2247703C|1998-09-22|2007-04-17|Nova Chemicals Ltd.|Dual reactor ethylene polymerization process|

---

EP0989140A1|1998-09-25|2000-03-29|Fina Research S.A.|Production of multimodal polyethylene|

---

CN1136264C|1998-10-23|2004-01-28|三井化学株式会社|Ethylene copolymer and process for producing the same, resin composition containing the copolymer, and uses of these|

---

US6300433B1|1998-10-23|2001-10-09|Exxonmobil Chemical Patents Inc.|Olefin copolymerization process with bridged hafnocenes|

---

US6486088B1|1998-10-23|2002-11-26|Exxonmobil Chemical Patents Inc.|High activity carbenium-activated polymerization catalysts|

---

EP1175423A4|1999-03-10|2002-10-25|Univ Colorado State Res Found|Weakly coordinating anions containing polyfluoroalkoxide ligands|

---

EP1041113A1|1999-03-30|2000-10-04|Fina Research S.A.|Polyolefins and uses thereof|

---

AT420902T|1999-05-05|2009-01-15|Ineos Europe Ltd|ETHYLENE COPOLYMERS AND FILMS MANUFACTURED THEREOF|

---

TW495527B|1999-07-30|2002-07-21|Sumitomo Chemical Co|Ethylene polymer and resin composition for producing cast film, and process for producing cast film|

---

CA2379607A1|1999-09-29|2001-04-05|E.I. Du Pont De Nemours And Company|Manufacture of polyethylenes|

---

CN101434668B|1999-10-08|2012-02-22|三井化学株式会社|Polyolefins|

---

US6723398B1|1999-11-01|2004-04-20|Dow Global Technologies Inc.|Polymer blend and fabricated article made from diverse ethylene interpolymers|

---

US6388017B1|2000-05-24|2002-05-14|Phillips Petroleum Company|Process for producing a polymer composition|

---

US7125933B2|2000-06-22|2006-10-24|Univation Technologies, Llc|Very low density polyethylene blends|

---

US6403717B1|2000-07-12|2002-06-11|Univation Technologies, Llc|Ethylene inter-polymer blends|

---

MY137183A|2001-03-16|2009-01-30|Dow Global Technologies Inc|Method of making interpolymers and products made therefrom|

---

CA2343662C|2001-04-11|2010-01-05|Nova Chemicals Corporation|Plastic films|

---

ES2232767T3|2001-08-31|2005-06-01|Dow Global Technologies Inc.|MULTIMODAL POLYETHYLENE MATERIAL.|

---

EP1304353A1|2001-10-18|2003-04-23|Atofina Research S.A.|Physical blends of polyethylenes|

---

WO2003048213A1|2001-11-30|2003-06-12|Exxonmobil Chemical Patents, Inc.|Ethylene/alpha-olefin copolymer made with a non-single-site/single-site catalyst combination, its preparation and use|

---

EP1319685A1|2001-12-14|2003-06-18|ATOFINA Research|Physical blends of polyethylenes|

---

DK1546254T3|2002-09-23|2008-04-14|Dow Global Technologies Inc|Polymer Compositions for Extrusion Coating|

---

US7396881B2|2002-10-01|2008-07-08|Exxonmobil Chemical Patents Inc.|Polyethylene compositions for rotational molding|

---

JP2006501351A|2002-10-01|2006-01-12|エクソンモービル・ケミカル・パテンツ・インク|Polyethylene composition for rotational molding|

---

EP1636311B1|2003-06-10|2016-10-12|Dow Global Technologies LLC|Film layers made from ethylene polymer blends|

---

US6870010B1|2003-12-01|2005-03-22|Univation Technologies, Llc|Low haze high strength polyethylene compositions|

---

US7041617B2|2004-01-09|2006-05-09|Chevron Phillips Chemical Company, L.P.|Catalyst compositions and polyolefins for extrusion coating applications|

---

CN103172961B|2005-03-17|2016-08-17|陶氏环球技术有限责任公司|Utilize impact-resistant modified to thermoplastic of ethylene/alpha-olefin interpolymer|

---

US7514504B2|2004-04-01|2009-04-07|Fina Technology, Inc.|Polyethylene blends with good contact transparency|

---

US7193017B2|2004-08-13|2007-03-20|Univation Technologies, Llc|High strength biomodal polyethylene compositions|

---

EP1650236A1|2004-10-21|2006-04-26|Total Petrochemicals Research Feluy|Activating agents for hafnium based metallocene components|

---

JP2006124567A|2004-10-29|2006-05-18|Tosoh Corp|Polyethylene resin composition and film composed of the same|

---

US7439306B2|2004-11-23|2008-10-21|Exxonmobil Chemical Patents Inc.|Polyethylene blends with improved Vicat softening point|

---

CN101155841B|2005-02-09|2011-06-08|英尼奥斯欧洲有限公司|Copolymers and films thereof|

---

US7858702B2|2005-06-14|2010-12-28|Univation Technologies, Llc|Enhanced ESCR bimodal HDPE for blow molding applications|

---

US7868092B2|2005-06-14|2011-01-11|Univation Technologies, Llc|Bimodal polyethylene compositions for blow molding applications|

---

JP5055805B2|2005-09-30|2012-10-24|住友化学株式会社|Ethylene-α-olefin copolymer, resin composition and film|

---

WO2007060115A1|2005-11-28|2007-05-31|Basell Polyolefine Gmbh|Polyethylene composition suitable for the preparation of films and process for preparing the same|

---

JP2009001780A|2007-05-18|2009-01-08|Sumitomo Chemical Co Ltd|Ethylene polymer composition and film|

---

US8475898B2|2007-08-29|2013-07-02|Equistar Chemicals, Lp|Polyolefin resin blends for crack-resistant pipe|

---

KR101141494B1|2007-09-05|2012-05-03|에스케이이노베이션 주식회사|Ethylene copolymer having multiple pitch in molecular weight distribution and the method of preparing the same|

---

CN103254497B|2007-12-20|2015-11-18|埃克森美孚研究工程公司|Produce the online blend method of the blend of polypropylene and ethylene-propylene copolymer|

---

WO2009114661A1|2008-03-13|2009-09-17|Dow Global Technologies Inc.|Long chain branched , block or interconnected copolymers of ethylene in combination with one other polymer|

---

US8410217B2|2008-12-15|2013-04-02|Exxonmobil Chemical Patents Inc.|Thermoplastic polyolefin blends|

---

US8101685B2|2008-12-15|2012-01-24|Exxonmobil Chemical Patents Inc.|Thermoplastic elastomer polyolefin in-reactor blends and molded articles therefrom|

---

US8114946B2|2008-12-18|2012-02-14|Chevron Phillips Chemical Company Lp|Process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches|

---

JP5443904B2|2009-09-03|2014-03-19|東ソー株式会社|Ethylene resin injection foam molding|

---

WO2011073368A1|2009-12-18|2011-06-23|Total Petrochemicals Research Feluy|Method for replacing compatible ethylene polymerization catalysts|

---

EP2513156B1|2009-12-18|2014-03-19|Total Research & Technology Feluy|Method for replacing incompatible ethylene polymerization catalysts|

---

ES2621408T3|2010-04-13|2017-07-04|Univation Technologies, Llc|Mixtures of polymers and films made from them|

---

US20120028865A1|2010-07-28|2012-02-02|Sudhin Datta|Viscosity Modifiers Comprising Blends of Ethylene-Based Copolymers|

---

US8933175B2|2011-08-30|2015-01-13|Chevron Phillips Chemical Company Lp|Hyperbranched polymers and methods of making and using same|

---

US9068033B2|2012-12-21|2015-06-30|Exxonmobil Chemical Patents Inc.|Branched polyethylene with improved processing and high tear films made therefrom|

---

JP6393693B2|2012-12-27|2018-09-19|ダウ グローバル テクノロジーズ エルエルシー|Catalytic system for olefin polymerization.|

---

SG11201507471PA|2013-03-12|2015-10-29|Mitsui Chemicals Inc|Production method of olefin polymer and olefin polymerization catalyst|

---

JP6343886B2|2013-08-08|2018-06-20|東ソー株式会社|Polyethylene medical container|

---

US9181370B2|2013-11-06|2015-11-10|Chevron Phillips Chemical Company Lp|Low density polyolefin resins with low molecular weight and high molecular weight components, and films made therefrom|

---

CA2868640C|2014-10-21|2021-10-26|Nova Chemicals Corporation|Solution polymerization process|

---

EP3209722A2|2014-10-21|2017-08-30|Nova Chemicals S.A.|Ethylene interpolymer product with dilution index|

---

US9540457B1|2015-09-24|2017-01-10|Chevron Phillips Chemical Company Lp|Ziegler-natta—metallocene dual catalyst systems with activator-supports|

---

US10442920B2|2017-04-19|2019-10-15|Nova Chemicals S.A.|Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations|US10442920B2|2017-04-19|2019-10-15|Nova ChemicalsS.A.|Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations|

---

US10442921B2|2017-04-19|2019-10-15|Nova ChemicalsS.A.|Means for increasing the molecular weight and decreasing the density employing mixed homogeneous catalyst formulations|

---

US20190135960A1|2017-11-07|2019-05-09|Nova ChemicalsS.A.|Process to manufacture ethylene interpolymer products|

---

US10683376B2|2017-11-07|2020-06-16|Nova ChemicalsS.A.|Manufacturing ethylene interpolymer products at higher production rate|

---

US10995166B2|2017-11-07|2021-05-04|Nova ChemicalsS.A.|Ethylene interpolymer products and films|

---

CA3119155A1|2018-12-18|2020-06-25|Nova Chemicals Corporation|Multilayer films|

---

CN112739732A|2018-12-21|2021-04-30|Lg化学株式会社|Polyolefins|

---

WO2020178010A1|2019-03-04|2020-09-10|Borealis Ag|Polymerization process|

---

WO2021009191A1|2019-07-17|2021-01-21|Borealis Ag|Process for producing a polymer composition|

---

US11046843B2|2019-07-29|2021-06-29|Nova ChemicalsS.A.|Ethylene copolymers and films with excellent sealing properties|

---

WO2021064545A1|2019-10-01|2021-04-08|Nova ChemicalsS.A.|Control of unsaturation in polymers produced in solution process|

---

WO2021064546A1|2019-10-01|2021-04-08|Nova ChemicalsS.A.|High productivity polymerization with aryloxy ether ligand catalyst|

---

WO2021126443A2|2019-12-17|2021-06-24|Exxonmobil Chemical Patents Inc.|Solution polymerization process for making high-density polyethylene long-chain branching|

---

WO2022013711A1|2020-07-14|2022-01-20|Nova ChemicalsS.A.|Solution phase polymerization process|

法律状态:
2021-10-19| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

---

申请号 | 申请日 | 专利标题

---

US15/491,264|2017-04-19|

---

US15/491,264|US10442920B2|2017-04-19|2017-04-19|Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations|

---

PCT/IB2018/052659|WO2018193375A1|2017-04-19|2018-04-17|Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations|

---