ETHYLENE COPOLYMER, OLEPHINE POLYMERIZATION PROCESS TO PRODUCE AN ETHYLENE COPOLYMER AND FILM LAYER

专利摘要:
ethylene copolymer compositions, film and polymerization processes. ethylene copolymers having a relatively high melt flow ratio and a multimodal profile in an increasing temperature elution fractionation (tref) graph are described. copolymers can be made into film having good dart impact values and good rigidity properties under reduced extrusion pressures.
公开号:BR112015014121B1
申请号:R112015014121-8
申请日:2013-12-04
公开日:2021-04-06
发明作者:Victoria Ker；Patrick Lam；Yan Jiang；Peter Phung Minh Hoang；Charles Ashton Garret Carter；Darryl J. Morrison
申请人:Nova Chemicals (International) S.A.；
IPC主号:

专利说明:

[0001] [001] The present invention is directed to the preparation of polyethylene copolymers, the films made from them, as well as a polyethylene polymerization process. A phosphinimine type catalyst is used to make ethylene copolymers having a relatively high melt flow ratio (I21 / I2) and a multimodal TREF profile. Ethylene copolymers have a CDBI50 composition distribution width index of between 45% by weight and 75% by weight and can be made of film with good physical properties while exhibiting improved processability. PREVIOUS TECHNIQUE
[0002] [002] The demand for polyethylene products having an improved balance of physical properties and processability has led to the development of products having improved production capacity and has always improved properties for end use, such as enhanced film wear or impact properties with dart. Particularly useful is the development of polymer architectures for which polymer mixing strategies can be avoided by increasing polymer properties, as these strategies increase the cost.
[0003] [003] US Patent Application Publication No. 2011/0003099 describes the low linear melt flow ratio (MFR) polyethylene and the high linear melt flow ratio (MFR) polyethylene, which are distinguished by an I21 / I2 less than 30 and an I21 / I2 greater than 30, respectively.
[0004] [004] Resins having both a narrow molecular weight distribution and a low melt flow ratio are well known and include resins produced with metallocene catalysts and phosphinimine catalysts. Such resins include, for example, Exceed 1018CATM from ExxonMobil and those described in U.S. Patent No. 5,420,220 and Canadian Patent Application No. 2,734,167. These resins can be made into films having a good balance of physical and optical properties, but can be difficult to process in the absence of processing aids, as indicated, for example, by a relatively low production capacity in a film line. blown.
[0005] [005] Resins having a higher melt flow ratio are more attractive to film producers because they are generally easier to process. US Patents No. 6,255,426 and No. 6,476,171 and US Patent Application Publication No. 2011/0003099 each describe the production and use of resins having melt flow ratios that are in excess of 30, and that they have a moderately wide molecular weight distribution. The resins are thought to contain long chain branching. The polymers described in U.S. Patents No. 6,255,426 and No. 6,476,171 are made with a bridged bis-indenyl zirconocene catalyst and have a composition distribution width index (CDBI) greater than 75%. Resins have been referred to as EnableTM polymers (ExxonMobil) in the patent literature (see, for example, the Example Polymers described in US Patent Application Publication No. 2011/0003099), and although resins are relatively easy to process, they also have a good balance of strength and stiffness properties when blown on the film. For example, films have physical properties that were comparable to Exceed 1018CA materials despite their better shear thinning behavior. The polymers described in US Patent Application Publication No. 2011/0003099, include a new "Enable" type resin having a low melt index (I2 = 0.3), a relatively high melt flow ratio (I21 / I2 is 46-58) and a moderately wide molecular weight distribution (for example, Mw / Mn is 3.4). Polymers also have a single peak in a TREF profile, with a T (75) -T (25) less than 4 ° C.
[0006] [006] The manipulation of the co-monomer distribution profile has also provided new ethylene copolymer architectures, in an effort to improve the balance between the physical properties and the processability of the polymer.
[0007] [007] It is generally the case that metallocene catalysts and other so-called "single site catalysts" typically incorporate comonomer more uniformly than traditional Ziegler-Natta catalysts when used for the copolymerization of catalytic ethylene with alpha This fact is often demonstrated by measuring the composition distribution width index (CDBI) for the corresponding ethylene copolymers. The definition of the composition distribution width index (CDBI50) can be found in the publication PCT WO 93/03093 and US Patent No. 5,206,075 CDBI50 is conveniently determined using techniques that isolate the polymer fractions based on their solubility (and therefore their co-monomer content). increasing temperature elution (TREF), as described by Wild et al. J. Poly. Sci., Poly. Phys. Ed. Vol. 20, 1982, p441 can be used. Under the composition distribution curve, the CDBI50 is determined by establishing the percentage by weight of a sample of copolymer that has a comonomer content within 50% of the average co-monomer content on each median side. Generally, Ziegler-Natta catalysts produce ethylene copolymers with a lower CDBI50 than a single site catalyst, at a similar density consistent with a heterogeneously branched copolymer. Typically, a plurality of prominent peaks are observed by such polymers in a TREF (increasing temperature elution fractionation) analysis. Such peaks are consistent with the presence of heterogeneously branched material that generally includes a highly branched fraction, an average branched fraction and a higher density fraction having little or no short chain branching. In contrast, metallocenes and other single-site catalysts will more often produce ethylene copolymers having a CDBI50 greater than that of a Ziegler-Natta catalyst with a similar density and which often contain a single prominent peak in an analysis TREF, consistent with a homogeneous branched copolymer.
[0008] [008] Despite the above, the methods were developed to access polyethylene copolymer compositions having an extended comonomer distribution (that is, more like Ziegler-Natta), while otherwise maintaining the typical characteristics of the metallocene product and single-site catalyst resin, such as high impact resistance with blown film dart. Such resins can be transformed, for example, using a mixture of metallocene catalysts in a single reactor, using a plurality of polymerization reactors under different polymerization conditions, or by mixing metallocene producing ethylene copolymers.
[0009] [009] U.S. Patent Numbers 5,382,630, 5,382,631 and WO 93/03093 describe polyethylene copolymer blend compositions having wide or narrow molecular weight distributions, and wide or narrow co-monomer distributions. For example, a mixture can have a narrow molecular weight distribution, while simultaneously having a bimodal composition distribution. Alternatively, a mixture can have a wide molecular weight distribution, while simultaneously having a unimodal composition distribution. The mixtures are made by fusing mixture of two polyethylene resins with similar or different molecular weights and contents of similar or different co-monomers, in which each resin is formed using a metallocene catalyst in a gas phase reactor.
[0010] [010] U.S. Patent No. 7,018,710 describes mixtures comprising a high molecular weight component having a high co-monomer content and a low molecular weight component having a low co-monomer content. The mixture of ethylene copolymer, which results from the use of a metallocene catalyst in a cascade double reactor process, where each reactor is operated under different conditions (for example, a gas phase-slurry phase reactor in cascade), shows two distinct maximums in a TREF fractogram. The polymers were applied as a sealing layer on a thermo-adhesive film.
[0011] [011] A mixed catalyst system containing a "poor comonomer incorporator" and a "good comonomer incorporator" is described in U.S. Patent No. 6,828,394 and No. 7,141,632. The poor co-monomer incorporating the catalyst may be a metallocene having at least one fused ring cyclopentadienyl ligand, such as an indenyl ligand, with the appropriate substitution (for example, 1-postion alkyl substitution). The good catalyst incorporating the co-monomer was selected from a well-known metallocene matrix that was generally less sterically overloaded to the front end of the molecule than the poor co-monomer incorporator. These mixed catalyst systems produced polyethylene copolymers having a bimodal TREF distribution in which two elution peaks are well separated from each other, consistent with the presence of high and low density components. The mixed catalysts also produced ethylene copolymer having an expanded molecular weight distribution compared to the ethylene copolymer made with any of the only metallocene component catalysts.
[0012] [012] A mixed catalyst system comprising three different metallocene catalysts is described in U.S. Patent No. 6,384,158. Ethylene copolymers with extended molecular weight distributions were obtained when using these catalyst systems to polymerize ethylene with an alpha-olefin, such as 1-hexene.
[0013] [013] U.S. Patent Publication No. 2011/0212315 describes a linear ethylene copolymer having a bimodal or multimodal co-monomer distribution profile, as measured using DSC, TREF or CRYSTAF techniques. Copolymers maintain a high impact resistance with dart when blown on film and are relatively easy to process, as indicated by a reduced pseudoplasticity index, compared to ethylene copolymers having a unimodal co-monomer distribution profile. The exemplified ethylene copolymer compositions, which have a melt flow ratio less than 30, are made in a single gas phase reactor, using a mixed catalyst system comprising a metallocene catalyst and a metal catalyst. late transition.
[0014] [014] US Patent No. 7,534,847 demonstrates that the use of a chromium-based transition metal catalyst provides an ethylene copolymer having a bimodal co-monomer distribution (as indicated by CRYSTAF) with a CDBI less than 50% by weight (see Table 1 of US Patent No. 7,534,847). The patent teaches that copolymers can have a molecular weight distribution of about 1 to 8, significant amounts of unsaturation of the vinyl group, long chain branching and specific amounts of methyl groups as measured by CRYSTAF fractionation.
[0015] [015] U.S. Patent No. 6,932,592 describes very low density (i.e., <0.916 g / cc) ethylene copolymers produced with a bulky non-bridged bis-Cp metallocene catalyst. A preferred metallocene is bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride. The examples show that, in the gas phase, supported versions of this catalyst produce copolymer from ethylene and 1-hexene, which has a CDBI between 60 and 70% and a bimodal co-monomer distribution as measured by increasing temperature elution fractionation (TREF).
[0016] [016] U.S. Patent No. 6,420,507 describes a low density ethylene copolymer having a narrow molecular weight distribution (i.e., 1.5 to 3.0) and a bimodal TREF profile. The polymerization is carried out in a gas phase using a so-called "forced geometry" catalyst having an indenyl ligand.
[0017] [017] US Patents Numbers 6,248,845, 6,528,597, 7,381,783 and US Patent Application Publication No. 2008/0108768 disclose that a bulky ligand metallocene based on hafnium and a small amount of zirconium can be used. used to provide an ethylene / 1-hexene copolymer, which has a bimodal TREF profile. It is taught that the precursor compounds of hafnium chloride used to synthesize bulky metallocene catalysts are either contaminated with a small amount of zirconium chloride or zirconium chloride that can be added deliberately. The amounts of zirconium chloride present in the range of 0.1 mol% to 5 mol%. Thus, the final hafnocene catalysts contain small amounts (ie 0.1 to 5 mol%) of their zirconocene analogues. Since zirconium based catalysts may have a higher activity than their hafnium analogues, it is possible that the manufactured products have a significant contribution from the zirconocene species. If this is the case, then the result of the bimodal TREF profile may not be surprising. The patent provides data for mold and blown film applications that show that compared to Exceeded resins, polymers are more easily extruded, with lower engine load, higher throughput and reduced head pressure. The resins provide mold film with high wear values and blown film with high dart impact values.
[0018] [018] US Patents Numbers 6,956,088, 6,936,675, 7,179,876 and 7,172,816 describe that the use of a "substantially unique" bulky ligand hafnium catalyst provides an ethylene copolymer composition having a lower CDBI than 55%, especially below 45%, as determined by CRYSTAF. Call, that hafnocene catalysts derived from hafnium chloride are expected to have zirconocene contaminants present in small amounts. No. 7,179,876 still teach that the CDBI could be changed, under different temperature conditions when using hafnocene catalysts.The polymerization at lower temperatures provides ethylene copolymer having a broader composition distribution index (CDBI) with respect to polymers obtained at higher temperatures. For example, the use of hafnium bis (n-propylcyclopentadienyl) catalysts or bis (n-propylcyclopen difluoride) tadienyl) of hafnium in a gas phase reactor for the copolymerization of ethylene and 1-hexene at ≤ 80 ° C, provided copolymers having a CDBI between 20 and 35%, compared to the CDBI values between 40 and 50% for the copolymers obtained at 85 ° C. The polymers described can, for certain reasons, provide films having a wear value in the machine direction greater than 500 g / mil, an impact resistance with dart greater than 500 g / mil, as well as good rigidity. Polymers also have good processing capacity.
[0019] [019] U.S. Patent No. 5,281,679 describes bis-cyclopentadienyl metallocene catalysts that have secondary or tertiary carbon substituents on a cilcopentadienyl ring. The catalysts provide polyethylene materials with an increased molecular weight during gas phase polymerization.
[0020] [020] Bulky cyclic bridged metallocene catalysts are described in U.S. Patents No. 6,339,134 and No. 6,388,115, which provide ethylene polymers for easier processing.
[0021] [021] A hafnocene catalyst is used in U.S. Patent No. 7,875,690 to provide an ethylene copolymer in a gas phase fluidized bed reactor. The copolymer has a so-called "wide distribution of the orthogonal composition", which gives improved physical properties and low extractables. A wide distribution of the orthogonal composition is one, in which the co-monomer is incorporated predominantly in the high molecular weight chains. copolymers have a density of at least 0.927 g / cc Polyethylene copolymers having a similarly wide orthogonal composition but a lower density are described in US Patent No. 8,084,560 and US Patent Application Publication No. 2011 / 0040041A1 Again, a hafnocene catalyst is employed in a gas phase reactor to supply the ethylene copolymer.
[0022] [022] U.S. Patent No. 5,525,689 also describes the use of a hafnium-based metallocene catalyst for use in olefin polymerization. The polymers have a ratio of about I10 / I2 from 8 to 50, a density of about 0.85 to 0.92 g / cc, an Mw / Mn of up to 4.0, and were made in the gas phase.
[0023] [023] US Patent No. 8,114,946 describes ethylene copolymers that have a molecular weight distribution (Mw / Mn) that ranges from about 3.36 to 4.29, a reverse co-monomer incorporation and that contains low levels of long chain branching. The melt flow ratios of the described polymers are generally below about 30. A cyclopentadienyl / fluorenyl bridged metallocene catalyst having an unsaturated pendant group is used to make the ethylene copolymers. The patent application does not mention films or film properties.
[0024] [024] U.S. Patent No. 6,469,103 describes ethylene copolymer compositions that comprise a first and a second ethylene copolymer component. The individual components are defined using the ATREF-DV analytical methods that show a bimodal or multimodal structure in relation to the placement of co-monomer. The compositions have an I10 / I2 value greater than 6.6 and a relatively narrow molecular weight distribution (i.e., Mw / Mn is less than or equal to 3.3) consistent with the presence of long chain branching. The polymers are made using a dual solution reactor system with mixed catalysts.
[0025] [025] A process for the manufacture of ethylene polymer compositions that involves the use of at least two polymerization reactors is described in U.S. Patent No. 6,319,989. Ethylene copolymers have a molecular weight distribution greater than 4.0 and show two peaks when subjected to a fractionation of crystallization analyzes (CRYSTAF).
[0026] [026] US Patent No. 6,462,161 describes the use of any constrained geometry type catalyst or a bridged bis-CP metallocene catalyst to produce, in a single reactor, a polyolefin composition having long chain branching and a maximum molecular weight occurring in the part of the composition having the highest co-monomer content (i.e., a reverse comonomer distribution). Compositions made with a constrained geometry catalyst have multimodal TREF profiles, and relatively narrow molecular weight distributions (for example, the resins exemplified have an Mw / Mn of about 2.19 to 3.4, see Table 1 in the section examples of US Patent No. 6,462,161). Compositions made with a bridged bis-Cp metallocene catalyst have complex TREF profiles and some broader molecular weight distribution (for example, the example reins have an Mw / Mn of 3.43 or 6.0, see Table 1 in the Examples section of US Patent No. 6,462,161).
[0027] [027] Ethylene copolymers are taught in US Patent No. 7,968,659, which have a melt index of about 1.0 to 2.5, an Mw / Mn of about 3.5 to 4.5 , an elastic fusion module G '(G "= 500 Pa) of about 40 to 150 Pa and a flow activation energy (Ea) in the range of 28 to 45 kJ / mol. Constrained geometry catalysts are used to make the polymer compositions in the gas phase.
[0028] [028] US Patent No. 7,521,518 describes the use of a constrained geometry catalyst to provide an ethylene copolymer composition having a reverse co-monomer distribution, as determined by various cross-fractionation chromatography (CFC) parameters ) and a molecular weight distribution of about 2 to 10.
[0029] [029] US Patent No. 5,874,513 describes that the use of a mixture of components that gives rise to a supported metallocene catalyst can, in a gas phase reactor, provide an ethylene copolymer with homogeneous co-distribution. reduced monomer. The patent defines a parameter of the distribution of composition Cb which is representative of the distribution of comonomers within the polymeric composition. TREF analyzes of the copolymer composition showed a bimodal distribution.
[0030] [030] US Patent No. 6,441,116 describes a film comprising an ethylene copolymer with a composition distribution curve obtained by TREF that has four distinct areas, including an area that defines the peak that is assigned to a highly component branched.
[0031] [031] An alpha olefin / ethylene copolymer produced with a Ziegler-Natta catalyst and having more than about 17 weight percent of a high density fraction, as determined by analytical TREF methods, and a distribution of molecular weight (Mw / Mn) less than about 3.6 is described in US Patent No. 5,487,938. The high-density fraction has little short-chain branching, while the balance of the copolymer composition is referred to as the fraction containing short-chain branching. Thus, the data are consistent with a bimodal distribution of incorporation of co-monomer in the ethylene copolymer.
[0032] [032] U.S. Patent No. 6,642,340 describes an ethylene copolymer having a specific relationship between a melt flow rate and melt stress. The polymers further comprise between 0.5 and 8% by weight of a component eluting at not less than 100 ° C in a TREF analysis.
[0033] [033] The use of phosphinfinine catalysts for polymerization of gas phase olefin is the subject of U.S. Patent No. 5,965,677. The phosphinimine catalyst is an organometallic compound having a phosphinimine ligand, a cyclopentadienyl type ligand and two activable ligands, and which is supported on a suitable particle support, such as silica. The exemplified catalysts have the formula CpTi (N = P (tBu) 3) X2, where X was Cl, Me, Cl or -O- (2,6-iPr-C6H3), and Cp is cyclopentadienyl.
[0034] [034] In co-pending CA Patent Application No. 2,734,167, it showed that suitably substituted phosphinimine catalysts provided narrow molecular weight distribution copolymers which, when turned into film, showed a good balance of optical and physical properties.
[0035] [035] Polymers and films produced in the gas phase using various single-site catalysts, including so-called "phosphinimine" catalysts, have been described in Advances in Polyolefins II, Napa, California - October 24-27, 1999 ("Development of NOVA's Single Site Catalyst Technology for Use in the Gas Phase Process "- I. Coulter; D. Jeremic; A. Kazakov; I. McKay).
[0036] [036] In a description made at the Canadian Society 2002 for Chemical Conference ("Cyclopentadienyl Phosphinimine Titanium Catalysts -Structure, Activity and Product Relationships in Heterogeneous Olefin Polymerization." RP Spence; I. McKay; C. Carter; L. Koch; D. Jeremic; J. Muir ;. A. Kazakov, NOVA Research and Technology Center, CIC, 2002), it was demonstrated that the indenyl and cyclopentadienyl ligands varied substituted with phosphinimine catalyst bearing were active for the polymerization in ethylene gas phase when in supported form.
[0037] [037] U.S. Patent Application Publication No. 2008/0045406 describes a supported phosphinimine catalyst that comprises a C6F5-substituted indenyl ligand. The catalyst was activated with an ionic activator having an active proton for use in the polymerization of ethylene with 1-hexene.
[0038] [038] U.S. Patent Application Publication No. 2006/0122054 describes the use of a dual catalyst formulation, a component of which is a phosphinimine catalyst having an indenyl ligand substituted by n-butyl. The patent is directed to the formation of bimodal resins suitable for application in tubes. DESCRIPTION OF THE INVENTION
[0039] [039] It has been reported that a polymerization catalyst system comprising a single phosphinimine catalyst can provide an ethylene copolymer having a multimodal co-monomer distribution profile and average molecular weight distribution when used in a single reactor. The invention reduces the need for polymer mixtures, mixed catalysts, or mixed reactor technologies in the formation of polyethylene resin, which is easy to process and has a good balance of physical properties.
[0040] [040] An ethylene copolymer comprising ethylene and an alpha-olefin having 3-8 carbon atoms is provided, the copolymer having a density of about 0.916 g / cc to 0.936 g / cc, a melting index (I2 ) of about 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about from 3.6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 45% by weight at 75 % by weight, as determined by TREF, and which satisfies the following ratio: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)].
[0041] [041] An ethylene copolymer comprising ethylene and an alpha-olefin having 3-8 carbon atoms is provided, the copolymer having a density of about 0.916 g / cc to 0.936 g / cc, a melting index (I2 ) of about 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about from 3.6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 45% by weight at 75 % by weight, as determined by TREF, and which satisfies the following ratios: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]; and δ × O ≤ 83.0 - 1.25 (CDBl50) / (Mw / Mn).
[0042] [042] An ethylene copolymer comprising ethylene and an alpha-olefin having 3-8 carbon atoms is provided, the copolymer having a density of about 0.916 g / cc to 0.936 g / cc, a melting index (I2 ) of about 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about from 3.6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 45% by weight at 75 % by weight, as determined by TREF, and which satisfies the following ratios: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]; and δ × O ≤ 80.7 - (CDBl50) / (Mw / Mn) at a δXO of about 550 to 700.
[0043] [043] An ethylene copolymer comprising ethylene and an alpha-olefin having 3-8 carbon atoms is provided, the copolymer having a density of about 0.916 g / cc to 0.936 g / cc, a melting index (I2 ) of about 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about from 3.6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 45% by weight at 75 % by weight, as determined by TREF, and which satisfies the following ratios: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]; and δ × O ≤ 80.7 - (CDBl50) / (Mw / Mn) at a δ × O of about 550 to 700; and δ × O ≤ 83.0 - 1.25 (CDBl50) / (Mw / Mn).
[0044] [044] An olefin polymerization process is provided to produce an ethylene copolymer, the process comprising contacting ethylene and at least one alpha-olefin having about 3-8 carbon atoms with a catalyst system polymerization in a single gas phase reactor; the ethylene copolymer having a density of about 0.916 g / cc to 0.936 g / cc, a melt index (I2) of about 0.1 g / 10 min at 2.0 g / 10 min, a flow rate melting range (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about 3.6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR , a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 45% by weight to 75% by weight, as determined by TREF and which satisfies the following relationship: (Mw / Mn) ≥ 72 [( I21 / I2) -1 + 10-6 (Mn)]; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[0045] [045] An olefin polymerization process is provided to produce an ethylene copolymer, the process comprising contacting ethylene and at least one alpha-olefin having 3-8 carbon atoms with a polymerization catalyst system in a single gas phase reactor; the ethylene copolymer having a density of about 0.916 g / cc to 0.936 g / cc, a melt index (I2) of about 0.1 g / 10 min at 2.0 g / 10 min, a flow rate melting range (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about 3.6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR , a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 45% by weight to 75% by weight, as determined by TREF and which satisfies the following relationships: (Mw / Mn) ≥ 72 [( I21 / I2) -1 + 10-6 (Mn)]; and δ × O ≤ 83.0 - 1.25 (CDBl5o) / (Mw / Mn); wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[0046] [046] An olefin polymerization process is provided to produce an ethylene copolymer, the process comprising contacting ethylene and at least one alpha-olefin having 3-8 carbon atoms with a polymerization catalyst system in a single gas phase reactor; the ethylene copolymer having a density of about 0.916 g / cc to 0.936 g / cc, a melt index (I2) of about 0.1 g / 10 min at 2.0 g / 10 min, a flow rate melting range (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about 3.6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR , a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 45% by weight to 75% by weight, as determined by TREF and which satisfies the following relationships: (Mw / Mn) ≥ 72 [( I21 / I2) -1 + 10-6 (Mn)]; and δ × O <80.7 - (CDBl50) / (Mw / Mn) at a δ × O of about 550 to 700; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[0047] [047] An olefin polymerization process is provided to produce an ethylene copolymer, the process comprising contacting ethylene and at least one alpha-olefin having 3-8 carbon atoms with a polymerization catalyst system in a single gas phase reactor; the ethylene copolymer having a density of about 0.916 g / cc to 0.936 g / cc, a melt index (I2) of about 0.1 g / 10 min at 2.0 g / 10 min, a flow rate melting range (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about 3.6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR , a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 45% by weight to 75% by weight, as determined by TREF and which satisfies the following relationships: (Mw / Mn) ≥ 72 [( I21 / I2) -1 + 10-6 (Mn)]; and δ × O ≤ 80.7 - (CDBl50) / (Mw / Mn) at a δ × O of about 550 to 700; and δ × O ≤83.0 - 1.25 (CDBl50) / (Mw / Mn); wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[0048] [048] A layer of film is provided that has a dart impact greater than 200 g / mil, an MD securing module at 1% greater than 140 MPa, a TD securing module at 1% greater than 175 MPa and an MD wear ratio to TD wear of 0.75 or less, where the film layer comprises an ethylene copolymer having a density of 0.916 g / cc to 0.930 g / cc, a melting index (I2) of about 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about 3.6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, a distribution width index of the CDBI50 composition from 50% by weight to 75% by weight, as determined by TREF, and which satisfies the following relationship: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)].
[0049] [049] A film layer is provided which has a dart impact greater than 200 g / mil, an MD securing module at 1% greater than 140 MPa, a TD securing module at 1% greater than 175 MPa and an MD wear to TD wear ratio of 0.75 or less, wherein the film layer comprises an ethylene copolymer having a density of about 0.916 g / cc to 0.930 g / cc, a melting index (I2) of about 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about 3 , 6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 50% by weight to 75% in weight, as determined by TREF, and which satisfies the following ratios: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]; and δ × O ≤ 83.0 - 1.25 (CDBl50) / (Mw / Mn).
[0050] [050] A film layer is provided which has a dart impact greater than 200 g / mil, an MD securing module at 1% greater than 140 MPa, a TD securing module at 1% greater than 175 MPa and an MD wear to TD wear ratio of 0.75 or less, wherein the film layer comprises an ethylene copolymer having a density of about 0.916 g / cc to 0.930 g / cc, a melting index (I2) of about 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about 3 , 6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 50% by weight to 75% in weight as determined by TREF, and which satisfies the following ratios: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]; and δ × O ≤ 80.7 - (CDBl50) / (Mw / Mn) at a δ × O of about 550 to 700.
[0051] [051] A film layer is provided which has a dart impact greater than 200 g / mil, an MD securing module at 1% greater than 140 MPa, a TD securing module at 1% greater than 175 MPa and an MD wear to TD wear ratio of 0.75 or less, wherein the film layer comprises an ethylene copolymer having a density of about 0.916 g / cc to 0.930 g / cc, a melting index (I2) of about 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of about 32 to 50, a molecular weight distribution (Mw / Mn) of about 3 , 6 to 6.5, a reverse co-monomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, a distribution width index of the CDBI50 composition of about 50% by weight to 75% in weight, as determined by TREF, and which satisfies the following ratios: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]; and δ × O ≤ 80.7 - (CDBl5o) / (Mw / Mn) at a δ × O of about 550 to 700; and δχO <83.0 - 1.25 (CDBl50) / (Mw / Mn). BRIEF DESCRIPTION OF THE DRAWINGS
[0052] [052] Figure 1A shows a fractionation analysis of increasing temperature elution (TREF) and the profile of an ethylene copolymer produced according to the present invention.
[0053] [053] Figure 1B shows a fractionation analysis of increasing temperature elution (TREF) and the profile of an ethylene copolymer produced according to the present invention.
[0054] [054] Figure 2 shows a gel permeation chromatograph (GPC) with detection of the refractive index, of an ethylene copolymer produced according to the present invention.
[0055] [055] Figure 3 shows a gel permeation chromatograph with Fourier transform infrared detection (GPC-FTIR) obtained for an ethylene copolymer produced according to the present invention. The co-monomer content, shown as the number of short chain branches per 1000 carbon atoms (y-axis), is given in relation to the molecular weight of the copolymer (x-axis). The upward sloping line (from left to right) is the short chain branch (in short chain branches per 1000 carbon atoms) determined by FTIR. As can be seen in the Figure, the number of short chain branches increases at higher molecular weights, and therefore the co-monomer incorporation is said to be "reverse".
[0056] [056] Figure 4A shows graphs of phase angle versus complex modulus and phase angle versus complex viscosity for comparative numbers 1 and 2 ethylene copolymer resins, as determined by dynamic mechanical analysis (DMA).
[0057] [057] Figure 4B shows graphs of the phase angle versus the complex modulus and the phase angle versus the complex viscosity for ethylene copolymer of the number 1 invention and for comparative ethylene copolymers of numbers 3 and 7, as determined by DMA.
[0058] [058] Figure 5 shows a graph of the equation: Mw / Mn = 72 [(I21 / I2) -1 + 10-6 (Mn)]. The values from equation 72 [(I21 / I2) -1 + 10-6 (Mn)] (the y axis) are plotted against the corresponding Mw / Mn values (the x axis) for the resins of the invention as 1-6, as well as for several commercially available resins that have an I2 melt index of 1.5 g / 10 min or less, and a density between 0.916 and 0.930 g / cm3.
[0059] [059] Figure 6 shows a graph of the equation: δXO = 83 - 1.25 (CDBI50) / (Mw / Mn). The values of the equation 80 - 1.25 (CDBI50) / (Mw / Mn) (the x axis) are plotted against the corresponding passage phase angle values (δXO) (the y axis) for resins of the invention 1- 6, as well as for several commercially available resins, which have an I2 melt index of 1.5 g / 10 min or less and a density between 0.916 and 0.930 g / cm3.
[0060] [060] Figure 7 shows a graph of the equation: δXO = 80.7 - (CDBI50) / (Mw / Mn). The values of the equation 80.7 - (CDBI50) / (Mw / Mn) (the x-axis) are plotted against the corresponding pass-through phase angle values (δXO) (the y-axis) for resins of the invention 1-6 , as well as for several commercially available resins, which have an I2 melt index of 1.5 g / 10 min or less and a density between 0.916 and 0.930 g / cm3. The dotted lines show that the resins have a δXO value between 550 and 700. BEST MODE FOR CARRYING OUT THE INVENTION
[0061] [061] The present invention provides ethylene copolymers having a relatively high melt flow ratio and a multimodal profile in an increasing temperature elution fractionation (TREF) graph. Copolymers can be made into film having high dart impact values and good stiffness properties under reduced extrusion pressures and good exit rates. Polymerization Catalyst System
[0062] [062] The polymerization catalyst system used in the present invention will comprise a single transition metal catalyst, but may comprise other components, such as, but not limited to, a support, catalyst activator, and catalyst modifiers. The term "single transition metal catalyst" and similar terms mean that, during the preparation of the polymerization catalyst system, only one type of active transition metal catalyst is included, and excludes polymerization catalyst systems that comprise two or more different active transition metal catalysts, such as mixed catalysts and dual catalysts.
[0063] [063] Preferably, the transition metal catalyst is an organometallic catalyst based on a Group 4 transition metal. An organometallic catalyst is understood to mean that the catalyst will have at least one ligand within the metal coordination sphere transition, which is bonded to the metal by means of at least one metal-carbon bond. Such catalysts can collectively be called "organotransition metal catalysts" or "Group 4 organotransition metal catalysts" when based on a Group 4 metal.
[0064] [064] Preferably, the organotransition metal catalyst is a single site catalyst based on a Group 4 metal (where the number refers to columns in the Periodic Table of the Elements using the IUPAC nomenclature). This includes titanium, hafnium and zirconium. The most preferred organotransition metal catalysts are Group 4 metal complexes in their highest oxidation state.
[0065] [065] A particular organotransition metal catalyst, which is especially useful in the present invention is a Group 4 organotransition metal catalyst, which further comprises a phosphinimine ligand. Any catalyst / compound / organometallic complex having a phosphinimine ligand and which can be used to make the most defined copolymer compositions and described below (in the section entitled "The Ethylene Copolymer Composition") are contemplated for use in the present invention. , organotransition metal catalysts having at least one phosphinimine ligand and which are active in polymerizing olefins to polymers are referred to as "phosphinimine catalysts".
[0066] [066] Transition metal catalysts generally require activation by one or more catalyst-activating or cocatalytic species in order to provide polymer. Thus, transition metal polymerization catalysts are sometimes called "pre-catalysts".
[0067] [067] In a preferred embodiment of the invention, the phosphinimine catalyst is defined by the formula: L (PI) MX2, where M is a transition metal of group 4 selected from Ti, Hf, Zr; PI is a phosphinimine ligand; L is a substituted or unsubstituted cyclopentadienyl ligand; and X is an activable ligand.
[0068] [068] In a preferred embodiment of the invention, the phosphinimine catalyst will have a phosphinimine ligand that is not bridged, or does not bridge with another ligand within the metal coordination sphere of the phosphinimine catalyst, such as, for example , a cyclopentadienyl-type ligand.
[0069] [069] In a preferred embodiment of the invention, the phosphinimine catalyst will have a ligand of the cyclopentadienyl type, which is not bridged, or does not bridge with another ligand within the metal coordination sphere of the phosphinimine catalyst, such as, for example, a phosphinimine ligand.
[0070] [070] The phosphinimine ligand is defined by the formula: R13P = N-, where each R1 is independently selected from the group consisting of a hydrogen atom; a halogen atom; a C1-20 hydrocarbon radical that is unsubstituted or additionally substituted by one or more halogen atom; a C1-20 alkyl radical; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical; a starch radical; a silyl radical; and a Germanyl radical; P is phosphorus and N is nitrogen (which bonds with metal M).
[0071] [071] In one embodiment of the invention, the phosphinimine ligand is chosen, so that each R1 is a hydrocarbyl radical. In a particular embodiment of the invention, the phosphinimine ligand is tri- (tertiary butyl) phosphinimine (i.e., where each R1 is a tertiary butyl group or a t-Bu group, for short).
[0072] [072] As used herein, the term "cyclopentadienyl-type" ligand is intended to include ligands that contain at least one ring of five carbon atoms, which is attached to the metal via eta-5 bonding (or, in some cases, eta-3). Thus, the term "cyclopentadienyl type" includes, for example, unsubstituted cyclopentadienyl, single or multiply substituted cyclopentadienyl, unsubstituted indenyl, single or multiply substituted indenyl, unsubstituted fluorenyl and single or multiply substituted fluorenyl. Hydrogenated versions of indenyl and fluorenyl ligands are also contemplated for use in the present invention, provided that the ring of five carbon atoms that binds to the metal via the eta-5 bond (or, in some cases, eta-3) remains intact . Substituents for a cyclopentadienyl ligand, an indenyl ligand (or hydrogenated version thereof) and a fluorenyl ligand (or a hydrogenated version thereof) can be selected from the group consisting of a hydrocarbyl C1-30 radical (hydrocarbyl radical) which can be unsubstituted or additionally substituted, for example, by a halide group and / or a hydrocarbyl, for example a suitable substituted C1-30 hydrocarbyl radical is a pentafluorobenzyl group, such as -CH2C6F5); a halogen atom; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical (each of which may be further substituted, for example, by a halide group and / or a hydrocarbyl); a starch radical, which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a phosphide radical that is unsubstituted or substituted by up to two C1-8 alkyl radicals; a silyl radical of the formula -Si (R ') 3, wherein each R' is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals; and a Germanyl radical of the formula -Ge (R ') 3, where R' is as defined immediately above.
[0073] [073] The term "perfluorinated aryl group" means that each hydrogen atom attached to a carbon atom in an aryl group has been replaced by a fluorine atom as is well understood in the art (for example, a perfluorinated or substituent phenyl group has the formula -C6F5).
[0074] [074] In one embodiment of the invention, the phosphinimine catalyst will have a single or multiply substituted indenyl ligand and a phosphinimine ligand that is replaced by three tertiary butyl substituents.
[0075] [075] An indenyl ligand (or "Ind" for short) as defined in the present invention will have carbon atoms of main structure with the numbering scheme provided below, so that the location of a substituent can be readily identified .
[0076] [076] In one embodiment of the invention, the phosphinimine catalyst will have a single substituted indenyl ligand and a phosphinimine ligand that is replaced by three tertiary butyl substituents.
[0077] [077] In one embodiment of the invention, the phosphinimine catalyst will have a single or multiply substituted indenyl ligand, where the substituent is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or a non-aryl group -substituted, and a substituted or unsubstituted benzyl group (for example, C6H5CH2-). Suitable substituents for the alkyl, aryl or benzyl group can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (e.g., a benzyl group), arylalkyl groups and halide groups.
[0078] [078] In one embodiment of the invention, the phosphinimine catalyst will have a single substituted indenyl ligand, R2-indenyl, wherein the R2 substituent is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group. Suitable substituents for an R2 alkyl, R2 aryl or R2 benzyl group can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (for example, a benzyl group), arylalkyl groups and halide groups.
[0079] [079] In one embodiment of the invention, the phosphinimine catalyst will have an indenyl ligand that has at least one substituent in position 1 (1-R2), where the substituent R2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group. Suitable substituents for an R2 alkyl, R2 aryl or R2 benzyl group can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (for example, a benzyl group), arylalkyl groups and halide groups.
[0080] [080] In one embodiment of the invention, the phosphinimine catalyst will have a single substituted indenyl ligand, 1-R2-Indenyl, where the R2 substituent is in position 1 of the indenyl ligand, and is a substituted or unsubstituted alkyl group , a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group. Suitable substituents for an R2 alkyl, R2 aryl or R2 benzyl group can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (for example, a benzyl group), arylalkyl groups and halide groups.
[0081] [081] In one embodiment of the invention, the phosphinimine catalyst will have a single substituted indenyl ligand, 1-R2-Indenyl, where the R2 substituent is a halide-substituted alkyl group (partially / totally), a halide-substituted benzyl group (partially / totally), or an aryl group substituted with halide (partially / totally).
[0082] [082] In one embodiment of the invention, the phosphinimine catalyst will have a single substituted indenyl ligand, 1-R2-Indenyl, where the R2 substituent is a halide substituted benzyl group (partially / totally).
[0083] [083] When present in an indenyl ligand, a benzyl group can be partially or totally replaced by halide atoms, preferably fluorine atoms. The aryl group of the benzyl group can be a perfluorinated aryl group, a fluorine-substituted phenyl group 2,6 (ie, ortho) or a fluorine-substituted phenyl group 2,4,6 (ie, ortho / para) or a fluorine-substituted phenyl group 2, 3, 5, 6 (i.e., ortho / meta), respectively. The benzyl group is, in one embodiment of the invention, located at position 1 of the indenyl ligand.
[0084] [084] In one embodiment of the invention, the phosphinimine catalyst will have a single substituted indenyl ligand, 1-R2-indenyl, where the R2 substituent is a pentafluorobenzyl (C6F5CH2-) group.
[0085] [085] In one embodiment of the invention, the phosphinimine catalyst has the formula: (1-R2- (Ind)) M (N = P (t-Bu) 3) X2, where R2 is a substituted or unsubstituted alkyl group -substituted, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, wherein the substituents for the alkyl, aryl or benzyl group are selected from the group consisting of alkyl, aryl, alkoxy, aryloxy , alkylaryl, arylalkyl and halide substituents; M is Ti, Zr or Hf; and X is an activable ligand.
[0086] [086] In one embodiment of the invention, the phosphinimine catalyst has the formula: (1-R2- (Ind)) M (N = P (t-Bu) 3) X2, where R2 is an alkyl group, a group aryl or a benzyl group, and each of the alkyl group, the aryl group, and the benzyl group can be unsubstituted or substituted by at least one fluorine atom; M is Ti, Zr or Hf; and X is an activable ligand.
[0087] [087] In one embodiment of the invention, the phosphinimine catalyst has the formula: (1-R2- (Ind)) M (N = P (t-Bu) 3) X2, where R2 is an alkyl group, a group aryl or a benzyl group, and each of the alkyl group, the aryl group, and the benzyl group can be unsubstituted or substituted by at least one halide atom; M is Ti, Zr or Hf; and X is an activable ligand.
[0088] [088] In one embodiment of the invention, the phosphinimine catalyst has the formula: (1-R2- (Ind)) M (N = P (t-Bu) 3) X2, where R2 is an alkyl group, a group aryl or a benzyl group, and wherein each of the alkyl group, the aryl group, and the benzyl group can be unsubstituted or substituted by at least one fluorine atom; and X is an activable ligand.
[0089] [089] In one embodiment of the invention, the phosphinimine catalyst has the formula: (1-C6F5CH2-Ind)) M (N = P (t-Bu) 3) X2, where M is Ti, Zr or Hf; and X is an activable ligand.
[0090] [090] In one embodiment of the invention, the phosphinimine catalyst has the formula: (1-C6F5CH2-Ind) Ti (N = P (t-Bu) 3) X2, where X is an activable ligand.
[0091] [091] Other organotransition metal catalysts that can also be contemplated for use in the present invention include metallocene catalysts (which have two cyclopentadienyl-type ligands), and constrained geometry catalysts (which have a starch-type ligand and one ligand of the cyclopentadienyl type). Some non-limiting examples of metallocene catalysts, which may or may not be useful, can be found in U.S. Patent Numbers 4,808,561; 4,701,432; 4,937,301; 5,324,800; 5,633,394; 4,935,397; 6,002,033 and 6,489,413, which are incorporated herein by reference. Some non-limiting examples of constrained geometry catalysts, which may or may not be useful, can be found in U.S. Patent Numbers 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,703,187 and 6,034,021, all of which are incorporated herein by reference in their entirety.
[0092] [092] In the present invention, the term "activable" means that ligand X can be cleaved from the metal center M via a protonolysis reaction or captured from the metal center M by acidic catalyst activating compounds or electrophilic compounds (also known as "cocatalyst" compounds), respectively, examples of which are described below. The activatable ligand X can also be transformed into another ligand, which is cleaved or taken up from the metal center M (for example, a halide can be converted to an alkyl group). Without intending to be limited by theory, protonolysis or abstraction reactions have generated an active "cationic" metal center that can polymerize olefins.
[0093] [093] In embodiments of the present invention, the activable ligand, X 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 C6-10 aryl or an aryloxy radical, each of hydrocarbyl, alkoxy, aryl, or aryl oxide radicals may be unsubstituted or additionally substituted by one or more halogens or another group; a C1-8 alkyl; a C1-8 alkoxy, a C6-10 aryl or aryloxy; a starch or a phosphide radical, but where X is not a cyclopentadienyl. Two ligands X can also be joined together and form, for example, a substituted or unsubstituted diene ligand (i.e., 1,3-butadiene); or a delocalized heteroatom-containing group, such as an acetate or acetamidinate group. In a convenient embodiment of the invention, each X is independently selected from the group consisting of a halide atom, a C1-4 alkyl radical and a benzyl radical.
[0094] [094] Particularly suitable activatable ligands are monoanionic, such as a halide (for example, chloride) or a hydrocarbyl group (for example, methyl, benzyl).
[0095] [095] The catalyst activator (or simply the "activator" for short) used to activate the transition metal polymerization catalyst can be any suitable activator, including one or more activators selected from the group consisting of alkylaluminoxanes and activators ionic, optionally together with an alkylating agent.
[0096] [096] Without wishing to be bound by theory, alkylaluminoxanes are thought to be aluminum complex compounds of the formula: R32Al1O (R3Al1O) mAl1R32, where each R3 is independently selected from the group consisting of hydrocarbyl C1-20 radicals in is from 3 to 50. Optionally, a hindered phenol can be added to the alkylaluminoxane to provide a 2: 1 to 5: 1 Al1: hindered phenol molar ratio when the hindered phenol is present.
[0097] [097] In one embodiment of the invention, R3 of alkylaluminoxane, is a methyl radical and m is 10 to 40.
[0098] [098] Alkylaluminoxanes are normally used in substantial molar excess compared to the amount of Group 4 transition metal in the organometallic compound / complex. The molar ratios of the Al1: Group 4 transition metal can be from about 10: 1 to about 10,000: 1, preferably from about 30: 1 to about 500: 1.
[0099] [099] In one embodiment of the invention, the catalyst activator is methylaluminoxane (MAO).
[0100] [0100] In one embodiment of the invention, the catalyst activator is modified methylaluminoxane (MMAO).
[0101] [0101] It is well known in the art, that alkylaluminoxane can have dual roles as both an alkylator and an activator. Thus, an alkylaluminoxane activator is often used in combination with activable ligands, such as halogens.
[0102] [0102] Alternatively, the catalyst activator of the present invention can be a combination of an alkylating agent (which can also serve as a scavenger) with an activator capable of ionizing group 4 of the transition metal catalyst (i.e., a ionic activator). In this context, the activator can be chosen from one or more alkylaluminoxane and / or an ionic activator, since an alkylaluminoxane can serve both as an activator and an alkylating agent.
[0103] [0103] When present, the alkylating agent can be selected from the group consisting of (R4) p MgX22-p, where X2 is a halide and each R4 is independently selected from the group consisting of C1-10 radicals alkyl ep is 1 or 2; R4Li, where R4 is as defined above, (R4) q ZnX22-q, where R4 is as defined above, X2 is halogen and q is 1 or 2; (R4) s Al2X23-s, where R4 is as defined above, X2 is halogen and s is an integer from 1 to 3. Preferably, in the above compounds, R4 is a C1-4 alkyl radical, and X2 is chlorine. Commercially available compounds include triethyl aluminum (TEAL), diethyl aluminum chloride (DEAC), dibutyl magnesium ((Bu) 2Mg), and butyl ethyl magnesium (BuEtMg or BuMgEt). Alkylaluminoxanes can also be used as alkylating agents.
[0104] [0104] The ionic activator can be selected from the group consisting of: (i) compounds of the formula [R5] + [B (R6) 4] -, where B is a boron atom, R5 is an aromatic cation Cyclic C5-7 or a methyl triphenyl cation and each R6 is independently selected from the group consisting of phenyl radicals, which are substituted or unsubstituted with 3 to 5 substituents selected from the group consisting of an atom fluorine, a C1-4 alkyl or an alkoxy radical that is substituted or unsubstituted by a fluorine atom; and a silyl radical of the general formula --Si - (R7) 3; wherein each R7 is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical; and (ii) compounds of the formula [(R8) t ZH] + [B (R6) 4] -, where B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or phosphorus atom , t is 2 or 3 and R8 is selected from the group consisting of C1-8 alkyl radicals, a phenyl radical which is unsubstituted or substituted by up to three C1-4 alkyl radicals, or an R8 taken together with the nitrogen atom can form an anilinium radical and R6 is as defined above; and (iii) compounds of formula B (R6) 3, where R6 is as defined above.
[0105] [0105] In the above compounds, preferably, R6 is a radical of pentafluorophenyl, and R5 is a cation of triphenylmethyl, Z is a nitrogen atom and R8 is a C1-4 alkyl group or R8 taken together with the nitrogen atom forms an anilinium radical which is replaced by two C1-4 alkyl radicals.
[0106] [0106] Examples of compounds capable of ionizing the transition metal catalyst include the following compounds: tetra (phenyl) boron triethylammonium, tetra (phenyl) boron tripropylammon, tetra (phenyl) boron tri (n-butyl) ammonium, tetra trimethylammonium (p-tolyl) boron, tetra trimethylammonium (o-tolyl) boron, tetra tributylammonium (pentafluorophenyl) boron, tetra tripropylammonium (o, p-dimethylphenyl) boron, tetra tributylammonium (m, m-dimethylphenyl) boron, tetra (p-trifluoromethylphenyl) tributylammonium boron, tetra (pentafluorophenyl) tributylammonium boron, tetra (o-tolyl) tri (n-butyl) ammonium boron, N, tetra (phenyl) boron N-dimethylanilinium, N, Tetra (phenyl) boron N-diethylanilinium, N, tetra (phenyl) n-butylboro N-diethylanilinium, tetra (phenyl) boron, tetra (phenyl) boron, tetra- (isopropyl) ammonium (pentafluorophenyl) boron, tetra (phenyl) dicyclohexylammonium, boron, triphenylphosphonium tetra) phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimet ilphenyl) phosphonium tetra (phenyl) boron, tropilium tetraquispentafluorophenyl borate, triphenylmethyl tetraquispentafluorophenyl borate, benzene (diazonium) tetraquispentafluorophenyl borate, tropyl phenyltris-pentafluorophenyl boron, phenyltrilylphenyl boron, triphenyl , 5,6-tetrafluorophenyl) borate, triphenylmethyl tetrakis (2,3,5,6-tetrafluorophenyl) borate, benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate, tropilium tetrakis (3,4,5-trifluorophenyl) ) borate, benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate, tropilium tetrakis (1,2,2-trifluoroethyl) borate, trophenylmethyl tetrakis (1,2,2-trifluoroethyl) borate, benzene (diazonium) tetrakis (1,2,2-trifluoroethyl) borate, tropilium tetrakis (2,3,4,5-tetrafluorophenyl) borate, triphenylmethyletetrakis (2,3,4,5-tetrafluorophenyl) borate, and benzene (diazonium) tetrakis (2, 3,4,5-tetrafluorophenyl) borate.
[0107] [0107] Commercially available activators that are capable of ionizing the transition metal catalyst include: N, N-dimethylaniliniotetraquispentafluorophenyl borate ("[Me2NHPh] [B (C6F5) 4]"); and triphenylmethyl tetraquispentafluorophenyl borate ("[Ph3C] [B (C6F5) 4]"); and trispentafluorophenyl boron.
[0108] [0108] In an embodiment of the invention, the ion activating compounds can be used in amounts that provide a molar ratio of transition metal from Group 4 to boron that will be from 1: 1 to 1: 6.
[0109] [0109] Optionally, mixtures of alkylaluminoxanes and ionic activators can be used as activators for the organometallic complex.
[0110] [0110] In the present invention, the polymerization catalyst system will preferably comprise an inert support (note: the terms "support" and "inert support" are used interchangeably in the present invention). In a particular embodiment of the invention, the polymerization catalyst system comprises a phosphinimine catalyst which is supported on an inert support.
[0111] [0111] The inert support used in the present invention can be any support known in the art to be suitable for use with polymerization catalysts. For example, the support can be any porous or non-porous support material, such as talc, inorganic oxides, inorganic chlorides, aluminophosphates (i.e., AlPO4) and polymer supports (for example, polystyrene, etc.). Therefore, supports include Groups 2, 3, 4, 5, 13 and 14, usually metal oxides, such as silica, alumina, silica-alumina, magnesium oxide, magnesium chloride, zirconia, titania, clay (for example , montmorillonite) and mixtures thereof.
[0112] [0112] Agglomerate supports, such as silica and clay agglomerates, can also be used as a support in the present invention.
[0113] [0113] Supports are generally used in calcined form. An inorganic oxide support, for example, will contain hydroxyl groups with an acidic surface that will react with a polymerization catalyst. Before use, inorganic oxide can be dehydrated to remove water and reduce the concentration of surface hydroxyl groups. Calcination or dehydration of a support is well known in the art. In one embodiment of the invention, the support is calcined at temperatures above 200 ° C, or above 300 ° C, or above 400 ° C, or above 500 ° C. In other embodiments, the support is calcined at about 500 ° C to about 1000 ° C, or from about 600 ° C to about 900 ° C. The resulting support can be free of adsorbed water and can have a surface hydroxyl content of about 0.1 to 5 mmoles / g of support, or 0.5 to 3 mmoles / g. The amount of hydroxyl groups, on a silica support, can be determined according to the method described by J.B. Peri and A.L. Hensley Jr., in J. Phys. Chem., 72 (8), 1968, pg 2926.
[0114] [0114] The support material, in particular an inorganic oxide, normally has a surface area of about 10 to about 700 m2 / g, a pore volume in the range of about 0.1 to about 4, 0 cc / g and an average particle size of about 5 to about 500 μm. In a more specific embodiment, the support material has a surface area of about 50 to about 500 m2 / g, a pore volume in the range of about 0.5 to about 3.5 cc / g and a size of average particle between about 10 to about 200 μm. In another more specific embodiment of the support material it has a surface area of about 100 to about 400 m2 / g, a pore volume in the range of about 0.8 to about 3.0 cc / g and a size of average particle of about 5 to about 100 μm.
[0115] [0115] The support material, in particular, an inorganic oxide, typically has an average pore size (i.e., pore diameter) of about 10 to about 1000 Angstroms (Å.). In a more specific embodiment, the support material has an average pore size of about 50 to about 500 Å .. In another more specific embodiment, the support material has an average pore size of about 75 to about Å. 350 Å.
[0116] [0116] The surface area and pore volume of a support can be determined by nitrogen adsorption according to BET techniques, which are well known in the art and are described in the Journal of the American Chemical Society, 1938, v 60, pg 309 -319.
[0117] [0117] A silica support that is suitable for use in the present invention has a high surface area and is amorphous. By way of example only, useful silicas are commercially available under the trademark of Sylopol® 958, 955 and 2408 by Davison Catalysts, a Division of W.R. Grace and Company and ES-70W by Ineos Silica.
[0118] [0118] Agglomerate supports comprising a clay mineral and an inorganic oxide, can be prepared using a number of techniques well known in the art, including pelletizing, extrusion, drying or precipitation, spray drying, granule molding in a drum. rotating coating, and the like. A nodulation technique can also be used. Methods for making chipboard supports comprising a clay mineral and an inorganic oxide include spray drying, a clay mineral slurry and an inorganic oxide. Methods for making chipboard supports comprising a clay mineral and an inorganic oxide are described in U.S. Patent Numbers 6,686,306; 6,399,535; 6,734,131; 6,559,090 and 6,958,375.
[0119] [0119] An agglomerate of clay and inorganic oxide, which are useful in the present invention may have the following properties: a surface area of about 20 to about 800 m2 / g, preferably from 50 to about 600 m2 / g; particles with a volume density of about 0.15 to about 1 g / ml, preferably from about 0.20 to about 0.75 g / ml; an average pore diameter of about 30 to about 300 Angstroms (Å), preferably from about 60 to about 150 Å; a total pore volume of about 0.10 to about 2.0 cc / g, preferably about 0.5 to about 1.8 cc / g; and an average particle size of about 4 to 250 microns (μm), preferably about 8 to 100 microns.
[0120] [0120] Alternatively, a support, for example, a silica support, can be treated with one or more salts of the type: Zr (SO4) 2.4H2O, ZrO (NO3) 2 and Fe (NO3) 3, as taught in the Order Canadian Co-pending Patent No. 2,716,772. Supports that have been chemically treated in another way are also contemplated for use with the catalysts and processes of the present invention.
[0121] [0121] The present invention is not limited to any particular process for supporting a transition metal catalyst or components of the catalyst system. Processes for the deposition of such catalysts (for example, a phosphinimine catalyst), as well as a catalyst activator on a support are well known in the art (for some non-limiting examples of catalyst support methods, see "Supported Catalysts" ”By James H. Clark and Duncan J. Macquarrie, published online November 15, 2002 in the Kirk-Othmer Encyclopedia of Chemical Technology Copyright © 2001 by John Wiley & Sons, Inc .; for some non-limiting methods to support a catalyst of organotransition metal, see US Patent No. 5,965,677) For example, a transition metal catalyst (for example, a phosphinimine catalyst) can be added to a support by co-precipitation with the support material. The activator can be added to the support before and / or after the transition metal catalyst or together with the transition metal catalyst Optionally, the activator can be added to a transition metal catalyst In situ supported reaction or a transition metal catalyst can be added to the in situ support or a transition metal catalyst can be added to an in situ supported activator. A transition metal catalyst can be suspended or dissolved in a suitable diluent or solvent and then added to the support. Suitable solvents or thinners include, but are not limited to, hydrocarbons and mineral oil. A transition metal catalyst, for example, can be added to the solid support, in the form of a solid, solution or slurry, followed by the addition of the activator in solid form or as a solution or slurry. Transition metal catalyst (eg, phosphinimine catalyst), catalyst activator, and the support can be mixed together in the presence or absence of a solvent. Polymerization Process
[0122] [0122] The copolymer compositions of the present invention are preferably made using a single reactor, preferably a single gas phase or slurry phase reactor. The use of a polymerization catalyst system comprising a single transition metal catalyst in a single gas phase reactor is especially preferred.
[0123] [0123] Detailed descriptions of the slurry polymerization processes are widely reported in the patent literature. For example, particle polymerization, or a slurry process in which the temperature is kept below the temperature at which the polymer comes into solution is described in U.S. Patent No. 3,248,179. Other slurry processes include those that employ a cycle reactor and those that use a plurality of reactors with agitation in series, in parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous cycle or agitated tank processes. Other examples of slurry processes are described in U.S. Patent No. 4,613,484.
[0124] [0124] Slurry processes are conducted in the presence of a hydrocarbon diluent, such as an alkane (including isoalkanes), an aromatic or a cycloalkane. The diluent can also be the alpha olefin co-monomer used in copolymerizations. Alkane diluents include propane, butanes, (i.e., normal butane and / or isobutane), pentanes, hexanes, heptanes and octanes. Monomers can be soluble in (or miscible with) the diluent, but it is not the polymer (under polymerization conditions). The polymerization temperature is preferably from about 5 ° C to about 200 ° C, more preferably less than about 120 ° C, typically from about 10 ° C to 100 ° C. The reaction temperature is selected so that the ethylene copolymer is produced in the form of solid particles. The reaction pressure is influenced by the choice of diluent and reaction temperature. For example, pressures can range from 15 to 45 atmospheres (from about 220 to 660 psi or about 1500 to about 4600 kPa), when isobutane is used as a diluent (see, for example, US Patent No. 4,325,849 ) at approximately double (that is, from 30 to 90 atmospheres - about 440 to 1300 psi or about 3000-9100 kPa) when propane is used (see US patent No. 5,684,097). The pressure in a slurry process must be kept high enough to maintain at least part of the ethylene monomer in the liquid phase. The reaction typically takes place in a jacketed closed-loop reactor having an internal stirrer (for example, a paddle wheel) and at least one sedimentation leg. The catalyst, monomers and diluents are fed to the reactor in the form of liquids or suspensions. The slurry circulates through the reactor and the coating is used to control the temperature of the reactor. Through a series of elongation valves, the slurry enters a settling leg and is then stretched in pressure to expand the diluent and unreacted monomers and recover the polymer usually in a cyclone. The diluent and unreacted monomers are recovered and recycled back to the reactor.
[0125] [0125] A gas phase polymerization process is generally carried out in a fluidized bed reactor. Such gas-phase processes are widely described in the literature (see, for example, US Patents Numbers 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453 .471,5,462,999, 5,616,661 and 5,668,228). In general, a fluidized bed gas phase polymerization reactor employs a polymer "bed" and the catalyst, which is fluidized by a stream of monomer, co-monomer and other optional components that are at least partially gaseous. The heat is generated by the polymerization enthalpy of the monomer (and co-monomers) that flows through the bed. Unreacted monomer, co-monomer and other optional gaseous components come out of the fluidized bed and are placed in contact with a cooling system to remove heat. The cooled gas stream, including the monomer, co-monomer and other optional components (such as condensable liquids), is then recirculated through the polymerization zone, together with the "make-up" monomer (and co-monomer) ) to replace what was cured in the previous pass. Simultaneously, the polymer product is removed from the reactor. As will be appreciated by those skilled in the art, the "fluidized" nature of the polymerization bed helps to distribute / mix the reaction heat evenly and thus minimize the formation of localized temperature gradients.
[0126] [0126] The reactor pressure in a gas phase process can vary around atmospheric to around 600 psig. In a more specific embodiment, the pressure can vary from about 100 psig (690 kPa) to about 500 psig (3448 kPa). In another more specific embodiment, the pressure can range from about 200 psig (1379 kPa) to about 400 psig (2759 kPa). In yet another more specific embodiment, the pressure can vary from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).
[0127] [0127] The reactor temperature in a gas phase process can vary according to the heat of polymerization, as described above. In a specific embodiment, the temperature of the reactor can be between about 30 ° C to about 130 ° C. In another specific embodiment, the temperature of the reactor can be between about 60 ° C to about 120 ° C. In yet another specific embodiment, the temperature of the reactor can be between about 70 ° C to about 110 ° C. In yet another specific embodiment, the temperature of a gas phase process can be from about 70 ° C to about 100 ° C.
[0128] [0128] The fluidized bed process described above is well suited for the preparation of polyethylene, but other monomers (i.e., co-monomers) can also be employed. Monomers and co-monomers include ethylene and C3-12 alpha olefins, respectively, where C3-12 alpha olefins are unsubstituted or substituted by up to two C1-6 alkyl radicals, C8-12 aromatic vinyl monomers, which are not -replaced or substituted by up to two substituents selected from the group consisting of C1-4 alkyl radicals, C4-12 cyclic or straight chain diolefins that are unsubstituted or substituted by a C1-4 alkyl radical. Non-limiting illustrative examples of such alpha-olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, styrene, alpha methyl styrene, p-tert-butyl styrene, and constrained ring cyclic olefins, such as cyclobutene, cyclopentene, norbornene dicyclopentadiene, alkyl-substituted norbornenes, alkenyl-substituted norbornenes and the like (for example, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, bicycles (2 , 2.1) -hepta-2,5-diene).
[0129] [0129] In one embodiment, the invention is directed to a polymerization process involving the polymerization of ethylene with one or more comonomers, including linear or branched co-monomers having 3 to 30 carbon atoms, preferably 3-12 carbon atoms, more preferably 3 to 8 carbon atoms.
[0130] [0130] The process is particularly well suited for copolymerization reactions involving the polymerization of ethylene in combination with one or more of the co-monomers, such as alpha-olefin co-monomers, such as propylene, butene-1, pentene -1,4-methylpentene-1, hexene-1, octene-1, decene-1, styrene and cyclic and polycyclic olefins such as cyclopentene, norbornene and cyclohexene or a combination thereof. Other co-monomers for use with ethylene may include vinyl polar monomers, diolefins, such as 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, norbornadiene, and other unsaturated monomers, including acetylene and aldehyde monomers. Higher alpha-olefins and polyenes or macromers can also be used.
[0131] [0131] Preferably, the co-monomer is an alpha-olefin having 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms and more preferably, 4 to 10 carbon atoms.
[0132] [0132] In an embodiment of the invention, ethylene comprises at least 75% by weight of the total weight of monomer (i.e., ethylene) and co-monomer (i.e., alpha olefin) which is fed to a polymerization reactor.
[0133] [0133] In an embodiment of the invention, ethylene comprises at least 85% by weight of the total weight of monomer (i.e., ethylene) and co-monomer (i.e., alpha olefin) which is fed to a polymerization reactor.
[0134] [0134] In an embodiment of the invention, ethylene is polymerized with at least two different co-monomers to form a terpolymer and the like, the preferred comonomers are a combination of monomers, alpha-olefin monomers having 3 to 10 atoms of carbon, more preferably 3 to 8 carbon atoms, optionally with at least one diene monomer. Preferred terpolymers include combinations, such as ethylene / butene-1 / hexene-1, ethylene / propylene / butene-1, ethylene / propylene / hexene-1, ethylene / propylene / norbornadiene, ethylene / propylene / 1,4-hexadiene and the like.
[0135] [0135] In one embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single reactor in the presence of a polymerization catalyst system comprising a single organotransition metal catalyst of the Group 4.
[0136] [0136] In an embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single metal catalyst Group 4 organotransition process.
[0137] [0137] In one embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single reactor in the presence of a polymerization catalyst system comprising a single organotransition metal catalyst of the Group 4; a catalyst activator; and a support.
[0138] [0138] In one embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single metal catalyst organotransition of Group 4; a catalyst activator; and a support.
[0139] [0139] In an embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single metal catalyst transition, where the only transition metal catalyst is a Group 4 phosphinimine catalyst.
[0140] [0140] In one embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single metal catalyst transition, where the only transition metal catalyst is a Group 4 phosphinimine catalyst, having the formula: (1-R2-Indenyl) Ti (N = P (t-Bu) 3) X2;
[0141] [0141] where R2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, where the substituents for the alkyl, aryl or benzyl group are selected from from the group consisting of alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halide substituents; and where X is an activable ligand.
[0142] [0142] In one embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single gas phase reactor with a polymerization catalyst system comprising: a phosphinimine catalyst; an alkylaluminoxane co-catalyst; and a support.
[0143] [0143] In an embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single gas phase reactor with a polymerization catalyst system comprising: a phosphinimine catalyst; an alkylaluminoxane co-catalyst; a support; and a catalyst modifier (which is described below).
[0144] [0144] In one embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single reactor with a polymerization catalyst system comprising: a phosphinimine catalyst having the formula (1 -R2-Ind) Ti (N = P (t-Bu) 3) X2 where R2 is an alkyl group, an aryl group or a benzyl group, where each of the alkyl group, the aryl group, or the benzyl group it can be unsubstituted or substituted by at least one halide atom, and where X is an activable ligand; and an activator.
[0145] [0145] In an embodiment of the invention, an ethylene copolymer and an alpha-olefin of 3-8 carbon atoms are made in a single gas phase reactor with a polymerisation catalyst system comprising: a phosphinimine catalyst having the formula (1-R2-Ind) Ti (N = P (t-Bu) 3) X2 where R2 is an alkyl group, an aryl group or a benzyl group, where each of the alkyl group, the aryl group, or the benzyl group can be unsubstituted or substituted by at least one halide atom, where X is an activable ligand; an activator; and an inert support.
[0146] [0146] In one embodiment of the invention, an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms are made in a single gas phase reactor with a polymerisation catalyst system comprising: a phosphinimine catalyst having the formula (1-R2-Ind) Ti (N = P (t-Bu) 3) X2 where R2 is an alkyl group, an aryl group or a benzyl group, where each of the alkyl group, the aryl group, or the benzyl group can be unsubstituted or substituted by at least one halide atom, where X is an activable ligand; an activator; an inert support; and a catalyst modifier.
[0147] [0147] In one embodiment of the invention, the copolymer is a copolymer of ethylene and an alpha-olefin having 3-8 carbon atoms, and is made in a single gas phase reactor with a polymerization catalyst system comprising: a phosphinimine catalyst having the formula (1-C6F5CH2-Ind) Ti (N = P (t-Bu) 3) X2 where X is an activable ligand; an activator; and an inert support.
[0148] [0148] In one embodiment of the invention, the copolymer is a copolymer of ethylene and an alpha-olefin having 3-8 carbon atoms, and is made in a single gas phase reactor with a polymerization catalyst system comprising: a phosphinimine catalyst having the formula (1-C6F5CH2-Ind) Ti (N = P (t-Bu) 3) X2 where X is an activable linker; an activator; an inert support; and a catalyst modifier.
[0149] [0149] In an embodiment of the invention, an olefin polymerization process provides an ethylene copolymer, the process comprising contacting ethylene and at least one alpha-olefin having 3-8 carbon atoms, with a system polymerization catalyst in a single gas phase reactor; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, and a catalyst activator; and wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[0150] [0150] In one embodiment of the invention, an olefin polymerization process provides an ethylene copolymer, the process comprising contacting ethylene and at least one alpha-olefin having 3-8 carbon atoms, with a system polymerization catalyst in a single gas phase reactor; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[0151] [0151] In an embodiment of the invention, an olefin polymerization process provides a copolymer of ethylene, the process comprising bringing into contact ethylene and at least one alpha-olefin having 3-8 carbon atoms, with a system polymerization catalyst in a single gas phase reactor; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, and a catalyst activator; and wherein the transition metal catalyst is a single Group 4 phosphinimine catalyst.
[0152] [0152] In an embodiment of the invention, an olefin polymerization process provides an ethylene copolymer, the process comprising contacting ethylene and at least one alpha-olefin having 3-8 carbon atoms, with a system polymerization catalyst in a single gas phase reactor; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and wherein the only transition metal catalyst is a Group 4 phosphinimine catalyst.
[0153] [0153] In an embodiment of the invention, an olefin polymerization process provides an ethylene copolymer, the process comprising contacting ethylene and at least one alpha-olefin having 3-8 carbon atoms, with a system polymerization catalyst in a single gas phase reactor; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and where the only transition metal catalyst is a Group 4 phosphinimine catalyst having the formula: (1-R2-Indenyl) Ti (N = P (t-Bu) 3) X2 is a substituted or unsubstituted alkyl group substituted, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, where the substituents for the alkyl, aryl or benzyl group are selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halide substituents; and where X is an activable ligand.
[0154] [0154] The polymerization catalyst system can be fed to a reactor system in a number of ways. If the transition metal catalyst is supported on a suitable support, the transition metal catalyst can be fed to a reactor in a dry mode using a dry catalyst feeder, examples of which are well known in the art. Alternatively, a supported transition metal catalyst can be fed to a reactor as a slurry in a suitable diluent. If the transition metal catalyst is not supported, the catalyst can be fed to a reactor as a solution or as a slurry in a suitable solvent or diluents. The components of the polymerization catalyst system, which may include a transition metal catalyst, an activator, a scavenger, an inert support, and a catalyst modifier, may be combined before being added to a polymerization zone, or may combined on the route to a polymerization zone. To combine the components of the polymerization catalyst system on the route to a polymerization zone, which can be fed as solutions or slurries (in suitable solvents or thinners) using various configurations of feed lines that can become coincident before reaching the reactor. Such configurations can be designed to provide areas where the components of the catalyst system flowing into a reactor can mix and react with each other over several "safe" times that can be moderated by changing the flow rates of the solution or paste. fluid from the components of the catalyst system. Catalyst Modifier
[0155] [0155] A "catalyst modifier" is a compound that, when added to a polymerization catalyst system or used in the presence of it in adequate quantities, can reduce, prevent or mitigate at least one: fouling, leaves, variations temperature, and static level of a material in the polymerization reactor; can change the catalyst kinetics; and / or can change the properties of the copolymer product obtained in a polymerization process.
[0156] [0156] A long chain amine catalyst modifier can be added to a reactor zone (or associated processing equipment) separately from the polymerization catalyst system, as part of the polymerization catalyst system, or both, as described in co-pending CA Patent Application No. 2,742,461. The long chain amine can be a long chain substituted monoalkanolamine, or a long chain substituted dialcanolamine, as described in co-pending CA Patent Application No. 2,742,461, which is incorporated herein in its entirety.
[0157] [0157] In one embodiment of the invention, the catalyst modifier employed comprises at least one long-chain amine compound represented by the formula: R9R10xN ((CH2) nOH) y where R9 is a hydrocarbon group having from 5 to 30 carbon atoms, R10 is hydrogen or a hydrocarbyl group having from 1 to 30 carbon atoms, x is 1 or 0, Y is 1, when x is 1, y is 2 when X is 0, each n is independently an integer from 1 to 30, when y is 2, and n is an integer from 1 to 30, when y is 1.
[0158] [0158] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted monoalkanolamine represented by the formula R9R10N ((CH2) nOH) wherein R9 is a hydrocarbon group having 5 to 30 carbon atoms, R10 is a hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and n is an integer from 1-20.
[0159] [0159] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialcanolamine represented by the formula: R9N ((CH2) nOH) ((CH2) mOH) where R9 is a hydrocarbyl group having 5 to 30 enemy carbon atoms are whole numbers from 1-20.
[0160] [0160] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialcanolamine represented by the formula: R9N ((CH2) xOH) 2 where R9 is a hydrocarbyl group having 6 to 30 atoms of carbon, ex is an integer from 1-20.
[0161] [0161] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialcanolamine represented by the formula: R9N ((CH2) xOH) 2 wherein R9 is a hydrocarbyl group having 6 to 30 atoms of carbon, ex is 2 or 3.
[0162] [0162] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialcanolamine represented by the formula: R9N ((CH2) xOH) 2 where R9 is a linear hydrocarbon group having 6 to 30 atoms carbon, ex is 2 or 3.
[0163] [0163] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialcanolamine represented by the formula: R9N (CH2CH2OH) 2 wherein R9 is a linear hydrocarbon group having 6 to 30 carbon atoms.
[0164] [0164] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialcanolamine represented by the formula: R9N (CH2CH2OH) 2 wherein R9 is a linear, saturated alkyl group having 6 to 30 atoms of carbon.
[0165] [0165] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialcanolamine represented by the formula: R9N (CH2CH2OH) 2 wherein R9 is a hydrocarbyl group having 8 to 22 carbon atoms.
[0166] [0166] In one embodiment of the invention, the catalyst modifier comprises a long-chain substituted dialcanolamine represented by the formula: C18H37N (CH2CH2OH) 2.
[0167] [0167] In one embodiment of the invention, the catalyst modifier comprises long-chain substituted dialcanolamine represented by the formulas: C13H27N (CH2CH2OH) 2 and C15H31N (CH2CH2OH) 2.
[0168] [0168] In one embodiment of the invention, the catalyst modifier comprises a mixture of long-chain substituted dialcanolamine represented by the formula: R9N (CH2CH2OH) 2 wherein R9 is a hydrocarbyl group having 8 to 18 carbon atoms.
[0169] [0169] Non-limiting examples of catalyst modifiers that can be used in the present invention are Kemamine AS-990TM, Kemamine AS-650TM, Armostat-1800TM, bis-hydroxy-cocoamine, 2,2'-octadecyl-amino-bisethanol, and Atmer-163TM.
[0170] [0170] The amount of catalyst modifier added to a reactor (or other associated process equipment) is conveniently represented here as the parts per million (ppm) of catalyst modifier based on the weight of the copolymer produced.
[0171] [0171] The amount of modifier catalyst included in a polymerization catalyst system is conveniently represented here as a percentage by weight (% by weight) of catalyst modifier based on the total weight of the polymerization catalyst system (for example, the weight of the transition metal catalyst, the inert support, the co-catalyst and the catalyst modifier).
[0172] [0172] The catalyst modifier can be added to a polymerization reactor in a number of ways. The catalyst modifier can be added to a reactor system separately from the polymerization catalyst system or can be combined with the polymerization catalyst system, before feeding the combination to a reactor system.
[0173] [0173] If the catalyst modifier is added to the polymerization catalyst system before being added to a reactor, then the catalyst modifier can be added at any point during the preparation of the polymerization catalyst system. Thus, a transition metal catalyst, at least one activator, at least one inert support and at least one catalyst modifier can be combined in any order to form a polymerization catalyst system suitable for use in the present invention. In specific embodiments of the invention: the catalyst modifier can be added to a support after both the transition metal catalyst and the cocatalyst have been added; the catalyst modifier can be added to a support before either the transition metal catalyst or the co-catalyst is added; the catalyst modifier can be added to a support after the transition metal catalyst, but before the co-catalyst; the catalyst modifier can be added to a support after the co-catalyst, but before the transition metal catalyst. In addition, the catalyst modifier can be added in portions during any stage of the preparation of the polymerization catalyst system.
[0174] [0174] The catalyst modifier can be included in the polymerization catalyst system (or when appropriate, added to a component of the polymerization catalyst system or components that can comprise a transition metal catalyst, inert support and co-catalyst) in any suitable way. As a non-limiting example, the catalyst modifier can be mixed dry (if it is a solid) with the polymerization catalyst system (or a component of the polymerization catalyst system), or it can be added neat (if the catalyst is a liquid) or can be added as a solution or slurry in a suitable hydrocarbon solvent or diluent, respectively. The polymerization catalyst system (or components of the polymerization catalyst system) can also be put into solution or made into a slurry using suitable solvents or diluents, respectively, followed by the addition of the catalyst modifier (such as a solid or a pure liquid or as a solution or slurry in suitable solvents or thinners) or vice versa. Alternatively, the catalyst modifier can be deposited on a separate support and the resulting supported catalyst modifier mixed in the dry state or in a slurry with the polymerization catalyst system (or a component of the polymerization catalyst system).
[0175] [0175] In one embodiment of the present invention, the catalyst modifier is added to a polymerization catalyst system already comprising the only transition metal catalyst, the inert support and cocatalyst. The catalyst modifier can be added to the polymerization catalyst system off and before the addition of the polymerization catalyst system to the polymerization zone, or the catalyst modifier can be added to the polymerization catalyst system, or components en route to a reactor of polymerization. polymerization.
[0176] [0176] The catalyst modifier can be fed to a reactor system using any suitable method known to those skilled in the art. For example, the catalyst modifier can be fed to a reactor system as a solution or as a slurry in a suitable solvent or diluent, respectively. Suitable solvents or diluents are inert hydrocarbons, well known to those skilled in the art and generally include aromatics, paraffins and cycloparaffins such as, for example, benzene, toluene, xylene, cyclohexane, fuel oil, isobutane, mineral oil, kerosene and the like. Other specific examples include, but are not limited to, hexane, heptanes, isopentane and mixtures thereof. Alternatively, the catalyst modifier can be added to an inert support material and then fed to a polymerization reactor, such as dry food or slurry food. The catalyst modifier can be fed to several locations in a reactor system. When considering a fluidized bed process, for example, the catalyst modifier can be fed directly to any area of the reaction zone (for example, when added as a solution), or any area of the entrainment zone, or it can be fed to any area within the recirculation circuit, where such areas are considered to be effective sites, on which a catalyst modifier is fed.
[0177] [0177] When added as a solution or mixture with a solvent or diluent, respectively, the catalyst modifier can make, for example, from 0.1 to 30% by weight of the solution or mixture, or from 0.1 to 20% by weight, or from 0.1 to 10% by weight, or from 0.1 to 5% by weight or from 0.1 to 2.5% by weight or from 0.2 to 2.0% by weight, despite that one skilled in the art will recognize that even the widest ranges possibly can also be used and therefore the invention should not be limited in this regard.
[0178] [0178] The catalyst modifier can be added to a reactor with all or a portion of one or more of the monomers or the cycle gas.
[0179] [0179] The catalyst modifier can be added to a reactor via a dedicated feed line or added to any convenient feed stream, including an ethylene feed stream, a co-monomer feed stream, a feed line catalyst or a recycling line.
[0180] [0180] The catalyst modifier can be fed to a location in a fluidized bed system in a continuous or intermittent manner.
[0181] [0181] In one embodiment of the invention, the rate of addition of a catalyst modifier to a reactor will be programmed using measured reactor static levels (or other load indicators, such as reactor temperature), as programming inputs, so to maintain a constant or predetermined level of static (or, for example, temperature) in a polymerization reactor.
[0182] [0182] The catalyst modifier can be added to a reactor with a time before, during or after the start of the polymerization reaction.
[0183] [0183] The catalyst modifier can be added to the polymerization catalyst system or to one or more components of the polymerization catalyst system (for example, a phosphinimine catalyst, inert support, or co-catalyst) en route to a reaction zone .
[0184] [0184] In one embodiment of the invention, the catalyst modifier is added directly to a reaction zone, separately from the polymerization catalyst system. More typically, it is added by spraying a solution or mixture of the catalyst modifier directly to a reaction zone.
[0185] [0185] In one embodiment of the invention, the catalyst modifier is included (combined) with the polymerization catalyst system before adding the combination directly to a reaction zone.
[0186] [0186] In one embodiment of the invention, the catalyst modifier is added to a polymer seed bed present in a reactor before starting the polymerization reaction by introducing a catalyst.
[0187] [0187] In one embodiment of the invention, the catalyst modifier is added directly to a reaction zone, separately, from a polymerization catalyst system, and the catalyst modifier is added as a mixture with an inert hydrocarbon.
[0188] [0188] In one embodiment of the invention, the catalyst modifier is added directly to a reaction zone, separately, from a polymerization catalyst system, and the catalyst modifier is added as a mixture with an inert hydrocarbon, and is added during the polymerization reaction.
[0189] [0189] The total amount of catalyst modifier that can be fed to a reactor and / or included in the polymerization catalyst system is not specifically limited, but should not exceed an amount that causes the activity of the polymerization based catalyst system in organotransition metal falls below what would be commercially acceptable.
[0190] [0190] In this regard, the amount of the catalyst modifier fed to a reactor, in general, will not be greater than about 150 ppm, or 100 ppm, or 75 ppm, or 50 ppm, or 25 ppm (parts per million based on the weight of the (co) polymer being produced), while the amount of the catalyst modifier included in the polymerization catalyst system will generally not exceed about 10 weight percent (based on the total weight of the polymerization catalyst system) , including the catalyst modifier).
[0191] [0191] In the embodiments of the invention, the catalyst modifier fed to the reactor will be 150 to 0 ppm, and including narrower ranges within this range, such as, but not limited to, 150 to 1 ppm, or 150 to 5 ppm, or from 100 to 0 ppm, or from 100 to 1 ppm, or from 100 to 5 ppm, or from 75 to 0 ppm, or from 75 to 1 ppm, or from 75 to 5 ppm, or from 50 to 0 ppm, or 50 to 1 ppm, or 50 to 5 ppm, or 25 to 0 ppm, or 25 to 1 ppm, or 25 to 5 ppm (parts per million by weight of the polymer to be produced).
[0192] [0192] In embodiments of the invention, the amount of catalyst modifier included in the polymerization catalyst system will be 0 to 10 weight percent, and including narrower ranges within this range, such as, but not limited to, 0 to 6.0 per cent by weight, or from 0.25 to 6.0 per cent by weight, or from 0 to 5.0 per cent by weight, or from 0.25 to 5.0 per cent by weight, or 0 to 4.5 weight percent, or 0.5 to 4.5 weight percent, or 1.0 to 4.5 weight percent, or 0.75 to 4.0 percent weight weight, or from 0 to 4.0 percent by weight, or from 0.5 to 4.0 percent by weight, or from 1.0 to 4.0 percent by weight, or from 0 to 3.75 percent by percent by weight, or 0.25 to 3.75 percent by weight, or 0.5 to 3.5 percent by weight, or 1.25 to 3.75 percent by weight, or 1, 0 to 3.5 percent by weight, or 1.5 to 3.5 percent by weight, or 0.75 to 3.75 percent by weight, or 1.0 to 3.75 percent by weight (% by weight is the percentage by weight of the catalyst modifier based on the total weight of the s polymerization catalyst system; for example the combined weight of an organotransition metal catalyst, an inert support, a catalyst activator and a catalyst modifier).
[0193] [0193] Other catalyst modifiers can be used in the present invention and include compounds, such as metal carboxylate salts (see, US Patent Numbers 7,354,880; 6,300,436; 6,306,984; 6,391,819; 6,472,342 and 6,608,153, for example), polysulfones, polymeric polyamines and sulfonic acids (see, US Patents Numbers 6,562,924; 6,022,935 and 5,283,278, for example). Polyoxyethylenealkylamines, which are described, for example, in European Patent Application No. 107,127, can also be used. Other catalyst modifiers include aluminum stearate and aluminum oleate. Catalyst modifiers are commercially available under the OCTASTATtm and STADISTM brands The STADIS catalyst modifier is described in U.S. Patent Numbers 7,476,715; 6,562,924 and 5,026,795 and is available from Octel Starreon. STADIS generally comprises a polysulfone copolymer, a polymeric amine and an oil-soluble sulfonic acid.
[0194] [0194] Commercially available catalyst modifiers sometimes contain unacceptable amounts of water for use with polymerization catalysts. Thus, the catalyst modifier can be treated with a substance that eliminates water (for example, with the same reaction, to form inert products, or adsorption or absorption methods), such as an alkyl metal scavenger or molecular sieves. . See, for example, U.S. Patent Application Publication No. 2011/0184124 for the use of a sequestering compound to remove water from a metal carboxylate antistatic agent. Alternatively, and preferably, a catalyst modifier can be dried under reduced pressure and high temperatures to reduce the amount of water present (see, the Examples section below). For example, a catalyst modifier can be treated with high temperatures (for example, at least 10 ° C above room temperature or room temperature) under reduced pressure (for example, below atmospheric pressure) to distill off water, as can be achieved through a dynamic vacuum pump. Kidnapper
[0195] [0195] Optionally, the scavengers are added to the polymerization process. The present invention can be carried out in the presence of any suitable scavenger or scavengers. Kidnappers are well known in the art.
[0196] [0196] In one embodiment of the invention, sequestrants are organoaluminium compounds that have the formula: Al3 (X3) n (X4) 3-n, where (X3) is a hydrocarbil having from 1 to about 20 carbon atoms; (X4) is selected from alkoxide or aryloxide, any of which having from 1 to about 20 carbon atoms; halide; or hydride; and n is an integer from 1 to 3, inclusive; or alkylaluminoxanes having the formula: R32Al1O (R3Al1O) mAl1R32, wherein each R3 is independently selected from the group consisting of C1-20 hydrocarbon radicals and is 3 to 50. Some preferred non-limiting sequestrants useful in the present invention include triisobutylaluminium , triethyl aluminum, trimethyl aluminum or other trialkyl aluminum compounds.
[0197] [0197] The scavenger can be used in any suitable amount, but by way of non-limiting examples only, it can be present in an amount to provide an molar ratio of Al: M (where M is the metal of the organometallic compound) of about 20 to about 2000, or about 50 to about 1000, or about 100 to about 500. Generally, the scavenger is added to the reactor before the catalyst and in the absence of additional poisons and decreases over the course of the time to 0, or is added continuously.
[0198] [0198] Optionally, hijackers can be supported independently. For example, an inorganic oxide that has been treated with an organoaluminium or alkylaluminoxane compound can be added to the polymerization reactor. The method of adding the organoaluminium or alkylaluminoxane compounds to the support is not specifically defined and is carried out by procedures well known in the art. The Composition of Ethylene Copolymer
[0199] [0199] In the present invention, the term "ethylene copolymer" is used interchangeably with the term "copolymer", or "polyethylene copolymer" and all denote a polymer consisting of polymerized ethylene units and at least one type of alpha -polymerized olefin.
[0200] [0200] In the present invention, ethylene copolymer compositions are preferably mixtures of polymers, but optionally cannot be used as a component in a polymer mixture. The term "mixture" of polymer here means to denote a dry mixture of two dissimilar or different polymers, in reactor mixtures that derive from the use of systems with multiple catalysts or mixed in a single reactor zone, and mixtures that result from the use of a catalyst in at least two reactors that operate under different polymerization conditions, or mixtures that involve the use of at least two different catalysts in one or more reactors under the same or different conditions (for example, a resulting mixture from the reactors in series, each running under different conditions or with different catalysts).
[0201] [0201] Preferably, the ethylene copolymer compositions are the copolymers of ethylene and an alpha-olefin selected from 1-butene, 1-hexene and 1-octene.
[0202] [0202] In embodiments of the invention, the ethylene copolymer composition will comprise at least 75% by weight of ethylene units, or at least 80% by weight of ethylene units, or at least 85% by weight of ethylene units with the balance being an alpha-olefin unit, based on the weight of the ethylene copolymer composition.
[0203] [0203] In embodiments of the invention, the ethylene copolymer will have a melt index (I2) of 0.01 to 3.0 g / 10 min, or 0.1 to 2.5 g / 10 min, or 0 , 1 to 2.0 g / 10 min, or from 0.25 to 2.0 g / 10 min, or from 0.01 to 1.0 g / 10 min, or from 0.1 to 1.0 g / 10 min, or less than 1.0 g / 10 min, or 0.1 to less than 1.0 g / 10 min, or 0.25 to 1.0 g / 10 min, or 0, 25 to 0.9 g / 10 min, or from 0.25 to 0.80 g / 10 min, or from 0.2 to 0.9 g / 10 min, or from 0.20 to 0.85 g / 10 min, or from 0.25 to 0.85 g / 10 min. In embodiments of the invention, the ethylene copolymer will have a melt index (I2) of more than 1.0 to 2.0 g / 10 min, or greater than 1.0 to 1.75 g / 10 min, or greater than 1.0 to 1.5 g / 10 min.
[0204] [0204] In embodiments of the invention, the ethylene copolymer will have a density of 0.916 g / cc to 0.936 g / cc, including narrower ranges within this range, such as, for example, 0.916 g / cc to 0.935 g / cc , or from 0.916 g / cc to 0.932 g / cc, or from 0.916 g / cc to 0.930 g / cc, or from 0.917 g / cc to 0.932 g / cc, or from 0.916 g / cc to 0.930 g / cc, or 0.917 g / cc to 0.930 g / cc, or 0.916 g / cc to 0.925 g / cc, or 0.917 g / cc to 0.927 g / cc, or 0.917 g / cc to 0.926 g / cc, or 0.917 g / cc to 0.925 g / cc, or from 0.917 g / cc to 0.923 g / cc, from 0.918 g / cc to 0.932 g / cc, or from 0.918 g / cc to 0.930 g / cc, or from 0.918 to 0.930 g / cc, or from 0.918 to 0.928 g / cc, or from 0.920 to 0.935 (note: "g" means grams; "cc" means cubic centimeter, cm3).
[0205] [0205] In one embodiment of the invention, the ethylene copolymer will have a density of 0.916 g / cc to 0.936 g / cc. In one embodiment of the invention, the ethylene copolymer will have a density greater than 0.916 g / cc to less than 0.930 g / cc. In one embodiment of the invention, the ethylene copolymer will have a density of 0.917 g / cc to 0.927 g / cc. In one embodiment of the invention, the ethylene copolymer composition will have a density of 0.918 g / cc to 0.927 g / cc.
[0206] [0206] The ethylene copolymer of the present invention can have a unimodal, wide unimodal, bimodal, or multimodal profile in a gel permeation chromatography (GPC) curve generated according to the ASTM D6474-99 method. The term "unimodal" is defined here to mean that there will only be a significant or maximum peak evident on the GPC curve. A unimodal profile includes a wide unimodal profile. By the term "bimodal" it is meant that in addition to a first peak, there will be a secondary peak or shoulder, which represents a component of higher or lower molecular weight (that is, the molecular weight distribution, it can be said that has two maximums on a molecular weight distribution curve). Alternatively, the term "bimodal" denotes the presence of two maxima in a molecular weight distribution curve generated according to the ASTM D6474-99 method. The term "multimodal" denotes the presence of two or more maxima of a molecular weight distribution curve generated according to the ASTM D6474-99 method.
[0207] [0207] In one embodiment of the invention, the ethylene copolymer will have a unimodal profile on a gel permeation chromatography (GPC) curve generated according to the ASTM D6474-99 method. The term "unimodal" is defined here to mean that there will only be a significant or maximum peak evident on the GPC curve. A unimodal profile includes a wide unimodal distribution curve or profile.
[0208] [0208] In embodiments of the invention, the ethylene copolymer will have an average molecular weight by weight (Mw), as determined by gel permeation chromatography (GPC) from 30,000 to 250,000, including narrower ranges within this range, such as, for example, from 50,000 to 200,000, or from 50,000 to 175,000, or from 75,000 to 150,000, or from 80,000 to 130,000.
[0209] [0209] In embodiments of the invention, the ethylene copolymer will have an average number of molecular weight (Mn), as determined by gel permeation chromatography (GPC) from 5,000 to 100,000, including narrower ranges within this range , such as, for example, from 7,500 to 100,000, or from 7,500 to 75,000, or from 7500 to 50000, or from 10,000 to 100,000, or from 10,000 to 75,000, or from 10,000 to 50,000.
[0210] [0210] In embodiments of the invention, the ethylene copolymer will have an average molecular weight Z (Mz) as determined by gel permeation chromatography (GPC) from 50,000 to 1,000,000, including narrower ranges within this range, such as, for example, from 75,000 to 750,000, or from 100,000 to 500,000, or from 100,000 to 400,000, or from 125,000 to 375,000, or from 150,000 to 350,000, or from 175,000 to 375,000, or from 175,000 to 400,000, or from 200,000 to 400,000 or 225,000 to 375,000.
[0211] [0211] In embodiments of the invention, the ethylene copolymer will have a molecular weight distribution (Mw / Mn), as determined by gel permeation chromatography (GPC) from 3.5 to 7.0, including narrower ranges within this range, such as, for example, from 3.5 to 6.5, or from 3.6 to 6.5 or from 3.6 to 6.0 or from 3.5 to 5.5, or from 3.6 to 5.5, or from 3.5 to 5.0, or from 4.5 to 6.0, or from 4.0 to 6.0, or from 4.0 to 5.5.
[0212] [0212] In embodiments of the invention, the ethylene copolymer will have a distribution of the average molecular weight Z (Mw / Mn), as determined by gel permeation chromatography (GPC) from 2.0 to 5.5, including ranges narrower within this range, such as, for example, from 2.0 to 5.0, or from 2.0 to 4.5, or from 2.0 to 4.0, or from 2.0 to 2 , 5, or 2.0 to 3.0, or 2.0 to 3.5.
[0213] [0213] In one embodiment of the invention, the ethylene copolymer will have a flat co-monomer incorporation profile, as measured using gel permeation chromatography with Fourier Transformed Infrared Detection (GPC-FTIR). In one embodiment of the invention, the ethylene copolymer will have a negative (i.e., "normal") co-monomer incorporation profile as measured using GPC-FTIR. In one embodiment of the invention, the ethylene copolymer will have a partially reverse or reverse (i.e., "reverse") co-monomer incorporation profile, as measured using GPC-FTIR. If the co-monomer incorporation decreases with molecular weight, as measured using GPC-FTIR, the distribution is described as "normal" or "negative". If the co-monomer incorporation is approximately constant, with a molecular weight, as measured using GPC-FTIR, the co-monomer distribution is described as "flat" or "uniform". The terms "reverse co-monomer distribution" and "partially reverse co-monomer distribution" mean that, in the GPC-FTIR data obtained for the copolymer, there are one or more larger molecular weight components having a co-monomer incorporation greater than in one or more lower molecular weight segments. The term "reverse comonomer distribution (d)" is used here to mean that across the molecular weight range of the ethylene copolymer, the co-monomer contents for the various polymer fractions are not substantially uniform and the weight fractions Larger molecular molecules have proportionally larger co-monomer contents (ie, if the co-monomer incorporation increases with molecular weight, the distribution is described as "reverse" or "reversed"). When the comonomer incorporation increases with increasing molecular weight and then decreases, the co-monomer distribution is still considered "reverse", but it can also be described as "partially reverse".
[0214] [0214] In one embodiment of the invention, the ethylene copolymer has an inverted co-monomer incorporation profile, as measured using GPC-FTIR.
[0215] [0215] In one embodiment of the invention, the ethylene copolymer will have a co-monomer incorporation profile, as determined by GPC-FTIR that satisfies the following condition: SCB / 1000C to 200,000 Mw - SCB / 1000C to 50,000 Mw is greater than 0; where "-" is a minus sign, SCB / 1000C is the co-monomer content determined as the number of short chain branches per thousand carbon atoms and Mw is the corresponding molecular weight (that is, the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0216] [0216] In one embodiment of the invention, the ethylene copolymer will have a co-monomer incorporation profile, as determined by GPC-FTIR which satisfies the following condition: SCB / 1000C to 200,000 Mw - SCB / 1000C to 50,000 Mw is greater than 1.0; where SCB / 1000C is the co-monomer content determined as the number of short chain branches per thousand carbon atoms and Mw is the corresponding molecular weight (ie the absolute molecular weight) in a GPC or GPC-FTIR chromatography .
[0217] [0217] In one embodiment of the invention, the ethylene copolymer will have a co-monomer incorporation profile, as determined by GPC-FTIR which satisfies the following condition: SCB / 1000C to 200,000 Mw - SCB / 1000C to 50,000 Mw is greater than 2.0; where SCB / 1000C is the co-monomer content determined as the number of short chain branches per thousand carbon atoms and Mw is the corresponding molecular weight (ie the absolute molecular weight) in a GPC or GPC-FTIR chromatography .
[0218] [0218] In one embodiment of the invention, the ethylene copolymer will have a co-monomer incorporation profile, as determined by GPC-FTIR that satisfies the following condition: SCB / 1000C to 200,000 Mw - SCB / 1000C to 50,000 Mw > 3.0; where SCB / 1000C is the co-monomer content determined as the number of short chain branches per thousand carbon atoms and Mw is the corresponding molecular weight (ie the absolute molecular weight) in a GPC or GPC-FTIR chromatography .
[0219] [0219] In one embodiment of the invention, the ethylene copolymer will have a co-monomer incorporation profile, as determined by GPC-FTIR which satisfies the following condition: SCB / 1000C to 200,000 Mw - SCB / 1000C to 50,000 Mw > 4.0; where SCB / 1000C is the co-monomer content determined as the number of short chain branches per thousand carbon atoms and Mw is the corresponding molecular weight (that is, the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0220] [0220] In one embodiment of the invention, the ethylene copolymer will have a co-monomer incorporation profile, as determined by GPC-FTIR which satisfies the following condition: SCB / 1000C to 200,000 Mw - SCB / 1000C to 50,000 Mw > 5.0; where SCB / 1000C is the co-monomer content determined as the number of short chain branches per thousand carbon atoms and Mw is the corresponding molecular weight (that is, the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0221] [0221] In one embodiment of the invention, the ethylene copolymer will have a co-monomer incorporation profile, as determined by GPC-FTIR which satisfies the following condition: SCB / 1000C to 200,000 Mw - SCB / 1000C to 50,000 Mw > 6.0; where SCB / 1000C is the co-monomer content determined as the number of short chain branches per thousand carbon atoms and Mw is the corresponding molecular weight (that is, the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0222] [0222] In an embodiment of the invention, the ethylene copolymer will have a co-monomer incorporation profile, as determined by GPC-FTIR which satisfies the following condition: SCB / 1000C to 200,000 Mw - SCB / 1000C to 50,000 Mw from 2.0 to 8.0 including narrow ranges within this range; where SCB / 1000C is the co-monomer content determined as the number of short chain branches per thousand carbon atoms and Mw is the corresponding molecular weight (ie the absolute molecular weight) in a GPC or GPC-FTIR chromatography .
[0223] [0223] In one embodiment of the invention, the ethylene copolymer will have a co-monomer incorporation profile, as determined by GPC-FTIR which satisfies the following condition: SCB / 1000C to 200,000 Mw - SCB / 1000C to 50,000 Mw from 3.0 to 7.0 including narrow ranges within this range; where SCB / 1000C is the co-monomer content determined as the number of short chain branches per thousand carbon atoms and Mw is the corresponding molecular weight (ie the absolute molecular weight) in a GPC or GPC-FTIR chromatography .
[0224] [0224] In one embodiment of the invention, the ethylene copolymer will have a melt flow ratio (the MFR = I21 / I2) from 28 to 60 or from 30 to 60 or from 32 to 60. In other embodiments of the invention , the ethylene copolymer will have an I21 / I2 from 30 to 55, or from 30 to 50, or from 30 to 45, or from 32 to 50 or from 35 to 55, or from 36 to 50 or from 36 to 48 , or from 36 to 46, or from 35 to 50, or greater than 35 to less than 50, or greater than 35 to 50.
[0225] [0225] In one embodiment of the invention, the ethylene copolymer has a melt flow ratio (I21 / I2) greater than about 30 to 50. In one embodiment of the invention, the ethylene copolymer has a melt flow ratio melt (I21 / I2) from 32 to 50. In one embodiment of the invention, the ethylene copolymer has a melt flow ratio (I21 / I2) from 35 to 50. In one embodiment of the invention, the copolymer ethylene has a melt flow ratio (I21 / I2) from 30 to 55. In one embodiment of the invention, the ethylene copolymer has a melt flow ratio (I21 / I2) from 32 to 55. In one embodiment of the invention, the ethylene copolymer has a melt flow ratio (I21 / I2) from 35 to 55.
[0226] [0226] In embodiments of the invention, the ethylene copolymer will have a distribution width index of the CDBI50 composition, as determined by temperature elution fractionation (TREF) from 40% to 75% by weight, or 45% at 75% by weight, or from 50% to 75% by weight, or from 55% to 75% by weight, or from 60% to 75% by weight. In embodiments of the invention, the ethylene copolymer will have a CDBI50 from 50% to 70%, or 55% to 70%, or from 50% to 69%, or from 55% to 69%, or from 55% to 65 %, or from 60% to 75%, or from 60% to 70%, or from 60% to 69%, or from 55% to 67%, or from 60% to 66% (by weight).
[0227] [0227] In one embodiment of the invention, the ethylene copolymer has a CDBI50 from 50% by weight to 77% by weight. In an embodiment of the invention, the ethylene copolymer has a CDBI50 from 55% by weight to 75% by weight. In one embodiment of the invention, the ethylene copolymer has a CDBI50 from 60% by weight to 73% by weight.
[0228] [0228] The distribution of the composition of an ethylene copolymer can also be characterized by the value T (75) - T (25), where T (25) is the temperature at which 25% by weight of the eluted copolymer is obtained, and T (75) is the temperature at which 75% by weight of the eluted copolymer is obtained through a TREF experiment.
[0229] [0229] In one embodiment of the present invention, the ethylene copolymer will have a T (75) - T (25) from 5 to 25 ° C, as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T (75) - T (25) from 7 to 25 ° C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T (75) - T (25) from 10 to 25 ° C, as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T (75) - T (25) from 7 to 22.5 ° C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T (75) - T (25) from 7.0 to 20 ° C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T (75) -T (25) from 5 to 17.5 ° C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T (75) - T (25) from 7 to 17.5 ° C as determined by TREF.
[0230] [0230] In embodiments of the invention, the ethylene copolymer will have a CY α-parameter (also called the Carreau-Yasuda shear exponent) from 0.01 to 0.4, or from 0.05 to 0, 4, or from 0.05 to 0.3, or from 0.01 to 0.3, or from 0.01 to 0.25, or from 0.05 to 0.30, or from 0.05 to 0, 25.
[0231] [0231] In embodiments of the invention, the ethylene copolymer will have a normalized pseudoplasticity index, SHI @ 0.1 rad / s (ie η * 0.1 / η0) from 0.001 to 0.90, or from 0.001 to 0.8, or from 0.001 to 0.5, or less than 0.9, or less than 0.8, or less than 0.5.
[0232] [0232] In one embodiment of the invention, the ethylene copolymer will have a TREF profile, as measured by elution fractionation of increasing temperature, which is multimodal, comprising at least two peak elution intensities or peaks.
[0233] [0233] In one embodiment of the invention, the ethylene copolymer will have an amount of elution copolymer at a temperature of 40 ° C or less, less than 5% by weight, as determined by elution fractionation of increasing temperature ( TREF).
[0234] [0234] In an embodiment of the invention, the ethylene copolymer will have an amount of elution copolymer at a temperature of about 90 ° C 105 ° C, from 5 to 30% by weight, as determined by elution fractionation of increasing temperature (TREF). In an embodiment of the invention, from 5 to 25% by weight of the ethylene copolymer will be represented within a temperature range of about 90 ° C to 105 ° C in a TREF profile. In an embodiment of the invention, from 7.5 to 25% by weight of the ethylene copolymer will be represented within a temperature range of about 90 ° C to 105 ° C in a TREF profile. In an embodiment of the invention, from 10 to 25% by weight of the ethylene copolymer will be represented within a temperature range of about 90 ° C to 105 ° C in a TREF profile. In another embodiment of the invention, from 5 to 22.5% by weight of the ethylene copolymer will be represented at a temperature range of about 90 ° C to 105 ° C in a TREF profile. In another embodiment of the invention, from 5 to 20.0% by weight of the ethylene copolymer will be represented at a temperature range of about 90 ° C to 105 ° C in a TREF profile.
[0235] [0235] In embodiments of the invention, less than 1% by weight, or less than 0.5% by weight, or less than 0.05% by weight, or 0% by weight of the ethylene copolymer will elute at a temperature above 100 ° C in a TREF analysis.
[0236] [0236] In one embodiment of the invention, the ethylene copolymer will have a TREF profile, as measured by elution fractionation of increasing temperature, comprising: i) a multimodal TREF profile that comprises at least two maxima of light intensity. elution (or peaks); ii) less than 5% by weight of the copolymer represented at a temperature equal to or less than 40 ° C; and iii) from 5 to 25% by weight of the copolymer represented at a temperature of about 90 ° C to 105 ° C.
[0237] [0237] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile that comprises at least two elution intensity maximums (or peaks).
[0238] [0238] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by at least two intensity maximums (or peaks) that occur at elution temperatures T (low), and T (high), where T (low) is 60 ° C to 87 ° C, and T (high) is 88 ° C to 100 ° C.
[0239] [0239] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by at least two intensity maximums (or peaks) that occur at elution temperatures T (low), and T (high), where T (low) is 62 ° C to 87 ° C, and T (high) is 89 ° C to 100 ° C.
[0240] [0240] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by at least two intensity maximums (or peaks) that occur at elution temperatures T (low), and T (high), where T (low) is 65 ° C to 85 ° C, and T (high) is 90 ° C to 100 ° C.
[0241] [0241] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by at least two intensity maximums (or peaks) that occur at eluting temperatures T (low), and T (high), where T (low) is 65 ° C to 85 ° C, and T (high) is 90 ° C to 98 ° C.
[0242] [0242] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by at least two intensity maximums (or peaks) that occur at elution temperatures T (low), and T (high), where T (low) is 70 ° C to 85 ° C, and T (high) is 90 ° C to 98 ° C.
[0243] [0243] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by at least two intensity maximums (or peaks) that occur at elution temperatures T (low), and T (high), where T (low) is 70 ° C to 80 ° C, and T (high) is 90 ° C to 98 ° C.
[0244] [0244] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by at least two intensity maximums (or peaks) that occur at elution temperatures T (low), and T (high), where T (low) is 70 ° C to 80 ° C, and T (high) is 90 ° C to 95 ° C.
[0245] [0245] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by at least two elution intensity maximums (or peaks) that occur at elution temperatures T (low), and T (high ), where T (high) - (low) is 7.5 ° C to 35 ° C, or 10.0 ° C to 30 ° C, or 12.5 ° C to 30 ° C, or 7.0 ° C to 27 ° C, or 7 ° C to 25 ° C, or 10 ° C to 27 ° C, or 10 ° C to 25 ° C, or and 10 ° C to 22.5 ° C, or from 12.5 ° C to 22.5 ° C.
[0246] [0246] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by at least two intensity maximums (or peaks) that occur at elution temperatures T (low), and T (high), where T (low) is 65 ° C to 85 ° C, and T (high) is 90 ° C to 98 ° C, where T (high) - (low) is 7.5 ° C to 35 ° C, or from 10.0 ° C to 30 ° C, or from 12.5 ° C to 30 ° C, or from 7.0 ° C to 27 ° C, or from 7 ° C to 25 ° C , or from 10 ° C to 27 ° C, or from 10 ° C to 25 ° C, or from 10 ° C to 22.5 ° C, or from 12.5 ° C to 22.5 ° C.
[0247] [0247] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile that comprises at least three elution intensity maximums (or peaks).
[0248] [0248] In one embodiment of the invention, the ethylene copolymer has a trimodal TREF profile that comprises three maximums of elution intensity (or peaks).
[0249] [0249] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (average or "med" for abbreviate) and T (high), where the intensity of the T (low) and T (high) peaks is greater than the intensity of the T peak (med).
[0250] [0250] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (average or "med" for abbreviate) and T (high), where T (low) is 60 ° C to 87 ° C, T (high) is 88 ° C to 100 ° C, and T (med) is greater than T (low) , but less than T (high).
[0251] [0251] In an embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (average or "med" for abbreviate) and T (high), where T (low) is 62 ° C to 87 ° C, T (high) is 89 ° C to 100 ° C, and T (med) is greater than T (low) , but less than T (high).
[0252] [0252] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (average or "med" for abbreviate) and T (high), where T (low) is 65 ° C to 85 ° C, T (high) is 90 ° C to 100 ° C, and T (med) is greater than T (low) , but less than T (high).
[0253] [0253] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (average or "med" for abbreviate) and T (high), where T (low) is 65 ° C to 85 ° C, T (high) is 90 ° C to 98 ° C, and T (med) is greater than T (low) , but less than T (high).
[0254] [0254] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (average or "med" for abbreviate) and T (high), where T (low) is 65 ° C to 80 ° C, T (high) is 90 ° C to 98 ° C, and T (med) is greater than T (low) , but less than T (high).
[0255] [0255] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (average or "med" for abbreviate) and T (high), where T (low) is 65 ° C to 87 ° C, T (high) is 88 ° C to 100 ° C, and T (med) is greater than T (low) , but less than T (high), where T (high) - (low) is 7.5 ° C to 35 ° C, or 10.0 ° C to 30 ° C, or 12.5 ° C at 30 ° C, or from 7.0 ° C to 27 ° C, or from 7 ° C to 25 ° C, or from 10 ° C to 27 ° C, or from 10 ° C to 25 ° C.
[0256] [0256] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (average or "med" for abbreviate) and T (high), where T (low) is 62 ° C to 82 ° C, T (med) is 76 ° C to 89 ° C, but is greater than T (low), and T ( high) is 90 ° C to 100 ° C. In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (mean or "med" for short) and T (high), where T (low) is 65 ° C to 80 ° C, T (med) is 75 ° C to 90 ° C, but is greater than T (low), and T (high) is from 90 ° C to 100 ° C, but it is greater than T (med). In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (mean or "med" for short) and T (high), where T (low) is 67 ° C to 78 ° C, T (med) is 79 ° C to 89 ° C, and T (high) is 90 ° C to 100 ° C. In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (mean or "med" for short) and T (high), where T (low) is 67 ° C to 78 ° C, T (med) is 80 ° C to 87 ° C, and T (high) is 88 ° C to 98 ° C.
[0257] [0257] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (mean or "med" for short) ) and T (high), where T (med) -T (low) is 3 ° C to 25 ° C, or 5 ° C to 20 ° C; or from 5 ° C to 15 ° C, or from 7 ° C to 15 ° C.
[0258] [0258] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (mean or "med" for short) ) and T (high), where T (high) -T (med) is 3 ° C to 20 ° C, or 3 ° C to 17 ° C, or 3 ° C to 15 ° C, or 5 ° C to 20 ° C, or 5 ° C to 17 ° C, or 5 ° C to 15 ° C, or 7 ° C to 17 ° C, or 7 ° C to 15 ° C or 10 ° C to 17 ° C, or 10 ° C to 15 ° C.
[0259] [0259] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (mean or "med" for short) ) and T (high), where T (high) -T (low) is 15 ° C to 35 ° C, or 15 ° C to 30 ° C, or 17 ° C to 30 ° C, or 15 ° C to 27 ° C, or 17 ° C to 27 ° C, or 20 ° C to 30 ° C or 20 ° C to 27 ° C, or 15 ° C to 25 ° C or 15 ° C at 22.5 ° C.
[0260] [0260] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile that comprises three elution intensity maximums (or peaks) that occur at elution temperatures T (low), t (average or "med" for abbreviate) and T (high), where the intensity of the T (low) and T (high) peaks are greater than the intensity of the peak in T (med); and where T (med) -T (low) is 3 ° C to 25 ° C; where T (high) -T (med) is 5 ° C to 15 ° C; and where T (high) -T (low) is 15 ° C to 35 ° C.
[0261] [0261] In an embodiment of the invention, the ethylene copolymer has a multimodal TREF profile that comprises three elution intensity maximums (or peaks) that occur at elution temperatures T (low), T (average or "med" for abbreviate) and T (high), where the intensity of the T (low) and T (high) peaks are greater than the intensity of the peak in T (med); and where T (med) -T (low) is 3 ° C to 15 ° C; where T (high) - T (med) is 5 ° C to 15 ° C; and where T (high) - T (low) is 15 ° C to 30 ° C.
[0262] [0262] In one embodiment of the invention, the ethylene copolymer has two melting peaks, as measured by differential scanning calorimetry (DSC).
[0263] [0263] In embodiments of the invention, the ethylene copolymer will have a hexane extraction level of ≤ 3.0% by weight, or ≤ 2.0% by weight, or ≤ 1.5% by weight or ≤ 1.0 % by weight. In one embodiment of the invention, the copolymer has a hexane extraction level of 0.2 to 3.0% by weight, or 0.2 to 2.5% by weight, or 0.2 to 2.0% by weight. weight, or 0.2 to 1.0% by weight.
[0264] [0264] In one embodiment of the invention, the ethylene copolymer satisfies the ratio:
[0265] [0265] (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)].
[0266] [0266] In one embodiment of the invention, the ethylene copolymer satisfies the ratio: δχO ≤ 83.0 - 1.25 (CDBl5o) / (Mw / Mn), where δχO is the passing phase angle from a graph Van Gurp-Palmen (VGP) as determined by dynamic mechanical analysis (DMA) and CDBI50 is the co-monomer distribution width index, as determined by TREF analyzes.
[0267] [0267] In one embodiment of the invention, the ethylene copolymer satisfies the ratio: δχO ≤ 80.7 - (CDBl5o) / (Mw / Mn), at a δχO of 55 ° to 70 °, where δχO is the phase angle pass-through from a Van Gurp-Palmen (VGP) graph, as determined by dynamic mechanical analysis (DMA) and CDBI50 is the co-monomer distribution width index, as determined by TREF analyzes.
[0268] [0268] In one embodiment of the invention, the ethylene copolymer satisfies the following ratios: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)] and δχO ≤ 83.0 - 1, 25 (CDBl50) / (Mw / Mn) where δχO is the passing phase angle from a Van Gurp-Palmen graph (VGP) as determined by dynamic mechanical analysis (DMA) and CDBI50 is the distribution width index co-monomer as determined by TREF analyzes.
[0269] [0269] In one embodiment of the invention, the ethylene copolymer satisfies the following ratios: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]; and δχO ≤ 80.7 - (CDBl50) / (Mw / Mn) at an δχO of 55 ° to 70 °; where δχO is the angle of passage phase from a Van Gurp-Palmen graph (VGP), as determined by dynamic mechanical analysis (DMA) and CDBI50 is the width index of the comonomer distribution, as determined by TREF analyzes .
[0270] [0270] In one embodiment of the invention, the ethylene copolymer satisfies the following ratios: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]; and δχO ≤ 80.7 - (CDBl50) / (Mw / Mn) at an δχO of 55 ° to 70 °; and δχO ≤ 83.0 - 1.25 (CDBl50) / (Mw / Mn), where δχO is the passage phase angle from a Van Gurp-Palmen graph (VGP), as determined by dynamic mechanical analysis ( DMA) and CDBI50 is the co-monomer distribution width index, as determined by TREF analyzes. Film Production
[0271] [0271] The extrusion film process is a well-known process for preparing plastic film. The process uses an extruder that heats, melts and transmits the molten plastic and forces it through an annular mold. Typical extrusion temperatures are 330 to 500 ° F, especially 350 to 460 ° F.
[0272] [0272] The polyethylene copolymer film is removed from the mold and formed into a tube shape and eventually passed through a pair of drawing and grooving cylinders. The internal compressed air is then introduced from a mandrel causing the tube to increase in diameter forming a "bubble" of the desired size. Thus, the blown film is stretched in two directions, that is, in the axial direction (by using forced air that "blows out" the diameter of the bubble) and in the longitudinal direction of the bubble (by the action of a winding element which pull the bubble through the machinery). External air is also introduced around the circumference of the bubble to cool the molten material as it leaves the mold. The film width is varied by introducing more or less internal air into the bubble, thereby increasing or decreasing the size of the bubble. Film thickness is mainly controlled by increasing or decreasing the speed of the drawing cylinder and groove cylinder to control the drawing rate.
[0273] [0273] The bubble is then grouped immediately after passing through the drawing and groove cylinders. The cooled film can then be further processed by cutting or sealing to produce a variety of consumer products. Although not intended to be limited by theory, it is generally believed by those skilled in the blown film making technique that the physical properties of the finished films are influenced both by the molecular structure of the ethylene copolymer and by the processing conditions. For example, processing conditions are designed to influence the degree of molecular orientation (both in the machine direction and the axial or transverse direction).
[0274] [0274] A balance of "machine direction" ("MD") and "transverse direction" ("TD" - which is perpendicular to the MD) molecular orientation is generally considered desirable for the films associated with the invention (for example, Dart Impact Resistance, Machine Direction and Cross Direction Wear Properties may be affected).
[0275] [0275] Thus, it is recognized that these stretching forces on the "bubble" can affect the physical properties of the finished film. In particular, it is known that the "burst ratio" (i.e., the ratio of the diameter of the blown bubble to the diameter of the annular mold) can have a significant effect on the dart impact resistance and wear resistance of the finished film. .
[0276] [0276] The above description refers to the preparation of monolayer films. Multilayer films can be prepared by 1) a "coextrusion" process that allows more than one flow of molten polymer to be introduced into an annular mold, resulting in a multilayer film membrane or 2) a lamination process , in which the layers of film are laminated together.
[0277] [0277] In one embodiment of the invention, the films of the present invention are prepared using the blown film process described above.
[0278] [0278] An alternative process is the so-called molten film process, in which the polyethylene is melted in an extruder and then forced through a linear slit mold, thereby "layered overlay" of a thin flat film . The extrusion temperature for molten film is typically slightly warmer than that used in the blown film process (which generally operates at temperatures of about 450 to 550 ° F). In general, the molten film is cooled (quenched) more quickly than the blown film.
[0279] [0279] In one embodiment of the invention, the films of the present invention are prepared using a fused film process. Additions
[0280] [0280] The ethylene copolymer composition used in the present invention to make films, can also contain additives, such as, for example, primary antioxidants (such as, hindered phenols, including vitamin E); secondary antioxidants (especially phosphites and phosphonites); nucleating agents, plasticizers or processing aids for polymer PPAs (eg fluorine-elastomer and / or polyethylene glycol process aid), acid scavengers, stabilizers, anti-corrosion agents, blowing agents, other ultraviolet light absorbers , such as chain-breaking antioxidants, etc., sudden coolers, anti-static agents, gliding agents, anti-blocking agents, pigments, dyes and fillers and curing agents, such as peroxide.
[0281] [0281] These and other additives common in the polyolefin industry can be present in copolymer compositions from 0.01 to 50% by weight in one embodiment, and from 0.1 to 20% by weight in another embodiment, and from 1 at 5% by weight, in yet another embodiment, in which a desirable range can comprise any combination of any limit greater than% by weight with any limit less than% by weight.
[0282] [0282] In one embodiment of the invention, antioxidants and stabilizers, such as organic phosphites and phenolic antioxidants can be present in the copolymer compositions from 0.001 to 5% by weight in one embodiment, and from 0.01 to 0.8% by weight , in another modality, and from 0.02 to 0.5% by weight, in yet another modality. Non-limiting examples of organic phosphites that are suitable are tris (2,4-di-tert-butylphenyl) phosphite (IRGAFOS 168) and tris (nonyl-phenyl) phosphite (WESTON 399). Examples of non-limiting phenolic antioxidants include octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinamate (IRGANOX 1076) and pentaerythrityl tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1010 ); and 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate (IRGANOX 3114).
[0283] [0283] Fillers can be present in the ethylene copolymer composition from 0.1 to 50% by weight in one embodiment, and from 0.1 to 25% by weight of the composition, in another embodiment, and from 0.2 to 10% by weight, in yet another modality. Fillers include, but are not limited to, titanium dioxide, silicon carbide, silica (and other silica oxides, precipitated or not), antimony oxide, lead carbonate, white zinc, lithopone, zircon, corundum, spinel, apatite, Barytes powder, barium sulfate, magnesite, carbon black, dolomite, calcium carbonate, talc and hydrotalcite compounds of Mg, Ca, or Zn ions with Al, Cr or Fe and CO3 and / or HPO4 , hydrated or not; quartz powder, hydrochloric magnesium carbonate, glass fibers, clays, alumina, and other metal oxides and carbonates, metal hydroxides, chromium, phosphorus and brominated flame retardants, antimony trioxide, silica, silicone, and mixtures thereof . These fillers can include any other fillers and porous fillers and supports that are known in the art.
[0284] [0284] Fatty acid salts may also be present in the copolymer compositions. Such salts can be present from 0.001 to 2% by weight of the copolymer composition in one embodiment, and from 0.01 to 1% by weight, in another embodiment. Examples of fatty acid metal salts include lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, and erucic acid, suitable metals including Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb and so on. Desirable fatty acid salts are selected from magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, and magnesium oleate.
[0285] [0285] With regard to the physical process of producing the mixture of the ethylene copolymer and one or more additives, sufficient mixing must occur to ensure that a uniform mixture will be produced prior to conversion into finished products. The copolymer can be in any physical form when used to mix with one or more additives. In one embodiment, the reactor granules, defined as the polymer granules that are isolated from the polymerization reactor, are used to mix with the additives. The reactor granules have an average diameter of 10 μm to 5 mm, and 50 μm to 10 mm in another modality. Alternatively, the ethylene copolymer is in the form of pellets, such as, for example, having an average diameter of 1 mm to 6 mm, which is formed from the melt extrusion of the reactor granules.
[0286] [0286] One method for mixing the additives with the ethylene copolymer is to contact the components in a drum or other physical mixing means, the copolymer being in the form of reactor granules. This can be followed, if desired, by mixing a melt in an extruder. Another method of mixing the components is to melt the mixture with the copolymer pellets with the additives directly in an extruder, or any other melt mixing means. Film Properties
[0287] [0287] The film or film layer of the present invention is made from ethylene copolymers as defined above. Generally, an additive as described above is mixed with the ethylene copolymer prior to film production. Copolymers of ethylene and films have a balance of processing and mechanical properties. Therefore, the films of the present invention are made from an ethylene copolymer having an I2 melt index below 1.0 g / 10 min, which will have a dart impact resistance of ≥ 400 g / mil, an 1% MD secant module greater than 140 MPa, and 1% TD secant module greater than 170 MPa, in combination with good film processing production rates. Alternatively, the films of the present invention are made from an ethylene copolymer having an I2 melting index of between 1 and 2 g / 10 min, will have a dart impact resistance of ≥ 200 g / mil, a drying module 1% MD greater than 190 MPa, and a 1% TD drying module greater than 210 MPa, in combination with good film processing production rates.
[0288] [0288] In embodiments of the invention, the film will have a dart impact of ≥ 400 g / mil, or ≥ 450 g / mil, or ≥ 500 g / mil, or ≥ 550 g / mil, or ≥ 600 g / mil or 650 ≥g / mil or ≥ 700 g / mil. In one embodiment of the invention, the film will have a dart impact of 400 g / mil to 950 g / mil. In one embodiment of the invention, the film will have a dart impact of 400 g / mil to 850 g / mil. In another embodiment of the invention, the film will have a dart impact of 400 g / mil to 750 g / mil. In another embodiment of the invention, the film will have a dart impact from 500 g / mil to 950 g / mil. In another embodiment of the invention, the film will have a dart impact from 500 g / mil to 850 g / mil. In another embodiment of the invention, the film will impact with dart from 500 g / mil to 750 g / mil. In yet another embodiment of the invention, the film will impact with dart from 550 g / mil to 950 g / mil. In yet another embodiment of the invention, the film will have a dart impact of 550 g / mil to 850 g / mil. In yet another embodiment of the invention, the film will impact with dart from 550 g / mil to 750 g / mil. In yet another embodiment of the invention, the film will impact with dart from 600 g / mil to 950 g / mil. In yet another embodiment of the invention, the film will have a dart impact of 600 g / mil to 850 g / mil. In another embodiment of the invention, the film will have a dart impact of 400 g / mil to 700 g / mil. In another embodiment of the invention, the film will have a dart impact of 400 g / mil to 650 g / mil.
[0289] [0289] In one embodiment of the invention, the film will have a dart impact of ≥ 200 g / mil.
[0290] [0290] In embodiments of the invention, the film will have an MD wear to TD wear ratio (MD wear / TD wear) less than 0.75, or ≤ 0.70, or ≤ 0.60, or ≤ 0.50 , or ≤ 0.45, or ≤ 0.40, or ≤ 0.35, or ≤ 0.30. In another embodiment of the invention, the film will have an MD wear ratio for TD wear of 0.010 to 0.75. In yet another embodiment of the invention, the film will have an MD wear to TD wear ratio of 0.05 to 0.6. In yet another embodiment of the invention, the film will have a wear ratio MD to wear TD of 0.05 to 0.55. In still other embodiments of the invention, the film will have a wear ratio MD to wear TD of 0.1 to 0.50 or 0.1 to 0.35.
[0291] [0291] In the modalities of the invention, a 1 mil film will have a drying direction (MD) of 1% strain of machine steering of ≥ 140 MPa, or ≥ 150 MPa, or ≥ 160 MPa, or ≥ 175 MPa or ≥ 180 Mpa, or ≥ 190 MPa, or ≥ 200 Mpa, or § 210 MPa. In one embodiment of the invention, a 1 mil film will have a secant module (MD) of machine steering the 1% strain from 130 MPa to 300 MPa. In one embodiment of the invention, a 1 mil film will have a secant module (MD) of machine steering the 1% strain from 140 MPa to 300 MPa. In one embodiment of the invention, a 1 mil film will have a drying direction (MD) of machine steering the 1% strain from 140 MPa to 275 MPa. In one embodiment of the invention, a film of 1 mil will have a secant module (MD) of machine steering the 1% strain from 140 MPa to 250 MPa. In one embodiment of the invention, a 1 mil film will have a machine steering secant module (MD) of 1% strain from 150 MPa to 260 MPa. In one embodiment of the invention, a 1 mil film will have a machine steering secant module (MD) of 1% strain from 160 MPa to 260 MPa. In one embodiment of the invention, a 1 mil film will have a secant module (MD) of machine direction for the 1% strain of 160 MPa and 250 MPa. In another embodiment of the invention, a film of 1 mil will have a secant module (MD) of machine steering the 1% strain from 170 MPa to 250 MPa. In yet another embodiment of the invention, a film of 1 mil will have a drying module (MD) of machine steering the 1% strain from 140 MPa to 230 MPa. In yet another embodiment of the invention, a film of 1 mil will have a drying module (MD) of machine steering the strain of 1% from 180 MPa to 280 MPa. In yet another embodiment of the invention, a 1 mil film will have a 1% strain of machine steering (1) strain from 190 MPa to 280 MPa. In yet another embodiment of the invention, a 1 mil film will have a 1% straining machine direction (MD) strain from 180 MPa to 260 MPa.
[0292] [0292] In one embodiment of the invention, a 1 mil film will have a secant modulus (TD) of 1% cross-sectional strain of ≥ 170 MPa, or ≥ 180 MPa, or ≥ 190 MPa, or ≥ 200 MPa, or ≥ 210 MPa, or ≥ 220 MPa or ≥ 230 Mpa, or> 240 Mpa, or> 250 Mpa. In one embodiment of the invention, a 1 mil film will have a drying module (TD) of 1% transverse direction from 170 MPa to 310 MPa. In one embodiment of the invention, a 1 mil film will have a secant module (TD) of transversal direction to the 1% strain from 170 MPa to 300 MPa. In one embodiment of the invention, a 1 mil film will have a drying module (TD) of 1% transverse direction from 170 MPa to 290 MPa. In one embodiment of the invention, a 1 mil film will have a secant module (TD) of transversal direction to the 1% strain from 170 MPa to 280 MPa. In another embodiment of the invention, a film of 1 mil will have a drying module (TD) of transversal direction to the 1% strain from 180 MPa to 300 MPa. In another embodiment of the invention, a 1 mil film will have a drying module (TD) of 1% transverse direction from 180 MPa to 290 MPa. In yet another embodiment of the invention, a 1 mil film will have a drying module (TD) of transversal direction to the 1% strain from 190 MPa to 300 MPa. In another embodiment of the invention, a 1 mil film will have a drying module (TD) of 1% transverse direction from 190 MPa to 290 MPa. In another embodiment of the invention, a 1 mil film will have a drying module (TD) with a transverse direction of 1% strain from 200 MPa to 290 MPa.
[0293] [0293] The film layer or film can, by way of only non-limiting example, have a total thickness ranging from 0.5 mil to 4 mils (note: 1 mil = 0.0254 mm), which will depend, for example, the gap of the mold used during the overlapping of the layered film or blowing of the film.
[0294] [0294] The above description applies to monolayer films. However, the film of the present invention can be used in a multilayer film. Multilayer films can be made using a co-extrusion process or a lamination process. In co-extrusion, a plurality of molten polymer streams are fed to an annular (or flat melt) mold, resulting in a multilayer film upon cooling. In laminating, a plurality of films are joined together using, for example, adhesives, heat and pressure joints and the like. A multilayered film structure can, for example, contain the bonding layers and / or the sealing layers.
[0295] [0295] The film of the present invention can be a skin layer or a core layer and can be used in at least one or a plurality of layers in a multilayer film. The term "core" or the phrase "nuclear layer" refers to any layer of the inner film of a multilayer film. The phrase "layer of skin" refers to an outer layer of a multilayer film (for example, example, as used in the production of packaging products.) The phrase "sealing layer" refers to a film that is involved in sealing the film itself or to another layer of a multilayer film. refers to any inner layer that adheres the two layers together.
[0296] [0296] As an example only, the thickness of the multilayer films can be from about 0.5 thousand to about 10 thousand of total thickness.
[0297] [0297] The films can be used for heavy bags, shrink film, agricultural film, garbage bags and shopping bags. The films can be produced by blow extrusion, cast extrusion, co-extrusion and can also be incorporated into laminated structures. EXAMPLES General
[0298] [0298] All reactions involving compounds sensitive to air or moisture were conducted under nitrogen, using standard Schlenk and cannula techniques, or in a glove box. The reaction solvents were purified using the system described by Pangborn et al. in Organometallics 1996, v15, p.1518 or used directly after being stored on 4 Å activated molecular sieves. The methylaluminoxane used was a 10% MAO solution in toluene provided by Albemarle which was used as received. The support used was Sylopol 2408 silica obtained from W.R. Grace. & Co. The support was calcined by fluidization with air at 200 ° C for 2 hours followed by nitrogen at 600 ° C for 6 hours and stored under nitrogen.
[0299] [0299] The melting index, I2, in g / 10 min was determined on a Tinius Olsen Plastomer (Model MP993), according to Procedure A, ASTM D1238, (Operation Manual) at 190 ° C with a weight of 2 , 16 kg. The melt index, I10, was determined according to Procedure A, ASTM D1238, at 190 ° C with a weight of 10 kg. High load melt index, I21, in g / 10 min was determined according to Procedure A, ASTM D1238, at 190 ° C with a weight of 21.6 kg. The melt flow ratio (sometimes also called the melt index ratio) is I21 / I2.
[0300] [0300] The density of the polymer was determined in grams per cubic centimeter (g / cc) according to ASTM D792.
[0301] [0301] Molecular weight information (Mw, Mn and Mz in g / mol) and the molecular weight distribution (Mw / Mn), and the distribution of the average molecular weight z (Mz / Mw) were analyzed by permeation chromatography in gel (GPC), using an instrument sold under the trade name "Waters 150C", with 1,2,4-trichlorobenzene as the mobile phase at 140 ° C. The samples were prepared by dissolving the polymer in this solvent and were run without filtration. Molecular weights are expressed as polyethylene equivalents with a relative standard deviation of 2.9% for the number average molecular weight ("Mn") and 5.0% for the weight average molecular weight ("Mw"). Polymer sample solutions (1 to 2 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. The anti-oxidant 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. The sample solutions were chromatographed at 140 ° C in a 220 PL high temperature chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as a 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 columns from oxidative degradation. The injection volume of the sample was 200 mL. The raw data were processed using the Cirrus GPC software. The columns were calibrated with polystyrene standards of narrow distribution. 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.
[0302] [0302] The branching frequency of copolymer samples (ie, the short chain branching, SCB per 1000 carbons) and the C6 co-monomer content (% by weight) were determined by Fourier Transform Infrared Spectroscopy ( FTIR) according to the ASTM D6645-01 method. A Thermo-Nicolet 750 Magna-IR Spectrophotometer equipped with OMNIC software version 7.2a was used for the measurements.
[0303] [0303] The determination of the branching frequency as a function of molecular weight (and therefore the distribution of co-monomers) was performed using High Temperature Gel Permeation Chromatography (GPC) and FT-IR of the eluent. Polyethylene standards with known branch content, polystyrene and hydrocarbons with a known molecular weight were used for calibration.
[0304] [0304] Hexane extraction, using compression molded plates, was determined according to ASTM D5227.
[0305] [0305] To determine the distribution width index of the CDBI50 composition (which is also called CDBI (50) in the present invention so that CDBI50 and CDBI (50) are used interchangeably), a solubility distribution curve is generated first for the copolymer. This is achieved using data acquired from the TREF technique (see below). This solubility distribution curve is a graph of the weight fraction of the copolymer that is solubilized as a function of temperature. This is converted to a cumulative distribution curve of fraction by weight versus co-monomer content, from which CDBI50 is determined by establishing the weight percentage of a copolymer sample that has a co-monomer content within 50% of the average co-monomer content on each side of the median (see WO 93/03093 for the definition of CDBI50). The weight percentage of copolymer eluting from 90-105 ° C, is determined by calculating the area under the TREF curve, at an elution temperature of 90 to 105 ° C. The weight percentage of copolymer eluting below or at 40 ° C and above 100 ° C was similarly determined. For the purpose of simplifying the correlation of the composition with the elution temperature, all fractions are assumed to have a Mn ≧ 15,000, where Mn is the average molecular weight in number of the fraction. Any low weight fractions present generally represent a trivial portion of the polymer. The remainder of this description and the attached claims maintain this convention of assuming all fractions that have Mn ≧ 15,000 in the measurement of CDBI50.
[0306] [0306] The specific increasing temperature elution fractionation (TREF) method used here was as follows. Homogeneous polymer samples (pelletized, 50 to 150 mg) were introduced into the reactor vessel of a TREF crystallization unit (ChARTM Polymer). The reactor vessel was filled with 20 to 40 ml of 1,2,4-trichlorobenzene (TCB), and heated to the desired dissolution temperature (for example, 150 ° C) for 1 to 3 hours. The solution (0.5 to 1.5 ml) was then loaded onto a TREF column filled with stainless steel spheres. After equilibrating at a given stabilization temperature (eg 110 ° C) for 30 to 45 minutes, the polymer solution was allowed to crystallize with a temperature drop from the stabilization temperature at 30 ° C (0.1 or 0 , 2 ° C / minute). After equilibrating at 30 ° C for 30 minutes, the crystallized sample was eluted with TCB (0.5 or 0.75 mL / minute) with a temperature ramp of 30 ° C for the stabilization temperature (0.25 or 1 , 0 ° C / minute). The TREF column was cleaned at the end of the run for 30 minutes at the dissolving temperature. The data were processed using Polymer Char software, Excel spreadsheet and TREF software developed at home.
[0307] [0307] The TREF procedures described above are well known to those skilled in the art and can be used to determine the modality of a TREF profile, a CDBI50, a wt% copolymer eluting at or below 40 ° C, a % wt copolymer eluting above 100 ° C,% wt copolymer eluting from 90 ° C to 105 ° C, a T (75) - T (25) value, as well as temperatures or temperature ranges where maximum of elution intensity occur (peak elution).
[0308] [0308] Melting points, including a peak melting point (Tm) and the percentage crystallinity of the copolymers are determined using a DSC Q1000 Thermal Analyzer TA instrument at 10 ° C / min. In a DSC measurement, a heating-cooling-heating cycle, from room temperature to 200 ° C or vice versa, is applied to the polymers to minimize the thermomechanical history associated with them. The melting point and the percentage of crystallinity are determined by the primary peak temperature and the total area under the DSC curve, respectively, from the second heating data. The peak melting temperature Tm is the highest temperature peak, when two peaks are present in a bimodal DSC profile (typically, also having the highest peak height).
[0309] [0309] The melting strength of a polymer is measured in a Rosand RH-7 capillary rheometer (barrel diameter = 15 mm), with a flat mold, 2 mm in diameter, L / D ratio 10: 1 at 190 ° Ç. Pressure transducer: 10,000 psi (68.95 MPa). Piston Speed: 5.33 mm / min. Haul-off angle: 52 °. Incremental speed Haul-off: 50 - 80 m / min2 or 65 ± 15 m / min2. A molten polymer is extruded through a capillary mold at a constant rate, and then the polymer's filament is attracted by an increase in the Haul-off speed until it breaks. The maximum value of the force in the plateau region of a force versus the time curve is defined as the melt resistance for the polymer.
[0310] [0310] Dynamic Mechanical Analysis (DMA). Rheological measurements (eg, small strain oscillatory shear measurements (10%)) were performed on a Rheometrics SR5 dynamic stress rheometer with 25 mm diameter parallel plates in a frequency sweep mode under full nitrogen blanket . The polymer samples are properly stabilized with the anti-oxidant additives and then inserted into the test stand for at least one minute of preheating to ensure normal strength decreasing to zero. All DMA experiments are performed at 10% strain, 0.05 at 100 rad / s and 190 ° C. Orchestrator software is used to determine the viscoelastic parameters, including the storage module (G '), loss module (G "), phase angle (δ), complex module (G *) and the complex viscosity (η *).
[0311] [0311] Frequency data (ω) versus complex viscosity | η * (ω) | against were then fitted in curve using the empirical Carreau-Yasuda (CY) model with three modified parameters to obtain the zero shear viscosity η0, characteristic viscous relaxation time τη, and the width of the rheology parameter a. The simplified Carreau-Yasuda empirical model (CY) used is as follows: | η * (ω) | = η0 / [1 + (τη ω) a] (1 - n> / a where: | η * (ω) | = magnitude of complex shear viscosity; η0 = zero shear viscosity; τη = characteristic relaxation time; a = "amplitude" of the rheology parameter (which is also called "Carreau-Yasuda shear exponent" or "CY parameter-a" or simply "parameter-a" in the present invention); n = corrects the slope of the final power law, set at 2/11; and ω = angular frequency of oscillatory shear deformation. Details of the significance and interpretation of the CY model and derived parameters can be found at: CA Hieber and HH Chiang, Rheol. Acta, 28, 321 (1989); CA Hieber and HH Chiang, Polym. Eng. Sci., 32, 931 (1992); and RB Bird, RC Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987); each of which is incorporated herein by reference in its entirety.
[0312] [0312] The Pseudoplasticity Index (SHI) was determined according to the method referred to in US Patent Application No. 2011/0212315: SHI is defined as SHI (ω) = η * (ω) / η0 for any given frequency (ω) for the measurement of dynamic viscosity, where η0 is the zero shear viscosity @ 190 ° C, determined using the empirical Cox-Merz rule. η * is the viscosity complex @ 190 ° C, determinable by dynamic (sinusoidal) shear or copolymer deformation, as determined on a Rheometrics SR5 Stress rotation rheometer using parallel plate geometry. According to the Cox-Merz rule, when the frequency (ω) is expressed in radiant units, at low shear rates, the numerical value of η * is equal to that of conventional, intrinsic viscosity based on low shear capillary measurements. The skilled in the field of rheology is well versed with determination η0 in this way.
[0313] [0313] The films in the current examples were made on a blown film line manufactured by Battenfeld Gloucester Engineering Company of Gloucester, Massachusetts using a 4-inch mold diameter, and a mold range of 35 or 50 mil (note: a type of PPA fluoroelastomer was added to reverse resin 1 for film production purposes, competition analysis of resin 2 shows that about 250-300 ppm of a PPA fluoroelastomer is present; competitive resin 3 analysis suggests about 600 ppm of carbon wax and fluoroelastomer PPA, in total, are present). This blown film line has a standard output of over 100 pounds per hour and is equipped with a 50 horsepower engine. The speed of the screw was 35 to 50 RPM. The extending screw has a diameter of 2.5 mil and a length / diameter (L / D) ratio of 24/1. Melting Temperature and Frozen Line Height (FLH) are 420 to 430 ° F and 16 inches, respectively. The blown film bubble is air cooled. The typical blown ratio (BUR) for blown films prepared in this line is 1.5 / 1 to 4/1. An annular mold having a range of 35 mils was used for these experiments. The films in this example were prepared using a 2.5: 1 BUR target point and a 1.0 mils film target point.
[0314] [0314] The haze (%) was measured according to the procedures specified in ASTM D 1003-07, using a BYK-Gardner Haze meter (Model Haze-gard plus).
[0315] [0315] Dart impact resistance was measured in a dart impact test (Model D2085AB / P) by Kayeness Inc., in accordance with ASTM D-1709-04 (Method A).
[0316] [0316] Elmendorf (MD) and transverse (TD) wear resistances were measured on a ProTear ™ Wear Tester made by Thwing-Albert Instrument Co., according to ASTM D-1922.
[0317] [0317] Puncture resistance was measured on a Universal MTS Systems Checker (Model SMT (HIGH) -500N-192), according to ASTM D-5748.
[0318] [0318] The securing module MD or TD was measured on a Universal Main Instrument Tester 5 (Model TTC-102) at a crosshead speed of 0.2 in / min up to 10% strain, according to ASTM D-882 -10. The securing module MD or TD was determined by an initial slope of the strain-strain curve from a 1% strain origin.
[0319] [0319] Film tensile tests were carried out on a Universal Main Instrument Tester 5 (Model TTC-102), according to ASTM D-882-10.
[0320] [0320] Gloss was measured in a BYK-Gardner 45 ° Micro-Gloss unit, according to ASTM D2457-03.
[0321] [0321] A seal was prepared by squeezing two strips of 2.0 mil film between the top and bottom sealing bars heated in an SL-5 Sealer made by Lako Tool for 0.5 second, 40 psi sealing bar tightening the pressure for each temperature in the range from the beginning of the seal to melt through it. The sealing resistance or sealing parameter was measured as a function of the sealing temperature on a Universal Main Instrument Tester 5 (Model TTC-102), according to ASTM F88-09. Examples of the Invention Preparation of the Catalyst System
[0322] [0322] Syntheses of (1-C6F5CH2-indenyl) ((t-Bu) 3P = N) TiCl2. For distilled indene (15.0 g, 129 mmoles) in heptane (200 ml) BuLi (82 ml, 131 mmoles, 1.6 M in hexane) was added at room temperature. The resulting reaction mixture was stirred overnight. The mixture was filtered and the filter cake was washed with heptane (3 x 30 ml) to provide indenillithium (15.62 g, 99% yield). Indenillithium (6.387 g, 52.4 mmoles) was added as a solid over 5 minutes to a stirred solution of C6F5CH2-Br (13.65 g, 52.3 mmoles) in toluene (100 ml) at room temperature. The reaction mixture was heated to 50 ° C and stirred for 4 h. The product mixture was filtered and washed with toluene (3 x 20 ml). The combined filtrates were evaporated to dryness to obtain 1-C6F5CH2-indene (13.58 g, 88%). To a stirred slurry of TiCl4.2THF (1.72 g, 5.15 mmoles) in toluene (15 ml) was added (t-Bu) 3P = N-Li (1.12 g, 5 mmoles) solid at temperature environment. The resulting reaction mixture was heated to 100 ° C for 30 min and then allowed to cool to room temperature. This mixture containing ((t-Bu) 3P = N) TiCl3 (1.85 g, 5 mmoles) was used in the next reaction. To a THF solution (10 mL) of 1-C6F5CH2-indene (1.48 g, 5 mmol), cooled to -78 ° C was added n-butyllithium (3.28 mL, 5 mmol, 1.6 M in hexanes) over 10 minutes. The resulting dark orange solution was stirred for 20 minutes and then transferred through a double-ended needle to a toluene slurry of ((t-Bu) 3P = N) TiCl3 (1.85 g, 5 mmoles). Cooling was removed from the reaction mixture, which was stirred for an additional 30 minutes. The solvents were evaporated to obtain a yellow pasty residue. The solid was redissolved in toluene (70 ml) at 80 ° C and filtered hot. Toluene was evaporated to obtain pure (1-C6F5CH2-indene) ((t-Bu) 3P = N) TiCl2 (2.35 g, 74%).
[0323] [0323] Drying of the Catalyst Modifier. 950 g of commercially available Armostat® 1800 (melting point at 50 ° C, boiling point> 300 ° C), which were used as a catalyst modifier, were placed in a 2L round bottom flask and melted in a oil bath at 80 ° C. The oil bath temperature was then rinsed at 110 ° C and a high vacuum was applied while maintaining agitation. First, a lot of bubbles were seen due to the release of gas and moisture vapor. Approximately two hours later, the gas evolution ceased and heating / evacuation was continued for another hour. The Armostat 1800 material was then cooled to room temperature and stored under a nitrogen atmosphere until use.
[0324] [0324] To determine the moisture level in Armostat 1800, 15% by weight of a pre-dried Armostat solution in toluene was prepared and the moisture of the solution was determined by the Karl-Fischer titration method. The moisture levels in Armostat 1800 as received from the commercial supplier, as well as traditional dry methods (ie, drying the solution over molecular sieves) and using low pressure water distillation were determined. The non-purified catalyst modifier was found to make a 15 wt% toluene solution containing 138 ppm H2O. The catalyst modifier which was dried over molecular sieves was found to make a 15% by weight toluene solution having 15-20 ppm H2O. The catalyst modifier that was dried by vacuum water distillation was found to make a 15% by weight toluene solution having 14-16 ppm H2O. It has thus been shown that simple vacuum distillation to remove water is as effective as the drying methods that employ molecular sieves. In fact, vacuum distillation has an advantage over using molecular sieves as a drying agent, in that it is much less time consuming (molecular sieves took more than 2 days to dry enough catalyst modifier and several batches of sieves were needed) ), and more cost-effective (use of sieves led to a decrease in the concentration of the catalyst modifier in toluene solution, due to the absorption of the catalyst modifier in the sieves, and large amounts of solvent needed to sufficiently solubilize the catalyst modifier in order to to make effective contact with the sieves).
[0325] [0325] Preparation of the Supported Catalyst. Sylopol 2408 silica purchased from Grace Davison was calcined by fluidization with air at 200 ° C for 2 hours and subsequently with nitrogen at 600 ° C for 6 hours. 114.273 grams of calcined silica were added to 620 mL of toluene. 312.993 g of an MAO solution containing 4.5% by weight of Al purchased from Albemarle were added to the fluid silica paste quantitatively. The mixture was stirred for 2 hours at room temperature. The stirring speed should be such, so as not to break the silica particles. 2.742 grams of (1-C6F5CH2-indenyl) ((t-Bu) 3P = N) TiCl2 (prepared as above in Example 1) were weighed in a 500 ml Pyrex flask and 300 ml of toluene added. The metal complex solution was added to the silica slurry quantitatively. The resulting slurry was stirred for 2 hours at room temperature. 21.958 g of 18.55 wt% toluene solution of Armostat® 1800 were weighed in a small vial and transferred quantitatively to the silica slurry. The resulting mixture was stirred for an additional 30 minutes, after which the slurry was filtered, yielding a clear filtrate. The solid component was washed with toluene (2 x 150 ml) and then with pentane (2 x 150 ml). The final product was dried under vacuum between 450 and 200 mTorr and stored under nitrogen until use. The finished catalyst was pale orange to pale yellow in color. The catalyst had 2.7% by weight of Armostat present. Polymerization - TSR
[0326] [0326] Continuous ethylene gas / 1-hexene gas phase copolymerization experiments were conducted in a 56.4L Technical Scale Reactor (TSR) in continuous gas phase operation (for example, a configured TSR reactor, see Order for Erropeus Patent No. 659,773A1). Polymerizations of ethylene were carried out at 75 ° C-90 ° C with a total operating pressure of 300 pounds per manometric square inch (psig). The gas phase compositions for ethylene and 1-hexene were controlled by controlling the closed-loop process to the values of 65.0 and 0.5-2.0 mol%, respectively. Hydrogen was measured in the reactor at a molar feed rate of 0.00080.0020 in relation to the ethylene feed during polymerization. Nitrogen constituted the remainder of the gas phase mixture (approximately 34-64 mol%). A typical production rate for these conditions is 2.0 to 3.0 kg of polyethylene per hour. A seed was used and before starting the polymerization it was washed with a small amount of triethyl aluminum, TEAL to eliminate impurities. Before the introduction of the catalyst, TEAL was washed from the reactor. The catalyst was fed to the reactor along with a small amount of diluted TEAL solution (0.25% by weight) during the start-up phase. The addition of TEAL was stopped as soon as the desired polymer production rate was achieved. Alternatively, the reactor can be started with the catalyst feed line alone during the polymerization start-up phase (that is, without initially feeding the TEAL solution). The polymerization reaction was initiated under conditions of low co-monomer concentration, followed by gradual adjustment of the comonomer to the ethylene ratio to provide the density of the target polymer.
[0327] [0327] Pelleting of Granular Resins. 500 ppm of Irganox 1076 and 1000 ppm of Irgafos 168 were mixed dry with the granular resin before pelletizing. The resulting powder mixture was extruded on a Leistritz twin screw extruder with a screw diameter of 38 mm and an L / D ratio of 33/1 under a nitrogen atmosphere to minimize polymer degradation. The pelletizing conditions of the extruder were adjusted to a melting temperature of 210 ° C, an output rate of 20 to 25 lb / hr, a screw speed of 120 rpm and a pelletizer speed of 30 to 40 rpm. The pelleted resin was cooled and then collected for the characterization of the resin and evaluation of the film.
[0328] [0328] Catalyst composition information and steady state polymerization conditions are provided in Table 1 (C2 = ethylene; C6 = 1-hexene; H2 = hydrogen; and C6 / C2, for example, is the molar feed ratio of each component to the reactor). Polymer data for the resulting resins of the invention are provided in Table 2. The film data for the films of the invention made from the resins of the invention are provided in Table 3. Pilot Polymerization Plant
[0329] [0329] Ethylene / 1-hexene copolymerization experiments were conducted in a continuous fluidized bed gas phase for the pilot plant scale reactor. An example of a reactor configuration and typical process operating parameters are provided, for example, in U.S. Patent No. 8,338,551 B2 and European Patent Application No. 1,308,464 A1 (see, Examples 10 and 11). Polymerizations of ethylene were carried out at 80 ° C-85 ° C with a total operating pressure of 300 pounds per manometric square inch (psig). The gas phase compositions for ethylene and 1-hexene were controlled by controlling the closed-loop process for the values of 35-50.0 and 0.5-2.0 mol%, respectively. Hydrogen was measured in the reactor at a molar feed ratio of 0.0008-0.0015 in relation to the ethylene feed during polymerization. Nitrogen constituted the remaining part of the gas phase mixture (approximately 34-49 mol%). A typical production rate for these conditions is 100 to 250 kg of polyethylene per hour. A seed was used and before the polymerization started it was washed with a small amount of triethyl aluminum, TEAL to eliminate impurities. The gas composition required of ethylene, 1-hexene, hydrogen, nitrogen and pentane / isopentane in the reactor is built to reach quantities prior to catalyst injection. The pentane / isopentane level can vary from 9-17 mol% in the reactor. The reactor was started with the catalyst feed line alone, without additional cleaning with TEAL during the beginning of the polymerization. The polymerization reaction was initiated under conditions of low co-monomer concentration and higher hydrogen concentration, followed by gradual adjustment of the co-monomer for the ethylene ratio and hydrogen for the ethylene ratio to achieve the target polymer density and index of fusion. Granular resin pelleting was performed according to the TSR scale (see above).
[0330] [0330] Catalyst composition information and steady state polymerization conditions are provided in Table 1 (C2 = ethylene; C6 = 1-hexene; H2 = hydrogen; and C6 / C2, for example, is the molar feed ratio of each component to the reactor). The resulting polymer data for the resins of the invention are provided in Table 2. The film data for films of the invention made from the resins of the invention are provided in Table 3. Table 1
[0331] [0331] The phosphinimine catalyst compound (1,2- (n-propyl) (C6F5) Cp) Ti (N = P (t-Bu) 3) Cl2 was made in a similar manner to the procedure described in US Patent No. 7,531,602 (see Example 2).
[0332] [0332] Preparation of the Supported Catalyst. To a dehydrated silica slurry (122.42 g) in toluene (490 ml) was added a 10 wt% MAO solution (233.84 g 4.5 wt% Al in toluene) over 10 minutes. The container containing MAO was rinsed with toluene (2 x 10 mL) and added to the reaction mixture. The resulting slurry was stirred with a suspended stirrer assembly (200 rpm) for 1 hour at room temperature. To this slurry was added a solution of toluene (46 mL) of (1,2- (n-propyl) (C6F5) Cp) Ti (N = P (t-Bu) 3) Cl2 (2.28 g) over 10 minutes. This solution can be slightly heated to 45 ° C for a short period (5 minutes) to completely dissolve the molecule. The container containing the molecule was rinsed with toluene (2 x 10 mL) and added to the reaction mixture. After stirring for 2 hours (200 rpm) at room temperature a toluene solution (22 mL) of Armostat-1800 (which was previously dried according to the above method for "a Drying Catalyst Modifier") at 8.55% by weight was added to the slurry which was further stirred for 30 minutes. The slurry was filtered and rinsed with toluene (2 x 100 ml) and then with pentane (2 x 100 ml). The catalyst was dried in vacuo to less than 1.5% by weight of residual volatiles. The solid catalyst was isolated and stored under nitrogen until use. The catalyst had 2.7% by weight of Armostat present. Polymerization
[0333] [0333] Continuous ethylene gas / 1-hexene gas phase polymerization experiments were carried out in a 56.4L Technical Scale Reactor (TSR) operating in continuous gas phase. Polymerizations of ethylene were carried out at 75 ° C-90 ° C with a total operating pressure of 300 pounds per manometric square inch (psig). The gas phase compositions for ethylene and 1-hexene were controlled by controlling the closed-loop process to the values of 65.0 and 0.5-2.0 mol%, respectively. Hydrogen was measured in the reactor at a molar feed ratio of 0.0008-0.0015 in relation to the ethylene feed during polymerization. Nitrogen constituted the remaining part of the gas phase mixture (approximately 38 mol%). A typical production rate for these conditions is 2.0 to 3.0 kg of polyethylene per hour.
[0334] [0334] Pelleting of Granular Resins. 500 ppm of Irganox 1076 and 1000 ppm of Irgafos 168 were mixed dry with the granular resin before pelletizing. The resulting powder mixture was extruded on a Leistritz twin screw extruder with a screw diameter of 38 mm and an L / D ratio of 33/1 under a nitrogen atmosphere to minimize polymer degradation. The pelletizing conditions of the extruder were adjusted to a melting temperature of 210 ° C, an output rate of 20 to 25 lb / hr, a screw speed of 120 rpm and a pelletizer speed of 30 to 40 rpm. The pelleted resin was cooled and then collected for the characterization of resin and evaluation of the film.
[0335] [0335] Steady state polymerization conditions are given in Table 4 (C2 = ethylene; C6 = 1-hexene; C6 / C2 is the molar feed ratio of each component to the reactor). Polymer data for the resulting comparative resin 1 is provided in Table 5. The film data for films made from comparative resin 1 is provided in Table 6. Table 4
[0336] [0336] Also included in Table 5 are comparative resins 2-8. Corresponding film properties for comparative resins 2-8 are shown in Table 6. Comparative Resin 2 is a 1-hexene Exceed 1018CATM ethylene copolymer, which is commercially available from Exxon Mobil. Comparative Resin 3 is believed to be a representative Enable 20-05tm resin that is commercially available from Exxon Mobil. Comparative Resin 4 is believed to be a representative resin of Enable 20-10TM that is commercially available from Exxon Mobil. Comparative Resin 5 is a fused mixture of FP-019C and LF-Y819-A. LF-Y819 represents 5% by weight of the molten mixture. LF-Y819-A, is a low-density, high-pressure material that has an I2 melt index of 0.75 g / 10 min and a density of 0.919 g / cc, available from NOVA Chemicals. FPs-019-C is a low density linear material with an I2 melt index of 0.8 g / 10 min and a density of 0.918 g / cc, made using a Ziegler-Natta catalyst, also available from NOVA Chemicals. Comparative resins 6 and 7 are ELITE 5100GTM and ELITE 5400GTM, respectively, which are made using a dual reactor solution process with a mixed catalyst system and are commercially available from Dow Chemical Company. Comparative Resin 8 is DOWLEX 2045GTM, which is made with a Ziegler-Natta catalyst in a solution reactor, and is also commercially available from Dow Chemical Company. Table 5 Copolymer Properties
[0337] [0337] As shown in Tables 2 and 5, the ethylene copolymer compositions of the present invention (inv. 1-6) have a melt flow ratio that is distinct from a resin prepared with (1,2- ( n-propyl) (C6F5) Cp) Ti (N = P (t-Bu) 3) Cl2 (comp. 1) and commercially available from EXCEED 1018CATM (comp. 2). The resins of the invention (see inv. 1-6) have an MFR (i.e., I21 / I2) greater than 30, while comparative resins 1 and 2 each have a melt flow ratio of less than 30 In addition, copolymer compositions of the invention having a fractional melt index (inv. 1-5) have a similar MFR as an Enable 20-05 TM resin having a fractional melt index (comp. 3), but a profile of TREF very different. Likewise, a copolymer composition of the invention having a melt index of about 1.2 (inv. 6) has an Enable 20-10TM resin and a similar MFR having a melt index of about 1.1 (comp. 4), but a very different TREF profile. The TREF profile of the resins of the invention is multimodal (bimodal or trimodal with two or three prominent peaks separated by 5 ° C or more), while resins comp. 3 and 4, each has a single peak evident in the TREF analyzes. The resins of the invention 1-6 have a distribution width index of the composition CDBI50 less than 75% by weight whereas resins comp. 3 and 4, each has a CDBI50 greater than 85%. Comparison of the resins of the invention 1-6 with ELITE resins (comparative examples 6 and 7) shows that, although each one may have a multimodal TREF profile (note: Elite resin is a copolymer of ethylene and 1-octene, and the The resin of the invention is a copolymer of ethylene and 1-hexene), the resins of invention 1-6 have a wider molecular weight distribution (Mw / Mn greater than 4.0) and a larger MFR (I21 / I2 greater than than 32). Comparative resin 8, which is DOWLEX 2045G, and made using a Ziegler-Natta catalyst, has a bimodal TREF profile and an MFR less than 30.
[0338] [0338] When blown on film, resins of the 1/5 invention have good dart impact values, good rigidity, and are easy to process, as indicated by the low pseudoplasticity index (SHI) and high specific output rates.
[0339] [0339] As shown in Tables 3 and 6, the dart impact of fractional melt index resins, resins of invention 1, 3-5 are typically more than 500 g / mil and are almost as good as comp resin. 2, which has a much lower melt flow ratio (I21 / I2). One exception is resin inv. 2, which has a dart impact of 438 g / mil. The resins of invention 1, 3-5 also have a higher dart impact value than comparative resins of similar melt index and / or melt flow rate: compare, for example, comp. 3 (an Enable type resin) and resin comp. 5 (a fusion blend of LLDPE and HPLDPE) which have dart impact values of 473 g / mil and 317 g / mil, respectively, with resins of invention 1, 3, 4 and 5, which have an impact value with dart of 638 g / mil, 887 g / mil, 542 g / mil and 684 g / mil, respectively.
[0340] [0340] Resin of invention 6 (which has an I2 melting index of about 1.2 g / 10 min), has a slightly lower dart impact at 225 g / mil than that of comp resin. 4 to 286 g / ml (which has a similar melting index I2), but this may be due to the fact that it also has a higher density.
[0341] [0341] The stiffness of the resins of the invention 1-5, as indicated by the secant module TD 1% and secant module MD is similar or greater in comparison to comparative resins 2, 3 or 5. As shown in Tables 3 and 6, the resins of invention 1, 3-5 have an MD drying module at 1% greater than 190 MPa, when blown into a 1 mil film. Comparative resins 2, 3 and 5 have a 1% MD secant module of 137, 187, and 167 MPa, respectively, when blown into a 1 mil film. Resins of the invention 1-5 have a TD drying module at 1% greater than 210 MPa, when blown into a 1 mil film. Comparative resins 2, 3 and 5 have a 1% TD drying module of 166, 208 and 208 MPa, respectively, when blown into a 1 mil film. A similar comparison between resin inv. 6 (which has an I2 melt index of about 1.2 g / 10 min) with resin comp. 4 (which has an I2 melt index of 1.1 g / 10 min), which shows the resin inv. 6 which has TD and MD drying modules greater than 1%. Resin inv. 6 has a 1% MD secant module of 230 MPa and a 1% TD secant module of 255 MPa, while the resin comp. 4 has a 1% MD secant module of 156 MPa and a 1% TD secant module of 171 MPa.
[0342] [0342] In terms of processing capacity, the resins of the invention 1-5 are extruded with a specific production rate higher than the lower main pressure than comparative resin 2, which has a lower melt flow ratio (see Tables 3 and 6). Resins of the invention 1-5 have a similar specific output rate as compared to resin comp. 3, but generally with lower main extrusion pressure (with resin inv. 3 being an exception). Resin comp. 5 is a molten mixture comprising a linear low density LLDPE resin and 5 wt.% High pressure low density polyethylene resin (HPLDPE), which is known to impart improved processing capacity to an LLDPE, due to the presence of long chain branching. However, resins of the invention 1-5 show a higher specific output, even with lower extrusion head pressure than comparative resin 5 (see Tables 3 and 6).
[0343] [0343] As can be seen in Table 2, the resins of the invention having a fractional melting index I2, resins of the invention 1-5 have a reverse comonomer distribution, a multimodal TREF profile, a CDBI50 within a range of 45 at 75% by weight, an MFR within a range of 32 to 50, an Mw / Mn within a range of 3.5 to 6.0 and an I2 melting index of less than 1.0 g / 10 min. Also shown in Table 2, the resin of invention 6 has a reverse comonomer distribution, a multimodal TREF profile, a CDBI50 within a range of 45 to 75% by weight, an MFR within a range of 32 to 50, an Mw / Mn within a range of 3.5 to 6.0 and an I2 melt index of about 1.2 g / 10 min.
[0344] [0344] Each of the resins of the invention 1-6 shown in Table 2 also has a wide unimodal molecular weight distribution (see Figure 2 as representative of the inventive ethylene copolymers).
[0345] [0345] Representative TREF curves are shown in Figure 1A for the resin of invention 1 and in Figure 1B for the resin of invention 3. A representative GPC curve is shown for the resin of invention 1 in Figure 2. A GPC curve Representative -FTIR is shown by resin of invention 1 in Figure 3.
[0346] [0346] A van Gurp-Palmen analysis is a means by which to study a polymer architecture (for example, molecular weight distribution, linearity, etc.) as reflected by the polymer's fusion morphology. A VGP curve is simply a graph of the phase angle (δ) versus the complex modulus (G *), in which the two rheology parameters are obtained using the frequency sweep test in dynamic mechanical analysis (DMA). A change in a VGP curve from a baseline curve or a decrease in phase angles in the middle of the complex module range may indicate changes in the polymer's melting morphology.
[0347] [0347] A VGP plot allows a determination of the pass rheology parameter that is defined as the point of intersection obtained between the phase angle (δ) versus the complex modulus plot (G *) and a phase angle (δ) ) versus the complex viscosity graph (η *). Based on the theory of linear viscoelasticity, the VGP pass rheology parameter or "pass phase angle" (δ × O) occurs at a frequency (ω) that is equal to the unit. It is the phase angle, where G * and η * are equivalent. Therefore, the VGP pass rheology parameter can be determined in a single DMA test.
[0348] [0348] VGP pass graphics for resins sold under the trade names Exceed 1018CA (Comp. 2) and Enable (Comp. 3) are included in Figures 4A and 4B, respectively. The VGP pass charts for the resin of invention 1 are shown in Figure 4B. The VGP pass graphs for comparative resin 1, made according to comparative example 1, are included in Figure 4A. Finally, the resin sold under the trade name Elite 5400G (Comp. 7) is included in Figure 4B. The VGP crossing points are dependent on the architecture of the copolymer. Generally speaking, for resins that are easier to process, such as a copolymer of invention 1 and comparative resin 3, the VGP phase angle at which the passage occurs defined as δXO is less than for resins that are more difficult to process, such as comparative copolymers 1 and 2 (compare Figures 4A and 4B). For resins that are easier to process, the shape of the phase angle complex viscosity curves and the shape of the phase angle complex module curves are deflected and somewhat more like mirror images of each other, in relation to the curves obtained for the resins that are more difficult to process (compare the curves in Figure 4A with the curves in Figure 4B).
[0349] i) (Mw/Mn) ≥ 72 [(I21/I2)-1 + 10-6 (Mn)] ; ii) δXO ≤ 83,0 - 1,25 (CDBl50)/(Mw/Mn); e iii) δXO ≤ 80,7 - (CDBl50)/(Mw/Mn) a um δχο de cerca de 55° a 70°; onde δχο é o ângulo de fase de passagem, Mw, Mn, I21, I2 e CDBI50 são todos como definidos acima. Os dados fornecidos na Tabela 5, mostram que nenhuma das resinas comparativas 1-8 satisfaz a condição: i) (Mw/Mn) ≥ 72 [(I21/I2)-1 + 10-6 (Mn)] e que nenhuma das resinas comparativas 1-4, e 6-8 satisfaz qualquer uma das condições: ii) δχO ≤ 83,0 - 1,25 (CDBl50)/(Mw/Mn), ou iii) δχO ≤ 80,7 -(CDBI50)/(Mw/Mn) a um δχ<O de cerca de 55° a 70°.[0349] As shown in Table 2, all ethylene copolymers of invention 1-6 also satisfy one or more of the following ratios: i) (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]; ii) δXO ≤ 83.0 - 1.25 (CDBl50) / (Mw / Mn); and iii) δXO ≤ 80.7 - (CDBl50) / (Mw / Mn) at an δχο of about 55 ° to 70 °; where δχο is the passing phase angle, Mw, Mn, I21, I2 and CDBI50 are all as defined above. The data provided in Table 5, show that none of the comparative resins 1-8 satisfies the condition: i) (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)] and that none of the resins comparatives 1-4, and 6-8 satisfy any of the conditions: ii) δχO ≤ 83.0 - 1.25 (CDBl50) / (Mw / Mn), or iii) δχO ≤ 80.7 - (CDBI50) / ( Mw / Mn) at an δχ <O of about 55 ° to 70 °.
[0350] [0350] For further comparison, the ethylene copolymers of the invention 1-6 were plotted against several commercial resins known in Figure 5. Figure 5 shows a graph of the equation: (Mw / Mn) = 72 [(I21 / I2 ) -1 + 10-6 (Mn)], as well as a graph of Mw / Mn versus values 72 [(I21 / I2) -1 + 10-6 (Mn)] for resins of the invention 1-6, as well as several known commercial resins. The commercial resins included in Figure 5 for comparison purposes are all resins having an I2 melting index of 1.5 g / 10 min or less and a density between 0.916 and 0.930 g / cm3 and which are sold under the trade names , such as Elite ™, Exceed ™, Marflex ™, Starflex ™, Dowlex ™, SURPASS ™, SCLAIR ™, NOVAPOLTM and EnableTM. As can be seen from Figure 5, none of these commercial qualities satisfy the condition: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)]. In contrast to all resins of the invention 1 -6 that satisfy the condition: (Mw / Mn) ≥72 [(I21 / I2) -1 + 10-6 (Mn)]. This work demonstrates the distinct architecture of the ethylene copolymers of the invention.
[0351] [0351] For further comparison, the ethylene copolymers of the invention 1-6 were plotted against various commercial resins known in Figure 6. Figure 6 shows a graph of the equation: δχO = 83.0 - 1.25 (CDBl50) / (Mw / Mn), as well as a graph of δχO versus the values 83.0 - 1.25 (CDBl50) / (Mw / Mn) for the resins of the invention 1-6 and several known commercial resins. The commercial resins included in Figure 6 for comparison purposes are all resins having an I2 melting index of 1.5 g / 10 min or less and a density between 0.916 and 0.930 g / cm3 and which are sold under the trade names , such as Elite ™, Exceed ™, Marflex ™, Starflex ™, Dowlex ™, SURPASS ™, SCLAIR ™, NOVAPOL ™ and Enable ™. As can be seen from the figure, none of these commercial qualities satisfy the condition: δχO ≤ 83.0 - 1.25 (CDBl50) / (Mw / Mn). In contrast, most resins of the invention 1-6 satisfy the condition: δχO ≤ 83.0 - 1.25 (CDBl50) / (Mw / Mn). This work further demonstrates the distinctive architecture of the ethylene copolymers of the invention.
[0352] [0352] For further comparison, the ethylene copolymers of the invention 1-6 were plotted against various commercial resins known in Figure 7. Figure 7 shows a graph of the equation: δχO = 80.7 - (CDBl50) / (Mw / Mn), as well as a graph of δχO values versus 80.7 - (CDBl50) / (Mw / Mn) for the resins of the invention 1-6 and several known commercial resins. Figure 7 also shows that the inventive and commercial resins have an δχO of about 55 ° to 70 °. The commercial resins included in Figure 7, for comparison purposes are all resins having an I2 melting index of 1.5 g / 10 min or less and a density between 0.916 and 0.930 g / cm3 and which are sold under the names such as Elite ™, Exceed ™, Marflex ™, Starflex ™, Dowlex ™, SURPASS ™, SCLAIR ™, NOVAPOL ™ and Enable ™. As can be seen from Figure 7, none of these commercial qualities satisfy the condition, where δχO ≤ 80.7 - (CDBl5o) / (Mw / Mn) at an δχO of about 55 ° to 70 °. In contrast, all resins of the invention 1-6 satisfy the condition, where δχO ≤ 80.7 - (CDBl50) / (Mw / Mn) at an δχO of about 55 ° to 70 °. This work demonstrates the distinct architecture of the ethylene copolymers of the invention. INDUSTRIAL APPLICABILITY
[0353] [0353] Copolymerization of ethylene with transition metal catalysts is an important industrial process, which supplies the polymers that are used in numerous commercial applications, such as, for example, film extrusion for use in food packaging. The present invention provides ethylene copolymers that are relatively easy to process and that can be made of film having a good balance of physical properties, such as dart impact and stiffness.

权利要求:
Claims (22)
[0001]
Ethylene copolymer, CHARACTERIZED by the fact that it comprises ethylene and an alpha-olefin having 3 to 8 carbon atoms, the ethylene copolymer having a density of 0.916 g / cm3 to 0.936 g / cm3, a melting index (I2) of 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of 32 to 50, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5 , a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, and a distribution width index of the CDBI50 composition from 50% by weight to 75% by weight, as determined by TREF, and that still satisfies the relationship: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn)].
[0002]
Ethylene copolymer, according to claim 1, CHARACTERIZED by the fact that it still satisfies the relationship: δχO ≤ 80.7 - (CDBI50) / (Mw / Mn) at an δχO of 55 ° to 70 °; where δχO is the phase angle at which the complex modulus (G *) and the complex viscosity (η *) are numerically equivalent in a graph of phase angle versus complex modulus and complex viscosity as determined by dynamic mechanical analysis.
[0003]
Ethylene copolymer, according to claim 1 or 2, CHARACTERIZED by the fact that it still satisfies the ratio: δχO ≤ 83.0 - 1.25 (CDBI50) / (Mw / Mn); where δχO is the phase angle at which the complex modulus (G *) and the complex viscosity (η *) are numerically equivalent on a graph of phase angle versus complex and complex viscosity module as determined by dynamic mechanical analysis
[0004]
Ethylene copolymer, according to claim 1, CHARACTERIZED by the fact that the ethylene copolymer has a CDBI50 of 55% by weight to 75% by weight.
[0005]
Ethylene copolymer, according to claim 1, CHARACTERIZED by the fact that the ethylene copolymer has a density of 0.917 g / cm3 to 0.927 g / cm3.
[0006]
Ethylene copolymer, according to claim 1, CHARACTERIZED by the fact that the ethylene copolymer has a molecular weight distribution (Mw / Mn) of 4.0 to 6.0.
[0007]
Ethylene copolymer, according to claim 1, CHARACTERIZED by the fact that the copolymer has a multimodal TREF profile that comprises two maximum intensities that occur at elution temperatures T (low) and T (high); where T (low) is 65 ° C to 85 ° C and T (high) is 90 ° C to 98 ° C.
[0008]
Ethylene copolymer, according to claim 1, CHARACTERIZED by the fact that the alpha-olefin is 1-hexene.
[0009]
Ethylene copolymer, according to claim 1, CHARACTERIZED by the fact that the ethylene copolymer has an average molecular weight distribution Z (Mz / Mw) of 2.0 to 4.0.
[0010]
Ethylene copolymer, according to claim 1, CHARACTERIZED by the fact that the ethylene copolymer has a T (75) - T (25) of about 5 ° C to 20 ° C, as determined by TREF.
[0011]
Olefin polymerization process to produce an ethylene copolymer, the process CHARACTERIZED by the fact that it comprises contacting ethylene and at least one alpha-olefin having from 3 to 8 carbon atoms, with a polymerization catalyst system in one single gas phase reactor; the ethylene copolymer having a density of 0.916 g / cm3 to 0.936 g / cm3, a melt index (I2) of 0.1 g / 10 min at 2.0 g / 10 min, a melt flow ratio (I21 / I2) from 32 to 50, a molecular weight distribution (Mw / Mn) from 3.6 to 6.5, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, an index of distribution width of the CDBI50 composition from 50% by weight to 75% by weight, as determined by TREF and which satisfies the following relationship: (Mw / Mn) ≥ 72 [(I21 / I2) -1 + 10-6 (Mn )]; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[0012]
Olefin polymerization process according to claim 11, CHARACTERIZED by the fact that the Group 4 organotransition metal catalyst is a Group 4 phosphinimine catalyst.
[0013]
Olefin polymerization process, according to claim 12, CHARACTERIZED by the fact that the Group 4 phosphinimine catalyst has the general formula: (1-R2-lndenyl) Ti (N = P (t-Bu) 3) X2; wherein R2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, where the substituents for the alkyl, aryl or benzyl group are selected from the group which consists of alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halide substituents; and where X is an activable ligand.
[0014]
Olefin polymerization process according to claim 11, CHARACTERIZED by the fact that the catalyst activator is an alkylaluminoxane.
[0015]
Olefin polymerization process according to claim 11, CHARACTERIZED by the fact that the catalyst modifier comprises at least one long chain amine compound.
[0016]
Olefin polymerization process, according to claim 11, CHARACTERIZED by the fact that the ethylene copolymer still satisfies the ratio: δχO ≤ 80.7 - (CDBl5o) / (Mw / Mn) at an δχO of 55 ° to 70 °; where δχO is the phase angle at which the complex modulus (G *) and the complex viscosity (η *) are numerically equivalent in a graph of phase angle versus complex modulus and complex viscosity as determined by dynamic mechanical analysis.
[0017]
Olefin polymerization process, according to claim 11 or 16, CHARACTERIZED by the fact that the ethylene copolymer still satisfies the ratio: δχO ≤ 83.0 - 1.25 (CDBl5o) / (Mw / Mn); where δχO is the phase angle at which the complex modules (G *) and the complex viscosity (η *) are numerically equivalent in a graph of phase angle versus complex module and complex viscosity as determined by dynamic mechanical analysis.
[0018]
Film layer having a dart impact greater than 200 g / mil, an MD securing module 1% greater than 140 MPa, a TD securing module 1% greater than 175 MPa and an MD wear ratio for TD wear 0.75 or less, CHARACTERIZED by the fact that the film layer comprises an ethylene copolymer having a density of about 0.916 g / cm3 to 0.930 g / cm3, a melting index (I2) of 0.1 g / 10 min to 2.0 g / 10 min, a melt flow ratio (I21 / I2) of 32 to 50, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5, a distribution profile reverse comonomer as determined by GPC-FTIR, a multimodal TREF profile, a distribution width index of the CDBI50 composition from 50% by weight to 75% by weight, as determined by TREF, and which satisfies the following relationship: ( Mw / Mn) ≥ 72 [(I21 / I2) "1 + 10-6 (Mn)].
[0019]
Film layer according to claim 18, CHARACTERIZED by the fact that the film layer has an MD wear to TD wear ratio of 0.45 or less.
[0020]
Film layer, according to claim 18, CHARACTERIZED by the fact that the film layer has a dart impact greater than 500 g / mil.
[0021]
Film layer, according to claim 18, CHARACTERIZED by the fact that the ethylene copolymer still satisfies the ratio: δχO ≤ 80.7 - (CDBl5o) / (Mw / Mn) at an δχO of 55 ° to 70 °; where δχO is the phase angle at which the complex module (G *) and the complex viscosity (η *) are numerically equivalent on a graph of phase angle versus complex modules and complex viscosity as determined by dynamic mechanical analysis.
[0022]
Film layer, according to claim 18 or 21, CHARACTERIZED by the fact that the ethylene copolymer still satisfies the ratio: δχO ≤ 83.0 - 1.25 (CDBl5o) / (Mw / Mn); where δχO is the phase angle at which the complex modulus (G *) and the complex viscosity (η *) are numerically equivalent in a graph of phase angle versus complex modulus and complex viscosity as determined by dynamic mechanical analysis.

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2020-01-28| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-03-23| B09A| Decision: intention to grant|

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2021-04-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/12/2013, OBSERVADAS AS CONDICOES LEGAIS. |

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