WIDE MOLECULAR WEIGHT DISTRIBUTION POLYPROPYLENE RESINS

专利摘要:
polypropylene resins with wide molecular weight distribution. polypropylene resin comprising at least 50 mole% of propylene, a mwd (mw / mn) greater than 5, a branch index (g ') of at least 0.95 and a melt strength of at least 20 cn determined using an extensional rheometer at 190 ° c. a catalyst system comprising a ziegler-natta catalyst comprising an internal non-aromatic electron donor and first and second external electron donors comprising different organosilicon compounds and a method for producing a polypropylene resin comprising contacting propylene monomers under conditions of polymerization of propylene with the catalyst system are also disclosed.
公开号:BR112015009432B1
申请号:R112015009432-5
申请日:2013-10-08
公开日:2021-03-30
发明作者:Prasadarao Meka；Saifudin M. Abubakar；Shriley Yumin Chen；Todd S. Edwards
申请人:Exxonmobil Chemical Patents Inc.；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[1] Polypropylene resins and articles made from them. BACKGROUND
[2] The physical properties of propylene homopolymers formed by typical Ziegler-Natta polymerization are highly dependent on the stereoregularity of the polymer itself. Highly stereoregular polymers are generally crystalline, provide desired high bending modules and are formed with an appropriate choice of an electron donor. These highly crystalline polymers also exhibit high melting points, but inherently have low melt flow rates (MFR) which make them generally unsuitable for applications that require high processing rates, such as in injection molding, oriented films and heat bonded fibers. In addition, conventional polypropylene homopolymer and copolymer products formed from highly crystalline polypropylenes lack sufficient impact resistance for many uses.
[3] Polypropylene homopolymer or impact copolymer resins made from the traditional Ziegler-Natta catalyst based on phthalates or other internal electron donor systems containing aromatics and an external silane or diether electron donor result in a molecular weight distribution (MWD) in the range of 3 to 4.5 and, as such, have a very low melt strength without any evidence of deformation hardening under extension of melt elongation. Resins with a molecular weight distribution in the range of 3 to 4.5 are not suitable for conversion processes, such as blown film applications or monolayer or multilayer applications due to poor melt strength. Similar behavior is observed in sheet applications, deep drawing thermoforming and foaming. Other conversion applications requiring good melt strength for which these polymers are not suitable include profile extrusion, base material for thermoplastic vulcanized (TPV), biaxially oriented polypropylene (BOPP) film, blow molding applications, and the like.
[4] There is a need in the art for polypropylene resins having one or more properties, such as improved melt strength, improved stiffness and the like. There is also a need for such polypropylene resins suitable for use in blown film, in multilayer applications as a substitute for HDPE, sheets, drawn flat thermoforming and deep drawing applications, and / or foaming applications
[5] Related references include EP 0 757 069 A1; EP 2 000 504 A1; US 2003-088022; US 2007-054997; US 2008-311368; US 6,602,598; US 5,907,942; US 2003-118853; US 5,752,362; WO 2007/130277; WO 98/44011; and WO 2010/034461. SUMMARY
[6] In embodiments in accordance with the present disclosure, a polypropylene resin comprises at least 50 mol% of propylene, a MWD (Mw / Mn) greater than 5, a branch index (g ') of at least 0.95 and a fusion resistance of at least 20 cN determined using an extensional rheometer at 190 ° C.
[7] In embodiments, a catalyst system comprises a Ziegler-Natta catalyst comprising an internal non-aromatic electron donor and first and second external electron donors comprising different organosilicon compounds.
[8] In embodiments, a method for producing a polypropylene resin comprises contacting propylene monomers under propylene polymerization conditions with a catalyst system comprising a Ziegler-Natta catalyst comprising an internal, non-aromatic electron donor and first and second external electron donors comprising different organo-silicon compounds.
[9] This summary is provided to present a selection of concepts that are better described below in the detailed description. This summary is not intended to identify key or essential characteristics of the claimed object, nor is it intended to be used as an aid in limiting the scope of the claimed subject. Other and more objects, advantages and features of the present invention will be understood by reference to the claims that follow in this specification. BRIEF DESCRIPTION OF THE DRAWINGS
[10] Figure 1 is a graph plotting the intrinsic viscosity versus molecular weight of a propylene resin produced in accordance with the present disclosure.
[11] Figure 2 is a graph of the complex viscosity versus the angular frequency of a propylene resin produced in accordance with the present disclosure. DETAILED DESCRIPTION
[12] In situ polymerized materials (eg polypropylene) with improved melt strength, MWD, and elevated MFRs can be produced in a single stage polymerization conducted in the presence of certain Ziegler-Natta catalysts, which can optionally be supported, one donor internal non-aromatic electron and a mixture of two external electron donors. In any event, a polypropylene resin may comprise: at least 50 mol% of propylene, a melting strength of at least 20 cN or at least 50 cN determined using an extensive rheometer at 190 ° C, a branch index ( g ') of at least 0.95 and an MWD (Mw / Mn) greater than 5. In any embodiment, a Ziegler-Natta catalyst may comprise a Ziegler-Natta catalyst comprising an internal non-aromatic electron donor and first and second donors of external electrons comprising different organosilicon compounds. In any embodiment, a method for preparing a polypropylene resin may comprise contacting propylene monomers at a temperature and pressure or other appropriate propylene polymerization conditions in the presence of the catalyst system for the production of a polypropylene resin comprising at least minus 50 mol% of propylene and a melting strength of at least 20 cN determined using an extensional rheometer at 190 ° C. In any embodiment, the catalyst system can comprise a Ziegler-Natta catalyst comprising an internal non-aromatic electron donor and a first external electron donor having the formula R12Si (OR2) 2, in which each R1 is, independently, a hydrocarbon radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to Si is a secondary or tertiary carbon atom, and where each R2 is, independently, a hydrocarbyl radical comprising from 1 to 10 carbon atoms. In any event, the catalyst system further comprises a second external electron donor having the formula R3nSi (OR4) 4-n, where each R3 and R4 are independently a hydrocarbon radical comprising 1 to 10 carbon atoms, n is 1, 2 or 3 and the second external electron donor is different from the first external electron donor. Definitions
[13] For the purposes of the present invention and the claims, the new numbering scheme for the groups in the Periodic Table is used as in Chem. Eng. News, 1985, 63, 27. Therefore, a “Group 4 metal” is an element of Group 4 of the Periodic Table.
[14] The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group” are used interchangeably throughout this document unless otherwise specified. For purposes of disclosure, a hydrocarbon radical is defined as being radicals C1 to C20, or radicals C1 to C10 or radicals C6 to C20 or radicals C7 to C20 that can be linear, branched or cyclic, when appropriate (aromatic or non-aromatic); and includes hydrocarbyl radicals substituted with other hydrocarbyl radicals and / or one or more functional groups comprising elements from Groups 13 - 17 of the periodic table of elements. In addition, these two or more hydrocarbon radicals can together form a fused ring system, including partially or fully hydrogenated fused ring systems, which may include heterocyclic radicals.
[15] The term "substituted" means that a hydrogen atom and / or a carbon atom in the base structure has been replaced with a hydrocarbyl radical, and / or a functional group, and / or a heteroatom or a group containing heteroatom. In this sense, the term hydrocarbon radical includes groups containing heteroatom. For purposes here, a heteroatom is defined as any atom other than carbon and hydrogen. For example, methyl cyclopentadiene (Cp) is a Cp group, which is the base structure, replaced with a methyl radical, which can also be referred to as a methyl functional group, ethyl alcohol is an ethyl group, which is the base structure, substituted with a -OH functional group, and pyridine is a phenyl group having a carbon in the base structure of the benzene ring replaced by a nitrogen atom.
[16] For purposes here, unless otherwise indicated, a hydrocarbyl radical may be independently selected from substituted or unsubstituted methyl, ethyl, ethylene and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decila , undecila, dodecila, tridecila, te- tradecila, pentadecila, hexadecila, heptadecila, octadecila, nonadecila, eicosila, heneicosila, docosila, tricosila, tetracosila, pentacosila, hexacila, heptacosila, octacosila, nonacosila, triacontila , pentenila, hexenila, heptenila, octenila, nonenila, decenila, unde- cenila, dodecenila, tridecenila, tetradecenila, pentadecenila, hexade- cenila, heptadecenila, octadecenila, nonadecenila, eicosenila, heni- pentenacosenen, trenecenycosenylen - senila, heptacosenila, octacosenila, nonacosenila, triacontenila, propinila, butinila, pentinila, hexinila, heptinila, octinila, noninila, decinila, undecinila, dodecinila, tridecinila, tetradecin ila, pentadecinyl, hexadequinyl, heptadecinyl, octadecinyl, nonadecinyl, eicosinyl, heneicosinyl, docosinyl, tricosinyl, tetracosinyl, pentacosinyl, hexacosinyl, heptaxinin, octacosinyl, nonacosinyl, and triacontinyl.
[17] For purposes here, unless stated otherwise, hydrocarbyl radicals may also include isomers of saturated, partially unsaturated and aromatic cyclic structures in which the radical may additionally be subjected to the types of substitutions described above. The term "aryl", "aryl radical", or "aryl group" refers to aromatic cyclic structures, which can be replaced with hydrocarbon radicals and / or functional groups, as defined here. Examples of aryl radicals include: acenaftenyl, acenaphthenyl, acridinyl, anthracenyl, benzanthra-cenils, benzimidazolyl, benzisoxazolyl, benzofluorantenils, benzofuranil, benzoperilenils, benzopyrenils, benzothiazolyl, benzothiofenils, benzine, benzene, benzene, benzene, benzene choro-nenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, dibenzoanthracenils, fluoranthenyl, fluorenyl, furanyl, imidazolyl, indazolyl, indenopyrenyl, indolyl, indolinyl, isobenzofuranyl, isoindolyl, isoquinyl, isoquinolyl, isoquinyl , oxazolyl, phenanthrenyl, phenyl, purine, pyrazinyl, pyrazolyl, pyrenyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrole, quinazolinyl, quinolonyl, quinoxalinyl, thiazolyl, thiophenyl, and the like.
[18] For purposes here, the term “non-aromatic” refers to compounds, radicals, and / or functional groups without an aromatic character attributed to cyclic conjugated sp2 carbons having protons with a chemical change from TMS consistent with aromatic protons, or higher than 6, as easily understood by someone of minimal skill in the technique.
[19] It should be understood that for purposes here, when a radical is listed, it indicates that the base structure of the radical (the type of radical) and all other radicals formed when that radical is subjected to the substitutions defined above. Alkyl, alkenyl, and alkynyl radicals listed include all isomers including, where appropriate, cyclic isomers, for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (and substituted cyclopropyl analogs); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and nevopentyl (and substituted cyclobutyl and cyclopropyl analogs); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2- propenyl (and cyclobutenyl and cyclopropenyl). Cyclic compounds having substitutions include all forms of isomer, for example, methylphenyl would include ortho-methylphenyl, meta-methylphenyl and para-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl and 3,5-dimethylphenyl.
[20] Likewise, the terms "functional group", "group" and "substituent" are also used interchangeably throughout this document unless otherwise specified. For purposes here, a functional group includes organic and inorganic radicals or fractions comprising elements from Groups 13, 14, 15, 16 and 17 of the periodic table of elements. Suitable functional groups may include hydrocarbyl radicals, for example, alkyl radicals, alkene radicals, aryl radicals, and / or halogen (Cl, Br, I, F), O, S, Se, Te, NR * x, OR *, SeR *, TeR *, PR * x, AsR * x, SbR * x, SR *, BR * x, SiR * x, GeR * x, SnR * x, PbR * x, and / or the like, where R is a hydrocarbile C1 to C20 as defined above, where x is the appropriate integer to provide a neutral electron fraction. Other examples of functional groups include those commonly referred to as amines, imides, amides, ethers, alcohols (hydroxides), sulfides, sulfates, phosphides, halides, phosphonates, alkoxides, esters, carboxylates, aldehydes and the like.
[21] The polypropylene microstructure is determined by 13C-NMR spectroscopy including the concentration of isotactic and syndiotactic dyads ([m] and [r]), triads ([mm] and [rr]) and pentads ([mmmm] and [rrrr]). The designation "m" or "r" describes the stereochemistry of contiguous propylene groups, "m" referring to meso and "r" to racemic. Samples are dissolved in d2-1,1,2,2-tetrachloroethane and the spectra recorded at 125 ° C using a 100 MHz (or higher) NMR spectrometer. Polymer resonance peaks are referred to mmmm = 21.8 ppm. Calculations involved in the characterization of polymers by NMR are described by F. A. Bovey in Polymer Conformation and Configuration (Academic Press, New York 1969) and J. Randall in Polymer Sequence Determination, 13C-NMR Method (Academic Press, New York, 1977).
[22] For purposes here, a supported catalyst and / or activator refers to a catalyst compound, an activator or a combination thereof located on, in, or in communication with a support on which the activator, catalyst compound or a combination thereof is deposited on, vaporized with, attached to, incorporated within, adsorbed or absorbed on, adsorbed or absorbed on, the support.
[23] For purposes here, an "olefin," alternatively known as "alkene," is a linear, branched or cyclic compound comprising carbon and hydrogen having at least one double bond. For the purposes of this specification and the claims appended thereto, when a polymer or copolymer is said to comprise an olefin, the olefin present in that polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35% by weight to 55% by weight, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derivative units they are present in 35% by weight to 55% by weight, based on the weight of the copolymer.
[24] For purposes here, a "polymer" has two or more of the same or different "mer" units. A "homopolymer" is a polymer having mer units that are the same. A "copolymer" is a polymer having two or more mer units that are different from one another. A "terpolymer" is a polymer having three or more mer units that are different from one another. “Different” in reference to mer units indicates that the mer units differ from each other in at least one atom or are isomerically different. In this sense, the definition of copolymer, as used here, includes terpolymers and the like. An oligomer is usually a polymer having a low molecular weight, such as an Mn of less than 25,000 g / mol, or in an embodiment less than 2,500 g / mol, or a low number of mer units, such as 75 mer units or less . A "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mol% of ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least minus 50 mol% of propylene-derived units, and so on.
[25] For the purposes of this disclosure, the term “α-olefin” includes C2 to C22 oleifins. Non-limiting examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene , 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-hyenesicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1 -hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, 3,5,5-trimethyl -1-hexene, vinylcyclohexane, and vinylnorbornane. Non-limiting examples of cyclic olefins and diolefins include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene, 2-methylcyclopentene, 4-methylcyclopentene, vinylcycladiene , dicyclopentadiene, 5-ethylidene-2-norbornene, vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4- divinylcyclo -hexane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and 1,5-diallylcyclooctane.
[26] The terms "catalyst" and "catalyst compound" are defined to mean a compound capable of initiating polymerization catalysis under the appropriate conditions. In the description here, the catalyst can be described as a catalyst precursor, a pre-catalyst compound or a transition metal compound, and these terms are used interchangeably. A catalyst compound can be used alone to initiate catalysis or can be used in combination with an activator, an internal electron donor, one or more external electron donors and / or a cocatalyst to initiate catalysis. When the catalyst compound is combined with electron donors and / or cocatalysts to initiate catalysis, the catalyst compound is often referred to as a precursor catalyst precursor. A “catalyst system” is a combination of at least one catalyst compound, at least one internal electron donor, one or more external electron donors, a catalyst, and / or a support where the system can polymerize monomers to produce a polymer under polymerization conditions of appropriate temperature and pressure. For the purposes of this invention and the appended claims, when catalyst systems are described as comprising stable neutral forms of the components, it is well understood by one skilled in the art that the ionic form of the component is the form which reacts with the monomers to produce polymers.
[27] For purposes here, the term "catalyst productivity" is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising (W) grams of catalyst (cat), over a period of time ( T) hours; and can be expressed by the following formula: P / (T x W) and expressed in units of gPgcat-1h-1. “Conversion” is the amount of monomer that is converted to a polymer product and is reported as mol% and is calculated based on the yield of the polymer and the amount of monomer fed into the reactor. Catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kg P / mol cat).
[28] A “scavenger” is a compound that is usually added to facilitate oligomerization or polymerization by removing impurities. Some kidnappers can also act as activators and can be referred to as co-activators. A co-activator, which is not a sequester, can also be used in conjunction with an activator to form a catalyst system. In one embodiment, a co-activator can be pre-mixed with the catalyst compound to form an alkylated catalyst compound.
[29] A “propylene polymer” is a polymer that has at least 50 mol% of propylene. As used herein, Mn is the numerical average molecular weight as determined by proton nuclear magnetic resonance spectroscopy (1H NMR) or gel permeation chromatography (GPC), unless otherwise stated, Mw is the weight average molecular weight determined by gel permeation chromatography (GPC) and Mz is the average molecular weight z determined by GPC,% by weight is weight percentage and% by mol is molar percentage. The molecular weight distribution (MWD) is defined as being Mw divided by Mn. Unless otherwise specified, all molecular weight units, for example, Mw, Mn, Mz, are g / mol.
[30] The following abbreviations can be used across this specification: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, iso-butyl is isobutyl, sec-butyl refers to secondary butyl, tert-butyl, refers to tertiary butyl, n-butyl is normal butyl, pMe is para-methyl, Bz is benzyl, THF is tetrahydrofuran, Mes is mesityl, also known like 1,3,5-trimethylbenzene, Tol is toluene, TMS is trimethylsilyl, and MAO is methylalphaoxane. For purposes here, “RT” is room temperature, which is defined as 25 ° C, unless otherwise specified. All percentages are in percent by weight (% by weight), unless otherwise specified.
[31] For the present purposes, the number of carbon atoms of Mw, Mz, value g and g'vis can be determined using a High Temperature Size Exclusion Chromatograph (or Waters Corporation or Polymer Laboratories), equipped with three inline detectors, a differential refractive index (DRI) detector, a light scattering detector (LS) and a viscometer. Experimental details, including detector calibration, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, 6812-6820, (2001) and references therein. Three Polymer Laboratories PLgel 10mm Mixed-B LS columns are used. The nominal flow rate is 0.5 cm3 / min and the nominal injection volume is 300 μL. The various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at 145 ° C. Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4 trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 μm glass pre-filter and then through a 0.1 μm Teflon filter. The TCB is then degassed with an in-line degasser before entering the Size Exclusion Chromatograph. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB and then heating the mixture to 160 ° C with continuous stirring for 2 hours. All quantities are measured by gravimetry. The TCB densities used to express the polymer concentration in units of mass / volume are 1,463 g / ml at room temperature and 1,324 g / ml at 145 ° C. The injection concentration is 0.75 to 2.0 mg / ml, with lower concentrations being used for higher molecular weight samples. Before the execution of each sample, the DRI detector and injector are purged. The flow rate in the device is then increased to 0.5 ml / minute, and the DRI stabilizes for 8 to 9 hours before injecting the first sample. The LS laser is switched on for 1 to 1.5 hours before running the samples. The concentration, c, at each point in the chromatogram is calculated from the DRI signal subtracted from the base, IDRI, using the following equation: c = KDRIIDRI / (dn / dc) where KDRI is a constant determined by the DRI calibration, and ( dn / dc) is the increment of the refractive index for the system. The refractive index, n = 1,500 for TCB at 145 ° C and À = 690 nm. For the purposes of the present invention and the appended claims (dn / dc) = 0.104 for propylene polymers, 0.098 for butene polymers and 0.1 for others. Units in parameters throughout this description of the SEC method are such that the concentration is expressed in g / cm3, the molecular weight is expressed in g / mol, and intrinsic viscosity is expressed in dL / g.
[32] The LS detector is a Wyatt Technology High Temperature mini-DAWN. The molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model by static light scattering (MB Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):
Here, ΔR (θ) is the measured excess of the Rayleigh dispersion intensity at dispersion angle θ, c is the polymer concentration, determined from the DRI analysis, A2 is the second virial coefficient [for the purposes of the present invention, A2 = 0.0006 for propylene polymers, 0.0015 for butene polymers and 0.001 for others], (dn / dc) = 0.104 for propylene polymers, 0.098 for butene polymers and 0.1 for others, P (θ) is the form factor for a monodisperse random coil, and Ko is the optical constant for the system:
where NA is Avogadro's number, and (dn / dc) is the increment of the refractive index for the system. The refractive index, n = 1,500 for TCB at 145 ° C and À = 690 nm.
[33] A high temperature Viscotek Corporation viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine the specific viscosity. One transducer measures the total pressure drop between the detector, and the other, positioned between the two sides of the bridge, measures the differential pressure. The specific viscosity, ns, for the solution circulating through the viscometer is calculated from its outputs. The intrinsic viscosity, [n], at each point in the chromatogram is calculated from the following equation: ns = c [n] + 0.3 (c [n]) 2 where c is the concentration and was determined from the outlet DRI.
[34] The branching index (g'vis) is calculated using the SEC-DRI-LS-VIS method output as follows. The average intrinsic viscosity, [n] avg, of the sample is calculated by:
where the sums are on the chromatographic slices, i, between the limits of integration. The g'vis branch index, which is also referred to simply as g 'is defined as:
where, for the purposes of this invention and appended claims, α = 0.695 and k = 0.000579 for linear ethylene polymers, α = 0.705 k = 0.000262 for linear propylene polymers, and α = 0.695 and k = 0.000181 for polymers of linear linear butene. Mv is the average viscosity molecular weight based on the molecular weight determined by the LS analysis.
[35] The term “g”, also called a “g value” is defined as Rg2pm / Rg2ls, where Rgpm is the radius of rotation for the polymers, Rg2ls is the radius of rotation for the linear pattern, and Rgls = KsM0.58 where Ks is the power law coefficient (0.023 for linear polyethylene, 0.0171 for linear polypropylene, and 0.0145 for linear polybutene), and M is the molecular weight as described above, Rgpm = KTMαs. αs is the size coefficient for the polymer, KT is the power law coefficient for the polymer. See Macromolecules, 2001, 34, 6812-6820, for guidance on how to select a linear pattern having the molecular weight and comonomer content, and determining K coefficients and α exponents.
[36] For purposes here, a functionalized polymer comprises more than 0.1% by weight of a functional group and / or a g '<0.95, and / or is the product of a post reactor functionalization process or process grafting. In this sense, for purposes here a non-functionalized polymer comprises less than 0.1% by weight of a functional group, and / or is not the product of a post-reactor functionalization process, and / or is not a grafted polymer post reactor, and / or has a g '> 0.95 determined as described here. Ziegler-Natta Catalyst
[37] In any embodiment, Ziegler-Natta catalysts suitable for use in this document include solid titanium supported catalyst systems described in US Patents 4,990,479 and 5,159,021 and PCT Publication No. WO00 / 63261, and others. Briefly, the Ziegler-Natta catalyst can be obtained by: (1) suspending a dialkoxy magnesium compound in an aromatic hydrocarbon that is liquid at room temperatures; (2) contacting the dialkoxy hydrocarbon magnesium composition with a titanium halide and with an aromatic dicarboxylic acid diester; and (3) contact with the functionalized magnesium-hydrocarbon dialkoxide resulting from step (2) with additional titanium halide.
[38] In any embodiment, the catalyst system can be a solid titanium catalyst component comprising magnesium, titanium, halogen, an internal non-aromatic electron donor and two external electron donors. The solid titanium catalyst component, also referred to as a Ziegler-Natta catalyst, can be prepared by contacting a magnesium compound, a titanium compound and at least the internal electron donor. Examples of the titanium compound used in the preparation of the sodium titanium catalyst component include tetravalent titanium compounds that have the formula:
where R is a hydrocarbyl radical, X is a halogen atom and n is 0 to 4.
[39] In any embodiment, titanium compounds suitable for use in this document include titanium tetrahalides, such as TiCl4, TiBr4 and / or TiI4; titanium alkoxy trihalides including Ti (OCH3) Cl3, Ti (OC2H5) Cl3, Ti (O n-C4H9) Cl3, Ti (OC2H5) Br3 and / or Ti (O iso-C4H9) Br3; dialcoxytitanium dihalides including Ti (OCH3) 2Cl2, Ti (OC2H5) 2Cl2, Ti (O n-C4H9) 2Cl2 and / or Ti (OC2H5) 2Br2; trialcoxytitanium monohalides including Ti (OCH3) 3Cl, Ti (OC2H5) 3Cl, Ti (O n-C4H9) 3Cl and / or Ti (OC2H5) 3Br; and / or tetraloxy titaniums including Ti (OCH3) 4, Ti (OC2H5) 4 and / or Ti (O n-C4H9) 4.
[40] In any embodiment, the halogen-containing titanium compound can be a titanium tetrahalide or titanium tetrachloride. Titanium compounds can be used alone or in combination with each other. The titanium compound can be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.
[41] In any embodiment, the magnesium compound to be used in the preparation of the solid titanium catalyst component may include a magnesium compound having reducibility and / or a magnesium compound having no reducibility. Suitable magnesium compounds having reducibility may, for example, be magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Suitable examples of these reducible magnesium compounds include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride , magnesium chloride amyl, butyl ethoxy magnesium, ethyl butyl magnesium, and / or butyl magnesium halides. These magnesium compounds can be used alone or can form complexes with the organoaluminium cocatalyst, as described here. These magnesium compounds can be a liquid or a solid.
[42] Appropriate examples of magnesium compounds having no reducibility include magnesium halides, such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; alkoxy magnesium halides, such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, phenoxy magnesium chloride and methylphenoxy magnesium chloride; magnesium alkoxy, such as magnesium ethoxy, magnesium isopropoxy, magnesium butoxy, n-octoxy magnesium and 2-ethylhexoxy magnesium; magnesium aryloxy such as magnesium phenoxy and magnesium dimethylphenoxide; and / or magnesium carboxylates, such as magnesium laurate and magnesium stearate.
[43] In any embodiment, non-reproducible magnesium compounds can be compounds derived from magnesium compounds having reducibility, or they can be derivative compounds at the time of preparing the catalyst component. Magnesium compounds having no reducibility can be derived from compounds having reducibility by, for example, contacting magnesium compounds having reducibility with polysiloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols and the like.
[44] In any embodiment, magnesium compounds having reducibility and / or magnesium compounds having no reducibility can be complexes of the above magnesium compounds with other metals, or mixtures of them with other metal compounds. They can also be mixtures of two or more types of the above compounds. In any embodiment, halogen-containing magnesium compounds, including magnesium chloride, magnesium alkoxide chlorides and magnesium aryloxy chlorides can be used.
[45] In any embodiment, an appropriate solid catalyst component comprising an internal electron donor may be a suitable solid catalyst component comprising a non-aromatic internal electron donor is a solid catalyst sold by Lyondell-Basell Inc. under the trade name Avant ™ ZN-168. Such a catalyst is used to exemplify the invention; other catalyst systems supported on titanium are contemplated. Other mechanisms of use of catalyst are contemplated. Including, but not limited to, batch prepolymerization, in situ prepolymerization and other such mechanisms. Cocatalyst
[46] In any embodiment, supported Ziegler-Natta catalysts can be used in combination with a cocatalyst, also called here as a Ziegler-Natta cocatalyst. In any embodiment, compounds that contain at least one aluminum-carbon bond in the molecule can be used as the cocatalysts, also referred to here as an organoaluminium cocatalyst. Suitable organoaluminium compounds include organoaluminium compounds of the general formula: R1mAl (OR2) nHpXq where R1 and R2 are identical or different, and each represents a hydrocarbyl radical containing from 1 to 15 carbon atoms, or 1 to 4 carbon atoms; X represents a halogen atom; 0 <m <3, 0 <n <3, 0 <p <3 and 0 <q <3 and m + n + p + q = 3.
[47] Other suitable organoaluminium compounds include complex alkylated compounds of Group I metals and aluminum represented by the general formula: M1AlR14 where M1 is Li, Na, or K and R1 is as defined above.
[48] Suitable organoaluminium compounds include compounds represented by the following general formula: R1mAl (OR2) 3-m where R1 and R2 are as defined above, and m is preferably 1.5 <m <3; R1mAl (H) 3-m where R1 is as defined above, X is halogen, and m is 0 <m <3, or 2 <m <3; and / or R1mAl (OR2) nXq where R1 and R2 are as defined above, X is halogen, 0 <m <3, 0 <n <3, 0 <q <3 and m + n + q = 3
[49] Suitable examples of organoaluminium compounds include include trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum and tributyl aluminum; trialkenyl aluminum, such as triisopropyl aluminum; dialkyl aluminum alkoxides, such as diethyl aluminum ethoxide and dibutyl aluminum ethoxide; alkyl aluminum sesquialoxides, such as ethyl aluminum sesquietoxy and butyl aluminum sesquibutoxide; alkyl partially alkoxylated aluminum having an average composition represented by the general formula R12.5Al (OR2) 0.5; partially halogenated alkyl aluminum, for example, alkyl aluminum dihalides, such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; partially hydrogenated alkyl aluminum, for example, alkyl aluminum dihydrides, such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alkoxylated and halogenated alkyl aluminum, such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride and ethyl aluminum ethoxy bromide.
[50] In either embodiment, the organoaluminium compound can comprise two or more aluminum atoms linked through an oxygen or nitrogen atom. Examples include (C2H5) 2AlOAl (C2H5) 2, (C4H9) 2AlOAl (C4H9) 2, and / or methylaluminoxane (MAO). Other suitable examples include LiAl (C2H5) 4 and Li-Al (C7H15) 4. In either embodiment, the trialkyl aluminum and alkyl aluminum resulting from the bonding of at least two aluminum compounds can be used.
[51] In any modality, the cocatalyst can be an organoaluminium compound that is halogen free. Suitable halogen-free organoaluminium compounds are, in particular, unsubstituted branched alkylaluminium compounds of the formula AlR3, where R denotes an alkyl radical having 1 to 10 carbon atoms, such as, for example, trimethylaluminum, triethylaluminium, triisobutyl- aluminum and tridiisobutylaluminum. Additional compounds that are suitable for use as a cocatalyst are readily available and widely disclosed in the prior art, including US Patent No. 4,990,477. In any other modality, the organoaluminum Ziegler-Natta cocatalyst can be trimethylaluminum, triethylaluminium (TEAL) or a combination thereof. Internal Electron Donors
[52] Electron donors suitable for use here can generally be used in two ways in the formation of Ziegler-Natta catalysts and catalyst systems. In either embodiment, an internal electron donor can be used in the catalyst formation reaction when the transition metal halide is reacted with the metal hydride or metal alkyl. Examples of suitable internal electron donors include amines, amides, ethers, esters, esters, ketones, nitriles, phosphines, stilbenes, arsines, phosphorus-amides, thioethers, thioesters, aldehydes, alcoholates and salts of organic acids. In any event, the internal donor may be non-aromatic. The internal non-aromatic electron donor may comprise an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioethers, thioester, aldehyde, alcoholate, carboxylic acid or a combination thereof.
[53] In either embodiment, the solid titanium catalyst component can be prepared using an internal non-aromatic electron donor. Examples of suitable non-aromatic internal electron donors include electron donors containing oxygen such as alcohols, ketones, aldehydes, carboxylic acids, organic or inorganic oxide esters, ethers, acid amides and acid anhydrides; electron donors containing nitrogen such as ammonia, amines, nitriles, or isocyanates. Suitable examples include alcohols having from 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol and the like; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde and the like; organic acid esters having 2 to 30 carbon atoms including the desired esters to be included in the titanium catalyst component, such as methyl formate, ethyl formate, vinyl acetate, propyl acetate, octyl acetate, cycle acetate -hexyl, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloracetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, dibutyl maleate, diethyl butylmalonate, diethyl diethylmalonate , diethyl ethyl cyclohexanecarboxylate, diethyl 1,2-cyclohexanedicarboxylate, di (2-ethylhexyl) 1,2-cyclohexanedicarboxylate, gamma-butyrolactone, delta-valerolactone and / or ethylene carbonate; esters of inorganic acid such as ethyl silicate and butyl silicate; acid halides having 2 to 15 carbon atoms such as acetyl chloride and the like; ethers having 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and the like; acid amides such as acetamide and the like; acid anhydrides, such as acetic anhydride and the like; amines such as methylamine, ethylamine, triethylamine, tributylamine, tetramethylethylenediamine and the like; and nitriles such as acetonitrile, trinitrile and the like.
[54] In either embodiment, the internal non-aromatic electron donor may comprise a C1 to C20 diester of a substituted or unsubstituted C2 to C10 dicarboxylic acid. In any modality, the internal non-aromatic electron donor can be a succinate according to formula (I): in which
linear or branched alkyl, alkenyl or cycloalkyl; R3 to R6 are independently hydrogen, halogen or hydrocarbon radicals C1 to C20 linear or branched alkyl, alkenyl or cycloalkyl, where the radicals R3 to R6 are not joined together, where at least two of the radicals R3 to R6 are joined for form a cyclic divalent radical or a combination thereof.
[55] In any embodiment, R3 to R5 of formula I can be hydrogen and R6 can be a radical selected from the group consisting of a branched, secondary or tertiary primary alkyl or cycloalkyl radical having 3 to 20 carbon atoms.
[56] In any event, the internal donor may be a non-aromatic monosubstituted succinate compound. Suitable examples include diethyl secbutyl succinate, diethylhexyl succinate, diethyl cyclopropyl succinate, diethyl trimethylsilyl succinate, diethyl methoxysuccinate, diethyl cyclohexyl succinate, diethyl (cyclohexylmethyl) succinate, diethyl t-butyl succinate, diethyl isobutylsuccinyl, diethyl, isucutylsuccinyl, diethyl , 1,1trifluor-2-propyl) succinate, diisobutyl sec-butylsuccinate, diisobutylhexylsuccinate, diisobutyl cyclopropylsuccinate, diisobutyl trimethylsilylsuccinate, diisobutyl methoxisuccinate, diisobutyl cyclohexylsuccinate, diisobutyl-succinyl, succulent, cyclohexyl diisobutyl isopropyl succinate, diisobutyl neopentyl succinate, diisobutyl isopentyl succinate, diisobutyl (1,1,1-trifluor-2-propyl) succinate, dineopentyl sec-butyl succinate, dineopentyl hexyl succinate, dineopentyl cyclopropyl succinate, dineopentyl cyclone, dineopentyl succinate, dineopentyl cyclone entyl cyclohexyl succinate, dineopentyl (cyclohexylmethyl) succinate, dineopentyl tbutyl succinate, dineopentyl isobutyl succinate, dineopentyl isopropyl succinate, dineopentyl neopentyl succinate, and dineopentyl isopentyl succinylate and / or succinylate and / or succinylate.
[57] In any embodiment, the internal electron donor having a structure consistent with formula (I) can comprise at least two radicals from R3 to R6, which are different from hydrogen and are selected from the alkyl, alkenyl, and / or hydrocarbon group. or straight or branched C1 to C20 cycloalkyl, which may contain heteroatoms. In any modality, two different hydrogen radicals can be bonded to the same carbon atom. Suitable examples include 2,2-disubstituted succinates including diethyl 2,2-dimethyl succinate, diethyl 2-ethyl-2-methyl succinate, diethyl 2- (cyclohexylmethyl) - 2-isobutyl succinate, diethyl 2-cyclopentyl-2-n-propyl succinate, diethyl 2,2-diisobutyl succinate, diethyl 2-cyclohexyl-2-ethyl succinate, diethyl 2-isopropyl-2-methyl succinate, diethyl 2,2-diisopropyl diethyl 2isobutyl-2-ethyl succinate, diethyl 2- (1,1, 1-trifluor-2-propyl) -2-methylsuccinate, diethyl 2 isopentyl-2-isobutylsuccinate, diisobutyl 2,2dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2- (cyclohexylmethyl) -2-isobutylsuccinate, diisobutyl 2 -cyclopentyl-2-n-propylsuccinate, diisobutyl 2,2-diisobutylsuccinate, diisobutyl 2-cyclohexyl-2-ethylsuccinate, diisobutyl 2-isopropyl-2-methylsuccinate, diisobutyl 2-isobutyl-2-ethylsuccinate, diisobutyl 2- (1 , 1,1-trifluor-2-propyl) -2-methylsuccinate, diisobutyl 2-isopentyl-2-isobutylsuccinate, diisobutyl 2,2-diisopropylsuccinate, dineopentyl 2,2-dimethylsuccinate, dineopenti 1 2-ethyl-2-methylsuccinate, dineopentyl 2- (cyclohexylmethyl) -2isobutylsuccinate, dineopentyl 2-cyclopentyl-2-n-propylsuccinate, dineopentyl 2,2-diisobutylsuccinate, dineopentyl 2-cyclohexyl-2-ethylsuccinate , dineopentyl 2-isopropyl-2methylsuccinate, dineopentyl 2-isobutyl-2-ethylsuccinate, dineopentyl 2- (1,1,1-trifluor-2-propyl) -2-methylsuccinate, dineopentyl 2,2-diisopropylsuccinate, and / or dineopentyl 2-isopentyl-2isobutyl succinate.
[58] In any embodiment, at least two different hydrogen radicals can be bonded to the same carbon atom between R3 and R6. Examples include R3 and R5 or R4 and R6. Suitable non-aromatic succinate compounds include: diethyl 2,3-bis (trimethylsilyl) succinate, diethyl 2,2-secbutyl-3-methylsuccinate, diethyl 2- (3,3,3-trifluorpropyl) -3-methylsuccinate, diethyl 2 , 3bis (2-ethylbutyl) succinate, diethyl 2,3-diethyl-2-isopropylsuccinate, diethyl 2,3-diisopropyl-2methylsuccinate, diethyl 2,3-dicyclohexyl-2-methylsuccinate, diethyl 2,3-diisopropyl succinate , diethyl 2,3-bis (cyclohexylmethyl) succinate, diethyl 2,3-di-tbutyl succinate, diethyl 2,3-diisobutyl succinate, diethyl 2,3-dineopentyl succinate, diethyl 2,3-diisopentyl succinate, diethyl 2,3- ( 1-trifluormethyl-ethyl) succinate, diethyl 2-isopropyl-3-isobutyl succinate, diethyl 2-t-butyl-3-isopropyl succinate, diethyl 2-isopropyl-3-cyclohexyl succinate, diethyl 2-isopentyl-3cyclohexyl succinate, diethyl 2 -cyclohexyl-3-cyclopentyl succinate, diethyl 2,2,3,3-tetramethyl succinate, diethyl 2,2,3,3-tetraethyl succinate, diethyl 2,2,3,3-tetrapropyl succinate, diethyl 2,3-diethyl-2 , 3-diisopropyl succinate, diisobutyl 2,3-bis (trimethyl ylyl) succinate, diisobutyl 2,2-sec-butyl-3-methylsuccinate, diisobutyl 2- (3,3,3-trifluorpropyl) -3-methylsuccinate, diisobutyl 2,3-bis (2-ethylbutyl) succinate, diisobutyl 2, 3-diethyl-2 isopropylsuccinate, diisobutyl 2,3-diisopropyl-2-methylsuccinate, diisobutyl 2,3-dicyclohexyl2-methylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisobutyl 2,3-bis (cyclohexylmethyl) succinate , diisobutyl 2,3-di-t-butyl succinate, diisobutyl 2,3-diisobutyl succinate, diisobutyl 2,3-dineopentyl succinate, diisobutyl 2,3-diisopentyl succinate, diisobutyl 2,3- (1,1,1-trifluor-2-propyl ) succinate, diisobutyl 2,3-n-propylsuccinate, diisobutyl 2-isopropyl-3ibutylsuccinate, diisobutyl 2-terbutyl-3-ipropylsuccinate, diisobutyl 2-isopropyl-3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate diisobutyl 2- n-propyl-3 (cyclohexylmethyl) succinate, diisobutyl 2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl 2,2,3,3-tetramethylsuccinate, diisobutyl 2,2,3,3-tetraethylsuccinate, diisobutyl 2 , 2,3,3- tetrapropyl succinate, diisobutyl 2,3-diethyl-2,3-diisopropyl succinate, dineopentyl 2,3bis (trimethylsilyl) succinate, dineopentyl 2,2-di-sec-butyl-3-methylsuccinate, dineopentyl 2 (3,3,3- trifluorpropyl) -3-methyl succinate, dineopentyl 2,3 bis (2-ethylbutyl) succinate, dineopentyl 2,3-diethyl-2-isopropyl succinate, dineopentyl 2,3-diisopropyl-2-methyl succinate, dineopentyl 2,3-dicyclohexyl- 2- methylsuccinate, dineopentyl 2,3-diisopropyl succinate, dineopentyl 2,3-bis (cyclohexylmethyl) succinate, dineopentyl 2,3-di-t-butyl succinate, dine-opentyl 2,3-diisobutilsuccinate, dineopentyl 2,3 dineopentyl succinate, dineopentyl 2,3-diisopentyl succinate, dineopentyl 2,3- (1,1,1-trifluor-2-propyl) succinate, dineopentyl 2,3-n-propyl succinate, dineopentyl 2-isopropyl-3-isobutyl succinate, dineopentyl 2-t- butyl-3-isopropyl succinate, dineopentyl 2-isopropyl-3-cyclohexyl succinate, dineopentyl 2-isopentyl-3-cyclohexyl succinate, dineopentyl 2-n-propyl-3- (cyclohexylmethyl) succinate, dineopentyl 2 cyclo- H exil-3-cyclopentyl succinate, dineopentyl 2,2,3,3-tetramethyl succinate, dineopentyl 2,2,3,3-tetraethyl succinate, dineopentyl 2,2,3,3-tetrapropyl succinate, and / or dineopentyl 2,3-diethyl 2, 3- diisopropyl succinate.
[59] In any embodiment, the compounds according to formula (I) can include two or four of the radicals R3 to R6 attached to the same carbon atom that are linked together to form a cyclic multivalent radical. Examples of suitable compounds include 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,5-dimethyl-cyclopentane, 1- (ethoxycarbonyl) - 1- (ethoxyacetylmethyl) -2-methylcyclohexane, and / u 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane.
[60] For purposes here, all of the aforementioned compounds can be used in the form of pure stereoisomers or in the form of mixtures of the enantiomers, or mixture of diastereoisomers and enantiomers. When a pure isomer is to be used, it can be isolated using common known techniques. In particular, some of the succinates of the present invention can be used as rac or meso pure forms, or as mixtures thereof, respectively.
[61] In either embodiment, the internal electron donor compound can be selected from the group consisting of diethyl 2,3-diisopropyl succinate, diisobutyl 2,3-diisopropyl succinate, di-n-butyl 2,3-diisopropyl succinate, diethyl 2,3 -dicyclohexyl-2-methylsuccinate, diisobutyl 2,3-dicyclohexyl-2-methylsuccinate, diisobutyl 2,2-dimethylsuccinate, diethyl 2,2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diisobutyl 2-ethyl- 2- methylsuccinate, diethyl 2- (cyclohexylmethyl) -3-ethyl-3-methylsuccinate, diisobutyl 2- (cyclohexylmethyl) -3-ethyl-3-methylsuccinate, and combinations of the same. External Electron Donors
[62] In any modality, in conjunction with an internal donor, two or more external electron donors can also be used in combination with a catalyst. External electron donors include, but are not limited to, organic silicon compounds, for example, tetraethoxysilane (TEOS), methylcyclohexldimethoxysilane (MCMS), propyltriethoxysilane (PTES) and dicyclopentidimethoxysilane (DCPMS). Internal and external electron donors are described, for example, in US 4,535,068. The use of organic silicon compounds as external electron donors is described, for example, in US 4,218,339; US 4,395,360; US 4,328,122; and US 4,473,660. External electron donors act to control stereoregularity that affects the amount of isotactic versus atactic polymers produced in a given system. The more stereoregular polymer-roisotactic is more crystalline, which leads to a material with a higher flexion modulus. Highly crystalline isotactic polymers also exhibit lower MFRs as a result of a reduced hydrogen response during polymerization. The stereoregulation capacity and hydrogen response of a given external electron donor are directly and inversely related. The DCPMS donor has a substantially lower hydrogen response than the PTES donor, but produces a significantly higher level of stereoregularity than PTES.
[63] In either embodiment, the two external electron donors A and B, also referred to here as the first external electron donor and the second external electron donor, can be selected in such a way that the melting flow rate MFR ( A) homopolypropylene obtained by homopolymerization of propylene using the first external electron donor (A) in combination with the solid titanium catalyst component and the organoaluminium compound catalyst component and the MFR (B) of homopolypropylene obtained by homopolymerization of propylene using the second external electron donor (B) under the same conditions as in the case of using the external electron donor (A) have the following relationship: 1.2 <log [MFR (B) / MFR (A) ] <1.4.
[64] The external electron donors to be used in the preparation of the electron donor catalyst component can be those electron donors that are used in the preparation of the solid titanium catalyst component. In either embodiment, each of the external electron donors (A) and (B) can comprise organic silicon compounds.
[65] In any event, one or more of the external electron donors may comprise an organic silicon compound of the formula: R3nSi (OR4) 4-n in which R3 and R4 independently represent a hydrocarbon radical and 0 <n <4.
[66] Examples of suitable organic silicon compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyl-dimethoxysilane, dimethyldiethoxysilane, diisopropylthietoysilane, t-butylmethyl-n-dietoxysilane, t-butylmethyldisethoxyethyl, phenylmethoxyethyl, phenylmethoxy , bis-o-tolyldimethoxy-silane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bisethyl-phenyldimethoxy-silane, dicyclohexyl-methoxy-ethylene-methoxy-ethylene, cyclohexyl-methoxy-ethylene-cyclohexyl-hexane , vinyl trimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, [gamma] -chloropropyltri-methoxysilane, methyltriethoxyethyl, triethylethyl, triethylsilane, vinyl , gamma-am inopropyltri-ethoxysilane, chlorotriethoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanotrietoxysilane, 2-norbornanomethylmethoxy-silane, ethyl silicate, butyl silicate, vinylethyl-methyloxy-methyloxy-methyloxy-methyloxy-methyloxy or dimethyltetraethoxydisiloxane.
[67] In either embodiment, one of the two or more organic silicon compounds can comprise the formula: R12Si (OR2) 2 where R1 represents a hydrocarbyl radical in which the carbon adjacent to Si is secondary or tertiary. Suitable examples include substituted and unsubstituted alkyl groups, such as isopropyl, sec-butyl, t-butyl and t-amyl groups, cycloalkyl groups, such as cyclopentyl and cyclohexyl groups, cycloalkenyl groups, such as a cyclopentenyl group and aryl groups, such as phenyl and tolyl groups. In any embodiment, R2 can represent a hydrocarbyl radical or a hydrocarbyl radical having 1 to 5 carbon atoms or a hydrocarbyl radical having 1 or 2 carbon atoms.
[68] Examples of suitable organic silicon compound include diisopropylmethoxysilane, diisopropylldiethoxysilane, diisohydrobutyl silane, di-t-butyldimethoxy silane, di-t-amyldimethoxysilane, dicyclopentildimethoxysilane, dicyclohexylsimethysilane, dicyclohexyl-dildo , bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane and / or bis-ethylphenyldimethoxysilane.
[69] In either embodiment, the organic silicon compound can be represented by the following general formula: R1nSi (OR2) 4-n where n is 2, R1 represents a hydrocarbyl radical and at least one of the two hydrocarbyl radicals is a group of hydrocarbon in which the carbon adjacent to Si is a primary carbon. Examples of suitable hydrocarbon groups include alkyl groups, such as ethyl, n-propyl and n-butyl groups, aralkyl groups, such as cumyl and benzyl groups, and alkenyl groups, such as a vinyl group and the like.
[70] In any embodiment, R2 may represent a hydrocarbyl radical preferably having 1 to 5 carbon atoms or 1 to 2 carbon atoms. Suitable examples of organic silicon compounds in which n is 2 include diethyldimethoxysilane, dipropyldimethoxysilane, di-n-butyldimethoxysilane, dibenzyl-dimethoxysilane and / or divinyldimethoxysilane.
[71] Examples of suitable compounds when 0 <n <2 or 2 <n <4 include R1 being an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group and R2 represents a hydrocarbyl radical having 1 to 5 carbon atoms or 1 to 2 carbon atoms.
[72] Suitable examples of organic silicon compounds in which 0 <n <2 or 2 <n <4 include trimethylmethoxysilane, trimethylethoxysilane, methyl-phenyldimethoxysilane, methyltri-methoxysilane, t-butyl-methyldimethoxysilane, t-butylmethyldiethoxysilane, t-amyl- dimetoxissilano methyl, fenilmetildimetoxissilano, cyclohexyl hexilmetildimethóxi- silane, cyclohexyl hexilmetildietoxissilano, ethyltrimethoxysilane, etiltrietóxi- silane, viniltrietóxi silane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, decyl trimethoxysilane, deciltrietoxissilano, metoxissilano feniltri-, propyltriethoxysilane, butyl triethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, 2-norbornanotrimethoxysilane and / or 2-norbornanotrietoxysilane.
[73] In any form, external electron donors include methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, propyltriethoxylethylsilane, butyltriethoxysilane, phenyltriethoxylsilane, phenyltriethoxylane, phenylmethoxylane, phenylmethoxylane, phenylmethoxylane, phenylmethoxylane.
[74] In either embodiment, the organic silicon compounds disclosed above can be used in such a way that a compound capable of being transformed into such an organic silicon compound is added at the time of polymerization or preliminarily polymerizing an olefin and the organic compound silicon can be formed in situ during polymerization or preliminary polymerization of olefin.
[75] In any modality, a first external electron donor can have the formula R12Si (OR2) 2, in which each R1 is, independently, a hydrocarbyl radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to Si it is a secondary or tertiary carbon atom, and each R2 is, independently, a hydrocarbyl radical comprising from 1 to 10 carbon atoms; and a second external electron donor having the formula R3nSi (OR4) 4-n, wherein each R3 and R4 are, independently, a hydrocarbon radical comprising from 1 to 10 carbon atoms, and n is 1, 2 or 3; and the second external electron donor is different from the first external electron donor.
[76] In either mode, the first ex-suit electron donor and the second external electron donor can be selected from the group consisting of tetraethoxysilane, methyl-cyclohexyldimethoxysilane, propyltriethoxysilane, dicyclopentidimethoxysilane and their combinations. In any embodiment, the Ziegler-Natta catalyst system can comprise 2.5 mol% to less than 50 mol% of the first external electron donor and greater than 50 mol% of a second external electron donor based on the total molar% of external electron donors. In either embodiment, the first electron donor may comprise, consist of, or consist essentially of dicyclopentyldimethoxysilane (DCPMS) and the second external electron donor may comprise, consist of, or consist essentially of propyltriethoxysilane (PTES).
[77] In any modality, a relationship between the first external electron donor and the second external electron donor can be defined by the equation: 1.2 log [MFR (B) / MFR (A)] 1,4, where MFR (A) is a first melt flow rate of a homopolymer formed by propylene monomers polymerizing in the presence of the Ziegler-Natta catalyst and the first external electron donor, and where MFR (B) is a second rate of fusion flow of a homopolymer formed by the polymerization of propylene monomers in the presence of Ziegler-Natta catalyst and the second external electron donor, and in which the MFR (A) is smaller than the MFR (B). Polymerization Process
[78] In either embodiment, a method for making polypropylene resin may comprise contacting propylene monomers under propylene polymerization conditions with a catalyst system to produce a polypropylene resin comprising at least 50 mol% of propylene, an MWD greater than 5 and a melt resistance of at least 20 cN determined using an extensional rheometer at 190 ° C, the catalyst system comprising: a Ziegler-Natta catalyst comprising an internal non-aromatic electron donor; and first and second external electron donors comprising different organosilicon compounds. In any modality, the first external electron donor can have the formula R12Si (OR2) 2, in which each R1 is, independently, a hydrocarbon radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to Si is a secondary or tertiary carbon atom, and wherein each R2 is, independently, a hydrocarbyl radical comprising 1 to 10 carbon atoms; and the second external electron donor has the formula R3nSi (OR4) 4-n, wherein each R3 and R4 are, independently, a hydrocarbon radical comprising from 1 to 10 carbon atoms, n is 1, 2 or 3; and the second ex-suit electron donor is different from the first external electron donor.
[79] In any event, the internal non-aromatic electron donor may comprise an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioether, thioester, aldehyde, alcoholate, carboxylic acid or a combination thereof, or a C1 to C20 diester of a substituted or unsubstituted C2 to C10 dicarboxylic acid or a succinate according to the formula:
wherein R1 and R2 are, independently, linear or branched C1 to C20 alkyl, alkenyl or cycloalkyl hydrocarbon radicals; R3 to R6 are, independently, hydrogen, halogen or straight or branched C1 to C20 alkyl, alkenyl or cycloalkyl radicals, where radicals R3 to R6 are not joined together, or at least two of the radicals R3 to R6 are joined to form a radical cyclic divalent, or a combination thereof.
[80] In any embodiment, the polymerization process according to the present disclosure may include contacting propylene with any embodiment described here of the catalyst system under polymerization conditions. In any modality, the polymerization process can include a preliminary polymerization step. Preliminary polymerization may include using the Zie- gler-Natta catalyst system comprising the internal non-aromatic electron donor in combination with at least one aluminum organ cocatalyst portion, where at least a portion of the external electron donors is present, in which the catalyst system is used in a higher concentration than used in the subsequent “main” polymerization process.
[81] In any embodiment, the concentration of the catalyst system in the preliminary polymerization based on the moles of titanium present, can be from 0.01 to 200 millimoles, or 0.05 to 100 millimoles, calculated as a titanium atom per liter of an inert hydrocarbon medium. In any embodiment, the organoaluminium cocatalyst can be present in an amount sufficient to produce 0.1 to 500 g, or 0.3 to 300 g, of a polymer per gram of the titanium catalyst present and can be present in 0, 1 to 100 moles, or 0.5 to 50 moles per mole of the titanium atom present in the catalyst component.
[82] In either embodiment, preliminary polymerization can be carried out under light conditions in an inert hydrocarbon medium in which an olefin and catalyst components are present. Examples of such inert hydrocarbon media used include aliphatic hydrocarbons, such as propane, butane, combed, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons, such as cyclopentane, cyclohexane, methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene and xylene; halogenated hydrocarbons, such as ethylene chloride and chlorobenzene; and mixtures thereof. The olefin used in the preliminary polymerization can be the same as an olefin to be used in the main polymerization.
[83] In any event, the reaction temperature for the preliminary polymerization can be a point at which the resulting preliminary polymerization does not substantially dissolve in the inert hydrocarbon medium, which can be from -20 to + 100 ° C or - 20 to + 80 ° C, or 0 to 40 ° C.
[84] In either embodiment, during preliminary polymerization, a molecular weight control agent, such as hydrogen, can be used. The molecular weight control agent can, desirably, be used in an amount such that the polymer obtained by preliminary polymerization has properties consistent with the intended product. In either embodiment, preliminary polymerization can be carried out so that 0.1 to 1000 g, or 0.3 to 300 g, of a polymer are formed per gram of the titanium catalyst.
[85] In any embodiment, a method for preparing a polypropylene resin may comprise contacting propylene monomers at a temperature and pressure in the presence of a catalyst system for the production of a propylene resin comprising at least 50 mol% of propylene, wherein the catalyst system comprises: a Ziegler-Natta catalyst comprising an internal non-aromatic electron donor; a first external electron donor having the formula R12Si (OR2) 2, in which each R1 independently is a hydrocarbyl radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to Si is a secondary or tertiary carbon atom, and in that each R2 is independently a hydrocarbon radical comprising from 1 to 10 carbon atoms; and a second external electron donor having the formula R3nSi (OR4) 4-n, wherein each R3 and R4 are independently a hydrocarbon radical comprising from 1 to 10 carbon atoms, n is 1, 2, or 3; and the second external electron donor is different from the first external electron donor.
[86] In either embodiment, the propylene polymer resin can have a melting strength of at least 20 cN determined using an extensional rheometer at 190 ° C.
[87] In any embodiment, the olefin may comprise or consist essentially of propylene. In any embodiment, the olefin may comprise from 0 to 49% of an alpha olefin other than propylene, as defined herein. In any embodiment, the alpha olefin can include ethylene, 1-butene, 4-methyl-1-pentene, 1-octene, or a combination thereof. In any embodiment, the olefin may comprise at least 50% by weight of propylene, or at least 75% by weight, or at least 99% by weight of propylene.
[88] In any modality, the polymerization of the olefin can be carried out in the gas phase, in the liquid phase, in the volume phase, in the paste phase or any combination thereof.
[89] In either embodiment, the polymerization can be carried out by slurry polymerization, in which the inert hydrocarbon can be used as a reaction solvent, or a liquid olefin under the reaction conditions can be used as the solvent.
[90] In any mode, the titanium catalyst can be present in the reactor at 0.005 to 0.5 millimole, preferably 0.01 to 0.5 millimole, based on the soft base of Ti per liter of the reaction zone. In either embodiment, the organoaluminium cocatalyst can be present in an amount sufficient to produce 1 to 2000 moles or 5 to 500 moles of aluminum per mole of the titanium atom in the catalyst system. In any modality, the internal electron donor can be present in 0.2 to 5.0 or 0.5 to 2.0 per mole of Ti.
[91] In any modality the total amount of external electron donors can be from 0.001 to 50 moles, or 0.01 to 20 moles, or 0.05 to 10 moles of Si per mole of Ti present.
[92] In either embodiment, the first ex-suit electron donor can be present in the catalyst system from 2.5 to 50 mole% or from 2.5 to 10 mole% of the total amount of external electron donor present.
[93] In either embodiment, the polymerization process may include contacting the titanium catalyst component, the internal electron donor, the organoaluminium cocatalyst, and the two external electron donors with each other at the time of the main polymerization, before main polymerization, for example, at the time of preliminary polymerization, or a combination thereof. When contacting them before the main polymerization, two or more of these components can be freely selected and contacted. In any embodiment, two or more components can be contacted individually or partially and then contacted with each other in total to produce the catalyst system.
[94] In either embodiment, the components of the catalyst system can be contacted with each other before polymerization in an inert gas atmosphere, the individual components of the catalyst can be contacted with each other in an atmosphere of olefin. , or any combination thereof.
[95] In either embodiment, hydrogen can be used during polymerization to control the molecular weight and other properties of the resulting polymer.
[96] In any embodiment, the polymerization conditions can include a polymerization temperature of 20 to 200 ° C, or 50 to 180 ° C and an atmospheric pressure pressure of 100 kg / cm2, or 2 to 50 kg / cm2 . The polymerization process according to the present disclosure can be carried out in batches, semi-continuously or continuously. Polymerization can be carried out in two or more stages using two or more reactors under different reaction conditions using different internal electron donors, different external electron donors and / or different catalyst systems.
[97] In any embodiment, the polypropylene resin according to the present disclosure can be produced in a continuous volume reactor. A catalyst system comprising a titanium catalyst supported on magnesium chloride according to one or more embodiments of the present disclosure is used. The preparation of the catalyst can be carried out continuously in situ by contacting the catalytic solids, triethyl aluminum and the external electron donor system under conditions known in the art to yield stereospecific active catalyst for propylene polymerization. The activated catalyst can then be continuously fed to a prepolymerization reactor where it has been continuously polymerized in propylene until a productivity of approximately 100 to 400 g of polymer / g of cat. The prepolymerized catalyst can then be continuously fed to a slurry reactor by volume and the polymerization continued at 70 ° C to 80 ° C, for a residence time of 90 minutes. The reaction slurry (homopolymer granules in propylene by volume) can then be removed from the reactor and the polymer granules continuously separated from the liquid propylene. The polymer granules can then be separated from the unreacted monomer to produce a granular product for composition and / or mechanical properties. In any modality, hydrogen can be used in the reactor to control the melt flow rate of the polypropylene resin.
[98] In the case of impact copolymer resin production, the reactor granules by volume, after removing the monomer, can be fed directly to a gas phase reactor (GPR) where polymerization is continued under conditions known in the art to produce ethylene-propylene bipolymer within the pores of the polymer granules. The final product, designated in the art as an "impact copolymer" can be continuously removed from the gas phase reactor and separated from the unreacted monomer to produce a granular product for further composition and processing. The molecular weight of ethylene-propylene rubber or, more appropriately, the Intrinsic Viscosity (IV) of the rubber phase, can be controlled by the hydrogen concentration in the GPR.
[99] In any embodiment, the reactor granules can be stabilized with at least 0.01% by weight of an additive, for example, 0.15% by weight of Irganox ™ 1010, 0.05% by weight of Ul- tranox ™ 626A and / or with 0.075% by weight of sodium benzoate (fine form) and then pelletized, for example, in a 30 mm twin screw extruder Werner & Pfleiderer. Pellets can then be injection molded and / or subjected to further processing Polypropylene resins
[100] In any embodiment, a polypropylene resin can comprise at least 50 mol% of propylene and have a melting strength of at least 20 cN determined using an extensional rheometer at 190 ° C. For the purposes described herein, the melt strength of a polymer at a particular temperature, for example, 190 ° C, is determined with a Gottfert Rheotens Melt Strength Apparatus (e.g., Gottfert Rheotens 71.97). The measurement is performed by grasping the extrudate of a capillary rheometer (for example, a capillary rheometer Gottfert Rheograph 2002) or of an extruder equipped with a capillary matrix, after the extrudate has been extruded 100 mm using variable speed gears and increasing the speed of the gear at constant acceleration (12 mm / s2, starting from an initial calibration speed, zero force of 10 mm / s) until the molten polymer strand breaks. Cord strength is measured with an equilibrium beam in conjunction with a linear variable displacement transducer. The force required to extend and then break the extrudate is defined as the melt strength. The force is measured in centinewtons (cN). A typical curve of force versus wheel speed is known in the art for including a snore just before the cord breaks. In such cases, the plateau force is approximated by the midline between the oscillations.
[101] One of the most distinctive improvements in the present disclosure is an unexpectedly high melt strength. Melting strength is a key property of products used in blown film, thermoforming, blow molding, and the like processes. In a blown film process, high melt strength is required to maintain a stable bubble when operating at elevated temperatures and / or at high production rates, especially in large lines. If the melting strength is unacceptably low, holes are formed in a molten web which causes the bubble to collapse and occasionally tear. This, in turn, results in loss of production and can lead to subsequent quality problems if the material in the extruder starts to degrade during downtime. Low melt strength in linear polyethylenes prevents the film manufacturer from taking advantage of the excellent extraction characteristics inherent with most linear polyethylenes, unless a melt strength enhancer, such as LDPE, is added.
[102] A polypropylene resin according to any of the embodiments disclosed herein can comprise at least 50 mol% of propylene and have a melt strength of at least 35 cN, or at least 40 cN, or at least 45 cN, or at least 50 cN, or at least 55 cN, or at least 60 cN, or at least 65 cN, or at least 70 cN, or at least 75 cN, or at least 80 cN, or from 50 cN to 200 cN, or from 60 cN to 150 cN, or from 70 cN to 200 cN, or any combination thereof, determined using an extensional rheometer at 190 ° C, as described herein.
[103] A polypropylene resin according to any of the modalities disclosed here can comprise at least 50 mol% of propylene and has an MWD (Mw / Mn) greater than 5, or greater than or equal to 6, or from 6 to 20 , or 6 to 15, or any combination thereof.
[104] The polypropylene resin according to any of the embodiments disclosed herein can further comprise at least 75 mol%, or at least 80 mol%, or at least 90 mol%, or at least 95 mol%, or at least 99 mole% of propylene. In any embodiment, a polypropylene resin according to any of the embodiments disclosed here may be a propylene homopolymer.
[105] A propylene resin according to any of the modalities can comprise from 0.1 to 10 mol% of a comonomer. In any embodiment, the comonomer can be an alpha-olefin. In any modality, the comonomer can be selected from the group consisting of ethylene and C4 to C20 olefins.
[106] A polypropylene resin according to any of the modalities disclosed here can have a branching index (g ') of at least 0.95 or at least 0.99.
[107] A polypropylene resin according to any of the modalities disclosed here may have a stiffness greater than 2000 MPa or greater than 2100 MPa, or 290 kpsi (2000 MPa) to 360 kpsi (2500 MPa) determined in accordance with ASTM D790A in samples nucleated with 0.1% sodium benzoate.
[108] A polypropylene resin according to any of the modalities disclosed here can have a viscosity ratio greater than or equal to 35, or 40, or 45, or 35 to 80, determined at an angular frequency ratio of 0, 01 and at an angular frequency ratio of 100 rad / s (at an angular frequency ratio of 0.01 to 100 rad / s) at a constant strain of 10% at 190 ° C.
[109] A polypropylene resin according to any of the modalities disclosed here can have an MFR range of 0.1 to 100, or 0.3 to 10, when determined according to ASTM D1238 Condition L.
[110] A polypropylene resin according to the modalities disclosed here can be an impact copolymer. For these purposes, an impact copolymer refers to a resin comprising a homopolymer made in a volume polymerization reactor followed by transferring the granules to the gas phase reactor and making ethylene-propylene rubber inside the granules.
[111] In any embodiment, the polypropylene resin can be a polymer or non-functionalized resin. For the present purposes, a non-functionalized resin does not comprise grafted or otherwise processed post-reactor olefin polymers. By functionalized (or grafted) it is understood that several functional groups are incorporated, grafted, attached to and / or physically or chemically attached to the polymer backbone of the polymer being functionalized after formation of the base polymer. Examples of functionalized polymers include polymers in which functional groups are grafted onto the polymer structure or linker groups using radical copolymerization of a functional group, referred to in the art as graft copolymerization. Examples of functional groups used to produce functionalized polymers include unsaturated carboxylic acids, unsaturated carboxylic acid esters, acid anhydrides, diesters, salts, amides, imides, vinyl aromatic compounds, hydrolyzable unsaturated silane compounds, and halogenated hydrocarbons not saturated. Specific examples of unsaturated carboxylic acids and acid derivatives include, but are not limited to, maleic anhydride, citraconic anhydride, 2-methyl maleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic anhydride, bicycles anhydride [2,2, 1] -5-heptene-2,3-dicarboxylic and 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclic acid anhydride (2.2.2) oct-5-ene-2,3-dicarboxylic acid, 1,2,3,4,5, & g, lo-octahydronaphthalene-2,3- anhydride dicarboxylic, 2-oxa-1,3-diketospiro (4.4) non-7-ene, bicyclo acid anhydride (2.2.1) hept-5-eno-2,3-dicarboxylic, maleopimaric acid, tetrahydrophthalic anhydride, ani - norborn-5-ene-2,3-dicarboxylic acid drain, naic anhydride, methyl naic anhydride, hymic anhydride, methyl hyal anhydride and oxx-methyl-bicyclo (2.2.1) hept-5-ene-2 anhydride, 3-dicarboxylic (XMNA). Examples of the esters of unsaturated carboxylic acids include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. Hydrolyzable unsaturated silane compounds useful as functional groups present in functionalized polymers include a polymerizable unsaturated group radical having an alkoxysilyl group or a silyl group in its molecule. Examples include a compound having a hydrolyzable silyl group attached to a vinyl group and / or a hydrolyzable silyl group attached to the vinyl group via an alkylene group, and / or a compound having a hydrolyzable silyl group attached to an acid ester or amide acrylic, methacrylic acid or the like. Examples thereof include vinyltrichlorosilane, vinyltris (beta-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, monovinylsilane, and monoallylsilane. Examples of unsaturated halogenated hydrocarbons useful as functional groups include vinyl chloride and vinylidene chloride. For purposes here, functionalized polymers still include polymers grafted onto other polymers.
[112] A functionalized polymer is considered to have indications of long chain branching (i.e., a g 'less than 0.95) consistent with the cross-linking and intermolecular bonding associated with functionalized polymers.
[113] For the present purposes, a functionalized polymer comprises more than 0.1% by weight of a functional group and / or a g '<0.95 and / or is the product of a functionalization process or grafting-thiapospos reactor. Therefore, in one embodiment, the non-functionalized polymer may comprise less than 0.1% by weight of a functional group and / or is not the product of a post-reactor functionalization process and / or is not a grafted polymer. post reactor and / or has a g '> 0.95 determined as described herein.
[114] The resin can be produced by contacting propylene monomers under propylene polymerization conditions with a catalyst system comprising a Ziegler-Natta catalyst comprising an internal non-aromatic electron donor, and first and second external electron donors comprising different organosilicon compounds.
[115] In either embodiment, the resin may be free of functionalized polypropylene or comprise less than 5 percent by weight of selected functional groups of hydroxide, aryls, substituted aryls, halogens, alkoxies, carboxylates, esters, acrylates and carboxyl, based on the weight of the polypropylene resin, and where the number of polypropylene resin carbons involved in olefinic bonds is less than 5% of the total number of carbon atoms in the resin. In either embodiment, the resin may be free of post-reactor grafted polypropylene or comprise less than 5 weight percent post-reactor grafted polypropylene.
[116] A polypropylene resin according to any of the modalities disclosed here may have a heat distortion temperature greater than or equal to 100 ° C, determined according to ASTM D648 using a load of 0.45 MPa (66 psi) .
[117] The polypropylene resin according to any of the modalities disclosed here may have an isopentad percentage of more than 90%, or more than 95%, or more than 99%.
[118] A polypropylene resin according to any of the modalities disclosed here may comprise a mixture of several components. Mixtures can be formed using conventional equipment and methods, such as dry mixing the individual components and subsequently mixing by melting in a mixer, or mixing the components together directly in a mixer, such as a Banbury mixer, a mixer of Haake, a Brabender internal mixer, or a single or double screw extruder, which may include a composition extruder and a side arm extruder used directly downstream of a polymerization process which may include mixing powders or pellets from resins in the hopper of the film extruder. In addition, additives can be included in the mixture, in one or more components of the mixture and / or in a product formed from the mixture, such as a film as desired. Such additives are well known to those skilled in the art and can include, for example, fillers; antioxidants (for example, hindered phenolics, such as IRGANOXTM 1010 or IRGANOXTM 107 available from Ciba-Geigy); phosphites (for example, IRGAFOSTM 168 available from Ciba-Geigy); anti-sticky additives; tacking agents, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates and hydrogenated rosins; UV stabilizers; thermal stabilizers; anti-blocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; baby powder; and the like. In this sense, a polypropylene resin according to any of the modalities disclosed here can comprise even more than or equal to 0.01% w of one or more fillers; antioxidants; nonstick agents; stickiness agents; UV stabilizers; heat stabilizers, anti-blocking agents; release agents; antistatic agents; pigments; dyes; colorants; waxes; silica; baby powder; or a combination of them.
[119] A polypropylene resin according to any of the modalities disclosed here can comprise at least 50 mol% of propylene, has a melting strength of at least 20 cN determined using an extensional rheometer at 190 ° C, and an MWD ( Mw / Mn) greater than 5, in which the resin is produced by contacting propylene monomers at a temperature and pressure according to any method or process disclosed here using any modality or combination of modalities of the catalyst system as disclosed here.
[120] A polypropylene resin according to any of the modalities disclosed here can comprise at least 50 mol% of propylene, has a melting strength of at least 20 cN determined using an extensional rheometer at 190 ° C and an MWD (Mw / Mn) greater than 5, where the resin is produced by contacting propylene monomers at a temperature and pressure in the presence of a catalyst system comprising a Ziegler-Natta catalyst comprising an internal non-aromatic electron donor and two or more donors of external electrons. In any event, the first external electron donor may have the formula R12Si (OR2) 2, in which each R1 is independently a hydrocarbon radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to Si is an atom of secondary or tertiary carbon, and wherein each R2 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms; and the second external electron donor has the formula R3nSi (OR4) 4-n, in which each R3 and R4 are independently a hydrocarbon radical comprising from 1 to 10 carbon atoms, where n is 1, 2 or 3; and where the second external electron donor is different from the first external electron donor.
[121] In this sense, the present disclosure refers to the following modalities:
[122] E1. A polypropylene resin, comprising: at least 50 mol% of propylene; a MWD (Mw / Mn) greater than 5; a branch index (g ') of at least 0.95; and a melting resistance greater than 20 cN determined using an extensional rheometer at 190 ° C.
[123] E2. The resin of the E1 modality, where the MWD is from 6 to 15.
[124] E3. The resin of any of the above modalities, wherein the melt strength is 50 cN to 200 cN.
[125] E4. The resin of any of the above embodiments, comprising a viscosity ratio of 35 to 80 determined from the proportion of complex viscosity at 0.01 to 100 rad / s angular frequency at a fixed tension of 10% at 190 ° C.
[126] E5. The resin of any of the above modalities, having a heat distortion temperature greater than or equal to 100 ° C, determined according to ASTM D648 using a load of 0.45 MPa (66 psi).
[127] E6. The resin of any of the above embodiments, wherein the resin is an impact copolymer.
[128] E7. The resin of any of the above embodiments, wherein the resin comprises at least 99 mol% of propylene.
[129] E8. The resin of any of the above embodiments, wherein the resin comprises from 0.1 to 10 mol% of a comonomer selected from the group consisting of ethylene and C4 to C20 olefins.
[130] E9. The resin of any of the above modalities, comprising a percentage of isopentad greater than 95%.
[131] E10. The resin of any of the above modalities, having an MFR of 0.1 to 100, determined according to ASTM D1238 Condition L.
[132] E11. The resin of any of the above modalities, comprising a stiffness of 2000 MPa (290 kpsi) to 2500 MPa (360 kpsi) determined according to ASTM D790A in samples nucleated with 0.1% sodium benzoate.
[133] E12. The resin of any of the above embodiments, further comprising more than or equal to 0.01% by weight of one or more fillers; antioxidants; nonstick agents; stickiness agents; UV stabilizers; thermal stabilizers; anti-blocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; baby powder; or a combination of them.
[134] E13. The resin according to any of the above modalities, wherein the resin is produced by contacting propylene monomers under propylene polymerization conditions with a catalyst system comprising a Ziegler-Natta catalyst comprising an internal non-aromatic electron donor, and first and second external electron donors comprising different organosilicon compounds.
[135] E14. The resin of any of the above modalities, wherein the resin is free of functionalized polypropylene or comprises less than 5 percent by weight of selected functional groups of hydroxide, aryl, substituted aryl, halogens, alkoxides, carboxylates, esters, acrylates and carboxyl, based on the weight of the polypropylene resin, and where the number of carbons in the polypropylene resin involved in olefinic bonds is less than 5% of the total number of carbon atoms in the resin.
[136] E15. The resin of any of the above embodiments, wherein the resin is free of post-reactor grafted polypropylene or comprises less than 5 weight percent of the post-reactor grafted polypropylene.
[137] E16. A method for preparing a polypropylene resin, comprising: contacting propylene monomers under propylene polymerization conditions with a catalyst system to produce a polypropylene resin comprising at least 50 mol% of propylene, a MWD greater than 5 and a melt strength of at least 20 cN determined using an extensional rheometer at 190 ° C, the catalyst system comprising: a Ziegler-Natta catalyst comprising an internal non-aromatic electron donor; and first and second external electron donors comprising different organosilicon compounds.
[138] E17. The method of modality E16, in which: the first external electron donor has the formula R12Si (OR2) 2, in which each R1 independently is a hydrocarbon radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to Si it is a secondary or tertiary carbon atom, and each R2 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms; and the second external electron donor has the formula R3nSi (OR4) 4-n, where each R3 and R4 are independently a hydrocarbon radical comprising 1 to 10 carbon atoms, where n is 1, 2 or 3; and the second external electron donor is different from the first external electron donor.
[139] E18. The method of any of the above modalities, wherein the internal non-aromatic electron donor comprises an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioether, thioester, aldehyde, alcoholate, carboxylic acid or a combination of the same.
[140] E19. The method of any of the above modalities, wherein the internal non-aromatic electron donor comprises a C1 to C20 diester of a substituted or unsubstituted C2 to C10 dicarboxylic acid.
[141] E20. The method of any of the above modalities, in which the internal non-aromatic electron donor is a succinate according to the formula:
wherein R1 and R2 are, independently, linear or branched C1 to C20 straight, branched alkyl, alkenyl, or cycloalkyl hydrocarbon radicals; R3 to R6 are, independently, hydrogen, halogen or straight or branched C1 to C20 alkylene, alkenyl or cycloalkyl radicals, where R3 to R6 radicals are not joined together, or at least two of the radicals R3 to R6 are joined to form a radical cyclic divalent, or a combination thereof.
[142] E21. The method of any of the above modalities, in which the first external electron donor and the second external electron donor are selected from the group consisting of tetraethoxysilane, methylcyclohexyl dimethoxysilane, propyltriethoxysilane, dicyclopentyldimethoxysilane and combinations thereof.
[143] E22. The method of any of the above modalities, wherein the Ziegler-Natta catalyst system comprises a titanium-based Ziegler-Natta catalyst on a magnesium support.
[144] E23. The method of any of the above modalities, wherein the Ziegler-Natta catalyst system still comprises an organoaluminium Ziegler-Natta cocatalyst.
[145] E24. The method of any of the above modalities, wherein the Ziegler-Natta catalyst system comprises from 2.5 mol% to less than 50 mol% of the first electron donor based on the total molar% of external electron donors in which the the first electron donor comprises dicyclopentyldimethoxysilane (DCPMS) and more than 50 molar% of a second electron donor based on the total molar% of electron donors, where the second electron donor comprises propyltriethoxysilane (PTES).
[146] E25. The method of any of the above modalities, in which a relationship between the first external electron donor and the second external electron donor is defined by the equation: 1.2 log [MFR (b) / MFR (a)] 1,4 where MFR (a) is a first melt flow rate of a homopolymer formed by propylene monomers polymerizing in the presence of the Ziegler-Natta catalyst and the first external electron donor, and where MFR (b) is a second melt flow rate of a homopolymer formed by the polymerization of propylene monomers in the presence of Ziegler-Natta catalyst and the second external electron donor, and in which MFR (a) is less than MFR (b).
[147] E26. The method of any of the above modalities, in which the resin produced is in accordance with any of the E1 - E15 modes. EXAMPLES
[148] The following ASTM test methods in Table 1 and described above were used for physical property measurements.


[149] Melting Flow Rate (MFR): MFR is measured as per ASTM D1238, condition L, at 230 ° C and 2.16 kg of load using a melt index.
[150] Flexural modulus: The Flexural modulus is measured according to ASTM D790A using a crosshead speed of 1.27 mm / min (0.05 in / min) and a support extension of 50.8 mm (2 , 0 in) using an Instron machine.
[151] Tensile strength: Tensile strength in flow, elongation in flow and elongation at break were measured according to ASTM D 638, with a crosshead speed of 50.8 mm / min (2.0 in / min) , and a gauge length of 50.8 mm (2.0 in), using an Instron Machine.
[152] Notched Izod Impact Resistance: Notched Izod Impact Resistance is measured according to ASTM D256 at ambient temperature (21 ° C), using equipment made by Empire Technologies Inc.
[153] Thermal Distortion Temperature (HDT): HDT is measured according to ASTM D648 using a load of 0.45 MPa (66 psi).
[154] Polydispersity Index (PI): The Polydispersity Index is obtained from oscillatory shear data, from the crossing module and frequency as measured at 190 ° C, as described in Zeichner GR, Patel PD (1981 ), “A comprehensive study of polypropylene melt rheology”; Proceedings of the 2nd World Congress of Chemical Engineering, Montreal, Canada. Polymerization of Example 1:
[155] Example 1 was produced under pilot plant conditions in a continuous agitated tank reactor (CSTR). The titanium catalyst supported on magnesium chloride sold commercially as Avant ZN-168M is used with a mixture of external donor of propyltriethoxysilane and dicyclopentyldimethoxysilane. The preparation of the catalyst composition is carried out continuously in situ by counting the catalytic solids, triethyl aluminum and the external electron donor system under conditions known in the art to yield stereospecific active catalyst for propylene polymerization. The activated catalyst was continuously fed to a prepolymerization reactor where it was polymerized in propylene to a productivity of approximately 100 to 300 g of polymer / g of cat. The prepolymerized catalyst was then continuously fed to a continuously stirred tank reactor and the polymerization continued at 70 ° C to yield homopolymer. The concentration of hydrogen (chain transfer agent) used in the reactor is shown in Table 2. The slurry from the reactor was continuously removed from the polymerization reactor and the homopolymer granules are continuously separated from the liquid propylene. The granules were passed through a dryer to remove the residual monomer and collected in Gaylord boxes. Examples 2-7 were produced in the same way with varying hydrogen levels in the reactor to achieve the desired melt flow rate (MFR).
[156] The reactor homopolymer granules were stabilized with at least 0.090% by weight of Irganox ™ 1010, 0.045% by weight of Ultranox ™ 626A and 0.10% by weight of sodium benzoate (fine form) and pelleted in a double screw extruder (Werner & Pfleiderer 30 mm). The pellets were then injection molded using ASTM test samples and the physical properties tested according to the ASTM guidelines.


[157] Comparative Example 1 is Borealis Daploy ™ WB135HMS, a commercial grade post-reactor grafted polypropylene. Comparative Example 2 is a commercial grade polymer made with external methylcyclohexyl dimethoxy silane donor (MCMS) and a solid commercial catalyst THC-C series supplied by Toho Titanium Co. The Comparative Example 3 is an example of the polymer produced in accordance with US Patent 6,087,459, prepared under pilot plant conditions to provide a direct copaction of the polymers produced in accordance with the '459 patent for the present disclosure. The data are shown in Table 3.


[158] FIG. 1 shows the g 'branch index of Example 2 indicating no evidence of long chain branching. As is known to those skilled in the art, long chain branched polymers have a g 'branch index that decreases significantly below 1 although, as shown in FIG. 1, the g 'value remains close to 1.
[159] The branching index (g'vis, also called here as g ') is calculated using the output of the SEC-DRI-LS-VIS method (described on page 37 of US Patent 7,807,769 for g') as the follow. The mean intrinsic viscosity, [n] avg of the sample is calculated by:
where the sums are over the chromatographic slices, i, between the limits of integration. The g'vis branch index is defined as:

[160] FIG. 2 shows the complex viscosity vs. angular frequency for Example 2 compared to Comparative Examples 1 and 2. All shear / viscosity rheological experiments were conducted with an Anton Paar MCR500 Rheometer equipped with a 25 mm diameter parallel plate accessory. Disc samples were prepared by compression molding to a thickness of 2.5 mm and a diameter of 25 mm. The clearance between the two parallel plates was maintained at 1.90 mm for all measurements. Small amplitude oscillatory shear tests were performed as a function of angular frequency ([omega]) ranging from 0.01 to 500 rad / s at 190 ° C. A fixed strain of 10% was used to ensure that measurements were made within the linear viscoelastic range of the investigated materials.

权利要求:
Claims (15)
[0001]
1. Polypropylene resin, characterized by the fact that it comprises: at least 50 mole% of polypropylene; a MWD (Mw / Mn) greater than 5; a branch index (g ') of at least 0.95, determined as described herein; and a melt strength greater than 20 cN determined as described herein, using an extensional rheometer at 190 ° C.
[0002]
2. Resin, according to claim 1, characterized by the fact that the MWD is 6 to 15.
[0003]
3. Resin according to claim 1 or 2, characterized by the fact that the melt resistance is 50 cN to 200 cN.
[0004]
Resin according to any one of claims 1 to 3, characterized in that it comprises a viscosity ratio of 35 to 80 determined from the complex viscosity ratio at 0.01 to 100 rad / s of angular frequency at a deformation fixed at 10% at 190 ° C, complex viscosity ratio being determined as described herein.
[0005]
Resin according to any one of claims 1 to 4, characterized by the fact that it has a thermal distortion temperature greater than or equal to 100 ° C, determined according to ASTM D648 using a load of 0.45 MPa (66 psi).
[0006]
6. Resin according to any one of claims 1 to 5, characterized by the fact that the resin is an impact copolymer, which is a resin comprising a homopolymer made in a volume polymerization reactor followed by transfer of the granules thus obtained to a gas-phase reactor and making ethylene-propylene rubber inside the granules.
[0007]
Resin according to any one of claims 1 to 6, characterized in that the resin comprises at least 99 mole% of propylene.
[0008]
8. Resin according to any one of claims 1 to 6, characterized in that the resin comprises from 0.1 to 10 mole% of a comonomer selected from the group consisting of ethylene and C4 to C20 olefins.
[0009]
9. Resin according to any one of claims 1 to 8, characterized by the fact that it has a percentage of isopentad [mmmm] greater than 95%, where "m" describes the stereochemistry of contiguous propylene groups as meso, the percentage of isopentad being determined by 13C-NMR spectroscopy as described herein.
[0010]
10. Resin according to any one of claims 1 to 9, characterized by the fact that it has an MFR of 0.1 to 100 determined in accordance with ASTM D1238 Condition L.
[0011]
11. Resin according to any one of claims 1 to 10, characterized in that it comprises a rigidity of 2000 MPa (290 kpsi) to 2500 MPa (360 kpsi) determined according to ASTM D790A in samples nucleated with 0.1 % sodium benzoate.
[0012]
12. Resin according to any one of claims 1 to 11, characterized by the fact that it also comprises an amount greater than or equal to 0.01% by weight of one or more fillers; antioxidants; nonstick agents; stickiness agents; UV stabilizers; thermal stabilizers; anti-blocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; baby powder; or a combination of them.
[0013]
13. Resin according to any one of claims 1 to 12, characterized in that the resin is produced by contacting propylene monomers under propylene polymerization conditions with a catalyst system comprising a Ziegler-Natta catalyst comprising an internal electron donor non-aromatic and first and second external electron donors comprising different organosilicon compounds.
[0014]
14. Resin according to any one of claims 1 to 13, characterized in that the resin is free of functionalized polypropylene or comprises less than 5% by weight of selected functional groups of hydroxide, aryls, substituted aryls, halogens, alkoxies , carboxylates, esters, acrylates and carboxyl, based on the weight of the polypropylene resin, and where the number of polypropylene resin carbons involved in olefinic bonds is less than 5% of the total number of carbon atoms in the resin.
[0015]
15. Resin according to any one of claims 1 to 14, characterized in that the resin is free of post-reactor grafted polypropylene or comprises less than 5 weight percent post-reactor grafted polypropylene.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

EP0385765B1|1989-03-02|1995-05-03|Mitsui Petrochemical Industries, Ltd.|Process for polymerizing olefins and catalyst for polymerizing olefins|

---

IT1274503B|1995-05-15|1997-07-17|Montell North America Inc|HIGH TENACITY POLYOLEFINIC FIBERS|

---

US5641848A|1995-07-24|1997-06-24|Montell North America Inc.|Polypropylene blown film|

---

US5752362A|1996-03-12|1998-05-19|Tenneco Packaging|Stretch wrap films|

---

US6255426B1|1997-04-01|2001-07-03|Exxon Chemical Patents, Inc.|Easy processing linear low density polyethylene|

---

US5907942A|1997-05-21|1999-06-01|Tenneco Packaging|Stretch wrap films|

---

WO1999007752A1|1997-08-05|1999-02-18|Grand Polymer Co., Ltd.|Polypropylene resin composition and use thereof|

---

FI973816A0|1997-09-26|1997-09-26|Borealis As|Polypropen med Hoeg smaeltstyrka|

---

US6784269B2|1998-05-13|2004-08-31|Exxonmobil Chemical Patents Inc.|Polypropylene compositions methods of making the same|

---

US6087459A|1998-05-14|2000-07-11|Exxon Chemical Patents Inc.|Polymeric materials formed using blends of electron donors|

---

EP1115761B1|1998-08-26|2013-09-18|ExxonMobil Chemical Patents Inc.|Branched polypropylene compositions|

---

ES2269135T3|1999-04-15|2007-04-01|Basell Poliolefine Italia S.R.L.|COMPONENTS AND CATALYSTS FOR POLYMERIZATION OF OLEFINS.|

---

EP1059332A1|1999-06-10|2000-12-13|Fina Research S.A.|Polypropylene with high melt strength and drawability|

---

US6602598B1|1999-12-07|2003-08-05|Sls Patent Corporation|Quiet unwind stretch wrap film|

---

US6716939B2|2000-02-02|2004-04-06|Basell Poliolefine Italia S.P.A.|Components and catalysts for the polymerization of olefins|

---

EP1170305A1|2000-07-05|2002-01-09|ATOFINA Research|Production of polyolefins having improved properties|

---

US7172815B2|2001-10-03|2007-02-06|Pliant Corporation|Low gauge stretch wrap film|

---

AU2003250201B2|2002-08-01|2008-12-11|Basell Poliolefine Italia S.P.A.|Highly stereoregular polypropylene with improved properties|

---

US7807769B2|2002-09-20|2010-10-05|Exxonmobil Chemical Patents Inc.|Isotactic polypropylene produced from supercritical polymerization process|

---

MXPA06003931A|2003-10-07|2006-06-27|Dow Global Technologies Inc|Polypropylene composition for air quenched blown films.|

---

WO2007003523A1|2005-07-01|2007-01-11|Basell Poliolefine Italia S.R.L.|Propylene polymers having broad molecular weight distribution|

---

US7951873B2|2006-05-05|2011-05-31|Exxonmobil Chemical Patents Inc.|Linear low density polymer blends and articles made therefrom|

---

AT406393T|2006-07-10|2008-09-15|Borealis Tech Oy|BRANCH BRANCHED POLYPROPYLENE|

---

EP2000504A1|2007-06-08|2008-12-10|Borealis Technology Oy|Polymer composition with high impact resistance and high melt strength|

---

US8197927B2|2007-06-15|2012-06-12|Berry Plastics Corporation|Slip-cling stretch film|

---

WO2009007265A1|2007-07-10|2009-01-15|Basf Se|Stabilizer compositions|

---

AT556095T|2007-08-06|2012-05-15|Japan Polypropylene Corp|PROPYLENE POLYMER, MANUFACTURING METHOD, COMPOSITION, AND USE THEREOF|

---

US7939610B2|2008-05-22|2011-05-10|Exxonmobil Research And Engineering Company|Polymerization processes for broadened molecular weight distribution|

---

US20110212315A1|2008-09-25|2011-09-01|Basell Polyolefine Gmbh|Impact Resistant LLDPE Composition and Films Made Thereof|

---

WO2010037747A1|2008-10-01|2010-04-08|Borealis Ag|New sewage pipe material with improved properties|

---

EP2216346A1|2009-02-04|2010-08-11|Borealis AG|Process for the production of polyolefins with broad molecular weight distribution|

---

KR101068714B1|2009-03-09|2011-09-28|삼성토탈 주식회사|Polypropylene resin composition for foaming molding and a foam prepared using the same|

---

EP2325248B1|2009-11-16|2012-05-16|Borealis AG|Melt blown fibers of polypropylene compositions|

---

EP2341088B1|2009-12-30|2012-06-20|Borealis AG|BOPP with homogeneous film morphology|

---

EP2527376B1|2010-01-22|2017-07-19|China Petroleum & Chemical Corporation|Preparation method for propylene homopolymer having high melt strength|

---

CN102134290B|2010-01-22|2013-12-04|中国石油化工股份有限公司|Polypropylene with high melt strength and product thereof|

---

EP2386584A1|2010-05-11|2011-11-16|Borealis AG|Polypropylene composition suitable for extrusion coating|

---

BR112013008999A2|2010-10-14|2016-07-05|Reliance Ind Ltd|a process for the preparation of high melt strength polypropylene.|

---

ES2648254T3|2011-05-02|2017-12-29|Borealis Ag|Polypropylene for foam and polypropylene foam|

---

CN104508036B|2012-07-25|2018-02-16|博里利斯股份公司|The foam manufactured by the polypropylene with low-gel content|CN107840980B|2012-10-31|2021-05-25|埃克森美孚化学专利公司|Articles comprising broad molecular weight distribution polypropylene resins|

---

EP3601433A1|2017-03-29|2020-02-05|ExxonMobil Chemical Patents Inc.|Polyethylene compositions|

---

EP3253820A1|2015-02-04|2017-12-13|ExxonMobil Chemical Patents Inc.|Stabilized balanced melt strength and strain hardened polypropylene|

---

CN107207757A|2015-02-04|2017-09-26|埃克森美孚化学专利公司|The polypropylene of strain hardening, melt strength and shear shinning with balance|

---

EP3280767A4|2015-04-10|2018-12-05|ExxonMobil Chemical Patents Inc.|Extrusion of polypropylenes with organic peroxides|

---

WO2016175942A1|2015-04-28|2016-11-03|Exxonmobil Chemical Patents Inc.|Propylene-based impact copolymers|

---

CN107429021A|2015-05-29|2017-12-01|埃克森美孚化学专利公司|Thermoplastic sulfurized rubber comprising broad molecular weight distribution polypropylene|

---

CN107709008A|2015-08-13|2018-02-16|埃克森美孚化学专利公司|Multi-layer sheet containing high melt strength, propylene|

---

CN108290977B|2015-11-30|2020-05-19|埃克森美孚化学专利公司|Polypropylene for films and films obtained therefrom|

---

ES2765401T3|2015-12-21|2020-06-09|Borealis Ag|Items with improved optical properties|

---

EP3720907A1|2017-12-06|2020-10-14|ExxonMobil Chemical Patents Inc.|Low density foamed thermoplastic vulcanizate compositions|

---

EP3728458A1|2017-12-18|2020-10-28|ExxonMobil Chemical Patents Inc.|Thermoplastic vulcanizate conduits for transporting hydrocarbon fluids|

---

CN108129591B|2017-12-27|2021-05-28|杨翠|External electron donor composition, olefin polymerization catalyst system and application of external electron donor composition and olefin polymerization catalyst system|

---

WO2019199486A1|2018-04-10|2019-10-17|Exxonmobil Chemical Patents Inc.|Thermoplastic vulcanizale compositions|

---

EP3849791A1|2018-09-14|2021-07-21|ExxonMobil Chemical Patents Inc.|Thermoplastic vulcanizate compositions in polymeric inner / pressure sheaths of flexible pipes for oil & gas applications|

---

EP3850255A1|2018-09-14|2021-07-21|ExxonMobil Chemical Patents Inc.|Thermoplastic vulcanizate compositions their preparation and use in flexible tubular pipes|

---

EP3856836A1|2018-09-24|2021-08-04|ExxonMobil Chemical Patents Inc.|Thermoplastic blends and composites for flexible pipes|

---

CN113166499A|2018-09-24|2021-07-23|埃克森美孚化学专利公司|Crosslinked elastomer-polymer blends|

---

US20220017730A1|2018-11-16|2022-01-20|Exxonmobil Chemical Patents Inc.|Polyolefin Compositions Suitable for Films|

---

EP3941976A1|2019-03-21|2022-01-26|ExxonMobil Chemical Patents Inc.|Pipe including a thermoplastic vulcanizate composition|

---

CN113853403A|2019-06-13|2021-12-28|埃克森美孚化学专利公司|Automotive weatherseal formed from thermoplastic vulcanizate composition|

---

WO2020257630A1|2019-06-21|2020-12-24|Exxonmobil Chemical Patents Inc.|Thermoplastic vulcanizate compositions|

---

WO2021041051A1|2019-08-26|2021-03-04|Exxonmobil Chemical Patents Inc.|Thermoplastic vulcanizate compositions and thermoplastic olefinic compositions as insulating layers in non-flexible pipes|

---

WO2021040760A1|2019-08-28|2021-03-04|Exxonmobil Chemical Patents Inc.|Polyolefin compositions for films|

---

WO2021080803A1|2019-10-22|2021-04-29|Exxonmobil Chemical Patents Inc.|Impact copolymer compositions|

---

WO2021080813A1|2019-10-22|2021-04-29|Exxonmobil Chemical Patents Inc.|Thermoplastic vulcanizate compositions and processes for the production thereof|

---

WO2021167850A1|2020-02-17|2021-08-26|Exxonmobil Chemical Patents Inc.|Propylene-based polymer compositions having a high molecular weight tail|

---

WO2021188528A1|2020-03-18|2021-09-23|Exxonmobil Chemical Patents Inc.|Thermoplastic elastomer compositions their preparation and use in fiber-reinforced spoolable pipes|

---

WO2021188361A1|2020-03-20|2021-09-23|Exxonmobil Chemical Patents Inc.|Linear alpha-olefin copolymers and impact copolymers thereof|

---

WO2021202091A1|2020-03-30|2021-10-07|Exxonmobil Chemical Patents Inc.|Comb-block copolymers and methods thereof|

---

WO2021225813A1|2020-05-05|2021-11-11|Exxonmobil Chemical Patents Inc.|Pipe including a polymethylpentene thermoplastic polymer|

---

WO2021231362A1|2020-05-12|2021-11-18|Exxonmobil Chemical Patents Inc.|Thermoplastic elastomer compositions for use in pharmaceutical articles|

法律状态:
2020-04-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-02-09| B09A| Decision: intention to grant|

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2021-03-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/10/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261720617P| true| 2012-10-31|2012-10-31|

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US61/720,617|2012-10-31|

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EP13152302|2013-01-23|

---

EP13152302.9|2013-01-23|

---

PCT/US2013/063765|WO2014070386A1|2012-10-31|2013-10-08|Broad molecular weight distribution polypropylene resins|

---