Metallocenes and methods thereof

Abstract

The present disclosure provides a metallocene catalyst compound including at least one linking portion containing -Si-, a catalyst system including such a compound and their uses. The catalyst compound of the present disclosure can be a hafnium-containing compound having one or more silylneopentyl substituted and one or more cyclopentadiene ligands with at least one linking portion containing -Si. In another class of embodiments, the present disclosure relates to a polymerization method for producing a polyolefin polymer by a catalyst system, the catalyst system comprising one or more olefin polymerization catalysts, at least one activator and an optional carrier.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to USSN 62 / 882,091, filed August 2, 2019, which is incorporated herein by reference.

[0003] field

[0004] The present disclosure relates to metallocenes, catalyst systems comprising such compounds, and their uses. Moreover, the present disclosure relates to metallocenes comprising at least one linking moiety containing -Si-. The present disclosure further relates to polymer compositions produced by the methods described herein.

[0005] background

[0006] Olefin polymerization catalysts have great use in industry, and polyolefins are widely used commercially because of their strong physical properties. Therefore, there is an interest in finding new catalyst systems that increase the market value of catalysts and allow the production of polymers with improved properties. Polymer properties such as elasticity and processing properties are mainly controlled by the molecular weight, molecular weight distribution and comonomer content of the polymer.

[0007] Polyolefins such as polyethylene typically have comonomers (e.g., hexene) incorporated into the polyethylene backbone. These copolymers provide different physical properties than individual polyethylene and are typically produced in low pressure reactors using, for example, solution, slurry, or gas phase polymerization processes. Polymerization can be carried out in the presence of catalyst systems such as those using Ziegler-Natta catalysts, chromium-based catalysts, or metallocene catalysts.

[0008] There is a need for catalysts that have high productivity and are capable of producing customized polyolefin materials for various applications (e.g., having customized molecular weights (e.g., low Mw polymers for films, high Mw polymers for resins), customized comonomer content, and narrow polydispersity index). In particular, there is a need to develop new and improved catalyst systems for olefin polymerization to achieve polymer properties such as high melting points and high molecular weights.

[0009] References cited in the Information Disclosure Statement (37 CFR 1.97(h)): Miyake, S. et al. (1998) "Synthesis, Molecular Structure, and Racemate-Meso Intercoversion for rac-(Me2Si)2{η 5-C5H-3-(CHMe2)-5-Me}2MCI2(M+Ti and Zr),"Organometallics, v.17(25),pp.5528-5533; Licht,AI,et al.(2003)"CH-Aktivierungsreaktionen an substituierten Zirconocenkomplexen undderenVerwendung in der katalytischen Ethylenpolymerisation," J. of Organometallic Chem., v. 684, pp. 91-104; Siedle, AR, et al. (1995) "Stereochemical Nonrigidity in Metallocenium Ions," J. of Organometallic Chem., v. 497, pp. 119-125; US 2018 / 0334517; US 2018 / 0237554; US2018 / 0237558; US 2018 / 0237559; WO 2018 / 067259; KR2015 / 066484; US 2018 / 0265605; KR 2015058054.

[0010] Overview

[0011] The present disclosure relates to a catalyst compound represented by formula (I):

[0012]

[0013] in:

[0014] M is hafnium;

[0015] R 1 , R 2 , R 3 and R 4 Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon group, or R 16 -T 2 (R 17 )3, where R 16 is a C1-C4 hydrocarbon group, T 2 is a Group 13, 14, 15 or 16 element, and each R 17 are independently C1-C5 substituted or unsubstituted hydrocarbon groups;

[0016] R 5, R 6 , R 7 , R 8 and R 9 Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon, or –R 18 -T 3 (R 19 )3, where R 18 is a C1-C4 hydrocarbon group, T 3 is a Group 13, 14, 15 or 16 element, and each R 19 are independently C1-C5 substituted or unsubstituted hydrocarbon groups;

[0017] X 1 It is a monovalent anionic ligand;

[0018] R 10 and R 11 Each of which is independently hydrogen or C1-C 20 Hydrocarbyl, substituted hydrocarbyl, or R 10 and R 11 joined together to form substituted or unsubstituted, saturated or partially unsaturated, cyclic or polycyclic substituents;

[0019] R 12 and R 13 It is hydrogen;

[0020] n is 1, 2, 3, 4 or 5;

[0021] T 1 is a Group 13, 14 (excluding carbon), 15 or 16 element; and

[0022] R 14 and R 15 It's methyl.

[0023] In yet another embodiment, the present disclosure provides a catalyst system comprising an activator and the catalyst of the present disclosure.

[0024] In yet another embodiment, the present disclosure provides a catalyst system comprising an activator, a catalyst support, and the catalyst of the present disclosure.

[0025] In yet another embodiment, the present disclosure provides a polymerization process comprising contacting one or more olefin monomers with a catalyst system comprising an activator and the catalyst of the present disclosure.

[0026] In yet another embodiment, the present disclosure provides polyolefins formed by the catalyst systems and / or methods of the present disclosure.

[0027] BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 is a GPC-4D spectrum of a polyethylene copolymer formed by catalyst compound 1 in Example 1. FIG.

[0029] Figure 2 is a TREF diagram of the polyethylene copolymer formed by catalyst compound 1 in Example 1.

[0030] Detailed Description

[0031] The present disclosure provides catalyst compounds including at least one linking portion (e.g., -Si-linking portion) containing a Group 13, 14, 15, or 16 element, catalyst systems including such catalyst compounds, and their uses. In at least one embodiment, the present disclosure relates to metallocene compounds, metallocene-based catalyst systems, and their uses in polymerization processes for producing polyolefin polymers such as polyethylene polymers, polypropylene polymers, and copolymers. The catalyst compounds of the present disclosure can be hafnium-containing compounds having one or more cyclopentadiene ligands, wherein the cyclopentadiene ligands are substituted with one or more silyl neopentyl groups and connected to at least one Si-containing linking portion.

[0032] In another class of embodiments, the present disclosure is directed to a polymerization process for producing polyolefin polymers from a catalyst system comprising one or more olefin polymerization catalysts, at least one activator, and optionally a support.

[0033] For example, the present disclosure relates to a polymerization process for producing a polyethylene polymer, the process comprising reacting a catalyst system comprising one or more metallocene catalysts, at least one activator, and optionally at least one support with ethylene and one or more C3-C 10 The alpha-olefin comonomer is contacted under polymerization conditions.

[0034] The catalysts, catalyst systems and methods of the present disclosure can provide high Mw (e.g., 100,000 g / mol or greater), Mn values ​​of 100,000 g / mol or greater, narrow PDI (e.g., about 1.5 to about 3), high Mz values ​​(e.g., 500,000 g / mol or greater), MI values ​​of about 0.05 g / 10 min to about 2.5 g / 10 min, MIR values ​​of about 12 to 100, such as 12 to 50, g' values ​​of 0.97 or greater, visAlternatively, the catalysts, catalyst systems and methods of the present disclosure can provide low Mw (e.g., less than 100,000 g / mol), Mn values ​​less than 100,000 g / mol, narrow PDI (e.g., about 1.5 to about 3) and / or low Mz values ​​(e.g., less than 500,000 g / mol), MI values ​​of about 0.05 g / 10 min to about 2.5 g / 10 min, MIR values ​​of about 12 to 100, such as 12 to 50, g' values ​​of 0.97 or greater, vis The catalysts, catalyst systems and methods of the present disclosure are capable of providing polymers having a comonomer content of about 0.05 wt % to about 18 wt %.

[0035] For purposes of this disclosure, the numbering scheme for the Periodic Table Groups is used as in Chemical and Engineering News, Vol. 63, No. 5, p. 27 (1985). Thus, a "Group 4 metal" is an element from Group 4 of the Periodic Table, such as Hf, Ti, or Zr.

[0036] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tert-butyl, Cp is cyclopentadiene, Cp* is pentamethylcyclopentadienyl, PDI is polydispersity index, MAO is methylaluminoxane, SMAO is supported methylaluminoxane, NMR is nuclear magnetic resonance, THF is tetrahydrofuran, RPM is revolutions per minute, MI is melt index, MIR is melt index ratio, BOCD is broad normal composition distribution, MWD is molecular weight distribution, and HMW is high molecular weight.

[0037] This specification describes hafnium-containing metal complexes. The term complex is used to describe molecules in which ancillary ligands are coordinated to a central transition metal atom. The ligand is bulky and stably bonded to the transition metal to maintain its influence during the use of the catalyst, such as polymerization. The ligand can be coordinated to the transition metal by covalent bonds and / or electron-donating coordination or intermediate bonds. Transition metal complexes are usually activated using an activator to perform their polymerization or oligomerization functions, and without being bound by theory, it is believed that the activator produces a cation due to the removal of anionic groups (often referred to as leaving groups) from the transition metal.

[0038] As used herein, "olefin polymerization catalyst" refers to any catalyst, such as an organometallic complex or compound capable of coordination polyaddition, in which successive monomers are added to the monomer chain at the metal organic active center.

[0039] The terms "substituent," "radical," "group," and "moiety" are used interchangeably.

[0040] "Catalyst productivity" is a measure of how many grams of polymer (P) are produced over a period of T hours using a polymerization catalyst comprising Wg catalyst (cat), and can be expressed by the following formula: P / (T x W), with units of gPgcat-1hr-1. "Conversion" is the amount of monomer converted to polymer product, reported in mole %, and calculated based on the polymer yield and the amount of monomer charged to the reactor.

[0041] "BOCD" refers to a broad normal composition distribution in which the comonomers of the copolymer are primarily bound to high molecular weight chains or materials of the polyolefin polymer or composition. The distribution of short chain branches can be measured, for example, using temperature rising elution fractionation (TREF) in conjunction with a light scattering (LS) detector for determining the weight average molecular weight of molecules eluted from a TREF column at a given temperature. The combination of TREF and LS (TREF-LS) produces information about the width of the composition distribution and whether the comonomer content increases, decreases, or is uniform in polymer chains of different molecular weights. BOCD is described, for example, in U.S. Patent No. 8,378,043, Column 3, Line 34 to Column 4, Line 19 and U.S. Patent No. 8,476,392, Line 43 to Column 16, Line 54.

[0042] "Olefins" (or "alkenes") are linear, branched or cyclic compounds of carbon and hydrogen having at least one double bond. For purposes of this specification and the appended claims, when a polymer or copolymer is referred to as containing olefins, the olefins present in such polymer or copolymer are the polymerized form of the olefins. For example, when a copolymer is said to have an "ethylene" content of 35 wt%-55 wt%, it is understood that the mer units in the copolymer are derived from ethylene in the polymerization reaction and the derived units are present in an amount of 35 wt%-55 wt%, based on the weight of the copolymer. "Polymers" have two or more mer units that are the same or different. "Homopolymers" are polymers having the same mer units. "Copolymers" are polymers having two or more mer units that are different from each other. "Terpolymers" are polymers having three mer units that are different from each other. "Different" is used to refer to mer units and means that the mer units differ from each other by at least one atom or isomer. Therefore, as used herein, the definition of copolymers includes terpolymers. An "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 50 mol% of propylene-derived units, etc. An "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 50 mol% of propylene-derived units, etc.

[0043] The term "α-olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure ((R"R"')-C=CH2, wherein R" and R"' can independently be hydrogen or any hydrocarbon group; for example, R" is hydrogen and R"' is an alkyl group). "Linear α-olefin" is an α-olefin as defined in this paragraph, wherein R" is hydrogen and R"' is hydrogen or a straight chain alkyl group.

[0044] For purposes of this disclosure, ethylene shall be considered an alpha-olefin.

[0045] Unless otherwise indicated, the term “C n ” refers to one or more hydrocarbons having n carbon atoms per molecule, where n is a positive integer. The term “hydrocarbon” refers to a class of compounds containing hydrogen bonded to carbon, and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different values ​​of n. Similarly, “C m -C y "A group or compound is a group or compound that includes a total of m to y carbon atoms. Thus, C1-C50 Alkyl refers to an alkyl group comprising a total of about 1 to about 50 carbon atoms.

[0046] Unless otherwise indicated, (e.g., in the definition of "substituted hydrocarbyl," "substituted aryl," etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group (e.g., a hydrocarbyl, a heteroatom or a heteroatom-containing group such as a halogen (e.g., Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2)q-SiR*3, wherein q is 1 to 10 and each R* is independently a hydrocarbyl or a halocarbon group, and two or more R* may be linked together to form a substituted or unsubstituted, fully saturated, partially unsaturated or aromatic cyclic or polycyclic structure), or wherein at least one heteroatom has been inserted into the hydrocarbyl ring.

[0047] The term "substituted hydrocarbyl" refers to a hydrocarbyl group wherein at least one hydrogen atom of the hydrocarbyl group has been replaced by at least one heteroatom (e.g., a halogen such as Br, Cl, F, or I) or a heteroatom-containing group (e.g., a functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2)q-SiR*3, wherein q is 1-10 and each R* is independently a hydrocarbyl or a halocarbon group, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbyl ring. The term "hydrocarbyl-substituted phenyl" refers to a phenyl group wherein 1, 2, 3, 4, or 5 hydrogen groups have been replaced by a hydrocarbyl or substituted hydrocarbyl group. For example, a "hydrocarbyl-substituted phenyl" group may be represented by the formula:

[0048]

[0049] Where R a , R b , R c , R d and R e Each of which can be independently selected from hydrogen, C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, heteroatom or heteroatom-containing group (provided that R a , R b , R c , R d and Re At least one of them is not H), or R a , R b , R c , R d , and R e Two or more of these can be linked together to form C4-C 62 Cyclic or polycyclic hydrocarbon ring structures, or combinations thereof.

[0050] The term "substituted aromatic group" refers to an aromatic group in which one or more hydrogen groups are replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0051] The term "substituted phenyl" refers to a phenyl group in which one or more hydrogen groups are replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0052] The term "substituted naphthyl" refers to a naphthyl group in which one or more hydrogen groups are replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0053] The term "substituted benzyl" refers to a benzyl group in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom or a heteroatom-containing group. For example, the substituted benzyl group is represented by the following formula:

[0054]

[0055] Where R a’ , R b’ , R c’ , R d’ , R e’ and Z are each independently selected from hydrogen, C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon group, heteroatom or heteroatom-containing group (provided that R a’ , R b’ , R c’ , R d’ , R e’ and Z is not H), or R a’ , R b’ , R c’ , R d’ , R e’ and Z are linked together to form C4-C 62 Cyclic or polycyclic ring structures, or combinations thereof.

[0056] The terms "alkoxy" and "alkoxide" refer to an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group attached to an oxygen atom, and may include groups in which the alkyl / aryl group is C1-C10 The alkyl group may be a straight chain, a branched chain or a cyclic group. The alkyl group may be a saturated or an unsaturated group. Examples of suitable alkoxy groups may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy.

[0057] The term "alkenyl" refers to a straight, branched or cyclic hydrocarbon group having one or more double bonds. These alkenyls may be optionally substituted. Examples of suitable alkenyls may include vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, including their substituted analogs.

[0058] The terms "alkyl group" and "alkyl" are used interchangeably throughout this disclosure. For purposes of this disclosure, "alkyl" is defined as a C1-C 100 Alkyl, which may be linear, branched or cyclic. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, including substituted analogs thereof. A substituted alkyl group is a group in which at least one hydrogen atom of the alkyl group has been replaced by at least one non-hydrogen group such as a hydrocarbon group, a heteroatom or a heteroatom-containing group such as a halogen (e.g., Br, Cl, F or I) or at least one functional group (e.g., -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3 or -(CH2)-SiR*3, each R* independently being a hydrocarbon group or a halogenated carbon group, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0059] The term "aryl" or "aryl group" refers to aromatic rings and substituted variants thereof, for example phenyl, 2-methylphenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O or S. The term "aromatic" as used herein also refers to pseudoaromatic heterocycles, which are heterocyclic substituents having properties and structures similar to aromatic heterocyclic ligands (almost planar), but are not aromatic by definition; likewise, the term aromatic also refers to substituted aromatics.

[0060] If there are isomers of a named alkyl, alkenyl, alkoxide, or aryl group (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), reference to one member of the group (e.g., n-butyl) will explicitly disclose the remaining isomers in the family (e.g., isobutyl, sec-butyl, and tert-butyl). Likewise, reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0061] The term "ring atoms" refers to atoms that are part of a cyclic structure. According to this definition, benzyl has six ring atoms and tetrahydrofuran has five ring atoms.

[0062] A heterocycle is a ring having heteroatoms in the ring structure, as opposed to a heteroatom-substituted ring in which hydrogens on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle, while 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole.

[0063] The term "hydrocarbyl group" or "hydrocarbyl" may be used interchangeably and is defined to mean a group that includes only hydrogen and carbon atoms. For example, a hydrocarbyl group may be C1-C 100 The term "alkyl" refers to an alkyl radical, which may be linear, branched or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals may include, but are not limited to, alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl radicals such as phenyl, benzyl, naphthyl.

[0064] A "metallocene" catalyst compound is a transition metal catalyst compound having one, two, or three (e.g., one or two) substituted or unsubstituted cyclopentadienyl ligands bound to a transition metal, e.g., a metallocene catalyst is an organometallic compound containing at least one π-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety).

[0065] The term "cyclopentadienyl", also known as "Cp", refers to a class of coordination complexes that are monovalent anions derived from the hydride of cyclopentadiene and are capable of forming metallocene compounds with transition metals. Cp has 5 π electrons in 5 out-of-plane p orbitals on the C atom.

[0066] The term "pentamethylcyclopentadienyl", also known as Cp*, refers to a class of coordination complexes derived from cyclopentadiene. Cp* ligands are bulkier and more basic than unsubstituted Cp ligands, and thus have unique properties. Without being bound by theory, it is believed that Cp* is more electron-rich than unsubstituted Cp, Cp* is a stronger donor and is less easily removed from the metal. Therefore, its complexes may exhibit increased thermal stability. Its steric bulk may allow its separation from complexes with other fragile ligands. Its complexes also tend to be highly soluble in non-polar solvents.

[0067] Melt index (MI), for example, indicates the molecular weight of a polymer, while melt index ratio (MIR) indicates the molecular weight distribution. Polymers showing a higher MI have shorter polymer chain lengths. As MIR increases, the molecular weight distribution (MWD) of a polymer broadens. Polymers showing a narrower molecular weight distribution have a lower MIR.

[0068] By "linear polymer" is meant a polymer having few, if any, long chain branches and having a branching index (g') of about 0.967 or higher, such as about 0.979 or higher, such as about 0.98 or higher. vis The branching index is determined by using a high temperature gel permeation chromatography (GPC-4D) equipped with three online detectors, namely a differential refractive index detector (DRI), a light scattering (LS) detector and a viscometer.

[0069] Unless otherwise specified, "low comonomer content" as used herein is defined as a polyolefin having less than 8 wt% comonomer based on the total weight of the polyolefin. "High comonomer content" as used herein is defined as a polyolefin having greater than or equal to 8 wt% comonomer based on the total weight of the polyolefin.

[0070] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, wt% is the weight percent, and mol% is the mole percent. Molecular weight distribution (MWD), also known as polydispersity (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are g / mol.

[0071] As used herein, unless otherwise indicated, "high molecular weight" is defined as a number average molecular weight (Mn) value of 100,000 g / mol or greater. "Low molecular weight" is defined as a Mn value of less than 100,000 g / mol.

[0072] All melting points (Tm) are differential scanning calorimetry (DSC) first heat unless otherwise indicated.

[0073] "Catalyst system" is a combination of at least one catalyst compound, at least one activator, an optional co-activator and an optional support material. The terms "catalyst compound", "catalyst complex", "transition metal complex", "transition metal compound", "procatalyst compound" and "procatalyst complex" are used interchangeably. When "catalyst system" is used to describe such a pair before activation, it refers to the unactivated catalyst complex (procatalyst) together with the activator and the optional co-activator. When it is used to describe such a pair after activation, it refers to the activated complex and the activator or other charge balancing structural part. The transition metal compound can be neutral, as in the procatalyst, or a charged substance with a counter ion, as in an activated catalyst system. For the purposes of the present disclosure and the claims thereof, when the catalyst system is described as comprising a neutral stable form of a component, it is fully understood by those of ordinary skill in the art that the ionic form of the component is a form that reacts with a monomer to generate a polymer. A polymerization catalyst system is a catalyst system that enables monomers to be polymerized into a polymer. In addition, the catalyst compounds and activators represented by the formulas herein are intended to include neutral and ionic forms of the catalyst compounds and activators.

[0074] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a procatalyst compound, a catalyst compound, or a transition metal compound, and these terms may be used interchangeably.

[0075] An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "Lewis base" is a neutrally charged ligand that donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include diethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethyl sulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also a heterocyclic ring. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan.

[0076] Scavengers are compounds that can be added to promote polymerization by scavenging impurities. Some scavengers can also act as activators and can be referred to as co-activators. Co-activators that are not scavengers can also be used in combination with activators to form active catalysts. In at least one embodiment, the co-activator can be premixed with the transition metal compound to form an alkylated transition metal compound.

[0077] Non-coordinating anion (NCA) is defined as referring to such anion, which is not coordinated with the catalyst metal cation, or it is only weakly coordinated to the metal cation. The term NCA is also defined as including activators containing multi-component NCA, such as N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate containing acidic cationic groups and non-coordinating anions. The term NCA is also defined as including neutral Lewis acids that can react with catalysts to form activated substances by capturing anionic groups, such as tris (pentafluorophenyl) boron. Lewis acid is defined as a compound or element that can react with an electron donor to form a bond. NCA is weakly coordinated enough that Lewis bases such as olefin monomers can displace it from the catalyst center. Any metal or metalloid that can form a compatible weakly coordinated complex can be used or included in the non-coordinating anion. Suitable metals include but are not limited to aluminum, gold and platinum. Suitable metalloids include but are not limited to boron, aluminum, phosphorus and silicon.

[0078] The term "continuous" refers to a system that operates without interruption or stopping. For example, a continuous process for producing a polymer is one in which the reactants are continuously introduced into one or more reactors and the polymer product is continuously withdrawn.

[0079] Solution polymerization refers to a polymerization process in which the polymer is dissolved in a liquid polymerization medium such as an inert solvent or monomer or a blend thereof. Solution polymerization may be homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Suitable systems may not be turbid as described in Oliveira, JV (2000) "High-Pressure Phase Equilibria for Polypropylene- Hydrocarbon Systems," Ind. Eng. Chem. Res., v. 39 (12), pp. 4627-4633.

[0080] Bulk polymerization refers to a polymerization process in which the monomers and / or comonomers being polymerized are used as solvents or diluents, and little or no inert solvents are used as solvents or diluents. A small amount of inert solvents may be used as carriers for catalysts and scavengers. Bulk polymerization systems contain less than 25% by weight of inert solvents or diluents, such as less than 10% by weight, such as less than 1% by weight, such as 0% by weight.

[0081] The BOCD index can be defined as described in U.S. Pat. No. 9,290,593 (the '593 patent, which is incorporated herein by reference in its entirety) by the following equation:

[0082] BOCD index = (SCB content on the high molecular weight side - SCB content on the low molecular weight side) / (SCB content on the low molecular weight side),

[0083] wherein the "SCB content on the high molecular weight side" refers to the content of SCB (the number of branches / 1,000 carbon atoms) contained in a polymer chain having a molecular weight equal to or greater than Mw of the polyolefin and equal to or less than 1.3×Mw, and the "SCB content on the low molecular weight side" refers to the content of SCB (the number of branches / 1,000 carbon atoms) contained in a polymer chain having a molecular weight equal to or greater than 0.7×Mw of the polyolefin and less than Mw. The BOCD index defined by the above equation may be in the range of 1 to 5, such as in the range of 2 to 4, such as in the range of 2 to 3.5. See also FIG. 1 and FIG. 2 of the '593 patent. Figure 2 (Characterization of BOCD polymer structure using GPC-FTIR data).

[0084] The width of the composition distribution can be measured by T 75 -T 25 The value is used to characterize, where T 25 is the temperature at which 25% of the eluted polymer is obtained in the TREF experiment described in this article, T 75 is the temperature at which 75% of the eluted polymer is obtained. The composition distribution is also determined by F 80 The F value is characterized by the fraction of polymer that elutes below 80°C in the TREF-LS experiments described in this article. 80 The value indicates that the proportion of comonomer in the polymer molecule is high. The normal composition distribution consists of M greater than 1 60 / M 90 Value definition, where M 60 is the molecular weight of the polymer fraction eluted at 60 °C in the TREF-LS experiment described herein, and M 90 is the molecular weight of the polymer fraction eluting at 90°C in the TREF-LS experiment.

[0085] Transition Metal Complexes

[0086] In at least one embodiment, the present disclosure relates to novel metallocene transition metal complexes wherein the complexes include at least one cyclopentadienyl ligand having a suitable combination of substituents and attached to, for example, at least one Group 13, 14 (excluding carbon), 15, or 16 element.

[0087] In at least one embodiment, the present disclosure is directed to novel bridged metallocene transition metal complexes wherein the complexes include at least one cyclopentadienyl ligand having a suitable combination of substituents and attached to, for example, at least one -Si- group.

[0088] The linking moiety may be characterized in that it has a -Si-Y- or -Ge-Y- structure, wherein Y is an unsubstituted hydrocarbon group or a substituted hydrocarbon group, for example, Y is a C1-C 10 Hydrocarbon.

[0089] In at least one embodiment, the catalyst compound is represented by formula (I):

[0090]

[0091] in:

[0092] M is hafnium;

[0093] R 1 , R 2 , R 3 and R 4 Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon group, or R 16 -T 2 (R 17 )3, where R 16 is a C1-C4 hydrocarbon group, T 2 is a Group 13, 14, 15 or 16 element, and each R 17 are independently C1-C5 substituted or unsubstituted hydrocarbon groups (e.g. -R 16 -Si(R 17 )3, where R 16 is a C1-C4 hydrocarbon group, and each R 17 Independently C1-C 20 substituted or unsubstituted hydrocarbon groups);

[0094] R 5 , R 6 , R 7 , R 8 and R 9 Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon, or –R 18 -T 3 (R 19 )3, where R 18 is a C1-C4 hydrocarbon group, T 3 is a Group 13, 14, 15 or 16 element, and each R 19 are independently C1-C5 substituted or unsubstituted hydrocarbon groups (e.g. -R 18 -Si(R 19 )3, where R 18 is a C1-C4 hydrocarbon group, and each R 19 Independently C1-C20 substituted or unsubstituted hydrocarbon groups);

[0095] X 1 It is a monovalent anionic ligand;

[0096] R 10 and R 11 Each of which is independently hydrogen or C1-C 20 Hydrocarbyl, substituted hydrocarbyl, or R 10 and R 11 joined together to form substituted or unsubstituted, saturated or partially unsaturated, cyclic or polycyclic substituents;

[0097] R 12 and R 13 It is hydrogen;

[0098] n is 1, 2, 3, 4 or 5;

[0099] T 1 is a Group 13, 14 (excluding carbon), 15 or 16 element; and

[0100] R 14 and R 15 Independently C1-C 40 Substituted or unsubstituted hydrocarbon groups (e.g., independently C 1 -C 10 Substituted or unsubstituted hydrocarbon groups, such as R 14 and / or R 15 is methyl).

[0101] T 1 , T 2 and T 3 may independently be an element of Group 13, 14 (excluding carbon), 15 or 16, such as T 1 , T 2 and T 3 can be independently Si or Ge. In at least one embodiment, T 1 is Si. In at least one embodiment, T 1 , T 2 and T 3 It's Si.

[0102] Moreover, -((R 14 )(R 15 )T 1 )-, where T 1 Can be Si, and R 14 and R 15 It can be methyl. For example, -((R 14 )(R 15 )T1 )- can be a linking group -(Me)2Si-.

[0103] R 1 , R 2 , R 3 and R 4 Each of which can independently be hydrogen, alcohol radical, C1-C 40 Substituted or unsubstituted hydrocarbon group, or -R 16 -Si(R 17 )3, where R 16 It can be a C1-C4 hydrocarbon group, and each R 17 Can be C1-C independently 20 Substituted or unsubstituted hydrocarbon groups.

[0104] R 5 , R 6 , R 7 , R 8 and R 9 Each of which can independently be hydrogen, alcohol radical, C1-C 40 Substituted or unsubstituted hydrocarbon group, or -R 18 -Si(R 19 )3, where R 18 It can be a C1-C4 hydrocarbon group and each R 19 Can be C1-C independently 20 Substituted or unsubstituted hydrocarbon group. At least one R 19 Can be C1-C 20 Substituted or unsubstituted hydrocarbon group. 5 , R 6 , R 7 , R 8 and R 9 At least one of them can be -R 18 -Si(R 19 )3 or -R 18 -C(R 19 )3, where R 18 It can be a C1-C4 hydrocarbon group, and each R 19 Can be C1-C independently 20 Substituted or unsubstituted hydrocarbon groups.

[0105] R 10 and R 11 Each of which can independently be hydrogen or C1-C 20 Hydrocarbyl, substituted hydrocarbyl, or R 10 and R 11 The substituents may be linked together to form a substituted or unsubstituted, saturated or partially unsaturated cyclic or polycyclic substituent.

[0106] In at least one embodiment, R 1 , R 2 , R 3 and R 4 At least one of them is independently C1-C 40 Substituted or unsubstituted hydrocarbon or -R 16 -Si(R 17 )3, where R 16 is a C1-C4 hydrocarbon group, and each R 17 Independently C1-C 20 a substituted or unsubstituted hydrocarbon group, and R 1 , R 2 , R 3 and R 4 At least one of them is hydrogen.

[0107] In at least one embodiment, R 1 and R 2 Together do not form a ring and / or R 2 and R 3 Together they do not form a ring, or R 3 and R 4 Together they do not form a ring, or R 4 and R 5 In another embodiment, R 5 and R 6 Together do not form a ring and / or R 6 and R 7 Together they do not form a ring, or R 7 and R 8 Together they do not form a ring, or R 8 and R 9 Together they do not form a ring, or R 9 and R 5 Together they do not form a ring.

[0108] In at least one embodiment, R 1 , R 2 , R 3 and R 4 It's hydrogen.

[0109] Moreover, R 5 , R 6 , R 7 , R 8 and R 9 At least one of them can be independently C1-C 40 Substituted or unsubstituted hydrocarbon or -R 18 -Si(R 19 )3, where R 18It can be a C1-C4 hydrocarbon group, and each R 19 Can be C1-C independently 20 a substituted or unsubstituted hydrocarbon group, and each R 5 , R 6 , R 7 , R 8 , and R 9 Can be hydrogen. In at least one embodiment, R 5 , R 6 , R 7 , R 8 and R 9 One of them is -R 18 -Si(R 19 )3, where R 18 is a C1-C4 hydrocarbon group, each R 19 Independently C1-C 20 substituted or unsubstituted hydrocarbon group, and R 5 , R 6 , R 7 , R 8 and R 9 In another embodiment, R 5 Yes-R 18 -Si(R 19 )3, where R 18 is a C1 hydrocarbon group, and each R 19 Independently C1-C 20 In yet another embodiment, each R 19 It's methyl.

[0110] In at least one embodiment, R 5 , R 6 , R 7 , R 8 and R 9 is a methyl group, such that the Cp ligand is a Cp* ligand.

[0111] Furthermore, n may be 1-5, for example n may be 1-3, for example n may be 1, 2 or 3. Furthermore, q may be 1-5, for example q may be 1, 2, 3, 4 or 5. In at least one embodiment, n is 1 and q is 1.

[0112] R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R11 , R 12 and R 13 It can be hydrogen and R 5 Can be -R 18 -Si(R 19 )3, where R 18 may be a C1 hydrocarbon group, and each R 19 Can be C1-C independently 20 Unsubstituted hydrocarbon groups, such as R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 It can be hydrogen and R 5 Can be -R 18 -Si(R 19 )3, where R 18 can be -CH2-, and each R 19 It may be methyl.

[0113] X 1 It may be a monovalent anionic ligand.

[0114] Suitable for X 1 Exemplary groups of X may include 1,4-biphenyl, or 2,4-hexadiene, phenyl, or 1,4-bibenzyl. 1 It can be C1-C3 alkyl or alkoxy, C6-C 10 Aryl or aryloxy, C2-C4 alkenyl, C7-C 10 Arylalkyl, C7-C 12 an alkaryl group, or a halogen atom such as chlorine.

[0115] In at least one embodiment, X 1 Selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.

[0116] In at least one embodiment, the catalyst compound is one or more of the following:

[0117]

[0118]

[0119] In at least one embodiment, the catalyst compound represented by formula (I) is:

[0120]

[0121] In at least one embodiment, a catalyst compound is used, for example, the catalyst compound is not different. For the purposes of this disclosure, a metallocene catalyst compound is considered to be different from another metallocene catalyst compound if they differ by at least one atom. For example, "biscyclopentadienyl hafnium dichloride" is different from "(cyclopentadienyl) (2-methylcyclopentadienyl) hafnium dichloride", which is different from "(cyclopentadienyl) (2-methylcyclopentadienyl) zirconium dichloride". For the purposes of this disclosure, catalyst compounds that are only isomerically different are considered to be the same, unless otherwise specified. For example, racemic-tetramethyldisilyl-bis (trimethylsilylmethylcyclopentadienyl) hafnium dimethyl is considered to be the same as meso-tetramethyldisilyl-bis (trimethylsilylmethylcyclopentadienyl) hafnium dimethyl.

[0122] Method for preparing the catalyst compound

[0123] In at least one embodiment, the catalyst compound represented by formula (I) is prepared from an intermediate compound represented by formula (II) via -(C(R 10’ )(R 11’ ) n -T 1 '((R 14’ )(R 15’ )(R 20’ ))-structure part and M (such as Hf) are formed by intramolecular cyclometallation. The intermediate compound is represented by formula (II):

[0124]

[0125] in:

[0126] M' is hafnium;

[0127] R 1’ , R 2’ , R 3’ and R 4’ Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon group, or R 16’ -T 2’ (R 17’ )3, where R 16’ is a C1-C4 hydrocarbon group, T 2’is a Group 13, 14, 15 or 16 element, and each R 17’ are independently C1-C5 substituted or unsubstituted hydrocarbon groups (e.g. -R 16’ -Si(R 17’ )3, where R 16’ is a C1-C4 hydrocarbon group, and each R 17’ Independently C1-C 20 substituted or unsubstituted hydrocarbon groups);

[0128] R 5’ , R 6’ , R 7’ , R 8’ and R 9’ Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon, or –R 18’ -T 3’ (R 19’ )3, where R 18’ is a C1-C4 hydrocarbon group, T 3’ is a Group 13, 14, 15 or 16 element, and each R 19’ are independently C1-C5 substituted or unsubstituted hydrocarbon groups (e.g. -R 18’ -Si(R 19’ )3, where R 18’ is a C1-C4 hydrocarbon group, and each R 19’ Independently C1-C 20 substituted or unsubstituted hydrocarbon groups);

[0129] X 1’ and X 2’ Each of which is independently a monovalent anionic ligand;

[0130] R 10’ and R 11’ Each of which is independently hydrogen or C1-C 20 Hydrocarbyl, substituted hydrocarbyl, or R 10’ and R 11’ joined together to form substituted or unsubstituted, saturated or partially unsaturated or aromatic, cyclic or polycyclic substituents;

[0131] n' is 1, 2, 3, 4 or 5;

[0132] T 1’ is an element of Group 13, 14 (excluding carbon), 15 or 16;

[0133] R 14’ and R 15’ Each of which is independently C1-C40 Substituted or unsubstituted hydrocarbon groups (e.g. C1-C 20 or C1-C 10 ) substituted or unsubstituted hydrocarbon groups, such as R 14’ and / or R 15’ is methyl);

[0134] R 20’ is one or more carbon, substituted or unsubstituted hydrocarbon groups (e.g. C1-C 40 or C1-C 10 ) substituted or unsubstituted hydrocarbon groups, such as R 20’ is methyl, or R 14’ , R 15’ and / or R 20’ is methyl). In some embodiments, when the polymer is 20' When growing, R 20' Can be C 40 or more carbons, or C 100 or more carbons, or C 1000 or more carbons, or C 10,000 or more carbons, or C 20,000 Or more carbon.

[0135] In at least one embodiment, M' of the intermediate compound represented by formula (II) is Hf.

[0136] The intermediate compound represented by formula (II) has a T 1’ , T 2’ and T 3’ may independently be an element of Group 13, 14 (excluding carbon), 15 or 16, such as T 1’ , T 2’ and T 3’ is independently Si or Ge. In at least one embodiment, T 1’ , T 2’ and T 3’ is Si. In at least one embodiment, T 1’ It's Si.

[0137] In other embodiments, the intermediate compound represented by formula (II) has R 1’ , R 2’ , R 3’ and R 4’ At least one of them is independently C1-C 40 Substituted or unsubstituted hydrocarbon or -R 16’ -Si(R 17’ )3, where R 16’is a C1-C4 hydrocarbon group, and each R 17’ Independently C1-C 20 substituted or unsubstituted hydrocarbon group, and R 1’ , R 2’ , R 3’ and R 4’ At least one of them is hydrogen. For example, R 1’ , R 2’ , R 3’ and R 4’ It may be hydrogen.

[0138] In some other embodiments, the intermediate compound represented by formula (II) has R 5’ , R 6’ , R 7’ , R 8’ and R 9’ At least one of them is independently C1-C 40 Substituted or unsubstituted hydrocarbon or -R 18’ -Si(R 19’ )3, where R 18’ is a C1-C4 hydrocarbon group, and each R 19’ Independently C1-C 20 substituted or unsubstituted hydrocarbon group, and R 5’ , R 6’ , R 7’ , R 8’ and R 9’ In at least one embodiment, R of the intermediate compound represented by formula (II) is 5’ , R 6’ , R 7’ , R 8’ and R 9’ One of them is -R 18’ -Si(R 19’ )3, where R 18’ It can be a C1-C4 hydrocarbon group, and each R 19’ Can be C1-C independently 20 A substituted or unsubstituted hydrocarbon group, and R of the intermediate compound of formula (II) 5’ , R 6’ , R 7’ , R 8’ and R 9’ For example, R of the intermediate compound of formula (II) is 5’ Can be -R 18’ -Si(R 19’ )3, where R 18’ may be a C1 hydrocarbon group, and each R 19’Can be C1-C independently 20 In at least one embodiment, each R 19’ It's methyl.

[0139] Moreover, n' may be 1-5, for example, n' may be 1-3. In at least one embodiment, n' is 1. For example, n' of the intermediate compound represented by formula (II) may be 1, and R of the intermediate compound represented by formula (II) may be 1’ , R 2’ , R 3’ , R 4’ , R 6’ , R 7’ , R 8’ , R 9’ , R 10 and R 11’ It may be hydrogen.

[0140] X 1’ and X 2’ Each of X may independently be a monovalent anionic ligand. Alternatively, X 1’ and X 2’ They can also be linked together to form alkylene or conjugated C4-C 40 A diene ligand coordinated to M' in a metallocyclopentene manner.

[0141] Suitable for X 1’ and X 2’ Exemplary groups of may include 1,4-biphenyl or phenyl. 1’ and X 2’ can be the same and can be a C1-C3 alkyl or alkoxy group, a C6-C 10 Aryl or aryloxy group, C2-C4 alkenyl group, C7-C 10 Arylalkyl group, C7-C 12 an alkaryl group, or a halogen atom such as chlorine.

[0142] In at least one embodiment, X of the intermediate compound represented by formula (II) 1’ and X 2’ Each is independently selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.

[0143] In one aspect, the present disclosure provides the advantage that no separation of meso isomers from racemic isomers is performed after synthesis of the intermediate compounds disclosed herein. In certain aspects, the meso isomer is formed in a ratio of 99.9:0.1 or greater to the racemic isomer. The amount of racemic and meso isomers is determined by1 H NMR spectroscopy, and the atomic connections could be further established by single-crystal X-ray crystallography.

[0144] In at least one embodiment, an intermediate compound is used, for example, the intermediate compounds are not different. For the purposes of this disclosure, a metallocene intermediate compound is considered to be different from another metallocene intermediate compound if they differ by at least one atom. For example, "biscyclopentadienyl hafnium dichloride" is different from "(cyclopentadienyl)(2-methylcyclopentadienyl) hafnium dichloride". For the purposes of this disclosure, intermediate compounds that are only isomerically different are considered to be the same, unless otherwise specified. For example, racemic-tetramethyldisilyl-bis(trimethylsilylmethylcyclopentadienyl) hafnium dimethyl is considered to be the same as meso-tetramethyldisilyl-bis(trimethylsilylmethylcyclopentadienyl) hafnium dimethyl.

[0145] Synthesis of intermediate compounds and catalyst compounds

[0146] The following is a method for illustrating a method of preparing a catalyst compound represented by formula (I) as described herein and further illustrated in the examples. The metallocene of the present disclosure represented by formula (I) can be synthesized, wherein deprotonation can be performed by a metal salt of an alkyl anion (e.g., n-BuLi) to form a cyclopentadienide. Double deprotonation can be performed by an alkyl anion (e.g., n-BuLi) to form a dianion. The lithiation can be regioselective. The preparation of the catalyst compound of the present disclosure can include the reaction of a dianion with a metal halide (e.g., HfCl4). The alkylation reaction of a metal halide (e.g., HfCl4) can be performed with an alkyl anion (e.g., n-BuLi) or a Grignard reagent (e.g., BuMgBr) to form an intermediate compound (e.g., bis(n-BuLi)) represented by formula (II). 5 -trimethylsilylmethylcyclopentadienyl) hafnium dibutylate (Me3SiCH2Cp)2HfBu2). The pyrolysis reaction of the intermediate compound represented by formula (II) (e.g., (Me3SiCH2Cp)2HfBu2)) at a temperature of about 70°C to about 120°C (e.g., 90°C) can provide -C(R 10 ')(R 11 ')T 1’ ((R 14’ )(R 15’ )(R 20’))- (e.g., -CH2Si(CH3)3), which may be followed by chelation of the CH-activated moiety (e.g., -CH2Si(CH3)2-CH2-) between Hf and Cp. Without being bound by theory, the CH activation of the alkyl moiety (e.g., -CH3) may be accomplished by X 1’ or X 2’ At least one of the eliminations occurs. For example, X 1’ or X 2’ The elimination can be carried out by β-hydrogen elimination (for example, when X 1’ and X 2’ When it is butyl, X 1’ or X 2’ can be eliminated, for example, in the form of butenes), which can generate hydrogen.

[0147] Activator

[0148] The terms "co-catalyst" and "activator" are used interchangeably herein.

[0149] The catalyst system described herein may include the catalyst complex described above and an activator such as aluminoxane or a non-coordinating anion, and may be formed by combining the catalyst components described herein with an activator in any manner known in the literature, including combining them with a carrier such as silica. The catalyst system may also be added to a solution polymerization or bulk polymerization (in a monomer) or produced in a solution polymerization or bulk polymerization (in a monomer). The catalyst system of the present disclosure may have one or more activators and one, two or more catalyst components. An activator is defined as any compound capable of activating any of the above catalyst compounds by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators may include, for example, aluminoxanes, alkyl aluminums, ionizing activators (which may be neutral or ionic) and conventional types of cocatalysts. Suitable activators may include aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds, which capture a reactive, σ-bonded metal ligand, causing the metal compound to become a cation and provide a non-coordinating or weakly coordinating anion, such as a non-coordinating anion, that balances the charge.

[0150] In at least one embodiment, the catalyst system includes an activator and a catalyst compound of formula (I).

[0151] Aluminoxane Activator

[0152] Aluminoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes are generally a”’)-O-subunit oligomer, wherein R a”’ is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, for example when the extractable ligand is an alkyl, halogen, alkoxy or amino group. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. It may be appropriate to use visually transparent methylaluminoxane. Turbid or gelled aluminoxanes can be filtered to produce a transparent solution, or a transparent aluminoxane can be decanted from a turbid solution. A useful aluminoxane is a 3A-type modified methylaluminoxane (MMAO) cocatalyst (commercially available from Akzo Chemicals, Inc. under the trade name 3A-type modified methylaluminoxane, protected by patent number US 5,041,584, which is incorporated herein by reference). Another useful aluminoxane is the solid polymethylaluminoxane described in US Pat. Nos. 9,340,630, 8,404,880 and 8,975,209, which are incorporated herein by reference.

[0153] When the activator is an alumoxane (modified or unmodified), at least one embodiment selects a maximum activator amount of 5000 times Al / M in molar excess relative to the catalyst compound (based on metal catalytic sites). The minimum molar ratio of activator to catalyst compound can be 1:1. Alternative ranges can include 1:1-500:1, or 1:1-200:1, or 1:1-100:1, or 1:1-50:1. In an alternative embodiment, little or no alumoxane is used in the polymerization process described herein. For example, the alumoxane can be present in an amount of 0 mol%, or the alumoxane can be present in a molar ratio of aluminum to the catalyst compound transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0154] Ionizing / Non-coordinating Anion Activators

[0155] The term "non-coordinating anion" (NCA) refers to an anion that does not coordinate to a cation or only weakly coordinates to a cation so as to remain sufficiently unstable to be displaced by a Lewis base. "Compatible" non-coordinating anions are those anions that do not degrade to neutrality when the initially formed complex decomposes. In addition, the anion does not transfer anionic substituents or fragments to the cation so as to form a neutral transition metal compound and neutral by-products from the anion. Non-coordinating anions useful according to the present disclosure are those non-coordinating anions that are compatible, stabilize the transition metal cation in the sense of balancing its +1 ionic charge, and still remain sufficiently unstable to allow displacement to occur during polymerization. Suitable ionizing activators can include NCAs, such as compatible NCAs.

[0156] It is within the scope of the present disclosure to use neutral or ionic ionizing activators. It is also within the scope of the present disclosure to use neutral or ionic activators alone or in combination with aluminoxane or modified aluminoxane activators. For descriptions of suitable activators, see US8,658,556 and US6,211,105.

[0157] The catalyst system of the present disclosure may include at least one non-coordinating anion (NCA) activator. In at least one embodiment, a boron-containing NCA activator represented by the following formula may be used:

[0158] Z d + (A d- )

[0159] Where: Z is (LH) or a reducible Lewis acid; L is a Lewis base; H is hydrogen; (LH) is a Bronsted acid; A d- is a boron-containing non-coordinating anion having a charge d-; d is 1, 2 or 3.

[0160] The cationic component Z d + A Bronsted acid may be included, such as a proton or a protonated Lewis base or a reducible Lewis acid, which is capable of protonating the bulky ligand transition metal catalyst precursor or abstracting a moiety such as an alkyl or aryl group from the bulky ligand transition metal catalyst precursor to generate a cationic transition metal species.

[0161] The activated cation Z d + Moieties such as silver, cycloheptatrienyl cations, carbenium, ferrocene and mixtures such as mixtures of carbenium and ferrocene are also possible. d +The reducible Lewis acid may be a triarylcarbonium (wherein the aryl group may be substituted or unsubstituted, such as those represented by the following formula: (Ar3C + ), wherein Ar is an aromatic group or is substituted by a heteroatom, C1-C 40 Hydrocarbon or substituted C1-C 40 The reducible Lewis acid "Z" may include those represented by the formula: (Ph3C), wherein Ph is a substituted or unsubstituted phenyl group, such as a C1-C 40 Hydrocarbon or substituted C1-C 40 Hydrocarbon such as C1-C 20 Alkyl or aryl or substituted C1-C 20 Alkyl or aryl substituted phenyl, for example Z is triphenylcarbonium.

[0162] When Z d + Is the activating cation (LH) d + When the catalytic precursor is substituted with a phosphonium atom, it may be a Bronsted acid capable of donating a proton to a transition metal catalytic precursor to produce a transition metal cation, including ammonium, oxonium, phosphonium, silylium and mixtures thereof, such as ammonium of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, dioctadecylmethylamine, phosphonium derived from triethylphosphine, triphenylphosphine and diphenylphosphine, oxonium derived from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfonium derived from sulfides such as diethyl sulfide, tetrahydrothiophene, and mixtures thereof.

[0163] The anionic component A d- Including having the formula [M"k+Q n ] d- wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (e.g., 1, 2, 3 or 4); nk = d; M "is an element selected from Group 13 of the Periodic Table of Elements, such as boron or aluminum, and Q is independently a hydride, a bridged or unbridged dialkylamine, a halide, an alkoxide, an aryloxide, a hydrocarbon group, a substituted hydrocarbon group, a halogenated carbon group, a substituted halogenated carbon group, and a halogen-substituted hydrocarbon group, wherein Q has up to 20 carbon atoms, provided that Q is a halide ion no more than once. Each Q may be a fluorinated hydrocarbon group having 1 to 20 carbon atoms, for example, each Q is a fluorinated aryl group, and for example, each Q is a pentafluoroaryl group. Suitable A d-Examples also include diboron compounds, as disclosed in US Pat. No. 5,447,895, which is incorporated herein by reference in its entirety.

[0164] Illustrative, non-limiting examples of boron compounds that can be used as activating co-catalysts are those compounds described as activators in US Pat. No. 8,658,556, which is incorporated herein by reference.

[0165] The ionic stoichiometric activator Z d + (A d- ) can be one or more of the following: N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluorobiphenyl)borate, triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbonium tetrakis(perfluorophenyl)borate.

[0166] Bulk activators can also be used as NCAs herein. As used herein, "bulky activator" refers to an anionic activator represented by the formula:

[0167]

[0168] or

[0169]

[0170] in:

[0171] Each R A are independently halogen, such as fluorine;

[0172] Ar is a substituted or unsubstituted aryl group (eg, a substituted or unsubstituted phenyl group), for example, 40 Hydrocarbon such as C1-C 20 Alkyl or aryl substitution;

[0173] Each R B are independently halogen, C6-C 20 Substituted aromatic hydrocarbon groups or groups of the formula –O-Si-R D siloxy groups, where R D It is C1-C 20 A hydrocarbyl or hydrocarbylsilyl group (eg, R B is a fluorine or perfluorophenyl group);

[0174] Each R C It is halogen, C6-C 20 Substituted aromatic hydrocarbon groups or groups of the formula –O-Si-R D siloxy groups, where R D It is C1-C 20 A hydrocarbyl or hydrocarbylsilyl group (eg, R B is fluorine or C6 perfluoro aromatic hydrocarbon group); wherein R B and R C One or more saturated or unsaturated, substituted or unsubstituted rings (eg, R B and R C Forming a perfluorophenyl ring);

[0175] L is a Lewis base; (LH)+ is a Bronsted acid; d is 1, 2 or 3;

[0176] wherein the anion has a molecular weight greater than 1020 g / mol; and

[0177] wherein at least three of the substituents on the B atom each have a volume greater than 250 cubic Or more than 300 cubic meters Or more than 500 cubic meters The molecular volume of .

[0178] For example, (Ar3C) d + Can be (Ph3C) d + , wherein Ph is a substituted or unsubstituted phenyl group, for example, a C1-C 40 Hydrocarbon or substituted C1-C 40 Hydrocarbon groups such as C1-C 20 Alkyl or aryl or substituted C1-C 20 Alkyl or aryl substituted.

[0179] "Molecular volume" is used herein as an approximation of the sterically hindered volume of an activator molecule in solution. Comparing substituents having different molecular volumes allows a substituent having a smaller molecular volume to be considered "less bulky" than a substituent having a larger molecular volume. Conversely, a substituent having a larger molecular volume can be considered "more bulky" than a substituent having a smaller molecular volume.

[0180] Molecular volume can be calculated as reported in Girolami, GS (1994), "A Simple "Back of the Envelop" Method for Estimating the Densities and Molecular Volumes of Liquids and Solids", Journal of Chemical Education, Vol. 71, No. 11, pp. 962-964, which is incorporated herein by reference. The molecular volume (MV) in cubic angstroms is calculated using the following formula: MV = 8.3 V s , where V s is the scaled volume. s is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituent using the following relative volume table. For fused rings, each fused ring V s A decrease of 7.5%.

[0181]

[0182]

[0183] For a list of suitable bulky activators, see US Pat. No. 8,658,556, which is incorporated herein by reference.

[0184] In another embodiment, one or more of the NCA activators are selected from the activators described in US 6,211,105.

[0185] In at least one embodiment, the activator is selected from one or more of the following group: triarylcarbonium (e.g., triphenylcarbonium tetraphenylborate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluorobiphenyl)borate, triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

[0186] In another embodiment, the activator is selected from one or more of the following groups: trialkylammonium tetrakis (pentafluorophenyl) borate, N,N-dialkylanilinium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (perfluoronaphthyl) borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trialkylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis (2,3,4,6- trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di(isopropyl)ammoniumtetrakis(pentafluorophenyl)borate, (wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or tert-butyl).

[0187] Suitable activator to catalyst ratios, for example all NCA activator to catalyst ratios may be about 1:1 molar ratios. Alternative ranges include 0.1:1-100:1, or 0.5:1-200:1, or 1:1-500:1, or 1:1-1000:1. Suitable ranges may be 0.5:1-10:1, for example 1:1-5:1.

[0188] It is also within the scope of the present disclosure that the catalyst compounds may be combined with a combination of aluminoxane and NCA (see, for example, U.S. Patent Nos. 5,153,157 and 5,453,410, European Patent No. 0 573 120 Bl, and PCT Publication Nos. WO 1994 / 007928 and WO 1995 / 014044, all of which discuss the use of aluminoxanes in combination with ionizing activators).

[0189] Useful chain transfer agents can be hydrogen, alkylaluminoxane, compounds represented by the following formula: AlR3, ZnR2 (wherein each R is independently a C1-C8 aliphatic group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or their isomers) or combinations thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof.

[0190] Furthermore, the catalyst system of the present disclosure may include a metal alkenyl chain transfer agent represented by the formula:

[0191] Al(R') 3-v (R”)v

[0192] Where each R' can independently be C1-C 30 The hydrocarbon group, and / or each R" may independently be a C4-C 20 alkenyl; and v can be 0.1-3.

[0193] Optional scavenger or co-activator

[0194] In addition to these activator compounds, scavengers or co-activators may be used. Aluminum alkyl or aluminoxane compounds that may be used as scavengers or co-activators may include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), MMAO-3A, ​​and diethylzinc.

[0195] Optional carrier material

[0196] In some embodiments herein, the catalyst system may include an inert support material. The support material may be a porous support material, such as talc and inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support materials, or mixtures thereof.

[0197] The support material can be an inorganic oxide in finely divided form. Suitable inorganic oxide materials for use in the catalyst system herein can include metal oxides of Groups 2, 4, 13 and 14, such as silica, alumina and mixtures thereof. Other inorganic oxides that can be used alone or in combination with the silica or alumina can be magnesium oxide, titanium dioxide, zirconium oxide. However, other suitable support materials can be used, such as finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports can include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, phyllosilicates, zeolites, talc, clay. In addition, combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titania. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silica / clay, or mixtures thereof.

[0198] Support materials such as inorganic oxides may have a surface area of ​​about 10 m 2 / g-about 700m 2 / g surface area, about 0.1cm 3 / g-about 4.0cm 3 / g pore volume, and an average particle size of about 5 μm to about 500 μm. The surface area of ​​the support material can be about 50 m 2 / g-about 500m 2 / g, the pore volume can be about 0.5cm 3 / g-about 3.5cm 3 / g, and the average particle size can be from about 10 μm to about 200 μm. For example, the surface area of ​​the support material can be about 100 m 2 / g-about 400m 2 / g, the pore volume can be about 0.8cm 3 / g-about 3.0cm 3 / g, and the average particle size can be about 5 μm to about 100 μm. The average pore size of the support material useful in the present disclosure can be For example -about For example -about In at least one embodiment, the support material is high surface area amorphous silica (surface area = 300 m 2 / gm; pore volume = 1.65cm 3 For example, suitable silica can be obtained from Davison Chemical Division of WR Graceand Company under the trade name DAVISON TM 952 or DAVISON TM 955. In some other embodiments, DAVISON TM 948. Alternatively, the silica may be ES-70 TM Silica (PQ Corporation, Malvern, Pennsylvania), for example, which has been calcined (eg, at 875°C).

[0199] The support material should be dry, that is, free of absorbed water. Drying of the support material can be performed by heating or calcining at about 100°C to about 1000°C, such as at least about 600°C. When the support material is silica, it is heated to at least 200°C, such as about 200°C to about 850°C, such as about 600°C; and for a period of about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups for producing the supported catalyst system of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0200] The support material having reactive surface groups (e.g., hydroxyl groups) is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In at least one embodiment, the slurry of the support material is first contacted with the activator for a period of time ranging from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The solution of the catalyst compound is then contacted with a separated support / activator. In at least one embodiment, the supported catalyst system is generated in situ. In an alternative embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of time ranging from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The slurry of the supported catalyst compound is then contacted with an activator solution.

[0201] The mixture of the catalyst, activator and support is heated to about 0°C to about 70°C, such as to about 23°C to about 60°C, such as to room temperature. The contact time can be in the range of about 0.5 hours to about 24 hours, such as about 2 hours to about 16 hours or about 4 hours to about 8 hours.

[0202] Suitable non-polar solvents are materials in which all reactants used herein, such as activators and catalyst compounds, are at least partially soluble and are liquid at the reaction temperature. The non-polar solvent can be an alkane, such as isopentane, hexane, n-heptane, octane, nonane and decane, although various other materials can also be used, including cycloalkanes such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and ethylbenzene.

[0203] In at least one embodiment, the support material is supported methylaluminoxane, which is methylaluminoxane treated silica (see, for example, SMAO-ES70-875 described in the Experimental section below).

[0204] Aggregation methods

[0205] The present disclosure relates to a polymerization process in which monomers (e.g., ethylene, propylene) and optionally comonomers are contacted with a catalyst system described above comprising an activator and at least one catalyst compound. The catalyst compound and activator may be combined in any order. The catalyst compound and activator may be combined before contacting the monomers. Alternatively, the catalyst compound and activator may be introduced separately into a polymerization reactor where they are subsequently reacted to form an active catalyst.

[0206] The monomer may include substituted or unsubstituted C2-C 40 Alpha olefins, such as C2-C 20Alpha olefins, such as C2-C 12 α-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In at least one embodiment, the monomers include ethylene and optional comonomers, including one or more C3-C 40 Olefins, such as C4-C 20 Olefins, such as C6-C 12 Olefins. 40 The olefin monomers may be linear, branched or cyclic. 40 The cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups. In another embodiment, the monomers include propylene and optional comonomers including one or more ethylene or C4-C 40 Olefins, such as C4-C 20 Olefins, such as C6-C 12 Olefins. 40 The olefin monomers may be linear, branched or cyclic. 40 The cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups.

[0207] Exemplary C2-C 40 The olefin monomers and optional comonomers may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.

[0208] The polymerization process of the present disclosure can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry or gas phase polymerization process can be used. Such a method can be carried out in an intermittent, semi-intermittent or continuous manner. Homogeneous polymerization processes and slurry processes can be used. Bulk homogeneous processes can be used. Alternatively, no solvent or diluent is present or added to the reaction medium (except for a small amount of solvent or diluent used as a carrier for the catalyst system or other additives, or except for the amount of solvent or diluent commonly found in the monomer (e.g., propane in propylene)). In another embodiment, the method is a slurry process. The term "slurry polymerization process" used herein refers to a polymerization process in which a supported catalyst is used and the monomer is polymerized on the supported catalyst particles. At least 95wt% of the polymer product derived from the supported catalyst is in the form of particles, which are solid particles (not dissolved in the diluent).

[0209] Suitable diluents / solvents for polymerization may include non-coordinating inert liquids. Examples of diluents / solvents for polymerization may include: straight chain and branched hydrocarbons, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as those available on the market (Isopars TM ); fully halogenated hydrocarbons, such as fully fluorinated C 4-10 Alkanes; chlorobenzenes; and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, 1,3,5-trimethylbenzene, and xylene. Suitable solvents may also include liquid olefins that may be used as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In at least one embodiment, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, such as aromatic hydrocarbons present in the solvent in an amount of less than 1 wt %, such as less than 0.5 wt %, such as 0 wt %, based on the weight of the solvent.

[0210] In at least one embodiment, the feed concentration of monomers and comonomers used in the polymerization is 60 vol% solvent or less, such as 40 vol% or less, such as 20 vol% or less, based on the total volume of the feed stream. In at least one embodiment, the polymerization is carried out in a bulk process.

[0211] The polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polymer. Suitable temperatures and / or pressures include temperatures of about 0°C to about 300°C, such as about 20°C to about 200°C, such as about 35°C to about 160°C, such as about 80°C to about 160°C, such as about 90°C to about 140°C. The polymerization can be carried out at a pressure in the range of about 0.1 MPa to about 25 MPa, such as about 0.45 MPa to about 6 MPa, or about 0.5 MPa to about 4 MPa.

[0212] In suitable polymerizations, the run time of the reaction can be up to 300 minutes, such as in the range of about 5-250 minutes, such as in the range of about 10-120 minutes, such as in the range of about 20 minutes-90 minutes, such as in the range of about 30 minutes-60 minutes. In a continuous process, the run time can be the average residence time of the reactor. In at least one embodiment, the run time of the reaction is in the range of about 5 minutes to about 25 minutes.

[0213] In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa), such as 0.01 psig to 25 psig (0.07 kPa to 172 kPa), such as 0.1 psig to 10 psig (0.7 kPa to 70 kPa).

[0214] In at least one embodiment, little or no alumoxane is used in the process for producing the polymer. For example, alumoxane may be present at 0 mol%, or alumoxane may be present at a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0215] In at least one embodiment, the polymerization is: 1) carried out at a temperature of 0-300°C (e.g., 25°C-250°C, e.g., 80°C-160°C, e.g., 100°C-140°C); 2) carried out at a pressure of ambient pressure-10 MPa (e.g., 0.35 MPa-10 MPa, e.g., 0.45 MPa-6 MPa, e.g., 0.5 MPa-4 MPa); 3) carried out in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; e.g., wherein aromatic compounds are present in the solvent at a level of less than 1 wt%, e.g., less than 0.5 wt%, e.g., at 0 wt%, based on the weight of the solvent); 4) wherein the catalyst system used in the polymerization comprises less than 0.5 mol%, such as 0 mol%, of aluminoxane, or the aluminoxane is present in a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1; 5) the polymerization is carried out in one reaction zone; 6) optionally, a scavenger (e.g., a trialkylaluminum compound) is not present (e.g., present at a level of 0 mol%, or the scavenger is present in a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1); and 7) optionally, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig-50 psig (0.007 kPa-345 kPa) (e.g., 0.01 psig-25 psig (0.07 kPa-172 kPa), such as 0.1 psig-10 psig (0.7 kPa-70 kPa)). In at least one embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A "reaction zone" (also referred to as a "polymerization zone") is a vessel in which the polymerization occurs, such as a stirred tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered to be a separate polymerization zone. For multi-stage polymerization in a batch polymerization process, each polymerization stage is considered to be a separate polymerization zone. In at least one embodiment, the polymerization is carried out in one reaction zone. Room temperature is 23°C unless otherwise specified.

[0216] In at least one embodiment, the present disclosure provides a process for producing an ethylene-based polymer, comprising: polymerizing ethylene by contacting ethylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors connected in series or in parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form an ethylene-based polymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 5 psig to about 300 psig, such as about 10 psig to about 250 psig, such as about 30 psig to about 200 psig, such as about 20 psig to about 150 psig, such as about 50 psig to about 100 psig (e.g., 75 psig).

[0217] In another embodiment, the present disclosure provides a process for producing a propylene-based polymer, the process comprising: polymerizing propylene by contacting propylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors connected in series or in parallel at a reactor pressure of 0.5 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to form a propylene-based polymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 10 psig to about 300 psig, such as about 20 psig to about 250 psig, such as about 30 psig to about 200 psig, such as about 40 psig to about 150 psig, such as about 50 psig to about 100 psig (e.g., 75 psig).

[0218] In another embodiment, the present disclosure provides a method for producing an ethylene-α-olefin copolymer, the method comprising: reacting ethylene and at least one C3-C 20 The α-olefin (e.g., hexene) is contacted with the above catalyst system in one or more continuous stirred tank reactors or loop reactors connected in series or in parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to allow ethylene and the at least one C3-C 20 In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 10 psig to about 300 psig, such as about 20 psig to about 250 psig, such as about 30 psig to about 200 psig, such as about 40 psig to about 150 psig, such as about 50 psig to about 100 psig (e.g., 75 psig), or about 150 psig to about 300 psig (e.g., 200 psig).

[0219] In at least one embodiment, the process for producing an ethylene-α-olefin copolymer comprises: 20 The α-olefins are contacted with the above catalyst system in at least one gas phase reactor at a reactor pressure of 0.7 bar to 70 bar (e.g. 17 bar) and a reactor temperature of 20° C. to 150° C., e.g. 50° C. to 120° C., e.g. 70° C. to 110° C. (e.g. 85° C.) to allow ethylene and the at least one C3-C4 hydrocarbon to react with each other. 20 The α-olefin is polymerized to form an ethylene-α-olefin copolymer.

[0220] In another embodiment, the present disclosure provides a method for producing a propylene-α-olefin copolymer, the method comprising: reacting propylene and at least one ethylene and / or at least one C3-C 20 The α-olefins are contacted with the above catalyst system in one or more continuous stirred tank reactors or loop reactors connected in series or in parallel at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30° C. to 230° C. to allow the propylene and at least one ethylene and / or at least one C4-C 20 In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 10 psig to about 300 psig, such as about 20 psig to about 250 psig, such as about 30 psig to about 200 psig, such as about 40 psig to about 150 psig, such as about 50 psig to about 100 psig (e.g., 75 psig), or about 150 psig to about 300 psig (e.g., 200 psig).

[0221] In at least one embodiment, the conversion of olefin monomer is at least 10%, such as 20% or greater, such as 30% or greater, such as 50% or greater, such as 80% or greater, based on polymer yield and weight of monomer entering the reaction zone.

[0222] In at least one embodiment, little or no alumoxane is used in the process for producing the polymer. For example, the alumoxane is present at 0 mol%, or the alumoxane may be present at a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0223] In at least one embodiment, little or no scavenger is used in the process for producing ethylene polymers. For example, the scavenger (e.g., trialkylaluminum) is present at 0 mol%, or the scavenger is present at a scavenger metal to transition metal molar ratio of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1.

[0224] If desired, other additives may also be used in the polymerization, such as one or more scavengers, hydrogen, aluminum alkyls, or chain transfer agents (e.g., alkylaluminoxanes, compounds represented by the formula AlR3 or ZnR2 (wherein each R is independently a C1-C8 aliphatic group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof).

[0225] Solution polymerization

[0226] Solution polymerization is a polymerization process in which the polymer is dissolved in a liquid polymerization medium such as an inert solvent or monomer or a blend thereof. Solution polymerization is generally homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Such a system is not turbid as described in Oliveira, JV (2000) "High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems," Ind. Eng. Chem. Res., v. 39 (12), pp. 4627-4633. Solution polymerization may involve polymerization in a continuous reactor in which the polymer is formed, the starting monomers and catalyst materials provided are stirred to reduce or avoid concentration gradients, and in the reactor the monomer acts as a diluent or solvent, or in the reactor a hydrocarbon is used as a diluent or solvent. Suitable processes can be operated at a temperature of about 0°C to about 250°C, such as about 50°C to about 170°C, such as about 80°C to about 150°C, such as about 100°C to about 140°C and / or at a pressure of about 0.1 MPa or higher, such as 2 MPa or higher. The upper pressure limit is not strictly limited, but can be about 200 MPa or less, such as 120 MPa or less, such as 30 MPa or less. Temperature control in the reactor can generally be achieved by balancing the heat of polymerization and reactor cooling, which is carried out by automatic refrigeration of the reactor jacket or cooling coil for cooling the reactor contents, pre-cooled feed, evaporation of the liquid medium (diluent, monomer or solvent), or a combination of the three. Adiabatic reactors with pre-cooled feed can also be used. The purity, type and amount of the solvent can be optimized for a particular type of polymerization to obtain maximum catalyst productivity. The solvent can also be introduced as a catalyst support. Depending on the pressure and temperature, the solvent can be introduced as a gas phase or a liquid phase. Advantageously, the solvent can be kept in the liquid phase and introduced as a liquid. A solvent may be introduced in the feed to the polymerization reactor.

[0227] The method described herein can be a solution polymerization process, which can be carried out in a batch mode (e.g., batch, semi-batch) or in a continuous process. Suitable reactors can include kettles, loops and tube designs. In at least one embodiment, the method is carried out in a continuous manner and uses a double loop reactor configured in series. In at least one embodiment, the method is carried out in a continuous manner and uses a double continuous stirred tank reactor (CSTR) configured in series. In addition, the method can be carried out in a continuous manner and can use a tubular reactor. In another embodiment, the method is carried out in a continuous manner and uses a loop reactor and a CSTR configured in series. The method can also be carried out in a batch mode, and a single stirred tank reactor can be used.

[0228] Polyolefin products

[0229] The present disclosure relates to compositions of matter produced by the methods described herein.

[0230] In at least one embodiment, the methods described herein produce C2-C 20 Olefin homopolymers (such as polyethylene, polypropylene), or C2-C 20 Olefin copolymers (e.g. ethylene-octene, ethylene-propylene) and / or propylene-α-olefin copolymers such as C3-C 20 Copolymers (eg, propylene-hexene copolymers or propylene-octene copolymers) having a comonomer content (eg, wt% of C6) of about 0.05 wt% to about 25 wt%, such as about 0.05 wt% to about 18 wt%.

[0231] In at least one embodiment, the polymers of the present disclosure have an Mw of about 100,000 g / mol to about 3,000,000 g / mol, such as about 175,000 g / mol to about 2,500,000 g / mol, such as about 500,000 g / mol to about 2,250,000 g / mol, such as about 800,000 g / mol to about 1,500,000 g / mol. Alternatively, the polymers of the present disclosure have an Mw of less than 100,000 g / mol, such as about 500 g / mol to about 90,000 g / mol, such as about 2,500 g / mol to about 75,000 g / mol, such as about 5,000 g / mol to about 50,000 g / mol.

[0232] In at least one embodiment, the polymers of the present disclosure have an Mz of about 500,000 g / mol to about 15,000,000 g / mol, such as about 750,000 g / mol to about 12,500,000 g / mol, such as about 1,000,000 g / mol to about 10,000,000 g / mol, such as about 1,500,000 g / mol to about 8,000,000 g / mol, such as about 2,000,000 g / mol to about 7,000,000 g / mol. Alternatively, the polymers of the present disclosure have an Mz of less than 500,000 g / mol, such as about 500 g / mol to about 450,000 g / mol, such as about 5,000 g / mol to about 250,000 g / mol, such as about 10,000 g / mol to about 100,000 g / mol, such as about 5,000 g / mol to about 250,000 g / mol, such as about 25,000 g / mol to about 75,000 g / mol.

[0233] In at least one embodiment, the polymers of the present disclosure have an Mn of about 100,000 g / mol to about 2,000,000 g / mol, such as an Mn of about 175,000 g / mol to about 1,500,000 g / mol, such as an Mn of about 250,000 g / mol to about 1,250,000 g / mol, such as an Mn of about 350,000 g / mol to about 1,000,000 g / mol. Alternatively, the polymers of the present disclosure have an Mn of less than 100,000 g / mol, such as an Mn of about 500 g / mol to about 90,000 g / mol, such as an Mn of about 2,500 g / mol to about 75,000 g / mol, such as an Mn of about 5,000 g / mol to about 50,000 g / mol.

[0234] In at least one embodiment, the polymers of the present disclosure have a Mw / Mn (PDI) value of about 1 to about 5, such as about 2 to about 4, such as about 2.5 to about 3.5, such as about 3 to about 3.5, or about 1.5 to about 2.5.

[0235] Likewise, the disclosed process produces olefin polymers, such as polyethylene and polypropylene homopolymers and copolymers. In at least one embodiment, the polymer produced herein is a homopolymer of ethylene or has, for example, from about 0.05 wt % to about 25 wt % (or from about 0.5 wt % to about 20 wt %, or from about 1 wt % to about 15 wt %, such as from about 1 wt % to about 10 wt %, or from about 8 wt % to about 13 wt %) of one or more C3-C 20 Olefin comonomers (e.g. C3-C 12 In at least one embodiment, the monomer is ethylene and the comonomer is hexene, for example, about 0.05 wt% to about 18 wt% hexene, for example, about 0.1 wt% to about 16 wt% hexene, for example, about 2 wt% to about 14 wt% hexene, or about 8 wt% to about 14 wt% hexene, based on the weight of the polymer.

[0236] In at least one embodiment, the polymer produced herein is a homopolymer of propylene, or a C2 or C4-C6-C7-C8-C9-C10-C12-C16-C18-C10-C12 ... 20 One or more olefin comonomers (e.g. ethylene or C4-C 12In at least one embodiment, the monomer is propylene and the comonomer is hexene, such as about 0.05 wt % to about 18 wt % hexene, such as about 0.1 wt % to about 16 wt % hexene, such as about 2 wt % to about 14 wt % hexene, or about 8 wt % to about 14 wt % hexene, based on the weight of the polymer. In another embodiment, the polymer produced herein has a broad normal composition distribution.

[0237] In at least one embodiment, the polymers of the present disclosure have a melt index (I2) of about 0.05 g / 10 min to about 2.5 g / 10 min, such as about 0.1 g / 10 min to about 2 g / 10 min, such as about 0.5 g / 10 min to about 1.5 g / 10 min.

[0238] In at least one embodiment, the polymers of the present disclosure have a g' greater than 0.9, such as greater than 0.92, such as greater than 0.95, such as greater than 0.96. vis .

[0239] In at least one embodiment the polymer has a MIR value greater than 12, such as 12-100, such as 12-50, such as 14-45, such as 16-40, such as 18-35.

[0240] In at least one embodiment, the polymers produced herein have a Mw of about 100,000 g / mol to about 5,000,000 g / mol, a Mn of about 100,000 g / mol to about 2,000,000 g / mol, a Mz of about 500,000 g / mol to about 15,000,000 g / mol, and / or a Mw / Mn (PDI) of about 1.2-10, such as 1-5 (e.g., about 2.5).

[0241] In at least one embodiment, the polymers produced herein have a unimodal or multimodal molecular weight distribution as measured by gel permeation chromatography (GPC). By "unimodal" is meant that the GPC curve has one peak or inflection point. By "multimodal" is meant that the GPC curve has at least two peaks or inflection points. An inflection point is a point at which the sign of the second derivative of the curve changes (e.g., from negative to positive or vice versa). In at least one embodiment, the polymers produced herein have a bimodal molecular weight distribution as measured by gel permeation chromatography (GPC).

[0242] GPC 4-D

[0243] For the purposes of the claims, unless otherwise indicated, molecular weight distribution and moments (Mw, Mn, Mz, Mw / Mn, etc.), comonomer content and branching index (g') were determined using a high temperature gel permeation chromatograph (Polymer CharGPC-IR) equipped with a multi-channel band filter based infrared detector IR5 (wavelength region covering about 2,700 cm -1 - Approx. 3,000cm -1 (represents saturated CH stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-μm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) including about 300 ppm of the antioxidant BHT can be used as the mobile phase, with a nominal flow rate of about 1 mL / min and a nominal injection volume of about 200 μL. The entire system including the transfer line, column and detector can be contained in an oven maintained at about 145°C. A given amount of sample can be weighed and sealed in a standard vial, to which about 10 μL of a flow marker (heptane) is added. After the vial is loaded into the autosampler, the oligomer or polymer can be automatically dissolved in the instrument, and about 8 mL of a TCB solvent at about 160°C is added and continuously shaken. The sample solution concentration can be about 0.2-about 2 mg / ml, with lower concentrations used for higher molecular weight samples.

[0244] The concentration c at each point of the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal I using the following formula: c=αI, where α is a mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of ​​the concentration chromatogram within the elution volume to the injected mass equal to the predetermined concentration multiplied by the injection loop volume. Conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with a column calibration using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mole. The MW for each elution volume is calculated using the following equation:

[0245]

[0246] The variables with the subscript "PS" represent polystyrene, while the variables without the subscript represent the test sample. PS =0.67 and K PS=0.000175, α and K for other materials are calculated as published in the literature (see, e.g., Sun, T. et al. (2001) "Effect of Short Chain Branching on the Coil Dimensions of Polyolefins in Dilute Solution" Macromolecules, v.34, pp. 6812-6820), but for the purposes of the present disclosure and claims thereto, for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α=0.695+(0.01*(propylene weight fraction)) and K=0.000579-(0.0003502*(propylene weight fraction)); for linear ethylene polymers, α=0.695 and K=0.000579; for linear propylene polymers, α=0.705 and K=0.0002288; for linear butene polymers, α=0.695 and K= 0.000181; for ethylene-butene copolymer, α is 0.695 and K is 0.000579*(1- 0.0087*w2b+0.000018*(w2b) 2 ), where w2b is the overall weight percent of butene comonomer; for ethylene-hexene copolymers, α is 0.695 and K is 0.000579*(1-0.0075*w2b), where w2b is the overall weight percent of hexene comonomer; and for ethylene-octene copolymers, α is 0.695 and K is 0.000579*(1-0.0077*w2b), where w2b is the overall weight percent of octene comonomer. Unless otherwise stated, concentrations are in g / cm 3 The molecular weight is expressed in g / mol and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g.

[0247] The comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels, calibrated with a series of PE and PP homopolymer / copolymer standards whose nominal values ​​are predetermined by NMR or FTIR. In particular, this provides the number of methyl groups per 1,000 total carbons (CH3 / 1,000TC) as a function of molecular weight. The short chain branch (SCB) content per 1,000TC as a function of molecular weight is then calculated by applying a chain end correction to the CH3 / 1,000TC function, assuming that each chain is linear and terminated by a methyl group at each end. The weight percentage of the comonomer is then obtained from the following expression, where f is 0.3, 0.4, 0.6, 0.8, etc. for comonomers such as C3, C4, C6, C8, etc.:

[0248] w2=f*SCB / 1,000TC

[0249] The overall composition of the polymer from GPC-IR and GPC-4D analysis is obtained by considering the entire signal of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained:

[0250]

[0251] Then, as mentioned above in obtaining CH3 / 1,000TC as a function of molecular weight, the CH3 and CH2 signal ratios are calibrated identically to obtain the overall CH3 / 1,000TC. The overall number of methyl chain ends per 1,000TC (overall number of CH3 ends / 1,000TC) is obtained by weight averaging the chain end correction over the molecular weight range according to the following equation:

[0252] w2b=f*total CH3 / 1,000TC

[0253] Total SCB / 1,000TC = Total CH3 / 1,000TC - Total CH3 terminal number / 1,000TC

[0254] Wherein the whole SCB / 1,000TC is converted to the whole w2 in the same manner as above.

[0255] The LS detector was an 18-angle Wyatt Technology High Temperature DAWN HELEOS II. The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972):

[0256]

[0257] Here, ΔR(θ) is the hyper-Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined by IR5 analysis, A2 is the second virial coefficient, P(θ) is the morphology factor of the monodisperse random coils, and Ko is the optical constant of the system:

[0258]

[0259] Where NA is Avogadro's number, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145°C and λ=665nm is n=1.500. For the analysis of polyethylene homopolymer, ethylene-hexene copolymer and ethylene-octene copolymer, dn / dc=0.1048 ml / mg and A2=0.0015; for the analysis of ethylene-butene copolymer, dn / dc=0.1048*(1-0.00126*w2) ml / mg and A2=0.0015, where w2 is the weight percent of butene comonomer.

[0260] Use high temperature Agilent (or Viscotek Corporation) viscometer (it has four capillaries arranged into Wheatstone bridge structure, has two pressure sensors) to measure specific viscosity.A sensor measures the total pressure drop at the two ends of the detector, and another sensor between the two sides of the bridge measures differential pressure.The specific viscosity η s of the solution flowing through the viscometer is calculated by their output.The limiting viscosity [η] at each point in the chromatogram is calculated by the following formula:

[0261] [η] = ηs / c,

[0262] Where c is the concentration and is determined by the IR5 broadband channel output. The viscosity MW at each point is calculated as where α ps is 0.67 and K ps It is 0.000175.

[0263] Branching index (g' vis ) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity [η] of the sample avg Calculated by the following formula:

[0264]

[0265] The summation is performed between the integration limits for each chromatographic slice i. The branching index g' vis is defined as Where Mv is the viscosity average molecular weight based on molecular weight determined by LS analysis, and K and α are for a reference linear polymer as described above for purposes of this disclosure and claims. Unless otherwise indicated, concentrations are in g / cm 3 The w2b value is calculated as described above, the molecular weight is expressed in g / mole, and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g.

[0266] In at least one embodiment, the polymer produced has a composition distribution breadth index (CDBI) of 50% or greater, such as 60% or greater, such as 70% or greater. CDBI is a measure of the composition distribution of monomers within a polymer chain and is determined by the procedure described in PCT Publication No. WO1993 / 003093, published on February 18, 1993, specifically columns 7 and 8, and Wild, L. et al. (1982) "Determination of Branching Distributions in Polyethylene and Ethylene Copolymers," J. Poly. Sci., Poly. Phys. Ed., v. 20, pp. 441-455 and U.S. Patent No. 5,008,204, including ignoring the fraction with a weight average molecular weight (Mw) below 15,000 g / mol when determining the CDBI.

[0267] Blends

[0268] In another embodiment, the polymers produced herein (e.g., the polyethylene or polypropylene) are blended with one or more additional polymers and then formed into films, molded parts, or other articles. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymers of propylene with ethylene and / or butene and / or hexene, polybutene, ethylene-vinyl acetate copolymers, LDPE, LLDPE, HDPE, ethylene-vinyl acetate, ethylene-methyl acrylate copolymers, copolymers of acrylic acid, polymethyl methacrylate or any other polymer that can be polymerized by a high pressure free radical process, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), sulfurized EPR, EPDM, block copolymers, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetals, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0269] In at least one embodiment, the polymer (e.g., polyethylene or polypropylene) is present in the above blend in an amount of 10 wt% to 99 wt%, such as 20 wt% to 95 wt%, such as at least 30 wt% to 90 wt%, such as at least 40 wt% to 90 wt%, such as at least 50 wt% to 90 wt%, such as at least 60 wt% to 90 wt%, such as at least 70 to 90 wt%, based on the weight of the polymer in the blend.

[0270] The blends described above can be produced by mixing the polymers of the present disclosure with one or more polymers (described above), by connecting reactors together in series to prepare reactor blends, or by using more than one catalyst in the same reactor to produce multiple polymers. The polymers can be mixed together before being placed in the extruder, or can be mixed in the extruder.

[0271] The blend can be formed using conventional equipment and methods, for example, by dry blending the components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer such as a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder (which may include mixing extruders and side arm extruders used directly downstream of the polymerization process), which may include powders or pellets of the blended resins in the feed hopper of a film extruder. In addition, additives may be included in the blend, in one or more components of the blend, and / or in products such as films formed from the blend, as desired. Such additives are well known in the art and may include, for example: fillers; antioxidants (e.g., hindered phenols such as IRGANOX available from Ciba-Geigy); TM 1010 or IRGANOX TM 1076); phosphites (e.g., IRGAFOS available from Ciba-Geigy); TM 168); anti-slip additives; tackifiers, such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glyceryl stearate, and hydrogenated rosin; UV stabilizers; heat stabilizers; antiblocking agents; mold release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc.

[0272] film

[0273] Any of the aforementioned polymers, such as the aforementioned polypropylene or its blend, can be used in various final applications. Such applications include, for example, single or multilayer blow molding, extrusion and / or shrink film. These films can be formed by any known extrusion or coextrusion technology such as bubble film processing technology (wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uniaxial or biaxially oriented melt, then cooled to form a tubular blown film, This tubular blown film can then be axially cut and expanded to form a flat film). The film can then be non-oriented, uniaxially oriented or biaxially oriented to the same or different degree. One or more of the layers of the film can be oriented horizontally and / or longitudinally to the same or different degree. The uniaxial orientation can be completed using suitable cold stretching or hot stretching methods. Biaxial orientation can be completed using a tentering frame device or a double bubble process, and can occur before or after each layer is put together. For example, a polyethylene layer can be extrusion coated or laminated on an oriented polypropylene layer, or polyethylene and polypropylene can be coextruded into a film together, then oriented. Likewise, oriented polypropylene can be laminated to oriented polyethylene, or oriented polyethylene can be covered on polypropylene, and then optionally the combination can be oriented even further. For example, the film can be oriented in the machine direction (MD) at a ratio of up to 15, such as from about 5 to about 7, and in the transverse direction (TD) at a ratio of up to 15, such as from about 7 to about 9. However, in another embodiment, the film is oriented to the same extent in the MD and TD directions.

[0274] The thickness of the film may vary, depending on the intended application; however, films of 1 μm to 50 μm thickness may be suitable. Films intended for packaging may be 10 μm to 50 μm thick. The thickness of the sealant layer may be 0.2 μm to 50 μm. There may be a sealant layer on both the inner and outer surfaces of the film, or the sealant layer may be present on only the inner surface or only the outer surface.

[0275] In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma-ray irradiation, flame treatment, or microwaves.In at least one embodiment, one or both of the surface layers are modified by corona treatment.

[0276] List of implementation plans

[0277] Among other things, the present disclosure provides the following embodiments, each of which may be considered to optionally include any alternative embodiments.

[0278] Item 1. Catalyst compound represented by formula (I):

[0279]

[0280] in:

[0281] M is hafnium;

[0282] R 1 , R 2 , R 3 and R 4 Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon group, or R 16 -T 2 (R 17 )3, where R 16 is a C1-C4 hydrocarbon group, T 2 is a Group 13, 14, 15 or 16 element, and each R 17 are independently C1-C5 substituted or unsubstituted hydrocarbon groups (e.g. -R 16 -Si(R 17 )3, where R 16 is a C1-C4 hydrocarbon group, and each R 17 Independently C1-C 20 substituted or unsubstituted hydrocarbon groups);

[0283] R 5 , R 6 , R 7 , R 8 and R 9 Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon, or –R 18 -T 3 (R 19 )3, where R 18 is a C1-C4 hydrocarbon group, T 3 is a Group 13, 14, 15 or 16 element, and each R 19 are independently C1-C5 substituted or unsubstituted hydrocarbon groups (e.g. -R 18 -Si(R 19 )3, where R 18 is a C1-C4 hydrocarbon group, and each R 19 Independently C1-C 20 substituted or unsubstituted hydrocarbon groups);

[0284] X 1 It is a monovalent anionic ligand;

[0285] R 10 and R 11 Each of which is independently hydrogen or C1-C 20 Hydrocarbyl, substituted hydrocarbyl, or R10 and R 11 joined together to form substituted or unsubstituted, saturated or partially unsaturated, cyclic or polycyclic substituents;

[0286] R 12 and R 13 It is hydrogen;

[0287] n is 1, 2, 3, 4 or 5;

[0288] T 1 is a Group 13, 14 (excluding carbon), 15 or 16 element; and

[0289] R 14 and R 15 Independently C1-C 40 Substituted or unsubstituted hydrocarbon groups (e.g., independently C 1 -C 10 Substituted or unsubstituted hydrocarbon groups, such as R 14’ and / or R 15’ is methyl).

[0290] Item 2. The catalyst compound of Item 1, wherein T 1 It's Si.

[0291] Item 3. The catalyst compound of Item 1 or 2, wherein n is 1-3.

[0292] Item 4. The catalyst compound of any one of items 1 to 3, wherein n is 1.

[0293] Item 5. The catalyst compound of any one of Items 1 to 4, wherein R 1 , R 2 , R 3 and R 4 Each of which is independently hydrogen or C1-C 40 Substituted or unsubstituted hydrocarbon groups.

[0294] Item 6. The catalyst compound of any one of Items 1 to 5, wherein R 1 , R 2 , R 3 and R 4 It's hydrogen.

[0295] Item 7. The catalyst compound of any one of Items 1 to 6, wherein R 5 , R 6 , R 7 , R 8 and R 9 Each of which is independently hydrogen, C1-C 40 Substituted or unsubstituted hydrocarbon group, or -R18 -Si(R 19 )3, where R 18 is a C1-C4 hydrocarbon group, and each R 19 Independently C1-C 20 Substituted or unsubstituted hydrocarbon groups.

[0296] Item 8. The catalyst compound of any one of Items 1 to 7, wherein R 5 , R 6 , R 7 , R 8 and R 9 One of them is -R 18 -Si(R 19 )3, where R 18 is a C1-C4 hydrocarbon group, each R 19 Independently C1-C 20 substituted or unsubstituted hydrocarbon group, and R 5 , R 6 , R 7 , R 8 and R 9 The fourth is hydrogen.

[0297] Item 9. The catalyst compound of Item 7 or 8, wherein each R 19 are independently C1-C5 unsubstituted hydrocarbon groups.

[0298] Item 10. The catalyst compound of any one of Items 1 to 9, wherein R 18 is C1 and each R 19 It's methyl.

[0299] Item 11. The catalyst compound of any one of Items 1 to 10, wherein n is 1, and R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 It's hydrogen.

[0300] Item 12. The catalyst compound of any one of Items 1 to 11, wherein X 1 Selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.

[0301] Item 13. The catalyst compound of any one of Items 1 to 12, wherein X1 It's butyl.

[0302] Item 14. The catalyst compound of Item 1, wherein the catalyst compound is one or more of the following compounds:

[0303]

[0304]

[0305] Item 15. The catalyst compound of Item 14, wherein the catalyst compound is selected from:

[0306]

[0307] Item 16. A catalyst system comprising an activator and the catalyst compound of any one of items 1 to 15.

[0308] Item 17. The catalyst system of any one of Items 1 to 16, further comprising a support material.

[0309] Item 18. The catalyst system of any one of Items 1 to 17, wherein the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silica / clay, or a mixture thereof.

[0310] Item 19. The catalyst system of any one of Items 16-18, wherein the activator comprises a non-coordinating anion activator.

[0311] Item 20. The catalyst system of Item 19, wherein the activator is represented by the formula:

[0312] (Z)d + (A d- )

[0313] Wherein Z is (LH) or a reducible Lewis acid, L is a Lewis base; H is hydrogen; (LH) + is a Bronsted acid; A d- is a non-coordinating anion having a charge of d-; and d is an integer from 1 to 3.

[0314] Item 21. The catalyst system of Item 19, wherein the activator is represented by the formula:

[0315] (Z)d + (A d- )

[0316] Among them A d-is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula: (Ar3C + ), wherein Ar is an aryl group or an aryl group substituted by a heteroatom, C1-C 40 Hydrocarbon, or substituted C1-C 40 Hydrocarbon.

[0317] Item 22. The catalyst system of Item 19, wherein the activator is one or more of the following:

[0318] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0319] Dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate,

[0320] Dioctadecylmethylammonium tetra(perfluoronaphthyl)borate,

[0321] Triphenylcarbonium tetrakis(pentafluorophenyl)borate,

[0322] Trimethylammonium tetrakis(perfluoronaphthyl)borate,

[0323] Triethylammonium tetra(perfluoronaphthyl)borate,

[0324] Tripropylammonium tetrakis(perfluoronaphthyl)borate,

[0325] Tri(n-butyl)ammonium tetra(perfluoronaphthyl)borate,

[0326] Tri(tert-butyl)ammonium tetra(perfluoronaphthyl)borate,

[0327] N,N-Dimethylanilinium tetrakis(perfluoronaphthyl)borate,

[0328] N,N-Diethylanilinium tetrakis(perfluoronaphthyl)borate,

[0329] N,N-Dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,

[0330] Cycloheptatrienyl cation tetra(perfluoronaphthyl)borate,

[0331] Triphenylcarbonium tetrakis(perfluoronaphthyl)borate,

[0332] Triphenylphosphonium tetrakis(perfluoronaphthyl)borate,

[0333] Triethylsilylium tetrakis(perfluoronaphthyl)borate,

[0334] Benzene(diazo)tetra(perfluoronaphthyl)borate,

[0335] Trimethylammonium tetrakis(perfluorobiphenyl)borate,

[0336] Triethylammonium tetrakis(perfluorobiphenyl)borate,

[0337] Tripropylammonium tetrakis(perfluorobiphenyl)borate,

[0338] Tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,

[0339] Tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,

[0340] N,N-Dimethylanilinium tetrakis(perfluorobiphenyl)borate,

[0341] N,N-Diethylanilinium tetrakis(perfluorobiphenyl)borate,

[0342] N,N-Dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,

[0343] Cycloheptatrienyl cation tetrakis(perfluorobiphenyl)borate,

[0344] Triphenylcarbonium tetrakis(perfluorobiphenyl)borate,

[0345] Triphenylphosphonium tetrakis(perfluorobiphenyl)borate,

[0346] Triethylsilylium tetrakis(perfluorobiphenyl)borate,

[0347] Benzene(diazo)tetrakis(perfluorobiphenyl)borate,

[0348] [4-tert-butyl-PhNMe2H][(C6F3(C6F5)2)4B],

[0349] Trimethylammonium tetraphenylborate,

[0350] Triethylammonium tetraphenylborate,

[0351] Tripropylammonium tetraphenylborate,

[0352] Tri(n-butyl)ammonium tetraphenylborate,

[0353] Tri(tert-butyl)ammonium tetraphenylborate,

[0354] N,N-Dimethylanilinium tetraphenylborate,

[0355] N,N-Diethylanilinium tetraphenylborate,

[0356] N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,

[0357] Cycloheptatrienol cation tetraphenylborate,

[0358] Triphenylcarbonium tetraphenylborate,

[0359] Triphenylphosphonium tetraphenylborate,

[0360] Triethylsilylium tetraphenylborate,

[0361] Benzene(diazo)tetraphenylborate,

[0362] Trimethylammonium tetrakis(pentafluorophenyl)borate,

[0363] Triethylammonium tetrakis(pentafluorophenyl)borate,

[0364] Tripropylammonium tetrakis(pentafluorophenyl)borate,

[0365] Tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0366] Tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate,

[0367] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate,

[0368] N,N-Diethylanilinium tetrakis(pentafluorophenyl)borate,

[0369] N,N-Dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

[0370] Cycloheptatrienol tetrakis(pentafluorophenyl)borate,

[0371] Triphenylcarbonium tetrakis(pentafluorophenyl)borate,

[0372] Triphenylphosphonium tetrakis(pentafluorophenyl)borate,

[0373] Triethylsilylium tetrakis(pentafluorophenyl)borate,

[0374] Benzene(diazo)tetrakis(pentafluorophenyl)borate,

[0375] Trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0376] Triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0377] Tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0378] Tri(n-butyl)ammonium tetra(2,3,4,6-tetrafluoro-phenyl)borate,

[0379] Dimethyl(tert-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0380] N,N-Dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0381] N,N-Diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0382] N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0383] Cycloheptatrienol cation tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0384] Triphenylcarbonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0385] Triphenylphosphonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0386] Triethylsilylium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0387] Benzene(diazo)tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0388] Trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0389] Triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0390] Tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0391] Tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0392] Tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0393] N,N-Dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0394] N,N-Diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0395] N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0396] Cycloheptatrienol tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0397] Triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0398] Triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0399] Triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0400] Benzene(diazo)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

[0401] Di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate,

[0402] Dicyclohexylammonium tetrakis(pentafluorophenyl)borate,

[0403] Tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,

[0404] Tris(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,

[0405] Triphenylcarbonium tetrakis(perfluorophenyl)borate,

[0406] 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,

[0407] Tetrakis(pentafluorophenyl)borate,

[0408] 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, and

[0409] triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

[0410] Item 23. The catalyst system of Item 16, further comprising a metal olefinic chain transfer agent represented by the formula:

[0411] Al(R') 3-v (R”) v

[0412] Where each R' is independently C1-C 30 Hydrocarbyl group; each R" is independently a C4-C 20 alkenyl; and v is 0.1-3.

[0413] Item 24. The catalyst system of Item 16, wherein the activator comprises an alkylaluminoxane.

[0414] Item 25. The catalyst system of Item 24, wherein the aluminoxane is present in a molar ratio of aluminum to catalyst compound transition metal of 100:1 or greater.

[0415] Item 26. A method for producing an ethylene-α-olefin copolymer, the method comprising: reacting ethylene and at least one C3-C 20The α-olefins are contacted with the catalyst system of any one of items 16 to 25 in at least one gas phase reactor at a reactor pressure of 0.7 bar to 70 bar and a reactor temperature of 20° C. to 150° C. to react the ethylene and the at least one C3-C 20 The α-olefin is polymerized to form an ethylene-α-olefin copolymer.

[0416] Item 27. By making ethylene, at least one C3-C 20 An ethylene-α-olefin copolymer obtained by contacting an α-olefin and the catalyst system of any one of items 16 to 25 in at least one gas phase reactor, wherein the copolymer has a Mw value of 50,000-5,000,000, a Mn value of 100,000-2,000,000, a Mz value of 500,000-10,000,000, a Mw / Mn value of 1.2-10, a MI of about 0.05 g / 10 min to about 2.5 g / 10 min, a MIR value of 12-100, a g' value of greater than 0.9 vis , and a comonomer content of 0.05wt%-18wt%.

[0417] Item 28. By making ethylene, at least one C3-C 20 An ethylene-α-olefin copolymer obtained by contacting an α-olefin and the catalyst system of any one of items 16 to 25 in at least one gas phase reactor, wherein the copolymer has a Mw value of 500-100,000, a Mn value of 500-100,000, a Mz value of 500-500,000, a Mw / Mn value of 1.2-10, a MI of about 0.05 g / 10 min to about 2.5 g / 10 min, a MIR value of 12-50, a g' value of greater than 0.9 vis , and a comonomer content of 0.05wt% to 18wt%.

[0418] Item 29. The ethylene-α-olefin copolymer of any one of Items 27 or 28, wherein the copolymer has a broad normal composition distribution.

[0419] Item 30. The ethylene-α-olefin copolymer of any one of Items 27 or 28, wherein the copolymer has a bimodal molecular weight distribution as determined by gel permeation chromatography.

[0420] Item 31. Intermediate compound represented by formula (II):

[0421]

[0422] in:

[0423] M' is hafnium;

[0424] R1’ , R 2’ , R 3’ and R 4’ Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon group, or R 16’ -T 2’ (R 17’ )3, where R 16’ is a C1-C4 hydrocarbon group, T 2’ is a Group 13, 14, 15 or 16 element, and each R 17’ are independently C1-C5 substituted or unsubstituted hydrocarbon groups (e.g. -R 16’ -Si(R 17’ )3, where R 16’ is a C1-C4 hydrocarbon group, and each R 17’ Independently C1-C 20 substituted or unsubstituted hydrocarbon groups);

[0425] R 5’ , R 6’ , R 7’ , R 8’ and R 9’ Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon, or –R 18’ -Si(R 19’ )3, where R 18’ is a C1-C4 hydrocarbon group, T 3’ is a Group 13, 14, 15 or 16 element, and each R 19’ are independently C1-C5 substituted or unsubstituted hydrocarbon groups (e.g. -R 18’ -Si(R 19’ )3, where R 18’ is a C1-C4 hydrocarbon group, and each R 19’ Independently C1-C 20 substituted or unsubstituted hydrocarbon groups);

[0426] X 1’ and X 2’ Each of which is independently a monovalent anionic ligand;

[0427] R 10’ and R 11’ Each of which is independently hydrogen or C1-C 20 A hydrocarbon group or a substituted hydrocarbon group, or R 10’ and R 11’ joined together to form substituted or unsubstituted, saturated or partially unsaturated, cyclic or polycyclic substituents;

[0428] n' is 1, 2, 3, 4 or 5;

[0429] T 1’ is an element of Group 13, 14 (excluding carbon), 15 or 16;

[0430] R 14’ and R 15’ Each of which is independently C1-C 40 Substituted or unsubstituted hydrocarbon groups (e.g., independently C1-C 10 Substituted or unsubstituted hydrocarbon groups, such as R 14’ and / or R 15’ is methyl); and

[0431] R 20’ are independently C1 or more substituted or unsubstituted hydrocarbon groups (e.g. C1-C 40 or C1-C 10 Substituted or unsubstituted hydrocarbon groups, such as R 20’ is methyl, or R 14’ , R 15’ and / or R 20’ is methyl).

[0432] Item 32. The intermediate compound of Item 31, wherein T 1’ It's Si.

[0433] Item 33. The intermediate compound of Item 32, wherein n' is 1-3.

[0434] Item 34. The intermediate compound of Item 33, wherein n' is 1.

[0435] Item 35. The intermediate compound of Item 31, wherein R 1’ , R 2’ , R 3’ and R 4’ At least one of them is independently C1-C 40 Substituted or unsubstituted hydrocarbon or -R 16’ -Si(R 17’ )3, where R 16’ is a C1-C4 hydrocarbon group, and each R 17’ Independently C1-C 20 a substituted or unsubstituted hydrocarbon group, and R 1’ , R 2’ , R 3’ and R 4’ At least one of them is hydrogen.

[0436] Item 36. The intermediate compound of Item 35, wherein R1’ , R 2’ , R 3’ and R 4’ It's hydrogen.

[0437] Item 37. The intermediate compound of Item 31, wherein R 5’ , R 6’ , R 7’ , R 8’ and R 9’ At least one of them is independently C1-C 40 Substituted or unsubstituted hydrocarbon or -R 18’ -Si(R 19’ )3, where R 18’ is a C1-C4 hydrocarbon group, and each R 19’ Independently C1-C 20 substituted or unsubstituted hydrocarbon group, and R 5’ , R 6’ , R 7’ , R 8’ and R 9’ At least one of them is hydrogen.

[0438] Item 38. The intermediate compound of Item 37, wherein R 5’ , R 6’ , R 7’ , R 8’ and R 9’ One of them is -R 18’ -Si(R 19’ )3, where R 18’ is a C1-C4 hydrocarbon group, each R 19’ Independently C1-C 20 substituted or unsubstituted hydrocarbon group, and R 5’ , R 6’ , R 7’ , R 8’ and R 9’ The fourth is hydrogen.

[0439] Item 39. The intermediate compound of Item 37 or 38, wherein R 5’ Yes-R 18’ -Si(R 19’ )3, where R 18’ is a C1 hydrocarbon group, and each R 19’ Independently C1-C 20 Unsubstituted hydrocarbon.

[0440] Item 40. The intermediate compound of Item 39, wherein each R 19’ It's methyl.

[0441] Item 41. The intermediate compound of Item 31, wherein n' is 1, and R 1’ , R 2’ , R 3’ , R 4’ , R 6’ , R 7’ , R 8’ , R 9’ , R 10 ' and R 11’ It's hydrogen.

[0442] Item 42. The intermediate compound of any one of Items 31 to 41, wherein X 1’ and X 2’ Each of which is independently selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.

[0443] Item 43. The intermediate compound of Item 42, wherein X 1’ and X 2’ Each of which is butyl.

[0444] Item 44. A method comprising the following steps:

[0445] The intermediate compound represented by formula (II) is heated at a temperature of about 70°C to about 120°C for a period of about 1 hour to about 72 hours:

[0446]

[0447] in:

[0448] M' is hafnium;

[0449] R 1’ , R 2’ , R 3’ and R 4’ Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon, or –R 16’ -T 2’ (R 17’ )3, where R 16’ is a C1-C4 hydrocarbon group, T 2’ is a Group 13, 14, 15 or 16 element, and each R 17’ are independently C1-C5 substituted or unsubstituted hydrocarbon groups;

[0450] R 5’ , R 6’ , R 7’ , R 8’ and R 9’Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon, or –R 18’ -T 3’ (R 19’ )3, where R 18’ is a C1-C4 hydrocarbon group, T 3’ is a Group 13, 14, 15 or 16 element, and each R 19’ Independently C1-C 20 Substituted or unsubstituted hydrocarbon groups;

[0451] X 1’ and X 2’ Each of which is independently a monovalent anionic ligand;

[0452] R 10’ and R 11’ Each of which is independently hydrogen or C1-C 20 A hydrocarbon group or a substituted hydrocarbon group, or R 10’ and R 11’ joined together to form substituted or unsubstituted, saturated or partially unsaturated, cyclic or polycyclic substituents;

[0453] n' is 1, 2, 3, 4 or 5;

[0454] T 1’ is a Group 13, 14 (excluding carbon), 15 or 16 element; and

[0455] R 14’ and R 15’ Each of which is independently C1-C 40 Substituted or unsubstituted hydrocarbon groups;

[0456] R 20’ are independently C1 or greater substituted or unsubstituted hydrocarbon groups; and

[0457] A catalyst compound represented by formula (I) is obtained:

[0458]

[0459] in:

[0460] M is hafnium;

[0461] R 1 , R 2 , R 3 and R 4 Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon group, or R 16 -T 2(R 17 )3, where R 16 is a C1-C4 hydrocarbon group, T 2 is a Group 13, 14, 15 or 16 element, and each R 17 are independently C1-C5 substituted or unsubstituted hydrocarbon groups;

[0462] R 5 , R 6 , R 7 , R 8 and R 9 Each of which is independently hydrogen, alcohol, C1-C 40 Substituted or unsubstituted hydrocarbon, or –R 18 -T 3 (R 19 )3, where R 18 is a C1-C4 hydrocarbon group, T 3 is a Group 13, 14, 15 or 16 element, and each R 19 are independently C1-C5 substituted or unsubstituted hydrocarbon groups;

[0463] X 1 It is a monovalent anionic ligand;

[0464] R 10 and R 11 Each of which is independently hydrogen or C1-C 20 Hydrocarbyl, substituted hydrocarbyl, or R 10 and R 11 joined together to form substituted or unsubstituted, saturated or partially unsaturated, cyclic or polycyclic substituents;

[0465] R 12 and R 13 It is hydrogen;

[0466] n is 1, 2, 3, 4 or 5;

[0467] T 1 is a Group 13, 14 (excluding carbon), 15 or 16 element; and

[0468] R 14 and R 15 Independently C1-C 40 Substituted or unsubstituted hydrocarbon groups.

[0469] Item 45. The method of Item 44, wherein the heating comprises heating the intermediate compound represented by formula (II) at a temperature of about 85°C to about 95°C for a time of about 30 hours to about 40 hours.

[0470] experiment

[0471] Characterization

[0472] GPC 4-D

[0473] For the purposes of the claims, unless otherwise indicated, molecular weight distribution and moments (Mw, Mn, Mz, Mw / Mn, etc.), comonomer content and branching index (g') were determined using a high temperature gel permeation chromatograph (Polymer CharGPC-IR) equipped with a multi-channel band filter based infrared detector IR5 (wavelength region covering about 2,700 cm -1 - Approx. 3,000cm -1 (represents saturated CH stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-μm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) including about 300 ppm of the antioxidant BHT can be used as the mobile phase, with a nominal flow rate of about 1 mL / min and a nominal injection volume of about 200 μL. The entire system including the transfer line, column and detector can be contained in an oven maintained at about 145°C. A given amount of sample can be weighed and sealed in a standard vial, to which about 10 μL of a flow marker (heptane) is added. After the vial is loaded into the autosampler, the oligomer or polymer can be automatically dissolved in the instrument, and about 8 mL of a TCB solvent at about 160°C is added and continuously shaken. The sample solution concentration can be about 0.2-about 2 mg / ml, with lower concentrations used for higher molecular weight samples.

[0474] The concentration c at each point of the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal I using the following formula: c=αI, where α is a mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of ​​the concentration chromatogram within the elution volume to the injected mass equal to the predetermined concentration multiplied by the injection loop volume. Conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with a column calibration using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mole. The MW for each elution volume is calculated using the following equation:

[0475]

[0476] The variables with the subscript "PS" represent polystyrene, while the variables without the subscript represent the test sample. PS =0.67 and K PS=0.000175, α and K for other materials are calculated as published in the literature (see, e.g., Sun, T. et al. (2001) "Effect of Short Chain Branching on the Coil Dimensions of Polyolefins in Dilute Solution" Macromolecules, v.34, pp. 6812-6820), but for the purposes of the present disclosure and claims thereto, for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α=0.695+(0.01*(propylene weight fraction)) and K=0.000579-(0.0003502*(propylene weight fraction)); for linear ethylene polymers, α=0.695 and K=0.000579; for linear propylene polymers, α=0.705 and K=0.0002288; for linear butene polymers, α=0.695 and K= 0.000181; for ethylene-butene copolymer, α is 0.695 and K is 0.000579*(1- 0.0087*w2b+0.000018*(w2b) 2 ), where w2b is the overall weight percent of butene comonomer; for ethylene-hexene copolymers, α is 0.695 and K is 0.000579*(1-0.0075*w2b), where w2b is the overall weight percent of hexene comonomer; and for ethylene-octene copolymers, α is 0.695 and K is 0.000579*(1-0.0077*w2b), where w2b is the overall weight percent of octene comonomer. Unless otherwise stated, concentrations are in g / cm 3 The molecular weight is expressed in g / mol and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g.

[0477] The comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels, calibrated with a series of PE and PP homopolymer / copolymer standards whose nominal values ​​are predetermined by NMR or FTIR. In particular, this provides the number of methyl groups per 1,000 total carbons (CH3 / 1,000TC) as a function of molecular weight. The short chain branch (SCB) content per 1,000TC as a function of molecular weight is then calculated by applying a chain end correction to the CH3 / 1,000TC function, assuming that each chain is linear and terminated by a methyl group at each end. The weight percentage of the comonomer is then obtained from the following expression, where f is 0.3, 0.4, 0.6, 0.8, etc. for comonomers such as C3, C4, C6, C8, etc.:

[0478] w2=f*SCB / 1,000TC

[0479] The overall composition of the polymer from GPC-IR and GPC-4D analysis is obtained by considering the entire signal of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained:

[0480]

[0481] Then, as mentioned above in obtaining CH3 / 1,000TC as a function of molecular weight, the CH3 and CH2 signal ratios are calibrated identically to obtain the overall CH3 / 1,000TC. The overall number of methyl chain ends per 1,000TC (overall number of CH3 ends / 1,000TC) is obtained by weight averaging the chain end correction over the molecular weight range according to the following equation:

[0482] w2b=f*total CH3 / 1,000TC

[0483] Total SCB / 1,000TC = Total CH3 / 1,000TC - Total CH3 terminal number / 1,000TC

[0484] Wherein the whole SCB / 1,000TC is converted to the whole w2 in the same manner as above.

[0485] The LS detector was an 18-angle Wyatt Technology High Temperature DAWN HELEOS II. The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972):

[0486]

[0487] Here, ΔR(θ) is the hyper-Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined by IR5 analysis, A2 is the second virial coefficient, P(θ) is the morphology factor of the monodisperse random coils, and Ko is the optical constant of the system:

[0488]

[0489] Where NA is Avogadro's number, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145°C and λ=665nm is n=1.500. For the analysis of polyethylene homopolymer, ethylene-hexene copolymer and ethylene-octene copolymer, dn / dc=0.1048 ml / mg and A2=0.0015; for the analysis of ethylene-butene copolymer, dn / dc=0.1048*(1-0.00126*w2) ml / mg and A2=0.0015, where w2 is the weight percent of butene comonomer.

[0490] Use high temperature Agilent (or Viscotek Corporation) viscometer (it has four capillaries arranged into Wheatstone bridge structure, has two pressure sensors) to measure specific viscosity.A sensor measures the total pressure drop at the two ends of the detector, and another sensor between the two sides of the bridge measures differential pressure.The specific viscosity η s of the solution flowing through the viscometer is calculated by their output.The limiting viscosity [η] at each point in the chromatogram is calculated by the following formula:

[0491] [η] = ηs / c,

[0492] Where c is the concentration and is determined by the IR5 broadband channel output. The viscosity MW at each point is calculated as where α ps is 0.67 and K ps It is 0.000175.

[0493] Branching index (g' vis ) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity [η] of the sample avg Calculated by the following formula:

[0494]

[0495] The summation is performed between the integration limits for each chromatographic slice i. The branching index g' vis is defined as Where Mv is the viscosity average molecular weight based on molecular weight determined by LS analysis, and K and α are for a reference linear polymer as described above for purposes of this disclosure and claims. Unless otherwise indicated, concentrations are in g / cm 3 The w2b value is calculated as described above, the molecular weight is expressed in g / mole, and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g.

[0496] 1 H NMR:1 H NMR data were taken at room temperature in a 5 mm probe 1 The H frequency was collected on a Varian spectrometer of at least 400 MHz. The data were recorded using a maximum pulse width of 45°C, an 8 sec pulse interval and a signal average of 120 transients.

[0497] Gel Permeation Chromatography (GPC): High temperature size exclusion chromatography was performed using the automated "Rapid GPC" system described in US Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407 and 6,294,388, each of which is incorporated herein by reference. Molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD = Mw / Mn, sometimes also referred to as the polydispersity (PDI) of the polymer) were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 5,000 and 3,390,000). Samples were run using three Polymer Laboratories PLgel 10 μm Mixed-B 300x7.5 mm columns in series at an eluent flow rate of 2.0 mL / min (250 μL of polymer TCB solution was injected into the system) (135°C sample temperature, 165°C oven / column). No column extension correction was used. The HPLC-MS / ... Numerical analysis was performed using AutomationStudio software available from Freeslate or AutomationStudio software available from Freeslate. Molecular weights obtained are relative to linear polystyrene standards and are reported in g / mol.

[0498] Differential scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting points (T m ). The sample was pre-annealed at 220°C for 15 minutes and then allowed to cool to room temperature overnight. The sample was then heated to 220°C at a rate of 100°C / min and then cooled at a rate of 50°C / min. Melting points were collected during the heating period.

[0499] FT-IR: The weight percentage of comonomer (hexene) incorporated into the polymer was determined by fast FT-IR spectroscopy on a Bruker Equinox 55+IR in reflection mode. The samples were prepared in thin film form by evaporative deposition technique.

[0500] Unless otherwise indicated, melt index (MI, also referred to as I2) is measured according to ASTM D1238 at 190°C under a load of 2.16 kg. The units of MI are g / 10 min or dg / min.

[0501] Unless otherwise indicated, high load melt index (HLMI, also referred to as 121) is measured according to ASTM D1238 at 190°C under a load of 21.6 kg.

[0502] The melt index ratio (MIR) is the ratio of the high load melt index to the melt index (I21 / I2).

[0503] Unless otherwise indicated, all molecular weights are reported in g / mol. Example

[0504] Unless otherwise indicated, all operations were performed in an inert N2-purged glove box. All anhydrous solvents were purchased from Fisher Chemical and degassed and dried over molecular sieves before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and dried over molecular sieves before use. n-Butyl lithium (2.5 M in hexane) was purchased from Sigma-Aldrich. Hafnium tetrachloride (HfCl4) 99+%, trifluoromethanesulfonic acid trimethylsilylmethyl ester were purchased from TCIAmerica and used as received. Potassium cyclopentadienyl (KCp) was prepared according to literature procedures. 1 HNMR measurements were recorded on a 400 MHz Bruker spectrometer.

[0505] Synthesis of trimethylsilylmethylcyclopentadiene (Me3SiCH2CpH). Pure trimethylsilylmethyl trifluoromethanesulfonate (25.0 g, 105.8 mmol) was dissolved in 300 mL of ether and cooled to -25 °C, then solid potassium cyclopentadiene (11.14 g, 106.9 mmol) was slowly added to the mixture over a period of 10 to 15 minutes. The resulting mixture was stirred overnight at room temperature. Insoluble matter was filtered out. Volatiles were carefully removed from the reaction mixture under dynamic vacuum to avoid evaporation of volatile trimethylsilylmethylcyclopentadiene (Me3SiCH2CpH). The reaction flask (250 mL round-bottom flask) and the sintered glass containing diatomaceous earth were weighed to calculate the yield of the extracted product. The crude material was then extracted into pentane (3x50 mL) and used without any further purification. Yield: 15.47 g (95.2%). The crude material was recorded. 1 H NMR spectroscopy ensured product formation. 1 HNMR (400MHz, C6D6): δ- 0.05 (9H, s, Si-CH3), 1.77 (2H, d, J HH =1.2Hz, Me3Si-CH2), 2.83 (1H, sex, J HH =1.5Hz, Cp-CH), 5.80-6.49 (4H, m, Cp-CH)ppm.

[0506] Synthesis of trimethylsilylmethylcyclopentadiene lithium (Me3SiCH2CpLi). A hexane solution of n-butyl lithium (41.5 mL, 103.8 mmol, 2.5 M solution) was added dropwise to a pre-cooled solution of Me3SiCH2CpH (15.47 g, 101.7 mmol) at -25°C (in a 1:1 mixture of 200 mL pentane and ether) over a period of 40-50 minutes. The resulting mixture was gradually warmed to room temperature and then stirred overnight. Volatiles were removed in vacuo, and the remaining crude material was thoroughly washed with pentane. The final material was vacuum dried to obtain a colorless crystalline solid of Me3SiCH2CpLi in a yield of 13.6 g (84.6%). 1 HNMR (400MHz, THF-d8): δ-0.09 (9H, s, Si-CH3), 1.84 (2H, s, Me3Si-CH2), 5.36 (2H, t, J HH =2.6Hz, Cp-CH), 5.47(2H, t, J HH =2.6 Hz, Cp-CH)ppm.

[0507] Double (η 5-trimethylsilylmethylcyclopentadienyl)hafnium dichloride ((Me3SiCH2Cp)2HfCl2). Solid HfCl4 (25.0 g, 78 mmol) was slurried in pre-cooled ether (300 mL) at -25°C. Solid Me3SiCH2CpLi (24.75 g, 156 mmol) was added over a period of 20-30 minutes. The resulting mixture was stirred at room temperature overnight. All volatiles were removed in vacuo, and the crude material was then extracted into dichloromethane. The solvent was removed under reduced pressure to give spectrally pure (Me3SiCH2Cp)2HfCl2 as a colorless solid in a yield of 31.0 g (72%). 1 HNMR (400MHzC6D6): δ-0.11(18H,s,SiMe3-CH3), 2.18(4H,s,Me3Si-CH2), 5.68(8H,s,Cp-CH)ppm.

[0508] Double (η 5 Synthesis of (Me3SiCH2Cp)2HfBu2) with ((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) (((Me3SiCH2Cp)2HfBu2) ((((Me3SiCH2Cp)2HfBu2) ((((((((((( 1 H NMR 400MHz, C6D6): δ0.02 (18H, s, SiMe3-CH3), 0.28-0.24 (4H, m, Hf-CH2), 1.06 (6H, t, Hf-CH3), 1.45- 1.43 (4H, m, Hf-CH2), 1.59-1.55 (4H, m, Hf-CH2), 1.84 (4H, s, Me3Si-CH2), 5.57 (4H, t, Cp-CH), 5.63 (4H, t, Cp-CH) ppm.

[0509] (η 5 -trimethylsilylmethylcyclopentadienyl) (η 5- Synthesis of hafnium dimethylsilyl (methylene) methylcyclopentadienyl) butylate ((Me3SiCH2Cp) (CpCH2Si(Me)2CH2-)HfBu) (Catalyst 1). (Me3SiCH2Cp)2HfBu2 (2.1 g, 3.5 mmol) was dissolved in toluene (50 mL) and then heated at 90°C. 1 The progress of the reaction was monitored by H NMR spectroscopy and was complete within 36 hours to form the tuck-in catalyst compound 1. The volatiles were removed from the reaction mixture in vacuo and the residue was triturated with hexanes. Removal of the solvent gave the desired CH activated product (Me3SiCH2Cp)(CpCH2Si(Me)2CH2-)HfBu as a thick yellow oil in a yield of 1.61 g (80.6%). 1 H NMR (400MHz, C6D6): δ-1.22(1H,d,Hf-CH2(n-Bu)), -0.02(3H,s,SiMe3-CH3), 0.00(9H,s,SiMe3-CH3), 0.22(3H, s, SiMe3-CH3), 0.25 (2H, d, Hf-CH2 (-CH2SiMe2-)), 0.79 (1H, d, Hf-CH2 (n-Bu)), 1.06 (3H, t, Hf-CH3 (n-Bu)), 1.47-1.38 (2H, m, Hf-CH2(n-Bu)), 1.63-1.52(2H, m, Hf-CH2(n-Bu)), 1.90-1.82(3H, m, Me3Si-CH2), 2.01 (1H, d, Me3Si-CH2), 5.05-5.01 (2H, m, Cp-CH), 5.47-5.44 (1H, m, Cp-CH), 5.53-5.50 (3H, m, Cp-CH), 5.70-5.68 (2H, m, Cp-CH), 6.05-6.03 (1H, m, Cp-CH) ppm.

[0510] SMAO-ES70-875: Methylaluminoxane treated silica was prepared as follows: In a 4 L stirred vessel in a dry box, methylaluminoxane (MAO, 30 wt% solution in toluene, approximately 1,000 g) was added along with approximately 2,000 g of toluene. The solution was then stirred at 60 RPM for 5 minutes. Next, approximately 800 g of ES-70-875 silica was added to the vessel. The resulting slurry was then heated at 100°C and stirred at 120 RPM for 3 hours. The temperature was then reduced to 25°C and cooled to that temperature over 2 hours. After cooling, the vessel was set to 8 RPM and placed under vacuum for 72 hours. After emptying the vessel and sieving the loaded MAO, approximately 1,100 g of loaded MAO was collected.

[0511] ES-70-875 silica is ES70 TM Silica (PQ Corporation, Conshohocken, Pennsylvania) which had been calcined at about 875°C. TM The silica was heated to 880°C at the following heating rate and then calcined at 880°C for 4 hours:

[0512] ℃ ℃ / h ℃ Ambient temperature 100 200 200 50 300 300 133 400 400 200 800 800 50 880

[0513] Supported catalyst 1 was prepared as follows:

[0514] In the Celestir container, (η 5 -trimethylsilylmethylcyclopentadienyl) (η 5 -dimethylsilyl(methylene)methylcyclopentadienyl)hafnium butylate ((Me3SiCH2Cp)(CpCH2Si(Me)2CH2-)HfBu, Catalyst 1) (0.016 g, 30.0 umol) was added to a slurry of 1.0 g SMAO-ES70-875 in 10 mL toluene. The slurry / mixture was stirred for 3 hours and then filtered, washed with toluene (1 x 10 mL) and then washed with hexanes (2 x 10 mL). The supported catalyst was then dried under vacuum for 18 hours.

[0515] The preparation of ES 757 was carried out using a method similar to that described in US Pat. No. 7,579,415. TM Catalyst 2 ((bis(1,3-methyl, n-butylcyclopentadienyl)zirconium dichloride) supported on silica and activated with MAO).

[0516] General procedure for high productivity ethylene / 1-hexene polymerization and polymer characterization (Table 1):

[0517] Preparation of catalyst slurry for high productivity experiments: 45 mg of supported catalyst was weighed into a 20 mL glass vial in a drying oven. 15 mL of toluene was added to the vial to prepare a slurry containing 3 mg of supported catalyst / mL of slurry. The resulting mixture was vortexed before injection.

[0518] Starting Material Preparation: Solvents polymerization grade toluene and isohexane were provided by ExxonMobil Chemical Company and were thoroughly dried and degassed prior to use. Polymerization grade ethylene was used and further purified by passing it through a series of columns: a 500 cc Oxyclear column from Labclear (Oakland, CA) followed by a column filled with dry 1% ethanol purchased from Aldrich Chemical Company. Molecular sieve 500cm 3 Columns were packed with dry Molecular sieve 500cm 3 TnOAl (tri-n-octylaluminum, pure) was used as a 2 mmol / L toluene solution.

[0519] Preparation of catalyst slurry for high productivity experiments: 45 mg of supported catalyst was weighed into a 20 mL glass vial in a drying oven. 15 mL of toluene was added to the vial to prepare a slurry containing 3 mg of supported catalyst / mL of slurry. The resulting mixture was vortexed before injection.

[0520] High Productivity Polymerization:

[0521] The transition metal compounds were loaded as detailed in the Examples above. Solvents Polymerization grade toluene and isohexane were provided by ExxonMobil Chemical Company and were thoroughly dried and degassed prior to use. Polymerization grade ethylene was used and further purified by passing it through a series of columns: 500 cm 3 Oxyclear TM The column was then filled with dry Molecular sieve 500cm 3 Column, and packed with dry Molecular sieve 500cm 3 TnOAl was used as a 2 mmol / L toluene solution.

[0522] Reactor Description and Preparation:

[0523] The polymerization reaction was carried out in an inert atmosphere (N2) dry box using an autoclave equipped with an external heater for temperature control, a glass insert (internal volume of the reactor = 22.5 mL), a septum inlet, a regulated supply of nitrogen, ethylene and hexene and equipped with a disposable PEEK mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen before use.

[0524] Ethylene / 1-hexene copolymer:

[0525] The reactor was prepared as described above and then purged with ethylene. Isohexane, 1-hexene and TnOAl were added via syringe at room temperature and atmospheric pressure. The reactor was then heated to process temperature (85°C) and ethylene was fed at process pressure (130 psig, 896 kPa).

[0526] Table 1 illustrates the results of polymers with different properties obtained by polymerization of ethylene in the presence of 300ppm H2 under stirring at 800RPM. Under process conditions, transition metal compounds (100μL of 3mg / mL toluene slurry, unless otherwise stated) were added to the reactor by syringe. TnOAl was used as 200μL of 20mmol / L isohexane solution. Ethylene was allowed to enter (by using a computer-controlled solenoid valve) the autoclave during polymerization to maintain the reactor gauge pressure (±2psig). The reactor temperature was monitored and usually maintained within ±1°C. The polymerization reaction was stopped by adding about 50psi O2 / Ar (5mol% O2) gas mixture to the autoclave for about 30 seconds. The polymerization was terminated after adding a predetermined cumulative amount of ethylene or after a maximum polymerization time of 45 minutes. In addition to the quenching time for each experiment, Table 1 also reports the final conversion of the added / consumed ethylene (in psi). The reactor was cooled and vented. The polymer was isolated after removing the solvent in vacuo. The polymer products were characterized by Rapid GPC, Rapid DSC and FTIR.

[0527] It is found that the catalyst compound represented by formula (II) such as catalyst compound 1 is an active catalyst compound for olefin polymerization. Table 1 illustrates the formation of a controlled ethylene-hexene copolymer composition using a catalyst system comprising catalyst compound 1 and SMAO-ES70-875 activator. In addition, it is found that catalyst compound 1 is a good comonomer introducing agent, For example, there is a 1-hexene comonomer content of about 13wt% (experiment 1). It is also observed that the polymer has a comonomer content lower than 13wt%, wherein the hexene wt% value is in the range of about 2.45wt%-about 12.9wt%. By using catalyst compound 1, a narrower PDI value (for example, from 1.99 to 2.64) is observed compared with the comparative catalyst compound 2. In addition, by using catalyst compound 1, the PDI value increases as the hexene comonomer content in the polymer product increases. This trend is not observed when using comparative catalyst compound 2 (Table 1, Experiment 7 to Experiment 12). Without being bound by theory, the increase in PDI values ​​with increasing hexene comonomer content when using catalyst compound 1 may be due to tuckin activation and ligand modification as hexene inserts at a higher frequency.

[0528] As shown in Table 1, Catalyst Compound 1 provides high molecular weight polyolefins (e.g., Mw of about 800,000 g / mol to about 2,300,000 g / mol). As the hexene content increases, Tm decreases (e.g., Experiment 1 compared to Experiment 6), with Tm values ​​of about 112° C. to 126° C. In addition, higher Mn values, Mw values, and Mz values ​​were observed when Catalyst Compound 1 was used in the polymerization process, compared to Comparative Catalyst Compound 2.

[0529] Table 1

[0530]

[0531]

[0532] * Fast GPC

[0533] Table 1 (continued)

[0534]

[0535] Polymerization Example in Autoclave: A 2-liter autoclave reactor (Parker Autoclave Engineers Research Systems) was filled with 200-400 grams of granular NaCl. The salt was stirred (impeller speed was 100 to 200 RPM) and heated to a temperature above 100°C for 60 minutes under a continuous nitrogen purge in the room. This process reduced the residual oxygen and moisture in the reactor and salt bed. A solid scavenger (4-6 grams, loaded on ES70 calcined at 100°C) was added. TM About 7-17wt% TiBAl on silica) was loaded into a Whitey sample cylinder and added to the reactor under nitrogen filling. The reactor was adjusted to the desired reactor temperature (85°C) and ambient pressure. 21ssc (scc = standard cubic centimeter) of hydrogen was loaded into the reactor using a Brooks mass flow controller. Then 40ml of isopentane at room temperature was added using a Whitey sample cylinder and high pressure nitrogen was injected. Using ratio control, 3.99ml of comonomer (1-hexene) was pushed into the reactor from a syringe pump (Teledyne Isco) while filling the reactor with ethylene to a total pressure of about 240psig. In a glove box under an inert atmosphere of nitrogen, the solid catalyst was loaded into a small injection tube. The catalyst injection tube was connected to the reactor, and the catalyst was quickly loaded into the reactor with high pressure nitrogen up to 300psig-350psig, and the polymerization reaction time of 60 minutes was monitored. Ethylene monomer was added continuously to maintain a constant total reactor pressure of 300 to 350psig. Nitrogen was continuously injected to maintain a constant ethylene partial pressure. Comonomer and hydrogen were continuously added and adjusted to maintain appropriate gas phase ratios of comonomer / ethylene and hydrogen / ethylene, as monitored by gas chromatography. After the above reaction time, the reactor was vented and cooled to ambient pressure and ambient temperature. The reaction products were collected and weighed to obtain an approximate yield. The product was transferred to a standard 4L beaker filled with 2,000mL of distilled water and soap. The solution was rapidly stirred for 5 minutes or longer using a magnetic stirring plate and a stirring bar. The solution was then transferred to a separatory funnel and then allowed to stand. Heavy particles that fell to the bottom of the solution were washed away. The polymer was washed until the remaining water was free of particles. The polymer was collected by filtering a flask, dried overnight in an oven at 100°C, and the weight was measured to obtain the final isolated yield. The reaction and characterization data are reported in Table 2.

[0536] Table 2 reports the Mn, Mw, Mz, Mw / Mn and g' of the polyethylene copolymer produced after polymerization at 85°C for 1 hour using supported catalyst compound 1 as determined by GPC-4D (vis)The catalyst productivity of catalyst compound 1 and compound 2 is also listed in Table 2. When catalyst compound 1 was used for polymerization, high hexene incorporation (comonomer content of 10.84 wt%) and high linearity (g' vis The value was 0.967). In addition, the polymer produced using catalyst compound 1 had a broad normal composition distribution, indicating that most of the comonomer was incorporated into the high molecular weight (HMW) polymer chains. In addition, higher MI values ​​and catalyst productivity values ​​were observed when catalyst compound 1 was used for polymerization, compared to comparative catalyst compound 2.

[0537] Table 2

[0538]

[0539] Figure 1 is a GPC-4D spectrum of a polyethylene copolymer formed by Catalyst Compound 1. As shown in Figure 1, a broad normal composition distribution is observed because the hexene content in the high molecular weight portion of the composition increases compared to the hexene content in the low molecular weight portion of the composition.

[0540] Figure 2 is the TREF diagram of the polymer prepared using catalyst compound 1. Figure 2 As shown in Figure 1, catalyst compound 1 provides a bimodal composition distribution with 80.1% of the low density resin eluting at 70° C. and 19.8% of the high density portion eluting at 89° C. Without being bound by theory, the BOCD behavior observed by GPC-4D and the bimodality of the composition observed by TREF may be related to the increase in PDI as hexene increases in the polymer.

[0541] In general, the catalysts, catalyst systems and methods of the present disclosure can provide the formation of high molecular weight polymers. The catalysts, catalyst systems and methods of the present disclosure can also provide polymers having a range of comonomer contents, such as from about 0.05 wt % to about 18 wt %. In particular, the present disclosure can provide new and improved hafnium-containing metallocene catalysts with increased molecular weight capabilities.

[0542] Unless otherwise indicated, the phrase "consisting essentially of..." does not exclude the presence of other steps, elements or materials, whether or not specifically mentioned in the specification, as long as such steps, elements or materials do not affect the basic and novel characteristics of the present disclosure. In addition, the phrase does not exclude impurities and variants that are normally associated with the elements and materials used.

[0543] For the reason of brevity, only some scope is clearly disclosed in this article.However, the scope starting from any lower limit can be combined with any upper limit to describe the scope not clearly mentioned, and the scope starting from any lower limit can be combined with any other lower limit to describe the scope not clearly mentioned. Similarly, the scope starting from any upper limit can be combined with any other upper limit to describe the scope not clearly mentioned. In addition, each point or each value included between its endpoints in a scope, even if not clearly mentioned. Therefore, each point or each value can be used as its own lower limit or upper limit, with any other point or each value or any other lower limit or upper limit combination, to describe the scope not clearly mentioned.

[0544] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent that they are not inconsistent with this article. As can be clearly known by the aforementioned general description and specific embodiments, although the form of the present disclosure has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not desired that the present disclosure is limited thereby. Similarly, the term "comprising" is considered to be synonymous with the term "including". Similarly, when there is a transition phrase "comprising" before a composition, an element or an element group, it should be understood that we also think of the same composition or element group, wherein the composition, the element or the element group is guided by the transition phrase "essentially consisting of...", "consisting of...", "selected from the group consisting of..." or "is", and vice versa.

[0545] While the disclosure has been described with reference to a number of embodiments and examples, those skilled in the art having benefit of this disclosure will appreciate that other embodiments may be devised which do not depart from the spirit and scope of the disclosure disclosed herein.

Claims

1. A catalyst compound represented by formula (I): in: M is hafnium; R 1 , R 2 , R 3 and R 4 Each of which is independently hydrogen, C1-C 40 unsubstituted hydrocarbon group, or R 16 -T 2 (R 17 )3, where R 16 is a C1-C4 hydrocarbon group, T 2 is Si, and each R 17 are independently C1-C5 unsubstituted hydrocarbon groups; R 5 , R 6 , R 7 , R 8 and R 9 Each of which is independently hydrogen, C1-C 40 Unsubstituted hydrocarbon, or –R 18 -T 3 (R 19 )3, where R 18 is a C1-C4 hydrocarbon group, T 3 is Si, and each R 19 are independently C1-C5 unsubstituted hydrocarbon groups; X 1 It is a monovalent anionic ligand; R 10 and R 11 Each of which is independently hydrogen or C1-C 20 Hydrocarbyl, or R 10 and R 11 joined together to form unsubstituted, saturated or partially unsaturated, cyclic or polycyclic substituents; R 12 and R 13 It is hydrogen; n is 1, 2, 3, 4 or 5; T 1 is Si; and R 14 and R 15 Independently C1-C 40 Unsubstituted hydrocarbon.

2. The catalyst compound of claim 1, wherein: R 1 , R 2 , R 3 and R 4 At least one of them is R 16 -Si(R 17 )3, where R 16 is a C1-C4 hydrocarbon group, and each R 17 are independently C1-C5 unsubstituted hydrocarbon groups; and R 5 , R 6 , R 7 , R 8 and R 9 At least one of them is –R 18 -Si(R 19 )3, where R 18 is a C1-C4 hydrocarbon group, and each R 19 are independently C1-C5 unsubstituted hydrocarbon groups.

3. The catalyst compound of any one of claims 1 to 2, wherein n is 1, and R 14 and R 15 It's methyl.

4. The catalyst compound of claim 1, wherein R 1 , R 2 , R 3 and R 4 Each of which is independently hydrogen or C1-C 40 Unsubstituted hydrocarbon.

5. The catalyst compound of claim 4, wherein R 1 , R 2 , R 3 and R 4 It's hydrogen.

6. The catalyst compound according to any one of claims 1 to 2, wherein R 5 , R 6 , R 7 , R 8 and R 9 One of them is -R 18 -Si(R 19 )3, where R 18 is a C1-C4 hydrocarbon group, each R 19 are independently C1-C5 unsubstituted hydrocarbon groups, and R 5 , R 6 , R 7 , R 8 and R 9 The fourth is hydrogen.

7. The catalyst compound of claim 6, wherein R 18 is a C1 hydrocarbon group and each R 19 It's methyl.

8. The catalyst compound of any one of claims 1 to 2, wherein n is 1, and R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 It's hydrogen.

9. The catalyst compound according to any one of claims 1 to 2, wherein X 1 Selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.

10. The catalyst compound of claim 9, wherein X 1 It's butyl.

11. The catalyst compound of claim 1, wherein the catalyst compound is one or more of the following compounds:

12. The catalyst compound of claim 11, wherein the catalyst compound is selected from:

13. A catalyst system comprising an activator and the catalyst compound of any one of claims 1 to 12.

14. The catalyst system of claim 13, further comprising a support material.

15. The catalyst system of claim 14, wherein the support material is selected from the group consisting of Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica / clay, or mixtures thereof.

16. The catalyst system of any of claims 13-15, wherein the activator comprises a non-coordinating anion activator.

17. The catalyst system of claim 16, wherein the activator is represented by the formula: (Z)d+(Ad-) wherein Z is (LH) or a reducible Lewis acid, L is a Lewis base; H is hydrogen; (LH)+ is a Bronsted acid; Ad- is a non-coordinating anion having a charge d-; and d is an integer from 1 to 3.

18. The catalyst system of claim 16, wherein the activator is represented by the formula: (Z)d+(Ad-) wherein Ad- is a non-coordinating anion having a charge of d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula: (Ar3C+), wherein Ar is an aryl group or an aryl group substituted with a heteroatom, C1-C 40 Hydrocarbon, or substituted C1-C 40 Hydrocarbon.

19. The catalyst system of claim 16, wherein the activator is one or more of the following: N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate, Dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, Dioctadecylmethylammonium tetra(perfluoronaphthyl)borate, Triphenylcarbonium tetrakis(pentafluorophenyl)borate, Trimethylammonium tetrakis(perfluoronaphthyl)borate, Triethylammonium tetra(perfluoronaphthyl)borate, Tripropylammonium tetrakis(perfluoronaphthyl)borate, Tri(n-butyl)ammonium tetra(perfluoronaphthyl)borate, Tri(tert-butyl)ammonium tetra(perfluoronaphthyl)borate, N,N-Dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-Diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, cycloheptatrienyl cation tetrakis(perfluoronaphthyl)borate, Triphenylcarbonium tetrakis(perfluoronaphthyl)borate, Triphenylphosphonium tetrakis(perfluoronaphthyl)borate, Triethylsilylium tetrakis(perfluoronaphthyl)borate, Benzene(diazo)tetra(perfluoronaphthyl)borate, Trimethylammonium tetrakis(perfluorobiphenyl)borate, Triethylammonium tetrakis(perfluorobiphenyl)borate, Tripropylammonium tetrakis(perfluorobiphenyl)borate, Tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate, Tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate, N,N-Dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-Diethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, cycloheptatrienyl cation tetrakis(perfluorobiphenyl)borate, Triphenylcarbonium tetrakis(perfluorobiphenyl)borate, Triphenylphosphonium tetrakis(perfluorobiphenyl)borate, Triethylsilylium tetrakis(perfluorobiphenyl)borate, Benzene(diazo)tetrakis(perfluorobiphenyl)borate, [4-tert-butyl-PhNMe2H][(C6F3(C6F5)2)4B], Trimethylammonium tetraphenylborate, Triethylammonium tetraphenylborate, Tripropylammonium tetraphenylborate, Tri(n-butyl)ammonium tetraphenylborate, Tri(tert-butyl)ammonium tetraphenylborate, N,N-Dimethylanilinium tetraphenylborate, N,N-Diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, cycloheptatrienyl cation tetraphenylborate, Triphenylcarbonium tetraphenylborate, Triphenylphosphonium tetraphenylborate, Triethylsilylium tetraphenylborate, Benzene(diazo)tetraphenylborate, Trimethylammonium tetrakis(pentafluorophenyl)borate, Triethylammonium tetrakis(pentafluorophenyl)borate, Tripropylammonium tetrakis(pentafluorophenyl)borate, Tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, Tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-Diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, cycloheptatrienyl cation tetrakis(pentafluorophenyl)borate, Triphenylcarbonium tetrakis(pentafluorophenyl)borate, Triphenylphosphonium tetrakis(pentafluorophenyl)borate, Triethylsilylium tetrakis(pentafluorophenyl)borate, Benzene(diazo)tetrakis(pentafluorophenyl)borate, Trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, Triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, Tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, Tri(n-butyl)ammonium tetra(2,3,4,6-tetrafluoro-phenyl)borate, Dimethyl(tert-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-Dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-Diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(2,3,4,6-tetrafluorophenyl)borate, Cycloheptatrienol cation tetrakis(2,3,4,6-tetrafluorophenyl)borate, Triphenylcarbonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, Triphenylphosphonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, Triethylsilylium tetrakis(2,3,4,6-tetrafluorophenyl)borate, Benzene(diazo)tetrakis(2,3,4,6-tetrafluorophenyl)borate, Trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-Dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-Diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Cycloheptatrienol tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Benzene(diazo)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate, Dicyclohexylammonium tetrakis(pentafluorophenyl)borate, Tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, Tris(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, Triphenylcarbonium tetrakis(perfluorophenyl)borate, 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, Tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, and triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

20. The catalyst system of claim 13, further comprising a metal olefinic chain transfer agent represented by the formula: <h2 style=";text-align:left;direction:ltr">Al(R')<h2 style=";text-align:left;direction:ltr"> 3-v <h2 style=";text-align:left;direction:ltr"> (R”)<h2 style=";text-align:left;direction:ltr"> v Where each R' is independently C1-C 30 Hydrocarbyl group; each R" is independently a C4-C 20 alkenyl; and v is 0.1-3.

21. The catalyst system of claim 13, wherein the activator comprises an alkylaluminoxane.

22. The catalyst system of claim 21 wherein the alkylaluminoxane is present in a molar ratio of aluminum to catalyst compound transition metal of 100:1 or greater.

23. A process for producing an ethylene-α-olefin copolymer, the process comprising: By reacting ethylene and at least one C3-C 20 The alpha-olefins are contacted with the catalyst system according to any one of claims 13 to 22 in at least one gas phase reactor at a reactor pressure of 0.7 bar to 70 bar and a reactor temperature of 20° C. to 110° C. to react the ethylene and the at least one C3-C 20 The α-olefin is polymerized to form an ethylene-α-olefin copolymer.

24. By making ethylene, at least one C3-C 20 An ethylene-alpha-olefin copolymer obtained by contacting an alpha-olefin with a catalyst system according to any one of claims 13 to 22 in at least one gas phase reactor, wherein the copolymer has a Mw value of 50,000 to 5,000,000, a Mn value of 100,000 to 2,000,000, a Mz value of 500,000 to 10,000,000, a Mw / Mn value of 1.2 to 10, a melt index of 0.05 g / 10 min to 100 g / 10 min, a melt index ratio of 12 to 100, and a branching index g' greater than 0.9 vis , and a comonomer content of 0.05 wt% to 18 wt%, wherein the Mw, Mn and Mz are determined using high temperature gel permeation chromatography.

25. By making ethylene, at least one C3-C 20 An ethylene-alpha-olefin copolymer obtained by contacting an alpha-olefin and a catalyst system according to any one of claims 13 to 22 in at least one gas phase reactor, wherein the copolymer has a Mw value of 500 to 100,000, a Mn value of 500 to 100,000, a Mz value of 500 to 500,000, a Mw / Mn value of 1.2 to 10, a melt index of 0.05 g / 10 min to 100 g / 10 min, a melt index ratio of 12 to 100, and a branching index g' greater than 0.9 vis , and a comonomer content of 0.05 wt% to 18 wt%, wherein the Mw, Mn and Mz are determined using high temperature gel permeation chromatography.

26. The ethylene-α-olefin copolymer of any one of claims 24 or 25, wherein the copolymer has a composition distribution breadth index of 50% or more.

27. The ethylene-alpha-olefin copolymer of any one of claims 24 or 25, wherein the copolymer has a bimodal molecular weight distribution as determined by gel permeation chromatography.

28. A method comprising the steps of: The intermediate compound represented by formula (II) is heated at a temperature of 70°C to 120°C for a period of 1 hour to 72 hours: in: M' is hafnium; R 1’ , R 2’ , R 3’ and R 4’ Each of which is independently hydrogen, C1-C 40 Unsubstituted hydrocarbon, or –R 16’ -T 2’ (R 17’ )3, where R 16’ is a C1-C4 hydrocarbon group, T 2’ is Si, and each R 17’ are independently C1-C5 unsubstituted hydrocarbon groups; R 5’ , R 6’ , R 7’ , R 8’ and R 9’ Each of which is independently hydrogen, C1-C 40 Unsubstituted hydrocarbon, or –R 18’ -T 3’ (R 19’ )3, where R 18’ is a C1-C4 hydrocarbon group, T 3’ is Si, and each R 19’ Independently C1-C 20 unsubstituted hydrocarbon; X 1’ and X 2’ Each of which is independently a monovalent anionic ligand; R 10’ and R 11’ Each of which is independently hydrogen or C1-C 20 Hydrocarbyl, or R 10’ and R 11’ joined together to form unsubstituted, saturated or partially unsaturated, cyclic or polycyclic substituents; n' is 1, 2, 3, 4 or 5; T 1’ is Si; and R 14’ and R 15’ Each of which is independently C1-C 40 unsubstituted hydrocarbon; R 20’ is methyl; and A catalyst compound represented by formula (I) is obtained: in: M is hafnium; R 1 , R 2 , R 3 and R 4 Each of which is independently hydrogen, C1-C 40 unsubstituted hydrocarbon group, or R 16 -T 2 (R 17 )3, where R 16 is a C1-C4 hydrocarbon group, T 2 is Si, and each R 17 are independently C1-C5 unsubstituted hydrocarbon groups; R 5 , R 6 , R 7 , R 8 and R 9 Each of which is independently hydrogen, C1-C 40 Unsubstituted hydrocarbon, or –R 18 -T 3 (R 19 )3, where R 18 is a C1-C4 hydrocarbon group, T 3 is Si, and each R 19 are independently C1-C5 unsubstituted hydrocarbon groups; X 1 It is a monovalent anionic ligand; R 10 and R 11 Each of which is independently hydrogen or C1-C 20 Hydrocarbyl, or R 10 and R 11 joined together to form unsubstituted, saturated or partially unsaturated, cyclic or polycyclic substituents; R 12 and R 13 It is hydrogen; n is 1, 2, 3, 4 or 5; T 1 is Si; and R 14 and R 15 Independently C1-C 40 Unsubstituted hydrocarbon.

29. The method of claim 28, wherein the heating comprises heating the intermediate compound represented by formula (II) at a temperature of 85°C to 95°C for a period of 30 hours to 40 hours.

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