Methylaluminoxane cocatalyst for limiting the hydrocarbyl modification of a geometry-controlled procatalyst

Abstract

A process for polymerizing olefin monomers. The process includes reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, wherein the catalyst system comprises: a hydrocarbyl-modified methylaluminoxane having less than 25 mole % of trihydrocarbyl aluminum compounds AlR A1 R B1 R C1 based on the total moles of aluminum, wherein R A1 , R B1 , and R C1 are independently linear (C1-C 40 ) alkyl, branched (C1-C 40 ) alkyl, or (C6-C 40 ) aryl; and one or more procatalysts comprising a metal-ligand complex according to formula (I):

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 053,348, filed July 17, 2020, the entire disclosure of which is hereby incorporated by reference. Technical Field

[0003] The embodiments disclosed herein generally relate to hydrocarbon-modified methylaluminoxane activators for use in catalyst systems including restricted geometry catalysts (CGC). Background Technology

[0004] Olefin-based polymers, such as polyethylene, are produced through various catalyst systems and polymerization methods. The choice of such catalyst system used in the polymerization of olefin-based polymers is an important factor contributing to the properties and characteristics of these polymers.

[0005] Polyolefin polymerization methods can be varied in many ways to produce a variety of resulting polyolefin resins with different physical properties suitable for different applications. It is generally known that polyolefins can be produced in solution-phase polymerization, gas-phase polymerization, and / or slurry-phase polymerization in the presence of one or more catalyst systems in one or more reactors (e.g., in series or parallel). The use of activators to activate pre-catalyst compositions in polyolefin polymerization methods is generally known.

[0006] While methylaluminoxanes (MAO) are well-suited for activating confined geometry (CGC) catalysts, they are generally incompatible with solution methods due to their limited solubility in hydrocarbon solvents. To increase solubility, MAO is modified with longer alkyl chains, resulting in modified methylaluminoxanes (MMAO), which have a mixture of methyl groups and longer alkyl groups present within their structure. The amount of modifier and trialkylaluminum (AlR3) is important for maintaining the solubility and stability of MMAO in hydrocarbon solvents.

[0007] As part of the catalyst composition in α-olefin polymerization, the activator may possess characteristics that favor the production of α-olefin polymers and the final polymer composition including α-olefin polymers. Activator properties that increase α-olefin polymer yield include, but are not limited to: rapid activation of the main catalyst, high catalyst efficiency, high temperature resistance, consistent polymer composition, and selective deactivation.

[0008] Borate-based cocatalysts have significantly contributed to a fundamental understanding of the mechanisms of olefin polymerization and have enhanced the ability to precisely control the microstructure of polyolefins through intentional tuning of catalyst structure and methods. This has led to a surge of interest in mechanistic studies and the development of novel homogeneous olefin polymerization catalyst systems with precise control over the microstructure and properties of polyolefins. However, once the cation of the activator or cocatalyst activates the main catalyst, the ionic ions of the activator can remain in the polymer composition. As a result, the borate anion can influence the polymer composition. In particular, the size of the borate anion, its charge, its interaction with the surrounding medium, and the dissociation energy of the borate anion with available counterions will affect the ability of ions to diffuse through the surrounding medium (such as solvents, gels, or polymer materials).

[0009] Modified methylaluminoxane (MMAO) is used as an activator in some PE processes. However, MMAO has been found to negatively impact the performance of some catalysts (such as CGC catalysts) and negatively affect the production of polyolefin or polyethylene resins: negative impacts on polymerization methods include reduced catalyst activity, broadened compositional distribution of the resulting polymer, and negative impacts on pellet handling. Summary of the Invention

[0010] There is a ongoing need to develop a catalyst system that maintains catalyst efficiency, reactivity, and the ability to produce polymers with good physical properties.

[0011] Embodiments of this disclosure include a method for polymerizing olefin monomers. In one or more embodiments, the method includes reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system. The catalyst system comprises a hydrocarbon-modified methylaluminoxane and a main catalyst. Based on the total molar number of aluminum, a trialkylaluminum compound AlR is present, having a content of less than 25 mol%... A1 R B1 R C1 Hydrocarbon-modified methylaluminoxane, wherein R A1 R B1 and R C1 Independently for straight chains (C1-C) 40 Alkyl, branched (C1-C) 40 )alkyl or (C6-C 40 aryl; and one or more metal-ligand complexes comprising formula (I) as the main catalyst:

[0012]

[0013] In equation (I), Ti represents titanium. (X) n The subscript n is 1, 2, or 3. Each X is independently selected from unsaturated (C2-C3) 50Hydrocarbons, unsaturated (C2-C) 50 ) heterohydrocarbons, saturated (C2-C 50 ( ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C6-C 50 )Aryl, (C6-C 50 Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C) 12 Diene, halogen, -N(R) N )2 and -NCOR C Monodentate or bidentate ligands. Metal-ligand complexes are electrically neutral overall.

[0014] In formula (I), Cp is selected from cyclopentadienyl and R S The group consisting of substituted cyclopentadienyl groups, where Cp is η 5 The bonding mode of Ti is combined, where R S Choose independently the following groups: (C1-C 20 )alkyl, (C1-C 20 (heteroalkyl, (C1-C) 20 )Aryl or R S Substituents (C1-C) 20 )Aryl, (C1-C 20 ) heteroaryl or R S Substituents (C1-C) 20 Heteroaryl groups, in which two adjacent R groups S Groups may be optionally linked to form a ring.

[0015] In equation (I), N is nitrogen. Y is carbon or silicon; where Y is covalently bonded to Cp; and R 1 and R 2 Independently selected from -H, (C1-C 40 ) hydrocarbon group and (C1-C 40 ) heterohydrocarbon group; and R 3 Independently selected from (C1-C 40 ) hydrocarbon group and (C1-C 40 ) heterohydrocarbon group. Detailed Implementation

[0016] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, the provision of embodiments makes this disclosure thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art.

[0017] The following is a list of common abbreviations:

[0018] Me: Methyl; Et: Ethyl; Ph: Phenyl; Bn: Benzyl; i-Pr: Isopropyl; t-Bu: Tert-Butyl; t-Oct: Tert-Octyl (2,4,4-Trimethylpentan-2-yl); Tf: Trifluoromethanesulfonate; THF: Tetrahydrofuran; Et2O: Diethyl ether; CH2Cl2: Dichloromethane; CV: Column volume (used in column chromatography); EtOAc: Ethyl acetate; C6D6: Deuterated benzene or benzene-d6; CDCl3: Deuterium Chloroform substitute; Na2SO4: Sodium sulfate; MgSO4: Magnesium sulfate; HCl: Hydrogen chloride; n-BuLi: n-Butyllithium; t-BuLi: Tert-Butyllithium; MAO: Methylaluminoxane; MMAO: Modified methylaluminoxane; GC: Gas chromatography; LC: Liquid chromatography; NMR: Nuclear magnetic resonance; MS: Mass spectrometry; mmol: Millimole; mL: Milliliter; M: Mole; min or mins: Minute; h or hrs: Hour; d: Day.

[0019] The term "independently selected" is used in this document to refer to R groups, such as R 1 R 2 R 3 R 4 and R 5 They can be the same or different (e.g., R) 1 R 2 R 3 R 4 and R 5 All can be substituted alkyl groups or R 1 and R 2 It can be a substituted alkyl group and R 3 (This could be an aryl group, etc.). Chemical names associated with the R group are intended to convey the chemical structure that is generally accepted in the art as corresponding to the chemical structure of the chemical name. Therefore, chemical names are intended to supplement and describe, rather than exclude, structural definitions known to those skilled in the art.

[0020] The term "pre-catalyst" refers to a transition metal compound that, when combined with an activator, exhibits catalytic activity for olefin polymerization. The term "activator" refers to a compound that chemically reacts with the main catalyst in a manner that converts the main catalyst into a catalytically active catalyst. As used herein, the terms "co-catalyst" and "activator" are interchangeable.

[0021] When used to describe certain carbon-containing chemical groups, it has the form "(C x -C y The insertion of ")" indicates that the unsubstituted form of the chemical group has x to y carbon atoms, including both x and y. For example, (C1-C 50Alkyl groups are alkyl groups having 1 to 50 carbon atoms in their unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted with one or more substituents such as RS. (Using "(C") x -C y Insert the defined R S The substituted chemical group can contain more than y carbon atoms, depending on any group R. S The identity. For example, "using exactly one group R..." S Replacement (C1-C) 50 ) alkyl, wherein R S "Phenyl (-C6H5)" can contain 7 to 56 carbon atoms. Therefore, it is common practice to use "(C6H5)" when referring to phenyl groups. x -C y The inserted chemical group is replaced by one or more carbon-containing substituents R. S During substitution, both x and y are added with substituents R from all carbon atoms. S The minimum and maximum total number of carbon atoms in a chemical group are determined by the sum of the combinations of carbon atoms.

[0022] The term "substitution" means that at least one hydrogen atom (-H) bonded to a carbon atom in the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R). S (Substitution). The term "-H" refers to a hydrogen atom or hydrogen group covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly stated otherwise.

[0023] The term "(C1-C)" 50 "alkyl" refers to a saturated straight-chain or branched hydrocarbon group containing 1 to 50 carbon atoms; and the term "(C1-C50)" is used to indicate a saturated straight-chain or branched hydrocarbon group. 30 "alkyl" refers to a saturated straight-chain or branched hydrocarbon group with 1 to 30 carbon atoms. Each (C1-C2) group... 50 )alkyl and (C1-C 30 Each alkyl group may be unsubstituted or substituted with one or more R groups. S Replacement. In some examples, each hydrogen atom in the hydrocarbon group can be replaced by R. S Substitution, such as, for example, trifluoromethyl. Unsubstituted (C1-C2) 50 Examples of alkyl groups are unsubstituted (C1-C1) alkyl groups. 20 )alkyl; unsubstituted (C1-C 10 Alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C1-C5)alkyl 40Examples of alkyl groups are substituted (C1-C2) 20 )alkyl, substituted (C1-C 10 )alkyl, trifluoromethyl and [C 45 Alkyl group. The term "[C]" 45 "Alkyl" means that the group including the substituent has a maximum of 45 carbon atoms and is, for example, an R of a (C1-C5) alkyl group (such as, for example, methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl). S Replacement (C) 27 -C 40 )alkyl.

[0024] Terminology (C3-C) 50 Alkenyl refers to a branched or unbranched, cyclic or acyclic monovalent hydrocarbon group containing 3 to 50 carbon atoms, at least one double bond, and is unsubstituted or bonded by one or more R groups. S Substitution. Unsubstituted (C3-C) 50 Examples of alkenyl groups: n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, and cyclohexadienyl. Substituted (C3-C) 50 Examples of alkenyl groups: (2-trifluoromethyl)pent-1-enyl, (3-methyl)hex-1-enyl, (3-methyl)hex-1,4-dienyl and (Z)-1-(6-methylhept-3-en-1-yl)cyclohex-1-enyl.

[0025] The term "(C3-C)" 50 "Cycloalkyl" refers to a saturated cyclic hydrocarbon group with 3 to 50 carbon atoms that is not substituted or is surrounded by one or more R groups. S Substitution. Other cycloalkyl groups (e.g., (C x -C y Cycloalkyl groups are defined in a similar manner as having x to y carbon atoms and being unsubstituted or derived from one or more R groups. S Replaced. Unreplaced (C3-C) 40 Examples of cycloalkyl groups are unsubstituted (C3–C4) cycloalkyl groups. 20 )cycloalkyl, unsubstituted (C3–C 10 Cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3–C) 40 Examples of cycloalkyl groups are substituted (C3–C4) cycloalkyl groups. 20 )cycloalkyl, substituted (C3–C 10 )cycloalkyl and 1-fluorocyclohexyl.

[0026] The term "halogen atom" or "halogen" refers to a free radical of a fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) atom. The term "halide" refers to the anionic form of a halogen atom: fluoride ion (F...). - ), chloride ions (Cl) - ), bromide ions (Br) - ) or iodide ions (I - ).

[0027] The term "saturated" refers to the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. In saturated chemical groups, the presence of one or more substituents R... S In the case of substitution, one or more double or triple bonds may optionally be present in the substituent R. S In Chinese, the term "unsaturated" means containing one or more carbon-carbon double or triple bonds, or (in groups containing heteroatoms) one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds, excluding those that may be present in the substituent R. S (If any) double bonds in an aromatic ring or a heteroaromatic ring.

[0028] The term "hydrocarbon-modified methylaluminoxane" refers to a methylaluminoxane (MAO) structure containing a certain amount of trialkylaluminum. Hydrocarbon-modified methylaluminoxanes comprise a combination of a hydrocarbon-modified methylaluminoxane base and trialkylaluminum. The total molar amount of aluminum in a hydrocarbon-modified methylaluminoxane consists of the aluminum contribution from the number of aluminum moles from the hydrocarbon-modified methylaluminoxane base and the aluminum contribution from the number of aluminum moles from the trialkylaluminum. Based on the total molar amount of aluminum in a hydrocarbon-modified methylaluminoxane, it comprises more than 2.5 mol% trialkylaluminum. These additional hydrocarbon substituents can influence the subsequent aluminoxane structure and lead to differences in the distribution and size of the aluminoxane clusters (Bryliakov, KP et al., Macromolecular Chemistry and Physics (Macromol. Chem. Phys. 2006, 207, 327-335). Additional hydrocarbon substituents can also impart increased solubility of the aluminoxane in hydrocarbon solvents such as, but not limited to, hexane, heptane, methylcyclohexane, and ISOPAR E. TM As demonstrated in US5777143. Modified methylaluminoxane compositions are generally disclosed and can be prepared as described in US5066631 and US5728855, which are incorporated herein by reference.

[0029] Modified methylaluminoxane (MMAO) can be described as a mixture of aluminoxane structures and trialkylaluminate compounds. Trialkylaluminate compounds, such as trimethylaluminum, are used as scavengers to remove impurities that may deactivate olefin polymerization catalysts during polymerization. However, trialkylaluminate compounds are believed to be active in some polymerization systems. Catalyst inhibition was observed when trimethylaluminum was present in propylene homopolymerization with a hafnium thiocyanate catalyst at 60 °C (Busico, V. et al., Macromolecules, 2009, 42, 1789-1791). However, these observations suggest a difference between MAO activation and borate activation, and even in direct comparisons, only some difference between trimethylaluminum and the absence of trimethylaluminum may be captured. Furthermore, it is unclear whether these observations extend to other catalyst systems, ethylene polymerization, or polymerization at higher temperatures. In any case, the preference for soluble MAO necessitates the use of MMAO and therefore the presence of trialkylaluminate compounds.

[0030] In one or more embodiments, the method includes reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system. The catalyst system comprises a hydrocarbon-modified methylaluminoxane and a main catalyst. Based on the total molar amount of aluminum, a trialkylaluminum compound AlR is present, having a content of less than 25 mol%... A1 R B1 R C1 Hydrocarbon-modified methylaluminoxane, wherein R A1 R B1 and R C1 Independently for straight chains (C1-C) 40 Alkyl, branched (C1-C) 40 )alkyl or (C6-C 40 aryl; and one or more metal-ligand complexes comprising formula (I) as the main catalyst:

[0031]

[0032] In formula (I), Ti is titanium with an oxidation state of +2, +3, or +4. (X) n The subscript n is 1, 2, or 3. Each X is independently selected from unsaturated (C2-C3) 50 Hydrocarbons, unsaturated (C2-C) 50 ) heterohydrocarbons, saturated (C2-C 50 ( ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C6-C 50 )Aryl, (C6-C 50 Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C) 12 Diene, halogen, -N(R) N )2 and -NCOR CMonodentate or bidentate ligands. Metal-ligand complexes are electrically neutral overall.

[0033] In formula (I), Cp is selected from cyclopentadienyl and R S The group consisting of substituted cyclopentadienyl groups, where Cp is η 5 The bonding mode of Ti is combined, where R S Choose independently the following groups: (C1-C 20 )alkyl, (C1-C 20 (heteroalkyl, (C1-C) 20 )Aryl or R S Substituents (C1-C) 20 )Aryl, (C1-C 20 ) heteroaryl or R S Substituents (C1-C) 20 Heteroaryl groups, in which two adjacent R groups S Groups may be optionally linked to form a ring.

[0034] In equation (I), N is nitrogen. Y is carbon or silicon; where Y is covalently bonded to Cp; and R 1 and R 2 Independently selected from -H, (C1-C 40 ) hydrocarbon group and (C1-C 40 ) heterohydrocarbon group; and R 3 Independently selected from (C1-C 40 ) hydrocarbon group and (C1-C 40 ) heterohydrocarbon group.

[0035] Embodiments of this disclosure include methods for polymerizing olefin monomers. In one or more embodiments, the method includes reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system.

[0036] In some embodiments, the olefin monomer is (C3-C4) 20 α-olefins. In other embodiments, the olefin monomer is not (C3-C4). 20 α-olefins. In various embodiments, the olefin monomer is a cyclic olefin.

[0037] In various embodiments, the polymerization method disclosed herein does not include a borate activator.

[0038] In some embodiments, the hydrocarbon-modified methylaluminoxane in the polymerization method has less than 20 mol% trialkylaluminum based on the total molar number of aluminum. In some embodiments, the hydrocarbon-modified methylaluminoxane has less than 15 mol% trialkylaluminum based on the total molar number of hydrocarbon-modified methylaluminoxane. In one or more embodiments, the hydrocarbon-modified methylaluminoxane has less than 10 mol% trialkylaluminum based on the total molar number of hydrocarbon-modified methylaluminoxane. In various embodiments, the hydrocarbon-modified methylaluminoxane is a modified methylaluminoxane.

[0039] In some implementations, trialkylaluminum has the formula AlR A1 R B1 R C1 , where R A1 R B1 and R C1 Independently for straight chains (C1-C) 20 alkyl, straight-chain (C1-C) 15 )alkyl or straight-chain (C1-C 12 )alkyl. In one or more embodiments, R A1 R B1 and R C1 Independently, it is methyl, ethyl, propyl, 2-propyl, butyl, n-octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments, R A1 R B1 and R C1 They are the same. In other implementations, R A1 R B1 and R C1 At least one of them is different from the other R A1 R B1 and R C1 .

[0040] In one or more implementations, R 1 and R 2 Independently for (C1-C) 12 )alkyl or (C6-C 20 )Aryl. In some implementations, R 1 and R 2 It can be methyl, ethyl, propyl or phenyl.

[0041] In various implementation schemes, R 3 Independently is (C1-C 12 )alkyl. In some embodiments, R 3 It can be tert-butyl, tert-octyl, or ortho-octyl independently.

[0042] In some implementations, Cp is tetramethylcyclopentadienyl.

[0043] In one or more embodiments, Cp is selected from:

[0044]

[0045]

[0046] In some embodiments, the chemical groups (e.g., X and R) of the metal-ligand complex of formula (I) 1-3 Any or all of them may be unsubstituted. In other embodiments, the chemical groups X and R of the metal-ligand complex of formula (I) are... 1-3 None of them were controlled by one or more Rs. S Replacement, or any one or all of them being replaced by one or more R S Replacement. When two or more R S When bonded to the same chemical group of a metal-ligand complex of formula (I), each R of the chemical group S It can be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, chemical groups X and R 1-3 None of them were R S Total substitution, or any or all of them, can be replaced by R. S Complete replacement. In the case of R S In fully substituted chemical groups, each R S They can all be the same or can be selected independently. In one or more implementations, R S Selected from (C1-C) 20 ) hydrocarbon group, (C1-C 20 )alkyl, (C1-C 20 ) heterohydrocarbon group or (C1-C 20 Heteroalkyl groups.

[0047] This type (C1-C) 12 Examples of alkyl groups include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl, cyclopentyl, or cyclohexyl, butyl, tert-butyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, decyl, undecyl, and dodecyl.

[0048] In the metal-ligand complex according to formula (I), X is bonded to Ti via covalent or ionic bonds. In some embodiments, X may be a monoanionic ligand with a net oxidation state of -1. Each monoanionic ligand may independently be a hydride, (C1-C2) 40 ) hydrocarbon-based carbanion, (C1-C 40Heteroalkyl carbanions, halide ions, nitrate ions, carbonate ions, phosphate ions, sulfate ions, HC(O)O - HC(O)N(H) - (C1-C) 40 )hydrocarbon C(O)O - (C1-C) 40 )hydrocarbon group C(O)N((C1-C 20 (hydrocarbon group) - (C1-C) 40 Hydrocarbon group C(O)N(H) - R K R L B - R K R L N - R K O - R K S - R K R L P - or R M R K R L Si - , where each R K R L and R M Independently hydrogen, (C1-C 40 ) hydrocarbon group or (C1-C 40 ) heterohydrocarbon group, or R K and R L Together they form (C2-C) 40 ) hydrocarbon group or (C1-C 20 ) heterohydrocarbon group and R M As defined above.

[0049] In some implementations, X is a halogen, unsubstituted (C1-C2) 20 ) hydrocarbon group, unsubstituted (C1-C) 20 ) hydrocarbon group C(O)O- or R K R L N-, where R K and R L Each of them is independently unsubstituted (C1-C) 20 ) hydrocarbon group. In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10 ) hydrocarbon group (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C6) 10 ) hydrocarbon group C(O)O- or R K R L N-, where RK and R L Each of them is independently unsubstituted (C1-C) 10 ) hydrocarbon group.

[0050] In another embodiment, X is selected from: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. X is methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine. In one embodiment, n is 2, and at least two X groups are independently monoanionic monodentate ligands. In a specific embodiment, n is 2, and the two X groups are coupled to form a bidentate ligand. In another embodiment, the bidentate ligand is 2,2-dimethyl-2-dimethylsilane-1,3-diyl or 1,3-butadiene.

[0051] In some implementations, X is a substituted benzyl or heteroarylbenzyl.

[0052] In one or more embodiments, X is a bidentate ligand selected from the following:

[0053] The heteroatoms are coordinated with titanium metal through coordination covalent bonds.

[0054] In one or more embodiments, each X is independently -(CH2)SiR X 3, where each R X Independently for (C1-C) 30 )alkyl or (C1-C 30 ) heteroalkyl, and at least one R X For (C1-C 30 )alkyl. In some embodiments, when R X One of them is (C1-C) 30 When it is a heteroalkyl group, the heteroatom is silicon dioxide or an oxygen atom. In some embodiments, R X It can be methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0055] In one or more embodiments, X is -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(CH2CH3); -(CH2)Si(CH3)(CH2CH3)2, -(CH2)Si(CH2CH3)3, -(CH2)Si(CH3)2 (n-butyl), -(CH2)Si(CH3)2 (n-hexyl), -(CH2)Si(CH3)(n-octyl)R X -(CH2)Si(n-octyl)RX 2. -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), -CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as -CH2Si(CH3)2CH2TMS). Optionally, in some embodiments, according to the metal-ligand complex of formula (I), exactly two R X Covalent connection or exactly three R X Covalent connection.

[0056] In some implementations, X is -CH2Si(R) C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q Where the subscript Q is 0, 1, 2 or 3, and each R C Independently substituted or unsubstituted (C1-C) 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C) 30 ) heterohydrocarbon group.

[0057] In some implementations, X is selected from unsaturated (C2-C) 50 Hydrocarbons, unsaturated (C2-C) 50 ) heterohydrocarbons or saturated (C2-C) 50 ( ) heterohydrocarbons. In various embodiments, X is butadiene, cyclopentadiene, or pent-1,3-diene.

[0058] In one or more embodiments, the olefin polymerization method is a solution polymerization method.

[0059] In solution processes used for olefin polymerization, catalysts and co-catalyst components, such as scavengers and activators, are typically added as a homogeneous solution. In many solution processes, the solvent is a non-aromatic hydrocarbon. Using a homogeneous solution allows for greater flexibility in process configuration and permits the use of delivery and storage containers that do not require internal stirring, which is typically used in heterogeneous solutions. Co-catalysts that can be used as activators and scavengers in olefin polymerization, such as methylaluminoxanes, are generally insoluble in non-aromatic hydrocarbons.

[0060] co-catalyst components

[0061] Catalytic activity can be achieved by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions, including metal-ligand complexes of formula (I). For example, the main catalyst of a metal-ligand complex according to formula (I) can be made catalytically active by contacting the complex with an activated co-catalyst or by combining the complex with an activated co-catalyst. Furthermore, the metal-ligand complex according to formula (I) comprises both a neutral main catalyst form and a catalytic form that may be positively charged due to the loss of monomeric ionic ligands (such as benzyl or phenyl). Suitable activated co-catalysts herein include oligomeric aluminoxanes or modified alkylaluminoxanes.

[0062] Polyolefins

[0063] The catalytic system described in the preceding paragraphs is used in the polymerization of olefins (primarily ethylene and propylene) to form ethylene-based or propylene-based polymers. In some embodiments, the polymerization scheme contains only a single type of olefin or α-olefin, thereby forming a homopolymer. However, additional α-olefins may be incorporated into the polymerization process. These additional α-olefin comonomers typically have no more than 20 carbon atoms. For example, α-olefin comonomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or alternatively, from the group consisting of 1-hexene and 1-octene.

[0064] Ethylene-based polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers (such as α-olefins), may contain at least 50 mol% of ethylene-derived monomer units. All individual values ​​and subranges covered by “at least 50 mol%” are disclosed herein as separate embodiments; for example, ethylene-based polymers, i.e., homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, may contain at least 60 mol% of ethylene-derived monomer units; at least 70 mol% of ethylene-derived monomer units; at least 80 mol% of ethylene-derived monomer units; or 50 mol% to 100 mol% of ethylene-derived monomer units; or 80 mol% to 100 mol% of ethylene-derived monomer units.

[0065] In some embodiments, the ethylene-based polymer may comprise at least 90 mol% of ethylene-derived units. All individual values ​​and subranges from at least 90 mol% are included herein and disclosed herein as separate examples. For example, the ethylene-based polymer may comprise at least 93 mol% of ethylene-derived units; at least 96 mol% of units; at least 97 mol% of ethylene-derived units; or alternatively, 90 mol% to 100 mol% of ethylene-derived units; 90 mol% to 99.5 mol% of ethylene-derived units; or 97 mol% to 99.5 mol% of ethylene-derived units.

[0066] In some embodiments of the ethylene-based polymer, the additional α-olefin is less than 50 mol%; other embodiments include at least 1 mol% to 25 mol%; and in still other embodiments, the additional α-olefin includes at least 5 mol% to 103 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0067] Ethylene polymers can be produced using any conventional polymerization process. Such conventional polymerization methods include, but are not limited to, solution polymerization, gas-phase polymerization, slurry polymerization, and combinations thereof, using one or more conventional reactors such as ring reactors, isothermal reactors, fluidized bed gas-phase reactors, stirred tank reactors, parallel or series batch reactors, or any combination thereof.

[0068] In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual-reactor system, such as a dual-loop reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more co-catalysts. In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual-reactor system, such as a dual-loop reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more other catalysts. The catalyst system described herein can optionally be used in combination with one or more other catalysts in either the first or second reactor. In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual-reactor system, such as a dual-loop reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of a catalyst system as described herein.

[0069] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single-reactor system (e.g., a monocyclic reactor system), wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described in this disclosure and optionally one or more co-catalysts as described in the preceding paragraphs.

[0070] Ethylene-based polymers may further include one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. Ethylene-based polymers may contain any amount of additives. Ethylene-based polymers may contain a combined weight of about 0 to about 10% of such additives based on the weight of the ethylene-based polymer and one or more additives. Ethylene-based polymers may further include fillers, which may include, but are not limited to, organic or inorganic fillers. Based on the combined weight of the ethylene-based polymer and all additives or fillers, the ethylene-based polymer may contain about 0 to about 20% by weight of fillers, such as calcium carbonate, talc, or Mg(OH)₂. Ethylene-based polymers may further be blended with one or more polymers to form blends.

[0071] In some embodiments, polymerization methods for producing ethylene-based polymers may include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system according to this disclosure. The density of the polymer produced by such a catalyst system incorporating a metal-ligand complex of formula (I) may, for example, be 0.850 g / cm³ according to ASTM D792 (incorporated herein by reference in its entirety). 3 Up to 0.950 g / cm 3 0.860 g / cm 3 Up to 0.920 g / cm 3 0.865g / cm 3 Up to 0.900 g / cm 3 0.860 g / cm 3 Up to 0.900 g / cm 3 0.860 g / cm 3 Up to 0.890 g / cm 3 Or 0.865g / cm 3 Up to 0.890 g / cm 3 .

[0072] In another embodiment, the polymer produced by the catalyst system according to this disclosure has a melt flow ratio (I 10The melt index I2 is between 5 and 15, where the melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190°C and a load of 2.16 kg, and the melt index I... 10 Measured according to ASTM D1238 at 190°C and a 10kg load. In other embodiments, the melt flow ratio (I 10 The melt flow ratio is 5 to 10, and in another embodiment, the melt flow ratio is 5 to 9.

[0073] In some embodiments, the polymer produced by the catalyst system according to the present disclosure has a molecular weight distribution (MWD) of 1 to 25, wherein MWD is defined as M w / M n M w The weight-average molecular weight and M n The molecular weight is the number average. In other embodiments, the polymer produced by the catalyst system has a molecular weight distribution (MWD) of 1 to 6. Another embodiment includes a MWD of 1 to 3; and other embodiments include a MWD of 1.5 to 2.5.

[0074] Due to the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer, the embodiments of the catalyst system described in this disclosure produce unique polymer properties.

[0075] One or more features of this disclosure are illustrated by the following embodiments:

[0076] Example

[0077] Procedure for batch reactor polymerization. Raw materials (ethylene, 1-octene) and process solvent (a high-purity isoparaffin solvent with a narrow boiling range, commercially available under the brand name ISOPAR E from ExxonMobil Corporation)) are purified using molecular sieves and then introduced into the reaction environment. ISOPAR E and 1-octene are charged into a one-gallon (3.79 L) stirred autoclave reactor. The reactor is then heated to the desired temperature and ethylene is added to reach the desired pressure. Hydrogen is also added at this point, if necessary. A catalyst composition is prepared in a drying oven under an inert atmosphere by mixing the desired pre-catalyst and one or more optional additives with an additional solvent to obtain a total volume of approximately 15 mL–20 mL. The activated catalyst mixture is then rapidly injected into the reactor. The reactor pressure and temperature are kept constant by feeding ethylene during the polymerization reaction and cooling the reactor as needed. After 10 minutes, the ethylene feed is shut off and the solution is transferred to a nitrogen-purged resin tank. The polymer is thoroughly dried in a vacuum oven, and the reactor is thoroughly rinsed with hot ISOPAR E between polymerization runs.

[0078] Test methods

[0079] Unless otherwise indicated herein, the following analytical methods are used to describe various aspects of this disclosure:

[0080] Melt Flow Index

[0081] The melt index I2 (or I2) and I of the polymer sample 10 (Or I10) Measured according to ASTM D-1238 at 190°C and under loads of 2.16 kg and 10 kg, respectively. Their values ​​are reported in g / 10 min. The fraction of the polymer sample is measured by collecting the product polymer from the reactor, which produces a specific fraction or portion of the polymer composition. For example, a first polyethylene fraction can be collected from the reactor, resulting in a lower density, higher molecular weight component of the polymer composition. The polymer solution is dried under vacuum prior to melt index measurement.

[0082] density

[0083] Samples for density measurement are prepared according to ASTM D4703. According to ASTM D792, Method B involves measuring the sample within one hour of pressing it.

[0084] Gel permeation chromatography (GPC)

[0085] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven chamber was set to 160°C, and the column chamber to 150°C. The columns used were four Agilent "Mixed A" 30cm 20µm linear mixed-bed columns and a 20µm pre-column. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen injection. The injection volume was 200µL, and the flow rate was 1.0mL / min.

[0086] The GPC column assembly was calibrated using 21 polystyrene standards with narrow molecular weight distributions, ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures, with individual molecular weights spaced at least tenfold apart. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standard was prepared in 50 mL of solvent; for molecular weights less than 1,000,000, 0.05 g of polystyrene standard was prepared in 50 mL of solvent. The polystyrene standards were dissolved at 80°C and gently stirred for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, *Journal of Polymer Science*, Vol. 6, p. 621 (1968)).

[0087] M 聚乙烯 =A×(M) 聚苯乙烯 ) B (Equation 1)

[0088] Where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0089] A fifth-order polynomial was used to fit the calibration point for the corresponding polyethylene equivalent. A small adjustment to A (approximately 0.375 to 0.445) was made to correct for column resolution and band broadening effects, resulting in linear homopolymer polyethylene standards at 120,000 Mw.

[0090] Plate counting was performed on the GPC column assembly using decane (prepared as 0.04 g in 50 mL TCB and dissolved under slow stirring for 20 min). Plate counts and symmetry were measured at 200 μL injections according to the following equations (Equation 2 and Equation 3):

[0091]

[0092] Where RV is the retention volume in milliliters, peak width is in milliliters, peak maximum is the maximum height of the peak, and 1 / 2 height is 1 / 2 the height of the peak maximum.

[0093]

[0094] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the position of the peak value, one-tenth height is 1 / 10 of the peak maximum height, and a subsequent peak refers to the tail of a peak whose retention volume is later than the peak maximum, while a preceding peak refers to the front of a peak whose retention volume is earlier than the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0095] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / ml. Solvent (containing 200 ppm BHT) was added to a pre-bubbled, diaphragm-capped vial using a PolymerChar high-temperature autosampler. The sample was then dissolved at 160°C for 2 hours with "low-speed" shaking.

[0096] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equations 4-6, the PolymerChar GPCOne was used. TM The software, baseline-subtracted IR chromatograms at each equally spaced data collection point (i), and polyethylene equivalent molecular weight (Mn) obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) Mw (GPC) and Mz (GPC) The calculation.

[0097]

[0098]

[0099]

[0100] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (nominal flow rate) for each sample by comparing the RV (RV(FM sample)) of the corresponding decane peak within the sample with the RV (RV(FM calibrated)) of the alkane peak within the narrow standard calibration. It was then assumed that any variation in the decane marker peak time was linearly related to the flow rate (effective flow rate) throughout the run. To achieve the highest accuracy in the RV measurement of the flow marker peak, a least-squares fitting procedure was used to fit the peak values ​​of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibration based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 7. (Supported by PolymerChar GPCOne) TM The software processes the flow marker peaks. Acceptable flow rate correction ensures that the effective flow rate is within + / - 0.5% of the nominal flow rate.

[0101] Flow rate (effective) = Flow rate (nominal) * (RV (FM calibrated) / RV (FM sample)) (Equation 7)

[0102] Hydrocarbon-modified methylaluminoxane (MMAO) is available from Nouryon’s office in Chicago, Illinois, USA, and Albemarle’s headquarters in Charlotte, North Carolina, USA.

[0103] Analysis of hydrocarbon-modified methylaluminoxane activators

[0104] In a nitrogen atmosphere glove box, AlR will be used. A1 R B1 R C1The aluminum-based analyte was transferred to a balanced flask and the mass of the sample was recorded. The sample was diluted with methylcyclohexane and then quenched with methanol. The mixture was vortexed and allowed to react for more than 15 minutes, then the sample was removed from the glove box. The sample was further hydrolyzed by adding H₂SO₄. The flask was capped and shaken for five minutes. Periodic venting of the flask may be necessary depending on the aluminum concentration. The solution was transferred to a separatory funnel. The flask was rinsed repeatedly with water, adding each rinse from the process to the separatory funnel. The organic layer was discarded, and the remaining aqueous solution was transferred to a volumetric flask. The separatory funnel was rinsed further with water, adding each rinse to the volumetric flask. The flask was diluted to a known volume, thoroughly mixed, and analyzed by complexation with excess EDTA followed by back titration with ZnCl₂ using xylenol orange as an indicator.

[0105] AlR in hydrocarbon-modified methylaluminoxane A1 R B1 R C1 Compound calculations

[0106]

[0107]

[0108] Analyze AlR using the previously described method. A1 R B1 R C1 Compound content (Macromol.Chem.Phys.1996,197,1537; WO2009029857A1; Analytical Chemistry 1968,40(14),2150-2153; and Organometallics 2013,32(11),3354-3362)

[0109] Metal complexes are conveniently prepared via standard metallization and ligand exchange procedures involving transition metal sources and neutral multifunctional ligand sources. Alternatively, complexes can be prepared from corresponding transition metal tetraamides and alkylating agents (such as trimethylaluminum) via amide elimination and alkylation methods. The techniques employed are identical or similar to those disclosed in U.S. Patent Nos. 6,320,005, 6,103,657, WO 02 / 38628, WO 03 / 40195, and US-A-2004 / 0220050.

[0110] The general synthesis of CGC catalysts can be found in US6884857B1. The synthesis method of complex A can be found in US Patent No. 5,470,993 A; the synthesis method of complex B can be found in US Patent No. 5,965,756A; the synthesis method of complex C can be found in PCT application No. WO 1998 / 006726A1; the synthesis method of complex D can be found in US Patent No. 6,268,444; and the synthesis method of complex E can be found in PCT application No. WO 2001 / 042315 A1.

[0111] Suitable cocatalysts include those compounds previously known in the art for use with Group 4 metal olefin polymerization complexes. Examples of suitable activating cocatalysts include neutral Lewis acids, such as (C1-C1)-C2 ... 30 Group 13 compounds with substituted hydrocarbon groups, particularly tri(alkyl)aluminum or tri(alkyl)boron compounds and their halogenated (including perhalogenated) derivatives, having 1 to 10 carbons in each hydrocarbon or haloalkyl group, more particularly perfluorinated tri(aryl)boron compounds, and most particularly tri(pentafluorophenyl)borane; nonpolymerizable, compatible, noncoordinated ion-forming compounds (including those used under oxidizing conditions), particularly ammonium salts, phosphonium salts, oxonium salts, caronium salts, silylonium salts or sulfonium salts using compatible noncoordinated anions, or ferroceneonium salts, lead salts or silver salts using compatible noncoordinated anions; and combinations of the above-mentioned cation-forming co-catalysts and techniques. The aforementioned activation cocatalysts and activation techniques have previously been taught in the following references regarding different metal complexes for olefin polymerization: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, US-A-5,321,106, US-A-5,721,185, US-A-5,350,723, US-A-5,425,872, US-A-5,625,087, US-A-5,883,204, US-A-5,919,983, US-A-5,783,512, WO 99 / 15534 and WO99 / 42467.

[0112] The main catalysts A, B, C, D, and E have structures according to formula (I) and are as follows:

[0113]

[0114] Table 1: Alkylaluminoxane co-catalyst compositions

[0115]

[0116] The cocatalysts C3 and C4 are hydrocarbon-modified methylaluminoxane (MMAO), which contains a combination of isobutyl groups and methyl groups in a ratio of approximately 1:2.

[0117] The cocatalyst I1 is a modified methylaluminoxane (MMAO) containing a combination of octyl and methyl groups in a ratio of approximately 1:6.

[0118] Example 1 - Batch reactor polymerization using CGC main catalyst and comparative activator and modified aluminoxane.

[0119] The main catalysts A and B were tested in a batch reactor using C1, C2, C3, or C4 as activators, and the data are summarized in Tables 1-2. When the catalysts were activated with the co-catalyst I1 of this invention, the dry weight efficiency was higher compared with the comparative activator C1 or C3.

[0120] Table 1: Batch reactor polymerization data using complexes A and B with comparative co-catalysts C1, C2, and C3 and I1. .

[0121]

[0122] Operating conditions: 120°C, ISOPAR E (1470g), 1-octene (100g), hydrogen (40mmol), and pressurized to a total pressure of 410psi with ethylene. a This run was performed by adding C3 with an Al:Ti ratio of 50.

[0123] For the comparative cocatalysts, the molar ratio of catalyst to activator among the C1 cocatalysts is 1.2 and 4. For each embodiment of the invention, the molar ratio of activator to catalyst is 100 or 500. The catalyst system of the present invention contains linear modified alkyl groups and a low molar percentage of AlR. A1 R B1 R C1 Aluminoxane content. With branched alkyl groups and high molar percentage of AlR. A1 R B1 R C1 Compared to borane activators (such as C3), C1, or aluminoxane systems, I1 exhibits improved efficiency when used to activate catalysts with limited geometries. At higher aluminum loadings, I1 also provides better activity than the borate activator C2. Overall, the use of these aluminoxanes improves catalyst activity and narrows the molecular weight distribution.

[0124] Table 2: Batch reactor polymerization data using comparative co-catalysts C1, C2, and C3 and I1 as the primary catalyst. .

[0125]

[0126] Operating conditions: 120°C, ISOPAR E (1470g), 1-octene (150g). Hydrogen (40mmol), pressurized to a total pressure of 150psi with ethylene. This operation was carried out by adding C3 with an Al:Ti ratio of 50. b Use ethylene-modified operation (175 psi).

[0127] All operations involving air-sensitive materials were performed in oven-dried Schlenk-type glassware under strict O2 and moisture exclusion conditions, connected to a high-vacuum line (10). -6 Alternatively, it can be carried out in an MnO-filled MRaun glove box with a high-capacity recirculator (less than 1 ppm O2). Argon (Airgas, pre-purified grade) is passed through a loaded MnO deoxygenation column and activated Davison gas. Purification was performed using molecular sieve columns. Ethylene (Air Gases) was purified by passing it through an oxygen / moisture trap (Matheson, model MTRP-0042-XX). Hydrocarbon solvents (n-pentane, n-hexane, 1-hexene, methylcyclohexane, and toluene) were dried using an activated alumina column according to the method described by Grubbs (see Pangborn, AB; Giardello, MA; Grubbs, RH; Rosen, RK; Timmers, FJ, Safe and Convenient Procedure for Solvent Purification. Organometallics, 1996, 15(5), 1518-1520) and then transferred from the Na / K alloy under vacuum. Benzene-d6 and toluene-d8 (Cambridge Isotope Laboratories, 99+ atoms %D) were stored in vacuum on the Na / K alloy and transferred under vacuum immediately before use. 1,2-Difluorobenzene and chlorobenzene-d5 were dried with CaH2 and distilled under vacuum. Chloroform-d3 and 1,1,2,2-tetrachloroethane-d2 (Cambridge Isotope Laboratory, 99+ atoms % D) were used as accepted.

[0128] Equipment Standards

[0129] Unless otherwise stated, all solvents and reagents were obtained from commercial sources and used as is. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by activated alumina, and in some cases by Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glove box were purified by activated alumina. The samples were stored on molecular sieves and then further dried. Glassware used for moisture-sensitive reactions was dried overnight in an oven before use. NMR spectra were recorded on a Varian 400-MR and VNMRS-500 spectrometer. LC-MS analysis was performed using a Waters e2695 SeparationsModule coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation was performed on an XBridge C18 3.5 μm 2.1 x 50 mm column using a gradient of acetonitrile to water from 5:95 to 100:0, with 0.1% formic acid as the ionizing agent. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax EclipsePlus C18 1.8μm 2.1x50mm column coupled to an Agilent 6230 TOF Mass Spectrometer with electrospray ionization. 1 The H NMR data are reported as follows: chemical shifts (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quadruplet, p = quintuplet, sex = hexatuplet, sept = heptet and m = multiplicity), integration, and assignment). Low-field data from the inner tetramethylsilane (TMS, scale δ) are reported using the protons remaining in the deuterated solvent as a reference. 1 Chemical shifts (in ppm) from H NMR data. 1 H-decoupling method was used to determine 13 C NMR data were used, and chemical shifts (in ppm) were reported from the low field of tetramethylsilane (TMS, scale δ) compared to using protons remaining in the deuterated solvent as a reference.

Claims

1. A polymerization method for polymerizing olefin monomers to prepare polyolefins, the method comprising reacting ethylene with, optionally, one or more C3–C... 20 α-olefin monomers react in the presence of a catalyst system, wherein the catalyst system comprises: Based on the total molar number of aluminum, the active trialkyl aluminum compound AlR has a molar percentage of less than 25%. A1 R B1 R C1 Hydrocarbon-modified methylaluminoxane, wherein R A1 R B1 and R C1 Independently for straight-chain C1-C 40 Alkyl, branched C3-C 40 Alkyl or C6-C 40 Aryl; and One or more master catalysts comprising metal-ligand complexes according to formula (I): in: Ti stands for titanium. n is 1, 2, or 3; Each X is independently selected from unsaturated C2−C 50 heterohydrocarbon groups, saturated C2−C 50 heterohydrocarbon groups, C1−C 50 Monodentate or bidentate ligands for hydrocarbon groups and halogens; The metal-ligand complex is electrically neutral overall; Cp is selected from cyclopentadienyl and R S The group consisting of substituted cyclopentadienyl groups, wherein Cp is in η 5 The bonding mode of Ti is combined, where R S Independently select from the following groups: C1−C 20 Alkyl, C1−C 20 Heteroalkyl, C1−C 20 Aryl or C1−C 20 Heteroaryl groups, in which two adjacent R groups S Groups may be optionally linked to form a ring; N is nitrogen; Y is carbon or silicon and covalently bonded to Cp; and R 1 and R 2 Independently selected from −H, C1−C 40 hydrocarbon groups and C1−C 40 heterohydrocarbon group; R 3 Independently selected from C1−C 40 hydrocarbon groups and C1−C 40 heterohydrocarbon group; The catalyst system described herein does not contain borate activators.

2. The polymerization method according to claim 1, wherein the hydrocarbon-modified methylaluminoxane has less than 20 mol% trialkylaluminum based on the total molar amount of aluminum in the hydrocarbon-modified methylaluminoxane.

3. The polymerization method according to claim 1 or claim 2, wherein the hydrocarbon-modified methylaluminoxane has less than 15 mol% trialkylaluminum based on the total molar amount of aluminum in the hydrocarbon-modified methylaluminoxane.

4. The polymerization method according to claim 1 or claim 2, wherein the hydrocarbon-modified methylaluminoxane has less than 10 mol% trialkylaluminum based on the total molar amount of aluminum in the hydrocarbon-modified methylaluminoxane.

5. The polymerization method according to claim 1 or claim 2, wherein R A1 R B1 and R C1 Independently, it is a straight-chain C1-C 20 alkyl.

6. The polymerization method according to claim 1 or claim 2, wherein R A1 R B1 and R C1 It is methyl, ethyl, propyl, 2-propyl, butyl, n-octyl, nonyl, decyl, undecyl, or dodecyl.

7. The polymerization method according to claim 1 or claim 2, wherein the polyolefin has a content of 0.865 g / cm³. 3 Up to 0.890 g / cm 3 Density within the range.

8. The polymerization method according to claim 1 or claim 2, wherein the polyolefin has a molecular weight in the range of 30,000 g / mol to 100,000 g / mol.

9. The polymerization method according to claim 1 or claim 2, wherein R 1 and R 2 Independently C1−C 12 Alkyl or C6−C 20 Aryl.

10. The polymerization method according to claim 1 or claim 2, wherein R 1 and R 2 It can be methyl, ethyl, propyl or phenyl.

11. The polymerization method according to claim 1 or claim 2, wherein R 3 Independently C1−C 12 alkyl.

12. The polymerization method according to claim 1 or claim 2, wherein R 3 It can be tert-butyl, tert-octyl, or ortho-octyl independently.

13. The polymerization method according to claim 1, wherein Cp is independently tetramethylcyclopentadienyl.

14. The polymerization method according to claim 1 or claim 2, wherein Cp is selected from: 。 15. The polymerization method according to claim 1 or claim 2, wherein the polymerization method is a solution polymerization reaction.

16. The polymerization method according to claim 1 or claim 2, wherein each X is cyclopentadienyl or a substituted cyclopentadienyl group.

17. The polymerization method according to claim 1, wherein each X is independently selected from unsaturated C2−C 50 hydrocarbon groups and C6−C 50 Monodentate or bidentate ligands of heteroaryl groups.

18. The polymerization method according to claim 1, wherein each X is independently selected from C6−C 50 Aryl and C4−C 12 Monodentate or bidentate ligands of diene groups.

19. The polymerization method according to claim 1 or claim 2, wherein R A1 R B1 and R C1 At least one of them is a linear C1-C 15 alkyl.

20. The polymerization method according to claim 1 or claim 2, wherein R A1 R B1 and R C1 At least one of them is a linear C1-C 12 alkyl.

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