Multimodal polymerization process using a multicatalyst system

Abstract

This disclosure relates to a method for producing ethylene-based polymers by reacting ethylene and optionally one or more olefin monomers in one or more reactors in the presence of a catalyst system and optionally hydrogen. The catalyst system comprises two or more catalysts, wherein at least one catalyst is derived from a bis(biphenylphenoxy) main catalyst according to formula (I), and wherein at least one catalyst is derived from a guanidine main catalyst according to formula (V):

Description

Cross-reference to related applications

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 594,830, filed on October 31, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0002] The embodiments disclosed herein generally relate to olefin polymerization catalyst systems and methods, and more specifically to olefin polymerization catalyst systems comprising one or more bis(biphenylphenoxy) master catalysts and one or more guanidine master catalysts, and polymerization methods incorporating catalyst systems to produce bimodal polymers. Background Technology

[0003] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, have been produced using various catalyst systems. The choice of such catalyst system used in the polymerization of olefin-based polymers is a crucial factor contributing to the characterization and properties of these polymers. Although research has focused on developing catalyst systems suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, there remains a need to improve the efficiency of catalyst systems capable of producing polymers with differentiated molecular weights. Summary of the Invention

[0004] The embodiments disclosed herein address this need by combining catalysts derived from two different classes—bis(biphenylphenoxy) metal-ligand complexes (BPP catalysts) and guanidine complexes (GD catalysts).

[0005] Unbound by theory, the weight-average molecular weight of polymers produced by the GD catalyst is far more sensitive to hydrogen than that of polymers produced by the BPP catalyst. Therefore, the molecular weight distribution (the difference in molecular weight of polyethylene produced by the two catalysts) can be tailored by adjusting the hydrogen level without significantly altering other conditions. Small changes in hydrogen levels (such as a 5 mmol change) result in significant differences in the molecular weight of polymers produced by the GD catalyst. In contrast, the same increase in H2 leads to smaller changes in the molecular weight of polymers produced by the BPP catalyst. Figures 1A, 1B, and 1C illustrate the molecular weight variations of polyethylene produced by the BPP and GD catalysts.

[0006] Embodiments of this disclosure include a method for producing an ethylene-based polymer, the method comprising reacting ethylene and optionally one or more olefin monomers in one or more reactors in the presence of a catalyst system and optionally hydrogen; the catalyst system comprising two or more catalysts, wherein at least one catalyst is derived from a bis(biphenylphenoxy) main catalyst according to formula (I), and wherein at least one catalyst is derived from a guanidine main catalyst according to formula (V), as described below.

[0007] Attached Figure Description

[0008] Figure 1A shows two theoretical molecular weight distribution curves for two single-peak polymer compositions produced by BPP in the absence of hydrogen in the reactor chamber and by guanidine catalyst.

[0009] Figure 1B shows two theoretical molecular weight distribution curves for two unimodal polymer compositions produced by BPP and by a guanidine catalyst in a reactor chamber with 5 to 10 mmol of hydrogen.

[0010] Figure 1C shows two theoretical molecular weight distribution curves for two single-peak polymer compositions produced by BPP and by a guanidine catalyst in a reactor chamber with 20 mmol to 40 mmol of hydrogen.

[0011] Figure 2 These are molecular weight distribution curves of bimodal polymer compositions produced by BPP-1 and GD-1 reactors in the presence of different amounts of hydrogen in the reactor chamber. The amounts of hydrogen were 5 mmol, 20 mmol, and 40 mmol.

[0012] Figure 3 These are molecular weight distribution curves of bimodal polymer compositions produced by BPP-2 and GD-1 reactors in the presence of varying amounts of hydrogen in the reactor chamber. The amounts of hydrogen were 5 mmol, 20 mmol, and 40 mmol.

[0013] Figure 4 These are molecular weight distribution curves of bimodal polymer compositions produced by BPP-1 and GD-2 reactors in the presence of varying amounts of hydrogen in the reactor chamber. The amounts of hydrogen were 5 mmol, 20 mmol, and 40 mmol.

[0014] Figure 5These are molecular weight distribution curves of bimodal polymer compositions produced by BPP-1 and GD-3 in a reactor chamber with varying amounts of hydrogen: 5 mmol, 20 mmol, and 40 mmol. Detailed Implementation

[0015] Specific embodiments of the catalyst system will 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, providing 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.

[0016] The following is a list of common abbreviations:

[0017] R, Z, M, X, and n: as defined above; 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: deuterated chloroform; Na2SO4: sodium sulfate; MgSO4: magnesium sulfate; HCl: hydrogen chloride; n-BuLi: butyllithium; t-BuLi: tert-butyllithium; Cu2O: copper oxide (I); N,N'-DMEDA: N,N'-dimethylethylenediamine; K3PO4: tripotassium phosphate; Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium dichloride (II); PdCl (crotyl)Amphos: Chloro(crotyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II); Pd(dppf)Cl2: [1,1'-bis(diphenylphosphine)ferrocene]palladium(II) dichloride; AgNO3: Silver nitrate; K2CO3: Potassium carbonate; Cs2CO3: Cesium carbonate; i-PrOBPin: 2-Isopropoxy-4,4,5,5-Tetramethyl-1,3,2-dioxaborane; Br Cl2CCCl2Br: 1,2-Dibromotetrachloroethane; N2: Nitrogen; PhMe: Toluene; PPR: Parallel Pressure Reactor; MAO: Methylaluminoxane; MMAO: Modified Methylaluminoxane; GC: Gas Chromatography; GPC: Gel Permeation Chromatography; LC: Liquid Chromatography; NMR: Nuclear Magnetic Resonance; MS: Mass Spectrometry; mmol: millimole; mL: milliliter; M: mole; min or mins: minutes; h or hrs: hours; d: days; R fRetention fraction; TLC: Thin-layer chromatography; rpm: Rotational speed per minute; LogM: Logarithm of molecular weight; dWf: Change in weight fraction; dLogM: Logarithmic change in molecular weight; Mw: Weight-average molecular weight; Mn: Number-average molecular weight; Mz: z-mean molar mass.

[0018] The multiple options following the term "independently selected" are used in this document to refer to the various R groups that appear before the term, such as R 1 R 2 R 3 R 4 and R 5 They can be the same or different, without depending on the identity of any other groups appearing before the term.

[0019] The term "primary catalyst" refers to a compound that exhibits catalytic activity when combined with an activator. The term "activator" refers to a compound that reacts chemically with the primary catalyst in a manner that converts the primary catalyst into a catalytically active catalyst. As used herein, the terms "co-catalyst" and "activator" are interchangeable.

[0020] When used to describe certain carbon-containing chemical groups, the form is "(C x -C y The parenthetical expression “)” indicates that the unsubstituted form of the chemical group has x to y carbon atoms (inclusive). For example, (C1-C 50 Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be such as R S One or more substituents are substituted. Use "(C x -C y The chemical groups defined in parentheses () are R S The form of substitution can be based on any group R S The property contains more than y carbon atoms. For example, "exactly bound by a group R". S Replacement (C1-C) 50 ) alkyl, wherein R S The phenyl group (-C6H5) can contain 7 to 56 carbon atoms. Therefore, it is common practice to use the parenthetical phrase "(C6H5)" when referring to phenyl groups. x -C y The chemical group defined as ")" is substituent for one or more carbon atoms 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.

[0021] The term "substitution" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is substituted by a substituent (e.g., R). S Substitution. The term "total substitution" means that each hydrogen atom (H) bonded to the carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R). S Substitution. The term "multi-substitution" means that at least two, but fewer than all, of the hydrogen atoms bonded to the carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen group covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly stated otherwise.

[0022] The terms "halogen atom", "halogen", "halogen", "saturated", "unsaturated", and "(C1-C)" are used to describe the properties of halogen atoms, halogens, halides, saturated, unsaturated, and (C1-C) compounds. 50 )hydrocarbon group", (C1-C 50 )alkyl", (C1-C 18 )alkyl", (C6-C 50 )Aryl", (C3-C 50 )cycloalkyl", (C1-C 50 )alkylene", "heteroatom" and "(C1-C 50 "Heteroalkyl" is defined as in publication number WO2020185494A1.

[0023] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different types. Therefore, the general term polymer encompasses the term "homopolymer," which is typically used to refer to polymers prepared from only one type of monomer, and the term "copolymer," which refers to polymers prepared from two or more different monomers.

[0024] "Polyethylene" or "ethylene-based polymer" should mean a polymer comprising more than 50% by weight of units derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include low-density polyethylene (LDPE); linear low-density polyethylene (LLDPE); ultra-low-density polyethylene (ULDPE); very low-density polyethylene (VLDPE); single-point catalytic linear low-density polyethylene, including both linear low-density resins and substantially linear low-density resins (m-LLDPE); medium-density polyethylene (MDPE); and high-density polyethylene (HDPE).

[0025] As used herein, "multimodal" refers to a polymer produced by multiple polymer fractions, each produced by a different catalyst. Multimodal polymers can include bimodal polymers with two polymer fractions, trimodal ethylene-based polymers with three polymer fractions, or polymers with more than three polymer fractions.

[0026] Embodiments of this disclosure include a method for producing an ethylene-based polymer, the method comprising reacting ethylene and optionally one or more olefin monomers in one or more reactors in the presence of a catalyst system and optionally hydrogen.

[0027] The catalyst system comprises one or more bis(biphenylphenoxy) main catalysts according to formula (I) and one or more guanidine main catalysts according to formula (V).

[0028] Embodiments of this disclosure include a catalyst system comprising one or more bis(biphenylphenoxy) main catalysts according to formula (I):

[0029]

[0030] In formula (I), M1 is titanium, zirconium, hafnium, scandium, or yttrium; m is 1 or 2; n is 0, 1, or 2; and each X is an independently selected monodentate ligand from the following: (C1-C 50 ) hydrocarbon group, (C1-C 50 heteroalkyl groups, -CH2Si(R) C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q -CH2Ge(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3-Q (OR C ) Q -P(R) C ) 2-W (OR C ) W -P(O)(R C ) 2-W (OR C ) W -N(R) C )2、-NH(RC ), -N(Si(R) C )3)2、-NR C Si(R C )3、-NHSi(R C 3. -OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C )2、-N=CH(R C -N=CH2, -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R) C )C(O)R C -N(R) C )C(O)H、-NHC(O)R C -C(O)N(R) C )2、-C(O)NHR C -C(O)NH2, halogens, B(R) Y 4. Al(R) Y )4 or Ga(R Y )4 or hydrogen, where each R C Independently for (C1-C) 30 ) hydrocarbon group or (C1-C 30 ( ) heterohydrocarbon groups, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each R Y -H, (C1-C 30 A hydrocarbon group or halogen atom, wherein the X and Y ligands can link together to form a ring. Metal-ligand complexes are electrically neutral as a whole.

[0031] In the metal-ligand complex according to formula (I), each Y is bonded to M1 via a coordinate or ionic bond. In one or more embodiments, Y is a Lewis base. A Lewis base can be a compound or an ionic substance that can donate an electron pair to the acceptor compound. For the purposes of this specific embodiment, the acceptor compound is M1, which is the metal of the metal-ligand complex of formula (I). A Lewis base can be neutral or anionic. In some embodiments, a Lewis base can be a heterohydrocarbon or an unsaturated hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cyclic ethers, or sulfides. Examples of anionic hydrocarbons include, but are not limited to, cyclopentadienyl groups. Examples of neutral hydrocarbon Lewis bases include, but are not limited to, 1,3-butadiene.

[0032] In some implementations, the Lewis base is (C1-C1) 20 In some embodiments, the Lewis base is cyclopentadiene or 1,3-butadiene. In various embodiments, the Lewis base is (C1-C2) hydrocarbon. 20 The heteroatom of the heterohydrocarbon is oxygen. In some embodiments, Y is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0033] Additionally, each X and each Y can be a monodentate ligand, independent of any other ligand X and Y, and is halogenated, 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 R K and R L Each of them is independently unsubstituted (C1-C) 10 ) hydrocarbon group. In one or more embodiments of formula (I), X is benzyl, chlorine, -CH2SiMe3 or phenyl.

[0034] In another embodiment, each X and / or each Y is selected from: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. In some embodiments, each X is the same. In other embodiments, at least two Xs are different from each other. In embodiments in which at least two Xs are different from at least one X, X is one of the following: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine. In another embodiment, the bidentate ligand is 2,2-dimethyl-2-dimethylsilane-1,3-diyl or 1,3-butadiene.

[0035] In some embodiments, the chemical groups (e.g., X, Y, and R) of the metal-ligand complex of formula (I) 1 -R 16 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 -R 16 None of them, any one or all of them can be 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 -R 16 None, any, or all of them can be 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 they can be chosen independently.

[0036] In equation (I), L is (C1-C 40 ) hydrocarbon group or (C2-C 40 ( ) Heteroalkyl group. In one or more embodiments, L is selected from -CH2(CH2). m CH2-、-CH2Si(R C (R) D CH2-, -CH2Ge(R) C (R) D CH2-, -CH2(CH3)CH2CH*(CH3), bis(methylene)cyclohexyl-1,2-diyl; -CH2CH(R C CH2-, -CH2C(R) C )2CH2-, where each R in L C For (C1-C 20 ) hydrocarbon group, and R in L D For (C1-C 20 ) hydrocarbon group.

[0037] R 1 and R 16 Independently select from the following groups: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C )3、-P(R P )2、-N(R N )2、-OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、-N=C(R C )2、R CC(O)O-、R C OC(O)-, R C C(O)N(R)-、(R C )2NC(O)-, halogens, groups having formula (II), groups having formula (III), and groups having formula (IV):

[0038]

[0039] Where R 31-35 R 41-48 and R 51-59 Each of them is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C )3、-P(R P )2、-N(R N )2、-OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-, R C C(O)N(R N )-、(R C )2NC(O)- or halogen.

[0040] The group R in the metal-ligand complex of formula (I) 1 and R 16 They choose independently of each other. For example, R 1 It can be selected from groups having formula (II), (III) or (IV), and R 16 It can be (C1-C) 40 ) hydrocarbon group; or R 1 It can be selected from groups having formula (II), (III) or (IV), and R 16 Can be selected from R 1 Identical or different groups having formula (II), (III), or (IV). R 1 and R 16 Both can be groups having formula (II), wherein group R 31-35 In R 1 and R 16 The same or different. In other examples, R 1 and R 16Both can be groups having formula (III), where group R 41-48 In R 1 and R 16 The same or different; or R 1 and R 16 Both can be groups having formula (IV), where group R 51-59 In R 1 and R 16 The same or different.

[0041] In some implementation schemes, R 1 and R 16 At least one of them is a group having formula (II), wherein R 32 and R 34 It is tert-butyl. In one or more embodiments, R 32 and R 34 For (C1-C 12 ) hydrocarbon group or -Si[(C1-C 10 [alkyl]3.

[0042] In some implementations, when R 1 Or R 16 When at least one of them is a group having formula (III), R 43 and R 46 One or both of them are tert-butyl, and R 41-42 R 44-45 and R 47-48 For -H. In other implementations, R 42 and R 47 One or both of them are tert-butyl, and R 41 R 43-46 and R 48 For -H. In some implementations, R 42 and R 47 Both are -H. In various implementation schemes, R 42 and R 47 For (C1-C 20 ) hydrocarbon group or -Si[(C1-C 10 [alkyl]3. In other embodiments, R 43 and R 46 For (C1-C 20 ) hydrocarbon group or -Si(C1-C 10 [alkyl]3. In some embodiments, R 42 and R 43 Connect to form a ring structure, and R 46 and R 47 Connect to form a ring structure.

[0043] In the implementation plan, when R 1 Or R 16 When at least one of them is a group having formula (IV), each R 52 R 53 R 55 R 57 and R 58 -H, (C1-C 20 ) hydrocarbon group, -Si[(C1-C 20 [(C1-C)]3 or -Ge[(C1-C) 20 [3.] Hydrocarbon group. In some implementations, R 52 R 53 R 55 R 57 and R 58 At least one of them is (C3-C) 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10 [alkyl]3. In one or more embodiments, R 52 R 53 R 55 R 57 and R 58 At least two of them are (C3-C) 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10 [alkyl]3. In various embodiments, R 52 R 53 R 55 R 57 and R 58 At least three of them are (C3-C) 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10 [alkyl]3.

[0044] In some implementations, when R 1 Or R 16 When at least one of them is a group having formula (IV), R 52 R 53 R 55 R 57 and R 58 At least two of them are (C1-C 20 ) hydrocarbon group or -C(H)2Si[(C1-C 20 [3] )hydrocarbon group.

[0045] (C3-C 10Examples of alkyl groups include, but are not limited to: propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl.

[0046] In some embodiments of the metal-ligand catalyst according to formula (I), R 1 and R 16 Selected from 3,5-di-tert-butylphenyl; 2,4,6-trimethylphenyl; 2,4,6-triisopropylphenyl; 3,5-diisopropylphenyl; carbazolyl; carbazo-9-yl, 1,2,3,4-tetrahydrocarbazolyl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl; 3,6-bis-(3,5-di-tert-butylphenyl)carbazo-9-yl; 3,6-bis-(2,4-di-tert-butylphenyl)carbazo-9-yl; 3,6-Trimethylphenyl)carbazole-9-yl; 3,6-bis-(2,4,6-triisopropylphenyl)carbazole-9-yl; 2,7-di(tert-butyl)carbazole-9-yl; 2,7-di(tert-octyl)carbazole-9-yl; 2,7-diphenylcarbazole-9-yl; 2,7-bis(2,4,6-trimethylphenyl)carbazole-9-ylanthrayl; 1,2,3,4-tetramethylphenyl)carbazole-9-ylanthrayl Hydroanthracite; 1,2,3,4,5,6,7,8-octahydroanthracite; phenanthrene; 1,2,3,4,5,6,7,8-octahydrophenanthrene; 1,2,3,4-tetrahydronaphthyl; 2,6-dimethylphenyl; 2,6-diisopropylphenyl; 3,5-diphenylphenyl; 1-naphthyl; 2-methyl-1-naphthyl; 2-naphthyl; 1,2,3,4-tetrahydronaphth-5-yl; 1,2 3,4-Tetrahydronaphthyl-6-yl; anthracene-9-yl; 1,2,3,4-tetrahydroanthracene-9-yl; 1,2,3,4,5,6,7,8-octahydroanthracene-9-yl; 1,2,3,4,5,6,7,8-octahydrophenanthrene-9-yl; indole; dihydroindole; quinolinyl; 1,2,3,4-tetrahydroquinolinyl; isoquinolinyl; or 1,2,3,4-tetrahydroisoquinolinyl.

[0047] In equation (I), R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 and R 15 Independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C )3、-P(R P )2、-N(R N )2-OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-, R C C(O)N(R)-、(R C )2NC(O)- and halogens. Each R in formula (I) C R P and R N Independently for (C1-C) 30 ) hydrocarbon group, (C1-C 30 () Heterohydrocarbon group or -H.

[0048] In various implementation schemes, R 3 and R 14 For (C1-C 24 )alkyl. In one or more embodiments, R 3 and R 14 (C4-C) 24 )alkyl. In some embodiments, R 3 and R 14 The compounds are 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In the embodiments, R 3 and R 14 For -OR C , where R C For (C1-C 20 ) hydrocarbons, and in some embodiments, R C It can be methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl) or 1,1-dimethylethyl.

[0049] In one or more implementations, R 8 and R 9 One of them is not -H. In various implementation schemes, R 8 and R 9 At least one of them is (C1-C 24)alkyl. In some embodiments, R 8 and R 9 Both are (C1-C 24 )alkyl. In some embodiments, R 8 and R 9 It is methyl. In other embodiments, R 8 and R 9 It is a halogen.

[0050] In some implementation schemes, R 3 and R 14 R is methyl; in one or more embodiments, R 3 and R 14 (C4-C) 24 )alkyl. In some embodiments, R 8 and R 9 It is 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl.

[0051] In various implementation schemes, in the metal-ligand complex of formula (I), R 6 and R 11 It is a halogen. In some implementations, R 6 and R 11 For (C1-C 24 )alkyl. In various embodiments, R 6 and R 11 Independently selected from methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 It is tert-butyl. In the implementation plan, R 6 and R 11 For -OR C , where R C For (C1-C 20 ) hydrocarbon group, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), or 1,1-dimethylethyl. In other embodiments, R 6 and R 11 -SiR C 3, where each RC Independently for (C1-C) 20 ) hydrocarbon group, and in some embodiments, R C It can be methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl) or 1,1-dimethylethyl.

[0052] In some implementations, in the metal-ligand complex according to formula (I), R 8 and R 9 All are methyl. In other embodiments, R 8 and R 9 One of them is methyl, and R 8 and R 9 The other one is -H.

[0053] Embodiments of this disclosure include a catalyst system comprising one or more guanidine main catalysts according to formula (V):

[0054]

[0055] In equation (V), M 2 It can be made of titanium, zirconium, or hafnium. Each X 2 Independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 heteroalkyl groups, -CH2Si(R) C ) 3-J (OR C ) J 、-Si(R C ) 3-J (OR C ) J -OSi(R) C ) 3-J (OR C ) J -CH2Ge(R) C ) 3-J (OR C ) J -Ge(R) C ) 3-J (OR C ) J -P(R) C ) 2-K (OR C ) K -P(O)(R C ) 2-K (OR C ) K -N(R) C )2、-NH(R C ), -N(Si(R)C )3)2、-NR C Si(R C )3、-NHSi(R C 3. -OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C )2、-N=CH(R C -N=CH2, -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R) C )C(O)R C -N(R) C )C(O)H、-NHC(O)R C -C(O)N(R) C )2、-C(O)NHR C -C(O)NH2, halogens, B(R) Y 4. Al(R) Y )4 or Ga(R Y )4 or hydrogen, where each R C Independently for (C1-C) 30 ) hydrocarbon group or (C1-C 30 ) heterohydrocarbon groups, and each J It can be 0, 1, 2 or 3, and each K It can be 0, 1, or 2; each R Y -H, (C1-C 30 ) hydrocarbon group or halogen atom, in which two X 2 Ligands can link together to form a ring.

[0056] In some implementations, A in equation (V) is -C(R) 22 )C(R 23 )-、-CH(R 22 )CH(R 23 - or -CH(R) 22 )CH(R 23 )CH(R 24 )-, and R 21 R 22 R 23 R 24 and R 25 Independently for (C1-C) 50 ) hydrocarbon group, (C1-C 50(C6-C) heterohydrocarbon group, (C6-C) 30 )Aryl, (C5-C 30 () heteroaryl, as defined above. In various embodiments, in formula (V), A is -CH(R) 22 )CH(R 23 )CH(R 24 )-, and R 23 and R 24 Capable of connecting to form aromatic or non-aromatic rings, or R 24 and R 25 They can be linked to form aromatic or non-aromatic rings. In one or more embodiments, A is -C(R 22 )C(R 23 )-, and R 23 and R 25 They can be linked to form aromatic or non-aromatic rings. In some embodiments, in formula (V), A is -C(R) 22 )C(R 23 In one or more embodiments, in formula (V), A is -CH(R). 22 )CH(R 23 )CH(R 24 )-.

[0057] In various implementation schemes, R in equation (V) 22 R 23 and R 24 For (C1-C 20 )alkyl or -H, and R 21 and R 25 To replace (C6-C) 18 )Aryl. In some embodiments, in formula (V), R 22 R 23 and R 24 One of them is selected from halogen atoms, -OMe, and -NMe2. In one or more embodiments, R 22 R 23 and R 24 The constituents are independently selected from the group consisting of: methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, dimethylamino, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In various embodiments, in formula (V), R 26 R 27 R 28 R 29 and R 30 Each independently constitutes (C1-C)12 )alkyl, halogen-substituted (C1-C 12 )alkyl, halogen-substituted (C6-C 18 )Aryl, halogen-substituted (C3-C 50 )cycloalkyl or -H.

[0058] As mentioned above, the molecular weight of polymers produced by the GD catalyst is far more sensitive to hydrogen than that of polymers produced by the BPP catalyst. Therefore, the molecular weight distribution (the difference in molecular weight of polyethylene produced by the two catalysts) can be easily customized by adjusting the hydrogen level without significantly altering other conditions. Small changes in the hydrogen level result in large differences in the molecular weight of polymers produced by the GD catalyst. In contrast, the same increase in H2 results in smaller changes in the molecular weight of polymers produced by the BPP catalyst.

[0059] In an exemplary embodiment, the catalyst system may comprise a metal-ligand complex according to formula (I) having the structure of any one of the main catalysts BPP-1, BPP-2, BPP-3, BPP-4, BPP-5, BPP-6, BPP-7, BPP-8, and BPP-9:

[0060]

[0061] co-catalyst components

[0062] 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 formulas (I) and (V). For example, the main catalyst of the metal-ligand complex according to formulas (I) and (V) can be made catalytically active by contacting the complex with an activating cocatalyst or by combining the complex with an activating cocatalyst. Additionally, the metal-ligand complexes according to formulas (I) and (V) can comprise both a neutral main catalyst form and a catalytic form that may be positively charged due to the loss of a monoanionic ligand (such as benzyl or phenyl). Activating cocatalysts suitable for this document include alkylaluminum; polymeric or oligomeric aluminum oxanes (also known as aluminum oxanes); neutral Lewis acids; and non-polymeric, non-coordinated, ion-forming compounds (including those used under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means dihydrogenated monoalkylaluminum or dihalogenated monoalkylaluminum, hydrogenated dialkylaluminum or halodialkylaluminum, or trialkylaluminum. Examples of polymeric or oligomeric aluminum oxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0063] In some embodiments, the catalyst system does not contain additives. Additives are chemical reagents present during the polymerization reaction and do not inhibit olefin growth. In one or more embodiments, the catalyst system also contains additives. In some embodiments, the additives act as co-catalysts. In other embodiments, the additives act as scavengers or purifiers. A co-catalyst is a reagent that cooperates with the catalyst to catalyze the reaction or enhance the catalytic activity of the catalyst. Unbound by theory, when M1 in formula (I) is scandium or yttrium, ligand Y dissociates in the absence of a co-catalyst. However, it is also believed that a co-catalyst can promote the dissociation of any Lewis base present and coordinated to the metal center of the metal-ligand complex.

[0064] The purifying agent chelates impurities in the reactor before the main catalyst is added, and therefore does not constitute an activator.

[0065] Suitable additives may include, but are not limited to, alkylaluminum; polymeric or oligomeric aluminum oxanes (also known as aluminum oxanes); neutral Lewis acids; and non-polymeric, non-coordinated, ion-forming compounds (including those used under oxidizing conditions). Combinations of one or more of the foregoing additives with technologies are also considered.

[0066] Lewis acid activation cocatalysts contain (C1-C) as described herein. 20 A Group 13 metal compound with a hydrocarbon substituent. In some embodiments, the Group 13 metal compound is a tri((C1-C) group. 20 ()hydrocarbon-substituted aluminum or tri((C1-C) 20 (Hydrocarbon)-boron compounds. In other embodiments, the Group 13 metal compound is a tri(hydrocarbon)-substituted aluminum, tri((C1-C)-boron compound. 20 )hydro-boron compounds, tri((C1-C 10 Alkyl aluminum, tri((C6-C) 18 aryl boron compounds and their halogenated (including perhalogenated) derivatives. In other embodiments, the Group 13 metal compound is tris(fluorosubstituted phenyl)borane or tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C2)borane. 20 ) hydrocarbon-based ononium borates (e.g., triphenylmethyltetrafluoroborate) or tri((C1-C 20 )hydro-based)ammonium tetra((C1-C 20 (e.g., bis(octadecyl)methylammonium tetra(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to a nitrogen cation that is ((C1-C2) 20 )hydrocarbon group)4N + 、((C1-C 20 )hydrocarbon group)3N(H) + 、((C1-C 20)hydrocarbon group)2N(H)2 + (C1-C) 20 )hydrocarbon N(H)3 + or N(H)4 + Where there are two or more (C1-C) 20 When there are hydrocarbon groups, they can be the same or different.

[0067] The combination of neutral Lewis acid activation cocatalysts includes tris((C1-C4)alkyl)aluminum and tris((C6-C4)halogenated tris((C6-C4)alkyl)aluminum. 18 Mixtures of aryl boron compounds (especially tris(pentafluorophenyl)borane). Other embodiments are combinations of such neutral Lewis acid mixtures with polymeric or oligomeric aluminum oxanes, and combinations of single neutral Lewis acids (especially tris(pentafluorophenyl)borane) with polymeric or oligomeric aluminum oxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenyl)borane):(aluminoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenyl)borane):(aluminoxane)] is from 1:1:1 to 1:10:30, and in other embodiments from 1:1:1.5 to 1:5:10.

[0068] Catalytic systems comprising metal-ligand complexes of formulas (I) and (V) can be activated to form active catalyst compositions by combination with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activation cocatalysts include polymeric or oligomeric aluminum oxanes (especially methylaluminoxanes) and inert, compatible, noncoordinate, ionic compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate, and combinations thereof.

[0069] In some embodiments, one or more of the previously mentioned activation cocatalysts may be used in combination with each other. Specific examples of cocatalyst combinations are mixtures of tris((C1-C4)alkyl)aluminum, tris((C1-C4)alkyl)borane, or ammonium borate with oligomeric or polymeric aluminum oxane compounds. The ratio of the total molar number of one or more metal-ligand complexes of formulas (I) and (V) to the total molar number of one or more activation cocatalysts is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments at least 1:1000; and 10:1 or less, and in some other embodiments 1:1 or less. When an aluminum oxane is used alone as an activation cocatalyst, the molar number of the aluminum oxane used is at least 25 times the molar number of the metal-ligand complexes of formulas (I) and (V). In some other embodiments, when tris(pentafluorophenyl)borane is used alone as an activation cocatalyst, the ratio of the molar amount of tris(pentafluorophenyl)borane to the total molar amount of one or more metal-ligand complexes of formulas (I) and (V) is from 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activation cocatalyst is typically used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of formulas (I) and (V).

[0070] Aggregation methods

[0071] Embodiments of this disclosure include a method for producing ethylene-based polymers, the method comprising reacting ethylene and optionally one or more olefin monomers in one or more reactors in the presence of a catalyst system and optionally hydrogen. In some embodiments, the method occurs in the presence of hydrogen. In one or more embodiments, the amount of hydrogen may be greater than 0 mmol. In embodiments, the amount of hydrogen may range from greater than 0 mmol to less than or equal to 1,000 mmol. In embodiments, the amount of hydrogen may range from greater than 0 mmol to less than or equal to 500 mmol, greater than 0 mmol to less than or equal to 100 mmol, or greater than 0 mmol to less than or equal to 10 mmol. In some embodiments, the amount of hydrogen, expressed as mol%, is greater than 0.0 mol% to 4 mol%, calculated as the molar feed rate of fresh hydrogen / molar feed rate of fresh ethylene * 100.

[0072] The polyolefin compositions according to this disclosure can be produced using any conventional polymerization method. Such conventional polymerization methods include, but are not limited to, solution polymerization methods using one or more conventional reactors, such as loop reactors in parallel or in series, isothermal reactors, fluidized bed reactors, stirred tank reactors, batch reactors, and / or any combination thereof, particle-forming polymerization methods, and combinations thereof. In various embodiments, the polymerization method is a solution polymerization reaction.

[0073] In one embodiment, the polyolefin composition according to the present disclosure can be produced, for example, via solution-phase polymerization using one or more loop reactors, isothermal reactors, and combinations thereof.

[0074] Generally, solution-phase polymerization is carried out in one or more well-stirred reactors, such as one or more loop reactors or one or more spherical isothermal reactors, at temperatures ranging from 120°C to 300°C, 120°C to 250°C, 150°C to 300°C, 150°C to 250°C, or 160°C to 215°C, and at pressures ranging from 300 psi to 1500 psi; for example, at pressures ranging from 400 psi to 750 psi. Residence times in solution-phase polymerization are typically from 2 minutes to 30 minutes; for example, from 5 minutes to 15 minutes. Ethylene, one or more solvents, one or more high-temperature olefin polymerization catalyst systems, one or more cocatalysts and / or scavengers, and optionally one or more comonomers are continuously fed into one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents may be available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas. The resulting mixture of the ethylene-based polymer and solvent is then removed from the reactor and the ethylene-based polymer is separated. Solvents are typically recovered via solvent recovery units (i.e., heat exchangers and vapor-liquid separator drums) and then recycled back into the polymerization system.

[0075] In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a single-reactor system (e.g., a single loop reactor system), wherein ethylene and optionally one or more α-olefins are polymerized in the presence of one or more high-temperature olefin polymerization catalyst systems, optionally one or more other catalysts, and optionally one or more co-catalysts. In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a two-reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more α-olefins are polymerized in the presence of one or more olefin polymerization catalyst systems, optionally one or more other catalysts, and optionally one or more co-catalysts. In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a two-reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of one or more high-temperature olefin polymerization catalyst systems as described herein.

[0076] Polyolefins

[0077] The catalytic system described in the preceding paragraphs is used to polymerize olefins (primarily ethylene-based polymers). In some embodiments, the polymerization scheme contains only ethylene, resulting in an ethylene homopolymer. However, additional α-olefins can 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.

[0078] Ethylene-based polymers may comprise at least 60 wt% of ethylene-derived monomeric units; at least 70 wt% of ethylene-derived monomeric units; at least 80 wt% of ethylene-derived monomeric units; or 50 wt% to 100 wt% of ethylene-derived monomeric units; or 80 wt% to 100 wt% of ethylene-derived units. 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 embodiments. 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.

[0079] In some embodiments of the ethylene-based polymer, the additional α-olefin is less than 50%; other embodiments include at least 0.5 mol percent (mol%) to 25 mol%; and in still other embodiments, the additional α-olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0080] Ethylene-based polymers may also contain 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. Based on the combined weight of the ethylene-based polymer and one or more additives, the ethylene-based polymer may contain about 0% to about 10% of such 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.

[0081] Ethylene-based polymers may have, for example, a content of 0.850 g / cm³ according to ASTM D792 (which is incorporated herein by reference in its entirety). 3 Up to 0.960 g / cm 3 0.880 g / cm 3 Up to 0.920 g / cm 3 0.880 g / cm 3 Up to 0.910 g / cm 3or 0.880 g / cm 3 Up to 0.900 g / cm 3 The density.

[0082] Gel permeation chromatography (GPC)

[0083] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) connected to a Precision Detectors (now Agilent Technologies) 2-angle laser scattering (LS) detector model 2040 and four capillary viscometers (DV). For all absolute light scattering measurements, a 15-degree angle was used. The autosampler oven chamber was set to 160 degrees Celsius, and the column and detector chambers were set to 150 degrees Celsius. The columns used were four Agilent “Mixed A” 30 cm 20 μm linear mixed-bed columns. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen injection. The injection volume used was 200 μL, and the flow rate was 1.0 mL / min.

[0084] The GPC column assembly was calibrated using 21 polystyrene standards with narrow molecular weight distributions, ranging from 580 to 8,400,000, arranged in a six-cocktail mixture, 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 pre-dissolved at 80 °C with gentle stirring for 30 min, then cooled, and the room temperature solution was transferred to a 160 °C autosampler dissolution oven for 30 min. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).

[0085]

[0086] Where M is the molecular weight, A has a value of 0.41, and B equals 1.0.

[0087] A fifth-order polynomial is used to fit the calibration point for the corresponding polyethylene equivalent.

[0088] Total plate counts of the GPC column setup were performed using decane, which was introduced into the blank sample via a micropump controlled by a PolymerChar GPC-IR system. For four Agilent “Mixed A” 30 cm 20 μm linear mixed-bed columns, the plate count of the chromatographic system should be greater than 18,000.

[0089] 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 via a PolymerChar high-temperature autosampler. The sample was then dissolved at 160°C for 2 hours with "low-speed" shaking.

[0090] Mn (GPC) Mw (GPC) and Mz (GPC) The calculations are based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equation 2-4, using PolymerChar GPCOne. ™ The software combines baseline-subtracted IR chromatograms of each equidistant data collection point (i) with the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve of point (i) in Formula 1.

[0091]

[0092] To monitor deviations over time, a flow marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow 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 retention volume (RV(FM-calibrated)) of the decane 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. After calibration based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 5. (via PolymerChar GPCOne) ™ The software processes the flow marker peaks. Acceptable flow correction ensures that the effective flow rate is within + / - 0.5% of the nominal flow rate.

[0093]

[0094] Chain transfer constant calculation

[0095] The chain transfer constant was calculated using the Mayo formula shown in Equation 6, where Mn0 is Mn without any hydrogen added to the reactor, H2 and ethylene concentrations are liquid phase concentrations, and c CTH This is the ratio of the hydrogenolysis rate constant to the growth rate constant. The reactor volume is 3.414 L, the liquid phase ethylene concentration is estimated to be 0.539 M, and the estimated hydrogen concentrations for 10 mmol, 20 mmol, 40 mmol, 80 mmol, and 160 mmol H2 are 1.17 mM, 2.31 mM, 4.53 mM, 8.74 mM, and 16.3 mM, respectively. For each hydrogen loading, the Mn value is calculated using Equation 6. The Solver feature in MS Excel is used to change c. CTH The value of Mn is determined to minimize the sum of the squared deviations between the calculated Mn value and the experimental Mn values ​​for all hydrogen loads.

[0096]

[0097] Example

[0098] One or more features of this disclosure are illustrated by the following embodiments:

[0099]

[0100]

[0101] Synthesis scheme

[0102] All commercially available chemicals can be used without further purification. Unless otherwise specified, all synthesis was carried out in a glove box continuously purged with nitrogen. Tribenzyl(cyclopentadienyl)titanium(IV) (CpTiBn3) was prepared by reacting 3 equivalents of benzyl magnesium chloride with 1 equivalent of trichloro(cyclopentadienyl)titanium(IV). Tribenzyl(pentamethylcyclopentadienyl)titanium(IV) (Cp*TiBn3) was prepared by reacting 3 equivalents of benzyl magnesium chloride with 1 equivalent of trichloro(pentamethylcyclopentadienyl)titanium(IV).

[0103] Synthesis of 1,3-dimethyltrimethylimidazol-2-imine (IMesNH)

[0104]

[0105] In a nitrogen-purged glove box, 1,3-dimethyltrimethylimidazolium-2-ylene (1.13 g, 3.71 mmol, 1 equivalent) was dissolved in toluene at ambient temperature. After stirring for 5 minutes, trimethylsilyl azide (0.69 mL, 5.20 mmol, 1.4 equivalent) was added dropwise. The reaction mixture was heated to 115 °C and stirred for 24 hours. The reaction mixture was cooled to ambient temperature, filtered through a PTFE filter syringe, and concentrated. The residue was ground with hexane (2 × 2 mL) and dried under vacuum. The resulting solid was combined with methanol (2.25 mL, 15 equivalent) and stirred at 35 °C for 90 minutes. Volatiles were removed under vacuum, and the resulting crude product was ground with hexane (2 × 4 mL), washed with warm (35 °C) hexane (75 mL), and dried under vacuum. Yield: 0.560 g, 47%. 1 H NMR (400MHz, C6D6) δ 6.77 (s, 4H), 5.72 (s, 2H), 4.28 (s, 1H), 2.24 (s, 12H), 2.12 (s, 6H). 13 C NMR (101MHz, C6D6) δ 151.7, 137.7, 137.2, 134.3, 129.2, 112.0, 20.8, 17.9.

[0106] GD-1 Synthesis

[0107]

[0108] Step 1: In a glove box under N2 atmosphere, add 0.300 g (0.631 mmol) of 1,3-bis(2,6-diisopropylphenyl)-N-trimethylsilyl-imidazol-2-imine and 0.138 g (0.631 mmol) of trichloro(cyclopentan-2,4-dien-1-yl)titanium in 5 mL of dried and degassed toluene to a 40 mL vial equipped with a stir bar. Assemble the vial with a small reflux condenser and heat the orange-yellow reaction mixture at 80 °C for 3 hours. All substances dissolved with increasing temperature. Afterward, cool the reaction mixture to room temperature and add 20 mL of pentane. Place the vial in a refrigerator (-35 °C) for 6 days. Separate the yellow precipitate by filtration and wash with cold pentane (3 × 5 mL). The resulting yellow solid was dried under vacuum to give [[1,3-bis(2,6-diisopropylphenyl)23-imidazol-2-ylidene]amino]-dichloro-cyclopentan-2,4-dien-1-yl-titanium (0.321 g, 0.547 mmol, yield: 87%). 1H NMR (400MHz, benzene-d6) δ 7.24 (dd, J = 8.5, 6.9Hz, 2H), 7.13 (d, J =1.0Hz, 2H), 5.93 (s, 4H), 5.76 (s, 2H), 2.94 (hept, J = 6.8Hz, 4H), 1.49 (d, J = 6.8Hz, 12H), 1.07 (d, J = 6.9Hz, 12H).

[0109] Step 2: In a glove box under N2 atmosphere, add [[1,3-bis(2,6-diisopropylphenyl)imidazol-2-yl]amino]-dichloro-cyclopentan-2,4-dien-1-yl-titanium (0.300 g, 0.512 mmol) and 10 mL of dried, degassed toluene to a 40 mL vial equipped with a stir bar. Place the vial in a refrigerator (-35 °C) for 15 minutes, then slowly add magnesium bromo(methyl)magnesium (3.00 mol / L, 0.358 mL, 1.07 mmol) to the red suspension. The mixture gradually turns yellow / brown with a small amount of precipitate. Stir the reaction mixture at room temperature for 2 hours, then concentrate the reaction mixture to dryness. Absorb the substance in toluene / pentane (15 mL, 4:1) and then pass it through a diatomaceous earth stopper. Further extract the stopper with toluene / pentane (10 mL, 4:1). The combined yellow organic layers were concentrated to dryness to obtain GD-1 (0.240 g, 0.440 mmol, yield: 86%), which was a yellow powder. 1 HNMR (400MHz, benzene-d6) δ 7.22 (dd, J = 8.6, 6.8Hz, 2H), 7.13 (d, J = 8.1Hz, 4H), 5.89 (s, 2H), 5.73 (s, 5H), 3.24 - 3.09 (m, J = 6.6Hz, 4H), 1.39 (d, J =6.8Hz, 12H), 1.15 (d, J = 6.9Hz, 12H), 0.21 (s, 6H).

[0110] GD-2 Synthesis

[0111]

[0112] In a nitrogen-purged glove box, CpTiBn3 (50 mg, 0.13 mmol, 1 equivalent) was combined with C6D6 (0.4 mL) and a stir bar. The mixture was stirred at ambient temperature for 5 minutes until all substances dissolved, yielding a deep red solution. Separately, IMesNH (41 mg, 0.13 mmol, 1 equivalent) was dissolved in C6D6 (0.3 mL). The almost colorless ligand solution was then added dropwise to the Ti-containing solution at ambient temperature while stirring. Any remaining ligands were extracted using approximately 0.3 mL of additional C6D6 and transferred from their original vials to the reaction mixture. The resulting dark reddish-brown homogeneous mixture was stirred at ambient temperature for 20 hours. Subsequently, the reaction mixture was concentrated to an orange-red residue, which was then milled with hexane (2 × 2 mL) and dried under vacuum. The substance was absorbed in toluene (2 mL), filtered, and concentrated to half its original volume. Hexane was added to the concentrated toluene solution, producing slight turbidity. The contents of the vial were thoroughly mixed and then stored at -25°C for 24 hours. The precipitate was collected and dried under vacuum. Yield: 74 mg, 93%. 1 ¹H NMR (400MHz, C6D6) δ 7.19 - 7.12 (m, overlapping with NMR solvent, 4H) 6.86 (tt, J = 7.2, 1.3Hz, 2H), 6.77 (s, 4H), 6.72 (d, J = 7.3Hz, 4H), 5.59 (s, 2H), 5.48 (s, 5H), 2.45 (d, J = 9.1Hz, 2H), 2.21 (s, 12H), 2.18 (d, J = 9.2Hz, 2H), 2.08 (s, 6H). 13 C NMR (101MHz, C6D6) δ 153.1, 142.0, 139.4,136.8, 133.5, 129.5, 126.3, 120.3, 113.4, 113.1, 70.8, 21.0, 18.1.

[0113] Synthesis of 6,6'-(cyclopentaeno-1,3-diene-1,3-diyl)bis(1,2,3,4,5-pentafluorobenzene)

[0114]

[0115] A 250 mL round-bottom flask was filled with sodium cyclopentadienyl (2.4 M in THF, 9.6 mL, 2.0 g, 0.023 mmol, 1 equivalent), NaH (1.1 g, 0.046 mol, 2 equivalents), C6F6 (42 g, 0.23 mol, 10 equivalents), THF (100 mL), and a magnetic stir bar. The reaction mixture was refluxed under nitrogen for 3 days. The solvent was then removed under reduced pressure, and the residue was washed with pentane (3 × 50 mL). 100 mL of pentane and 20 mL of water were added, and the layers were separated. The organic layer was dried over Na2SO4, filtered through neutral alumina, and evaporated to give a white solid. The white solid was dissolved in 50 mL of hot ethanol and recrystallized to give white needle-like crystals (2.5 g, 27%).

[0116] 1 H NMR (500MHz, CDCl3) δ 7.35 - 7.28 (m, 2H), 4.05 (p, J = 1.7Hz, 2H). 19 F NMR (471MHz, CDCl3) δ -139.78 - -140.00 (m, 4H), -156.42 (t, J = 20.8Hz, 2H), -162.55 (td, J = 21.1, 6.9Hz, 4H).

[0117] Synthesis of Sodium (2,4-bis(perfluorophenyl)cyclopentan-2,4-dien-1-yl)

[0118]

[0119] In a nitrogen-filled glove box, 6,6'-(cyclopentaeno-1,3-diene-1,3-diyl)bis(1,2,3,4,5-pentafluorobenzene) (500 mg, 1.25 mmol, 1 equivalent), NaH (90 mg, 3.0 mmol, 3 equivalent), 10 mL of anhydrous THF, and a magnetic stir bar were added to a 20 mL vial. The addition of NaH changed the color of the reaction mixture from colorless to yellow. The reaction mixture was stirred at ambient temperature for 4 hours. The solvent was evaporated under reduced pressure to give a pale yellow solid. 10 mL of hexane was added to the solid, and the solid was filtered to obtain a solid residue, which was then dried under vacuum to obtain a white powder (125 mg, 98%).

[0120] 1 ¹H NMR (400MHz, benzene-d6) δ 7.45 (p, J = 2.6Hz, 1H), 6.95 (qd, J = 2.7, 1.7Hz, 2H). 19F NMR (376MHz, C6D6) δ -144.91 - -145.54 (m), -165.81 - -166.41(m), -168.34 (t, J = 21.7Hz).

[0121] Synthesis of IMesN(Me2NH)TiCl3

[0122]

[0123] In a nitrogen-filled glove box, (Me₂N)TiCl₃ (54 mg, 0.27 mmol, 1 equivalent) was added to a 7 mL glass vial along with Et₂O (8 mL) and a magnetic stir bar at ambient temperature. The mixture was stirred at ambient temperature for 15 minutes. In a separate vial, (IMesNH) ligand (87 mg, 0.27 mmol, 1 equivalent) was combined with Et₂O (6 mL). The pale yellow ligand solution was then added dropwise to the stirred solution of the Ti precursor at ambient temperature, causing a color change to bright red-orange with increased turbidity. The heterogeneous orange-red suspension was then stirred at ambient temperature for another 20 hours. The bright orange solid was collected in a disposable sintered glass funnel and washed with Et₂O (2 × 4 mL) and pentane (2 × 3 mL). The orange solid was further vacuum-dried and then stored at -25 °C. Yield: 0.100 g, 70%. 1 H NMR (500MHz, C6D6) δ 6.82 (s, 4H), 5.37 (s,2H), 2.75 (br s, 1H), 2.20 (s, 12H), 2.09 (s, 6H), 1.96 (s, 6H). 13 C NMR (126MHz, C6D6) δ 140.3, 136.3, 131.5, 129.7, 128.4, 114.5, 21.1, 18.0.

[0124] GD-3 Synthesis

[0125]

[0126] In a N2-filled glove box, 88 mg of the IMesN(Me2NH)TiCl3 adduct (1 equivalent) was added to a 20 mL vial, along with 6 mL of toluene. In another 20 mL vial, the sodium salt of the ligand (71.4 mg, 0.17 mmol, 1 equivalent) was dissolved in 7 mL of toluene. At room temperature, the Ti precursor solution was slowly added dropwise to the sodium salt of the bis-C6F5Cp ligand. The color of the reaction mixture changed from white to a reddish-orange. The reaction mixture was stirred at ambient temperature for 2 hours. The solvent was removed under vacuum. The insoluble yellow solid was washed three times with 2:1 toluene:hexane (10 mL). The residue was filtered through a sintered glass funnel to obtain an orange powder, which was then dried under vacuum to give the Ti-Cl2 complex (140 mg, 98%) as an orange powder.

[0127] 1 H NMR (500MHz, C6D6) δ 7.42 (s, 1H), 6.83 (s, 4H), 6.17 (s, 2H), 5.38 (s, 2H), 2.15 (d, J = 9.7Hz, 18H). 19 F NMR (471MHz, C6D6) δ -139.36 (d, J =23.8Hz), -156.67 (t, J = 21.7Hz), -163.60 (t, J = 24.4Hz).

[0128] In a nitrogen-filled glove box, a 20 mL vial was filled with a Ti-Cl2 complex (80 mg, 0.095 mmol, 1 equivalent), 5 mL of toluene, and a stir bar. A hexane solution of MeMgBr (0.076 mL of 3 (M) MeMgBr in hexane, 0.23 mmol, 2.4 equivalent) was added to the solution, and the reaction mixture was stirred at ambient temperature for 30 minutes. After the addition of MeMgBr, the color of the reactants changed from orange to deep yellow. The solution was filtered through a sintered glass funnel to obtain an orange-yellow filtrate. The filtrate was evaporated under vacuum to obtain a pale yellow solid. 2 mL of toluene was added to the pale yellow solid to dissolve it, followed by the addition of 10 mL of hexane. The slurry was filtered through a sintered glass funnel to obtain a pale yellow filtrate. The solvent was removed to obtain GD-3 (68 mg, 90%), a pale yellow solid.

[0129] 1 H NMR (400MHz, C6D6) δ 7.59 - 7.52 (m, 1H), 6.80 (s, 4H), 5.89 (s,2H), 5.55 (s, 2H), 2.15 (d, J = 9.6Hz, 18H), 0.06 (s, 6H).19 F NMR (376MHz, C6D6) δ -62.32 - -243.56 (m).

[0130] Polymerization reaction

[0131] The results of polymerization reactions combining exemplary guanidine master catalysts with exemplary bis(biphenylphenoxy) master catalysts are tabulated and discussed.

[0132] The raw materials (ethylene, 1-octene) and process solvent (a high-purity isoparaffin solvent with a narrow boiling range, commercially available under the trademark ISOPAR E from ExxonMobil Corporation) were purified using molecular sieves and then introduced into the reaction environment. ISOPAR E and 1-octene were charged into a one-gallon (3.79 L) stirred autoclave reactor. The reactor was then heated to the desired temperature and ethylene was added to reach the desired pressure. Hydrogen was also added at this point, if necessary. A catalyst composition was 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 was then rapidly injected into the reactor. The reactor pressure and temperature were kept constant by feeding ethylene during the polymerization reaction and cooling the reactor as needed. After 10 minutes, the ethylene feed was shut off and the solution was transferred to a nitrogen-purged resin reactor. The polymer was allowed to dry thoroughly in a vacuum oven, and the reactor was thoroughly rinsed with hot ISOPAR E between polymerization runs.

[0133] Aggregation conditions 3.79 L (1 Gal) batch reactor, 1250 g Isopar-E; combined main catalyst (formulas (I) and (V)): activator = 1:1.2; activator: ([HNMe(C 18 H 37 [2][B(C6F5)4]); An Al-containing co-catalyst, either butylated hydroxytoluene-triethylaluminum 2:1 adduct (BHT-TEA) or MMAO modified with n-octyl substituents to achieve a methyl:n-octyl ratio of approximately 6:1, was used at a given Al:total metal ratio (combined formulas (I) and (V)); the reaction time was 10 minutes. 160°C: 60 g 1-octene; ethylene, pressure up to 320 psi. 190°C: 65 g 1-octene; ethylene, pressure up to 410 psi. For various exemplary GD master catalysts and various exemplary BPP master catalysts, the change in weight-average molecular weight with the introduction of hydrogen at 160°C is recorded in Table 1.

[0134] Table 1: Changes in weight-average molecular weight when hydrogen is introduced at 160℃

[0135]

[0136] For various exemplary GD main catalysts and various exemplary BPP main catalysts, the change in weight-average molecular weight with the introduction of hydrogen at 190 °C is recorded in Table 2.

[0137] Table 2: Changes in weight-average molecular weight when hydrogen is introduced at 190℃

[0138]

[0139] Table 3 records the constants for chain transfer to hydrogen for various exemplary GD main catalysts and various exemplary BPP main catalysts.

[0140] Table 3: Constants for chain transfer to hydrogen (CH2) at 160 °C for the selected catalyst

[0141]

[0142] Table 4 records the number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz) of polymer compositions produced from GD-1 and BPP-1 at four different hydrogen concentrations at 160°C.

[0143] Table 4: Polymer compositions produced from GD-1 and BPP-1 at four different hydrogen loadings at 160°C

[0144]

[0145] BHT-TEA is used at a ratio of 50 (Al: total metals of formula (I) and (V)).

[0146] Table 5 records the Mn, Mw, and Mz of polymer compositions produced from GD-1 and BPP-2 at four different hydrogen concentrations at 190°C.

[0147] Table 5: Polymer compositions produced by GD-1 and BPP-2 at four different hydrogen loadings at 190°C

[0148]

[0149] BHT-TEA is used at a ratio of 50 (Al: total metals of formula (I) and (V)).

[0150] Table 6 records the Mn, Mw, and Mz of polymer compositions produced from GD-2 and BPP-1 at four different hydrogen concentrations at 160°C.

[0151] Table 6: Polymer compositions produced from GD-2 and BPP-1 at four different hydrogen loadings at 160°C

[0152]

[0153] MMAO is used at a ratio of 20 (Al: total metals of formula (I) and (V)).

[0154] Table 7 records the Mn, Mw, and Mz of polymer compositions produced from GD-3 and BPP-1 at four different hydrogen concentrations at 160°C.

[0155] Table 7: Polymer compositions produced from GD-3 and BPP-1 at four different hydrogen loadings at 160°C

[0156]

[0157] MMAO is used at a ratio of 20 (Al: total metals of formula (I) and (V)).

[0158] Referring to Table 1, where the catalysts were evaluated at 160 °C, when 10 mmol of hydrogen was first added to the catalysts GD-1, GD-2, and GD-3, the molecular weight M of the polymers obtained with the GD catalyst compared to those obtained with the GD catalyst not exposed to hydrogen was [not specified]. w The decrease was approximately 70% to 90% by weight. However, compared to the polymer obtained with a BPP catalyst not exposed to hydrogen, the M of the polymer obtained with the BPP catalyst was significantly lower. w It decreased only from about 10% by weight to 25% by weight.

[0159] Similarly, in Table 1, the molecular weight M of the polymer obtained by the GD catalyst is shown as the amount of hydrogen increases from 10 mmol to 20 mmol. w The yield decreased by approximately 40% to 50% by weight, while the yield of polymers using the BPP catalyst decreased by only approximately 10% to 25% by weight. This indicates that the BPP catalyst is less sensitive to increased hydrogen supply than the GD catalyst.

[0160] Furthermore, in Table 1, the molecular weight M of the polymer obtained by the GD catalyst is shown as the amount of hydrogen increases from 20 mmol to 40 mmol. w The decrease was approximately 35% to 50% by weight, while the decrease in polymer yielded by the BPP catalyst was only approximately 5% to 40% by weight. Similarly, this indicates that the BPP catalyst is less sensitive to increased hydrogen supply than the GD catalyst.

[0161] Referring now to Table 2, where the catalysts were evaluated at 190°C, when 10 mmol of hydrogen was first added to the catalysts GD-1, GD-2, and GD-3, the molecular weight M of the polymer obtained from the GD catalyst compared to the polymer obtained from the GD catalyst not exposed to hydrogen was... w The yield decreased by approximately 40% to 85% by weight. However, compared to the polymer obtained with a BPP catalyst not exposed to hydrogen, the M of the polymer obtained with the BPP catalyst was significantly lower. w It decreased only from about 5% by weight to 25% by weight.

[0162] Similarly, in Table 2, the molecular weight M of the polymer obtained by the GD catalyst is shown as the amount of hydrogen increases from 10 mmol to 20 mmol. w The yield decreased by approximately 35% to 45% by weight, while the yield of polymers using the BPP catalyst decreased by only approximately 10% to 30% by weight. This indicates that the BPP catalyst is less sensitive to increased hydrogen supply than the GD catalyst.

[0163] Furthermore, in Table 1, the molecular weight M of the polymer obtained by the GD catalyst is shown as the amount of hydrogen increases from 20 mmol to 40 mmol. w The yield decreased by approximately 40% to 50% by weight, while the yield of polymers using the BPP catalyst decreased by only approximately 5% to 40% by weight. Similarly, this indicates that the BPP catalyst is less sensitive to increased hydrogen supply than the GD catalyst.

[0164] In addition, such as Figures 2 to 5 As shown, the GD catalyst is more sensitive to the introduction of hydrogen than the BPP catalyst. Figures 2 to 5 In the diagram, each catalyst system exhibits two peaks at a given hydrogen concentration. The peak with the lowest LogM represents the product produced by the GD catalyst, and the peak with the highest LogM represents the product produced by the BPP catalyst. For example... Figures 2 to 5 As shown in each figure, when the hydrogen concentration increases from 5 mmol to 20 mmol, the LogM of the peak generated by the BPP catalyst decreases slightly, while the LogM of the peak generated by the GD catalyst decreases more significantly. Similarly, when the hydrogen concentration further increases from 20 mmol to 40 mmol, the LogM of the peak generated by the BPP catalyst again decreases slightly, while the LogM of the peak generated by the GD catalyst decreases more significantly. Therefore, the slight decrease in the LogM of the peak generated by the BPP catalyst compared to the more significant decrease in the LogM of the peak generated by the GD catalyst indicates that the GD catalyst is more sensitive to changes in hydrogen concentration than the BPP catalyst.

Claims

1. A method for producing an ethylene-based polymer, the method comprising reacting ethylene and optionally one or more olefin monomers in one or more reactors in the presence of a catalyst system and optionally hydrogen; said catalyst system comprising two or more catalysts, wherein at least one catalyst is derived from a bis(biphenylphenoxy) main catalyst according to formula (I), and wherein at least one catalyst is derived from a guanidine main catalyst according to formula (V): in, In equation (I): M1 can be titanium, zirconium, hafnium, scandium, or yttrium; Each X is independently selected from the following monodentate ligands: (C1-C 50 ) hydrocarbon group, (C1-C 50 heteroalkyl groups, -CH2Si(R) C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q -OSi(R) C ) 3-Q (OR C ) Q -CH2Ge(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3-Q (OR C ) Q -P(R) C ) 2-W (OR C ) W -P(O)(R C ) 2-W (OR C ) W -N(R) C )2、-NH(R C ), -N(Si(R) C )3)2、-NR C Si(R C )3、-NHSi(R C 3. -OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C )2、-N=CH(R C -N=CH2, -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R) C )C(O)R C -N(R) C )C(O)H、-NHC(O)R C -C(O)N(R) C )2、-C(O)NHR C -C(O)NH2, halogens, B(R) Y 4. Al(R) Y )4 or Ga(R Y )4 or hydrogen, where each R C Independently for (C1-C 30 ) hydrocarbon group or (C1-C 30 ( ) heterohydrocarbon groups, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each R Y -H, (C1-C 30 Hydrocarbon group or halogen atom; Each Y is an independent Lewis base; optionally, X and Y can be linked to form a ring. m is 1 or 2; n is 0, 1, or 2; p is 0, 1, or 2; R 1 and R 16 Independently select from the following groups: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C )3、-P(R P )2、-N(R N )2、-OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、-N=C(R C )2、R C C(O)O-、R C OC(O)-, R C C(O)N(R)-、(R C )2NC(O)-, halogens, groups having formula (II), groups having formula (III), and groups having formula (IV): Where R 31-35 R 41-48 and R 51-59 Each of them is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C )3、-P(R P )2、-N(R N )2、-OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-, R C C(O)N(R N )-、(R C )2NC(O)- or halogen; R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 and R 15 Independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -Si(R) C )3、-Ge(R C )3、-P(R P )2、-N(R N )2-OR C -SR C -NO2, -CN, -CF3, R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-, R C C(O)N(R)-、(R C )2NC(O)- and halogens; L is (C1-C 40 ) hydrocarbon group or (C2-C 40 ) heterohydrocarbon group; and Each R in equation (I) C R P and R N Independently for (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heterohydrocarbon group or -H; and: In equation (V), M 2 It can be made of titanium, zirconium, or hafnium; Each X 2 Independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 heteroalkyl groups, -CH2Si(R) C ) 3-J (OR C ) J 、-Si(R C ) 3-J (OR C ) J -OSi(R) C ) 3-J (OR C ) J -CH2Ge(R) C ) 3-J (OR C ) J -Ge(R) C ) 3-J (OR C ) J -P(R) C ) 2-K (OR C ) K -P(O)(R C ) 2-K (OR C ) K -N(R) C )2、-NH(R C ), -N(Si(R) C )3)2、-NR C Si(R C )3、-NHSi(R C 3. -OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C )2、-N=CH(R C -N=CH2, -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R) C )C(O)R C -N(R) C )C(O)H、-NHC(O)R C -C(O)N(R) C )2、-C(O)NHR C -C(O)NH2, halogens, B(R) Y 4. Al(R) Y )4 or Ga(R Y )4 or hydrogen, where each R C Independently for (C1-C 30 ) hydrocarbon group or (C1-C 30 ( ) heterohydrocarbon groups, and each J is 0, 1, 2 or 3, and each K is 0, 1 or 2; each R Y -H, (C1-C 30 Hydrocarbon group or halogen atom, wherein two X 2 Ligands can link together to form rings; A is -C(R) 22 )C(R 23 )-、CH(R 22 )CH(R 23 - or -CH(R) 22 )CH(R 23 )CH(R 24 )-, and optionally: R 21 and R 22 Capable of connecting to form aromatic or non-aromatic rings; or R 22 and R 23 Capable of connecting to form aromatic or non-aromatic rings; or When A is -CH(R) 22 )CH(R 23 )CH(R 24 When )-, R 23 and R 24 Capable of connecting to form aromatic or non-aromatic rings, or R 24 and R 25 Capable of connecting to form aromatic or non-aromatic rings; or When A is -C(R) 22 )C(R 23 - or -CH(R) 22 )CH(R 23 When )-, R 23 and R 25 They can connect to form aromatic or non-aromatic rings; R 21 R 22 R 23 R 24 and R 25 Independently for (C1-C 50 ) hydrocarbon group, (C1-C 50 (C6-C) heterohydrocarbon group, (C6-C) 30 )Aryl, (C5-C 30 ) heteroaryl; and R 26 R 27 R 28 R 29 and R 30 Each independently constitutes (C1-C) 12 )alkyl, halogen-substituted (C1-C 12 )alkyl, halogen-substituted (C6-C 18 )Aryl, halogen-substituted (C3-C 50 )cycloalkyl or -H.

2. The polymerization method according to claim 1, wherein the polymerization method occurs in the presence of hydrogen feed.

3. The polymerization method according to claim 1, wherein the polymerization method occurs in the absence of hydrogen feed.

4. The polymerization method according to claim 1, wherein R 1 and R 16 At least one of them is a group having formula (II) or a group having formula (III).

5. The polymerization method according to any one of the preceding claims, wherein R 8 and R 9 It is independently a (C1-C4) alkyl group.

6. The polymerization method according to any one of the preceding claims, wherein R 3 and R 14 For (C1-C 20 )alkyl.

7. The polymerization method according to any one of the preceding claims, wherein L is selected from -CH2(CH2). m CH2-、-CH2Si(R C (R) D CH2-, -CH2Ge(R) C (R) D CH2-, -CH2(CH3)CH2CH*(CH3), bis(methylene)cyclohexyl-1,2-diyl; -CH2CH(R C CH2-, -CH2C(R) C )2CH2-, where each R in L C For (C1-C 20 ) hydrocarbon group, and R in L D For (C1-C 20 ) hydrocarbon group.

8. The polymerization method according to any one of the preceding claims, wherein A is -C(R) 22 )C(R 23 - or -C(R) 22 )C(R 23 )C(R 24 )-.

9. The polymerization method according to any one of the preceding claims, wherein R 22 R 23 and R 24 For (C1-C 20 )alkyl or -H, and R 21 and R 25 To replace (C6-C) 18 Aryl.

10. The polymerization method according to any one of the preceding claims, wherein R 22 R 23 and R 24 The following are selected independently: methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, methoxy, dimethylamino, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl.

11. The polymerization method according to any one of the preceding claims, wherein the polymerization method is a solution polymerization reaction.

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