Ethylene solution polymerization method using Ziegler-Natta catalyst and pre-hydrogenation catalyst

Abstract

A method for polymerizing olefin monomers and a catalyst system is disclosed. The catalyst system comprises a post-metallocene pre-catalyst that does not produce hydrogen; a co-catalyst; and a catalyst having the formula Cp2TiX. n TiCp2 or Cp2TiX n The pre-hydrogenation catalyst, wherein each Cp is formed by at least one (C1-C2) catalyst. 10 )alkyl-substituted cyclopentadienyl; each X is independently a monoanion or neutral, wherein each X is independently (C1-C1) 40 hydrocarbons, (C1-C) 40 (C1-C) heterohydrocarbons, (C1-C) 40 ) hydrocarbon group, (C1-C 40 (a heterohydrocarbon group or a halogen atom; and n is 1 or 2.)

Description

[0001] Cross-reference of related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 881,184, filed July 31, 2019, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] Embodiments of this disclosure generally relate to catalyst compositions for polymerizing ethylene or for copolymerizing ethylene with one or more α-olefins, and to polymerization methods utilizing such catalyst compositions. Background Technology

[0004] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, were produced using various catalyst systems. 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] Ethylene-based polymers and propylene-based polymers are manufactured for a variety of articles. The polymerization methods for polyethylene and polypropylene can vary in many ways to produce a variety of resulting polyethylene resins with different physical properties, which make the resins suitable for different applications. Ethylene monomers, as well as optionally one or more comonomers, are present in a liquid diluent (such as a solvent), such as alkanes or isoalkanes, for example, isobutylene. Hydrogen may also be added to the reactor. Catalyst systems used to produce ethylene-based polymers typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (metallocene or non-metallocene) catalyst systems. The reactants in the diluent and catalyst systems are circulated around the reactor at elevated polymerization temperatures, thereby producing ethylene-based homopolymers or copolymers. A portion of the reaction mixture, comprising polyethylene product dissolved in the diluent, as well as unreacted ethylene and one or more optional comonomers, is periodically or continuously removed from the reactor. The reaction mixture, when removed from the reactor, can be processed to remove polyethylene product from the diluent and unreacted reactants, wherein the diluent and unreacted reactants are typically recycled back to the reactor. Alternatively, the reaction mixture can be fed into a second reactor connected in series with the first reactor, in which a second polyethylene fraction can be produced.

[0006] Diocene pre-hydrogenation catalysts have been used in (1) metallocene-catalyzed polymerization reactions to remove H2 generated by the metallocene polymerization catalyst; and (2) in one reactor of a connected reactor system to remove H2 carried from the previous reactor. By removing H2 from the catalyst system, H2 cannot terminate the polymerization chain, thereby increasing the molecular weight of the produced polymer. However, these applications of diocene catalysts for H2 removal are limited to gas-phase and slurry-phase polymerization reactions with reaction temperatures typically ranging from 60°C to 120°C. Summary of the Invention

[0007] There has been a persistent need to develop catalyst systems or pre-catalysts for producing high molecular weight polymers at high polymerization temperatures (120°C to 250°C). Furthermore, the catalyst system should possess high efficiency, high reactivity, and the ability to produce high molecular weight polymers (greater than 100,000 g / mol).

[0008] Embodiments of this disclosure include catalyst systems. The catalyst system includes a post-metallocene pre-catalyst that does not produce hydrogen; a co-catalyst; and a catalyst having the formula Cp2TiX2 or Cp2TiX. n Pre-hydrogenation catalyst for TiCp2. In formulas Cp2TiX2 and Cp2TiX... n In TiCp2, each Cp is optionally divided by at least one (C1-C2). 10 ) alkyl-substituted cyclopentadienyl; and each X is independently a halogen atom.

[0009] Embodiments of this disclosure include polymerization methods. A polymerization method for producing polyolefin polymers includes making (C2-C...) 12 α-olefins react in solution in the presence of the catalyst system disclosed herein. Detailed Implementation

[0010] Embodiments of this disclosure include catalyst systems. In one or more embodiments, the catalyst system includes a post-metallocene pre-catalyst that does not produce hydrogen; a co-catalyst; and a catalyst having the formula Cp2TiX. n Pre-hydrogenation catalysts for TiCp2 or Cp2TiX2. In the formulas Cp2TiX2 and Cp2TiX... n In TiCp2, each Cp is separated by at least one (C1-C2). 10 )alkyl-substituted cyclopentadienyl; each X is independently a monoanion or neutral, wherein each X is independently (C1-C 40 hydrocarbons, (C1-C) 40 ( ) heterohydrocarbons, (C1-C 40 ) hydrocarbon group, (C1-C 40 (a heterohydrocarbon group or a halogen atom; and n is 1 or 2.)

[0011] In various embodiments, the catalyst system comprises a post-metallocene pre-catalyst that does not produce hydrogen; and Cp2TiX2 treated with an alkylaluminum material. In the formula Cp2TiX2, each Cp is optionally separated by at least one (C1-C2) catalyst. 10 )alkyl-substituted cyclopentadienyl; each X is independently a monoanion or neutral, wherein each X is independently (C1-C 40 hydrocarbons, (C1-C) 40 ( ) heterohydrocarbons, (C1-C 40 ) hydrocarbon group, (C1-C 40 (a heterohydrocarbon group or a halogen atom; and n is 1 or 2.)

[0012] In embodiments of the catalyst system, the catalyst prior to hydrogenation has the formula Cp2TiX2. In the formulas Cp2TiX2 and Cp2TiX... n In TiCp2, each Cp is controlled by at least one R. 1 Substituted cyclopentadienyl group, wherein R 1 It is (C1-C) 10 )alkyl; and each X is independently (C1-C 40 hydrocarbons, (C1-C) 40 (Hydrocarbons, halogen atoms, (C1-C)) 40 ) heterohydrocarbon group, or (C1-C 40 ) hydrocarbon group; and n is 1 or 2.

[0013] In one or more embodiments, in the formulas Cp2TiX2 and Cp2TiX n In TiCp2, each Cp is separated by at least one R selected from methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, tert-octyl, n-nonyl, or n-decyl. 1 Substitution. In one or more embodiments, the catalyst prior to hydrogenation is selected from ethylated Cp2TiCl2, butylated Cp2TiCl2, and ethylated Cp2TiCl2.

[0014] In one or more embodiments, the pre-hydrogenation catalyst is selected from bis(cyclopentadienyl)titanium chloride, bis(methylcyclopentadienyl)titanium chloride, bis(ethylcyclopentadienyl)titanium chloride, and bis(butylcyclopentadienyl)titanium chloride.

[0015] In some embodiments, in the formula Cp2TiX2, each X is a substituted benzyl or a substituted heteroarylbenzyl. In other embodiments, X is selected from the group consisting of:

[0016]

[0017] In one or more embodiments of the catalyst system, the catalyst before hydrogenation is unsupported.

[0018] In one or more embodiments, the alkylaluminum material includes alkylaluminoxanes, modified alkylaluminoxanes, or alkylaluminum having the formula AlR3, wherein each R is independently (C1-C1). 40 hydrocarbons, (C1-C) 40 ( ) heterohydrocarbons, (C1-C 40 ) hydrocarbon group, (C1-C 40 The aluminum atom may contain a heteroalkyl group or a halogen atom. In various embodiments, the aluminum substance is the product of the reaction of AlR3 with water, an alcohol, a silanol, or a Lewis base (e.g., pyridine) or an alkylamine (monosubstituted, disubstituted, or trisubstituted alkylamine). A non-limiting list of products of the reaction of AlR3 with water, an alcohol, a silanol, or a Lewis base includes diisobutylalumina (DIBAO or DIBAL-O) or isobutylaluminoxane (IBAO).

[0019] In some embodiments, the alkylaluminum material is triisobutylaluminum (TiBAl) or an aluminum oxane. The alkylaluminum oxane can be (C1-C2) 10 ) Alkyl aluminum oxane or polymethyl aluminum oxane (PMAO) in polymeric form. PMAO can be a performance-enhanced polymethyl aluminum oxane (PMAO-IP), which is commercially available from AkzoNobel. (C1-C 10 Alkyl aluminum oxanes can be methyl aluminum oxane (MAO), modified methyl aluminum oxane (MMAO) (e.g., type 3A (MMAO-3A), type 7 (MMAO-7), or type 12 (MMAO-12) modified methyl aluminum oxane), ethyl aluminum oxane, n-propyl aluminum oxane, isopropyl aluminum oxane, butyl aluminum oxane, isobutyl aluminum oxane, n-pentyl aluminum oxane, neopentyl aluminum oxane, n-hexyl aluminum oxane, n-octyl aluminum oxane, 2-ethylhexyl aluminum oxane, cyclohexyl aluminum oxane, or 1-methylcyclopentyl aluminum oxane. Aryl aluminum oxanes can be (C6-C6) 10 Arylaluminoxanes, which may be phenylaluminoxanes, 2,6-dimethylphenylaluminoxanes, or naphthylaluminoxanes.

[0020] Modified methylaluminoxanes are a mixture of aluminoxane structures with methyl or longer alkyl substituents, which are generally considered to help improve the solubility of hydrocarbons or materials and increase their stability against gelation or other precipitation events that may occur due to long-term storage.

[0021] The non-hydrogen-producing post-metallocene pre-catalysts disclosed herein include non-metallocene pre-catalysts that do not produce H2 or produce less than or equal to 1 part per million (ppm) of H2, less than or equal to 0.5 ppm of H2, or less than or equal to 0.1 ppm of H2 under solution polymerization conditions. Polymerization conditions may include polymerization temperatures from 90°C to 250°C and pressures from 25 psig to 650 psig.

[0022] In one or more embodiments of the catalyst system, the pre-metallocene catalyst after non-hydrogen production is unsupported.

[0023] In one or more embodiments, the molar ratio of aluminum to titanium in the alkylaluminum material is from 2:1 to 20:1. In some embodiments, the molar ratio of aluminum to titanium is from 2.2:1 to 15:1 or from 2.5:1 to 8:1.

[0024] In one or more embodiments, the post-metallocene precatalyst that does not produce hydrogen includes a bis(phenylphenoxy) group IV precatalyst or a geometry-restricted group IV precatalyst.

[0025] According to some embodiments, the bis(phenylphenoxy) metal-ligand complex has a structure according to formula (I):

[0026]

[0027] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, said metal being in an oxidation state of +2, +3, or +4. (X) n The subscript n is 0, 1, or 2. When the subscript n is 1, X is a monodentate or bidentate ligand, and when the subscript n is 2, each X is selected from monodentate ligands.

[0028] In equation (I), L is a bibasic unit selected from the following groups: (C1-C 40 )hydroalkyl group, (C1-C 40 ) heterohydrocarbon group, -Si(R C )2-、-Si(R C )2OSi(R C )2-、-Si(R C )2C(R C )2-、-Si(R C )2Si(R C )2-、-Si(R C )2C(R C )2Si(R C )2-、-C(R C )2Si(R C )2C(R C )2-、-N(RN )C(R C )2-、-N(R N )N(R N )-、-C(R C )2N(R N )C(R C )2-、-Ge(R C )2-、-P(R P )-、-N(R N )-, -O-, -S-, -S(O)-, -S(O)2-, -N=C(R C )-, -C(O)O-, -OC(O)-, -C(O)N(R)-, and -N(R C )C(O)-.

[0029] In equation (I), each Z is independently selected from -O-, -S-, -N(R) N - or - P(R) P )-. R 1 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 R 15 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 (XI), groups having formula (XII), and groups having formula (XIII):

[0030]

[0031] In equations (XI), (XII), and (XIII), R 31 -R 35 R 41 -R 48 and R 51 -R 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, provided that R 1 or R 16 At least one of them is a group having formula (XI), a group having formula (XII), or a group having formula (XIII).

[0032] 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 Choose from those with formula (II), (III) or (IV) and R 1 Groups that are the same as or different from the group. 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 R16 Both can be groups having formula (III), where group R 41-48 In R 1 and R 16 The same or different in; 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.

[0033] In some implementations, 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.

[0034] In some implementations, when R 1 or R 16 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 Each of these is -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 Yes -H. In some implementations, R 42 and R 47 The two in it are -H.

[0035] In some implementations, R 3 and R 14 It is tert-octyl, n-octyl, methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl). In other embodiments, R 6 and R 11 It is a halogen. In some embodiments, R 3 and R 14 It is methyl; and R 6 and R 11 It is halogen.

[0036] In some embodiments of the metal-ligand complex of formula (I), when R 5-7 When it is fluorine, it does not exceed one R. 10-12 It is fluorine. In other embodiments, when R 10-12 When it is fluorine, R 5-7No more than one of them is fluorine. In other embodiments, R 5-7 And R 10-12 Less than four of them are fluorine. In one or more embodiments, R 7 R 8 R 9 and R 10 Yes -H. In some implementations, R 7 and R 10 It is a halogen. In some embodiments, R 5-7 Two of them are fluorine and R 10-12 Two of them are fluorine.

[0037] In one or more embodiments, in formula (I), L is selected from -CH2CH2CH2- or -(CH2). x GeR G 2(CH2) x - or -(CH2) x SiR2(CH2) x - where each x is independently 1, 2, or 3.

[0038] In formula (I), M in the metal-ligand complex can be a transition metal such as titanium (Ti), zirconium (Zr), or hafnium (Hf), and the oxidation state of the transition metal can be +2, +3, or +4. (X) refers to the number of ligands X that bind to or associate with metal M. n The subscript n is 1, 2 or 3.

[0039] In one or more embodiments, in formula (I), each X may be a monodentate ligand, wherein the monodentate ligand is halogenated and unsubstituted (C1-C1) independently of any other ligand X. 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.

[0040] In some embodiments, in formula (I), each X 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 a different one selected from methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-dimethylsilane-1,3-diyl or 1,3-butadiene.

[0041] In illustrative embodiments, the catalyst system may comprise a metal-ligand complex according to formula (I) having the structure of any one of the following PCAT-1, PCAT-2, PCAT-3.

[0042]

[0043] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-octyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 1A);

[0044] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-chloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 2A);

[0045] (2',2"-(propane-1,3-diylbis(oxy))bis(3'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 3A);

[0046] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 4A);

[0047] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-cyano-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 5A);

[0048] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-dimethylamino-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 6A);

[0049] (2',2"-(propane-1,3-diylbis(oxy))bis(3',5'-dimethyl-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 7A);

[0050] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-ethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 8A);

[0051] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5'-tert-butyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 9A);

[0052] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 10A);

[0053] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(9H-carbazol-9-yl)-5'-chloro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 11A);

[0054] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 12A);

[0055] (2',2"-(2,2-dimethyl-2-silylpropane-1,3-diylbis(oxy))bis(3',5'-dichloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 13A);

[0056] (2'2"-(2,2-dimethyl-2-silylpropane-1-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 14A);

[0057] (2',2"-(propane-1,3-diylbis(oxy))bis(3'-bromo-5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 15A);

[0058] (2',2"-(propane-1,3-diylbis(oxy))-(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(3",5"-dichloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 16A);

[0059] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5'-fluoro-3'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 17A);

[0060] (2',2"-(butane-1,4-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 18A);

[0061] (2',2"-(ethane-1,2-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium (pre-catalyst 19A);

[0062] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylzirconium (pre-catalyst 20A);

[0063] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3',5'-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyltitanium (pre-catalyst 24); and

[0064] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyltitanium (pre-catalyst 21A).

[0065] According to some embodiments, the post-metallocene precatalyst that does not produce hydrogen is a metal-ligand complex according to formula (II):

[0066]

[0067] In formula (II), M is a metal selected from any of the elements in groups 3 to 13 of the periodic table, the lanthanides and the actinides, and the metal is in an oxidation state of +2, +3 or +4.

[0068] In equation (II), each R A R B R C and R D It is -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)-, or halogen. Optionally, R A R B R C and R D Any two of them can be connected to form a non-aromatic ring or an aromatic ring. Q is boron, nitrogen, phosphorus, sulfur, oxygen, carbon, silicon, or germanium.

[0069] In equation (II), each X 2Independently a monodentate ligand, wherein the monodentate ligand is a monoanion or bis-anion, halogen, or unsubstituted (C1-C2) ligand. 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. (X 2 ) p The subscript p is 1, 2, or 3. In some implementations, (1) when X 2 When it is an anionic ligand, p is 2 smaller than the oxidation state of M; or (2) when X 2 When it is a dianionic ligand group, p is 1.

[0070] In illustrative embodiments, the catalyst system may comprise a metal-ligand complex having the structure of PCAT-4 according to formula (II):

[0071]

[0072] co-catalyst components

[0073] 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) or (II). For example, a pre-catalyst of a metal-ligand complex according to formula (I) or (II) can be made catalytically active by contacting the complex with an activated co-catalyst or by combining the complex with an activated co-catalyst. Additionally, the metal-ligand complex according to formula (I) or (II) comprises both a neutral pre-catalyst form and a catalytic form that may be positively charged due to the loss of a monomeric ionic ligand (such as benzyl or phenyl). Suitable activation co-catalysts used herein include alkylaluminum; polymeric or oligomeric alumoxanes (also known as aluminumoxanes); neutral Lewis acids; and non-polymeric, non-coordinated, ionic compounds (including those used under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activation co-catalysts and techniques are also contemplated. The term "alkylaluminum" refers to dihydrogenated monoalkylaluminum or dihalogenated monoalkylaluminum, hydrogenated dialkylaluminum or halodialkylaluminum, or trialkylaluminum. Examples of polymeric or oligomeric aluminum oxanes include methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, and isobutylaluminoxane.

[0074] Lewis acid activation cocatalysts contain (C1-C) as described herein. 20A 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-C2)-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 tri(fluorosubstituted phenyl)borane or tri(pentafluorophenyl)borane. In some embodiments, the activation cocatalyst is tri((C1-C)borane. 20 ) hydrocarbon borates (e.g., triphenylmethyltetrafluoroborate) or tri((C1-C 20 )hydro-based)ammonium tetra((C1-C 20 )hydro-2,4-di(octadecyl)methylammonium tetra(pentafluorophenyl)borane (e.g., bis(octadecyl)methylammonium tetra(pentafluorophenyl)borane). As used herein, the term "ammonium" means as ((C1-C) 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 + nitrogen cations, wherein each (C1-C 20 The hydrocarbon groups (when there are two or more) can be the same or different.

[0075] The combination of neutral Lewis acid activation cocatalysts comprises a mixture including tris((C1-C4)alkyl)aluminum and tris((C6-C4)halides. 18 Combinations 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.

[0076] Catalytic systems comprising metal-ligand complexes of formula (I) or (II) can be activated to form active catalyst compositions by combination with one or more cocatalysts (e.g., cation-forming cocatalysts, strong Lewis acids, or combinations thereof). Suitable activating cocatalysts comprise 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)methyl, tetra(pentafluorophenyl)borate (1-)amine, and combinations thereof.

[0077] In some embodiments, one or more of the aforementioned activating 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 formula (I) or (II) to the total molar number of one or more activating cocatalysts is from 1:10,000 to 100:1. In some embodiments, this ratio is from 1:5000, or from 1:1000, to 10:1 or to 1:1. When an aluminum oxane is used alone as an activating cocatalyst, preferably, the molar number of the aluminum oxane used is at least 100 times the molar number of the metal-ligand complex of formula (I) or (II). In some other embodiments, when tris(pentafluorophenyl)borane is used alone as an activating cocatalyst, the ratio of the molar amount of tris(pentafluorophenyl)borane to the total molar amount of one or more metal-ligand complexes of formula (I) or (II) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activating cocatalysts typically used are approximately equal in molar amount to the total molar amount of one or more metal-ligand complexes of formula (I) or (II).

[0078] Embodiments of this disclosure include polymerization methods. Polymerization methods for producing polyolefin polymers include reacting ethylene and optionally one or more α-olefin monomers in solution in the presence of a catalyst system disclosed herein, wherein the catalyst system comprises a post-metallocene pre-catalyst that does not produce hydrogen and a pre-hydrogenation catalyst as previously disclosed.

[0079] In one or more embodiments of the polymerization method, the one or more α-olefins may be (C2-C5) 12 α-olefins. In some embodiments, the polymerization method contains only a single type of olefin, ethylene. In some embodiments, the polymerization method includes α-olefins selected from (C3-C4). 12 α-olefin comonomers. In various embodiments, (C2-C 12α-olefin monomers include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, and combinations thereof. 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 from the group consisting of 1-hexene and 1-octene.

[0080] In one or more embodiments of the polymerization method, (C2-C 12 α-olefins react in a solution in a reactor at a reaction temperature of 150°C to 350°C.

[0081] Implementations of the polymerization methods include, but are not limited to, solution polymerization methods using one or more conventional reactors (e.g., parallel or series loop reactors, isothermal reactors, stirred tank reactors, batch reactors, or any combination thereof). In one embodiment, the polymerization method may include solution polymerization in a two-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 co-catalysts. The catalyst system described herein may optionally be present in the first or second reactor in combination with one or more other catalysts. In one embodiment, ethylene-based polymers may be produced via solution polymerization in a two-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 the catalyst system described herein.

[0082] In another embodiment, the polymerization method may include solution polymerization in a single reactor system, such as a single loop reactor system or a single stirred tank reactor, wherein ethylene is polymerized in the presence of a catalyst system described herein and optionally one or more co-catalysts described in the preceding paragraphs and optionally combined with one or more other catalysts.

[0083] Test methods

[0084] Gel permeation chromatography (GPC) method

[0085] For gel permeation chromatography (GPC), 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 PrecisionDetector (now Agilent Technologies) 2040 2-angle laser scattering (LS) detector. The autosampler oven chamber was set at 160°C, and the column chamber at 150°C. The column was a four-column Agilent "Mixed A" 30cm 20µm linear mixed-bed column. The chromatographic solvent was 1,2,4-trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). The solvent source was purged with nitrogen. The injection volume was 200 μL, and the flow rate was 1.0 mL / min.

[0086] GPC column arrays were calibrated using 21 polystyrene standards with narrow molecular weight distributions, ranging from 580 g / mol to 8,400,000 g / mol, arranged in a six-cocktail mixture, with individual molecular weights spaced at least ten times apart. These standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000 g / mol, polystyrene standards were prepared at a ratio of 0.025 g / 50 mL solvent, while for molecular weights less than 1,000,000 g / mol, standards were prepared at a ratio of 0.05 g / 50 mL solvent. The polystyrene standards were dissolved by gentle stirring at 80°C for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described by Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).

[0087] M 聚乙烯 =A×(M) 聚苯乙烯 ) B (EQ 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 corresponding polyethylene equivalent calibration point. A small adjustment to A (approximately 0.405 to 0.440) can be made to correct for column resolution and band broadening effects, resulting in the NIST standard NBS 1475 at 52,000 Mw.

[0090] Total plate counting in GPC column setups can be performed using decane (prepared at 0.04 g in 50 mL of TCB). Plate counting can be performed by injecting 200 μL of the solution according to the following equations (Equation 2) and symmetry (Equation 3):

[0091]

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

[0093]

[0094] In Equation 3, RV is the retention volume in milliliters, and peak width is in milliliters. The peak maximum is the position of the peak at its maximum value, and the one-tenth height is 1 / 10 of the height of the peak maximum. A "tail peak" refers to the peak whose retention volume is later than the peak maximum, and a "front peak" refers to the peak whose retention volume is earlier than the peak maximum. The plate count of the chromatographic system should be greater than 24,000, and the symmetry should be between 0.98 and 1.22.

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

[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 calculates Mn, Mw, and Mz of polyethylene equivalent molecular weight from baseline-subtracted IR chromatograms at each equidistant data collection point (i) and from the narrow standard calibration curve at point (i).

[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 alkyl peak within the narrow standard calibration. It was assumed that any variation in the decane marker peak time was related to a linear variation in the flow rate (effective flow rate) throughout the run. To facilitate the highest accuracy in RV measurement of the flow marker peak, a least-squares fitting routine was used to fit the peak 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 calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 7 (EQ 7). Processing of the flow marker peak was performed via PolymerChar GPCOne. TM The software performs the adjustment. An acceptable flow rate correction should ensure that the effective flow rate is within + / - 2% of the nominal flow rate.

[0101] Effective flow rate = Effective flow rate * (RV(FM calibration) / RV(FM sample)) (EQ 7)

[0102] Short chain branch measurement.

[0103] The short-chain branching per 1000 total carbons (SCDB / 1000TC) was measured according to the method described in the “Molecular Weight Comonomer Distribution Index (MWCDI)” section of WO2015200743A1.

[0104] Catalyst efficiency

[0105] Catalyst efficiency is calculated based on the amount of ethylene consumed per gram of metal in the pre-polymerization catalyst during polymerization (g ethylene / g metal). The metal count refers to the number of grams of metal contributed by the metal in the pre-polymerization catalyst and excludes Ti from the pre-hydrogenation catalyst of the alkylated ditizocene.

[0106] Solution-Batch Reactor Copolymerization Test Method

[0107] A batch reactor is charged with a specified amount of 1-octene and Isopar E, with a total amount of 1580 g. The reactor contents are heated to the desired polymerization temperature, and then saturated with ethylene in the presence of a specified amount of molecular hydrogen (H2). A solution of a non-hydrogen-producing post-metallocene pre-catalyst and a co-catalyst is mixed at a molar ratio of co-catalyst to pre-catalyst of 1.2:1, and then MMAO-3A is added to the mixture at a molar ratio of 50 / 1 to pre-catalyst. An alkylation titanocene hydrogenation pre-catalyst (Cp2TiCl2-TiBAl or Cp2TiCl2-MMAO-3A) is added to the mixture. The contents are immediately injected into the reactor. The amount of pre-catalyst is adjusted to maintain the ethylene consumption during polymerization within approximately 10-30 g to avoid large temperature spikes in the reactor at the start of polymerization. The pressure in the reactor was maintained at 3100 kPa (equivalent to 450 psi) using an ethylene flow to compensate for the pressure drop caused by ethylene consumption during polymerization. After a 10-minute reaction time, the bottom valve was opened and the reactor contents were transferred to a glass vessel. The contents of the vessel were poured onto a polyester film-lined tray, allowed to cool completely, and dried at standard temperature and pressure. The dried contents were further dried under reduced pressure to obtain the product, a poly(ethylene-copoly-1-octene) copolymer.

[0108] Catalyst efficiency

[0109] Catalyst efficiency is calculated based on the amount of ethylene consumed during polymerization per gram of metal in the prepolymerization catalyst (g ethylene / g metal). The metal count refers to the number of grams of metal contributed by the metal in the prepolymerization catalyst and does not include Ti in the pre-alkylation titanoceramsite hydrogenation catalyst.

[0110] Example

[0111] The following examples are provided to illustrate the implementation methods described in this disclosure, and these examples are not intended to limit the scope of this disclosure or its appended claims.

[0112] Preparation of post-metallocene pre-catalysts that do not produce hydrogen

[0113] PCAT-1 is typically synthesized according to Example I4 in WO2017058981 by replacing HfCl4 in Example I4 with an equimolar amount of ZrCl4.

[0114] PCAT-2. PCAT-2 is synthesized according to Example A11 in WO2007136494.

[0115] PCAT-3. PCAT-3 was synthesized according to Example 23 in WO2018183700A1.

[0116] PCAT-4 is synthesized according to Example 7 of US6268444B1.

[0117]

[0118] Co-catalyst (co-catalyst 1). Co-catalyst 1 is a methyl di((C) group of tetra(pentafluorophenyl)borate. 14 -C 18 alkyl ammonium salts, which can be converted into long-chain trialkylamines (Armeen) TM M2HT (available from Akzo Nobel), HCl, and Li[B(C6F5)4] were reacted to prepare the catalyst. This preparation is disclosed in Example 2 of US 5,919,983. Co-catalyst 1 was purchased from Boulder Scientific.

[0119] Preparation of modified hydrogenation catalysts

[0120] Alkylation of titanium cadmium pre-hydrogenation catalyst Cp2TiCl2-Al( i Bu)3. Add 0.544 g of Cp₂TiCl₂, 4 mL of Isopar E solvent, and a stir bar to a 4 ounce bottle to form a mixture. Add 38.0 mL of 1.0 M triisobutylaluminum (Al( i A hexane solution of Bu(3) was slowly added to the mixture over 10 minutes with stirring. Solid Cp2TiCl2 became soluble and formed a blue solution. (The remaining text appears to be incomplete and requires further context.) i The molar ratio of Al from Bu)3 to Ti from Cp2TiCl2 in the solution is 17.4.

[0121] Alkylated titanocene pre-hydrogenation catalyst Cp₂TiCl₂-MMAO-3A. ​​A solution of 50.0 mmol of MMAO-3A containing 7 wt% aluminum in heptane (27 mL) was added to 1.0 mmol of Cp₂TiCl₂ under stirring. Solid Cp₂TiCl₂ became soluble and formed a blue solution. The molar ratio of Al from MMAO-3A to Ti from Cp₂TiCl₂ was 50.

[0122] MMAO-3A. ​​It has an approximate molecular formula [(CH3)]. 0.7 (iso-C4H9) 0.3 AlO; CAS Registry No. 146905-79-5] and obtained as a heptane solution from Akzo Nobel NV, type 3A modified methylaluminoxane (MMAO-3A).

[0123] The polymerization of ethylene and α-olefins, particularly ethylene and 1-octene, was carried out in the presence of different amounts of H2 to establish the relationship between (1) the weight-average molecular weight (Mw) of the polymer and the amount of H2; (2) the change in molecular weight; and (3) the level of short-chain branching. The properties of the resulting polymers and catalyst systems are recorded in Tables 1 to 8.

[0124] The solution batch reactor polymerization experiments (the data of which are provided in Tables 1 to 8) were conducted using the previously described solution batch reactor method.

[0125] Table 1: Cp2TiCl2-Al with and without pre-hydrogenation catalyst ( i Bu)3's aggregation PCAT-1

[0126]

[0127] Δ(Mw)(%) is calculated as the percentage increase in polymer Mw relative to the Mw of the polymer obtained under the same polymerization conditions without the use of a pre-hydrogenation catalyst. In IE1 and IE2, each Δ(Mw)(%) is calculated based on the molecular weight of the polymer produced in CE1.

[0128] In Comparative Example 1 (CE1), Innovative Example 1 (IE1), and Innovative Example 2 (IE2), the polymerization conditions included hydrogen. The catalyst systems for IE1 and IE2 included PCAT-1 and the pre-hydrogenation catalyst Cp2TiCl2-Al (… i Bu)3. The CE1 catalyst system lacks a pre-hydrogenation catalyst. The polymers produced in IE1 and IE2 have larger molecular weights than those produced in CE1. Furthermore, the short-chain branching ratio (SCB / 1000TC) per 1000 total carbon atoms in the polymers produced in IE1 and IE2 is similar to that in the polymer of CE1.

[0129] The polymerization conditions of Comparative Example 2 (CE2) and Comparative Example 3 (CE3) lacked hydrogen. In the absence of H2, the pre-hydrogenation catalyst Cp2TiCl2-Al ( i The polymer produced by the catalyst system of Bu)3 has a lower molecular weight than the polymer produced by the catalyst system of CE3, which lacks a pre-hydrogenation catalyst. The lower molecular weight of the polymer in CE2 indicates that the post-metallocene pre-catalyst PCAT-1 does not produce H2 or does not produce an amount of H2 that significantly reduces the polymer's molecular weight. Conversely, it is believed that the addition of the alkylated dititanium pyrocene pre-hydrogenation catalyst Cp2TiCl2-Al( iBu)3, the molecular weight of the polymer in CE2 is smaller than that of the polymer in CE3. Without being bound by theory, the participation of alkyl Al substances in the pre-hydrogenation catalyst in the polymer induces a chain transfer reaction, which results in the lower molecular weight of the polymer in CE2.

[0130] Table 2. Polymerization of PCAT-1 with and without pre-hydrogenation catalyst Cp2TiCl2-MMAO-3A

[0131]

[0132] For each embodiment in the examples in Table 2, the pre-hydrogenation catalyst used in the polymerization reaction was Cp2TiCl2-MMAO-3A. ​​In each embodiment in Table 2, the temperature, ethylene pressure, and initial octene amount were the same, and the molar ratio of PCAT-1 to Cp2TiCl2 differed. The molecular weight of the polymers produced in the embodiments of Table 2 increased relative to the amount of pre-hydrogenation catalyst present in the system.

[0133] Table 3. Cp2TiCl2-Al with and without hydrogenation catalyst (with / without) i The polymerization of Bu)3 and Cp2TiCl2-MMAO-3A into PCAT-2

[0134]

[0135] When hydrogen is present in the reactor system, it is produced by a catalyst system with PCAT-2 and a hydrogenation catalyst Cp2TiCl2-Al ( i The molecular weight of the polymer produced by Bu)3 is greater than that of the polymer produced by the comparative catalyst system of CE5.

[0136] With PCAT-1 and Cp2TiCl2-Al ( i Compared to the catalyst system containing Bu)3, the catalyst system containing PCAT-2 and Cp2TiCl2-Al( i The catalyst system of Bu)3 produced polymers with a greater amount of short-chain branching (comonomer incorporation).

[0137] Table 4: Cp2TiCl2-Al with and without pre-hydrogenation catalyst ( i Bu)3's aggregation PCAT-3

[0138]

[0139] Examples CE9 (without hydrogenation catalyst) and IE11 and IE12 (including hydrogenation catalyst and post-metallocene pre-catalyst that does not produce hydrogen) were all performed in the presence of hydrogen. The polymers produced by the catalyst systems of IE11 and IE12 have larger molecular weights than the polymers produced in CE9.

[0140] In Examples CE10 and CE11, the polymerization reaction was carried out without the addition of hydrogen. Example CE10, which includes both a pre-hydrogenation catalyst and a post-metallocene pre-catalyst, produces a polymer with a smaller molecular weight than the polymer produced by the catalyst system CE11, which lacks a pre-hydrogenation catalyst. This indicates that the post-metallocene pre-catalyst PCAT-3 does not produce H2 or does not produce a significant amount of H2 to reduce the polymer's molecular weight.

[0141] To obtain the results in Table 5, the polymerization temperature and the amount of comonomer were varied, and the polymerization reaction was carried out without the addition of hydrogen.

[0142] Table 5: Cp2TiCl2-Al with and without pre-hydrogenation catalyst (without H2 addition) i Bu)3's aggregation PCAT-3

[0143]

[0144] When polymerization is carried out without the addition of hydrogen, the polymer produced by a catalyst system including a pre-hydrogenation catalyst and a post-metallocene pre-catalyst (PCAT-3) has a smaller molecular weight than the polymer produced by a catalyst system lacking a pre-hydrogenation catalyst, regardless of temperature and comonomer content. This observation further confirms that the post-metallocene pre-catalyst PCAT-3 does not generate enough H2 to significantly reduce the polymer molecular weight.

[0145] Table 6: Polymerization of PCAT-3 with and without pre-hydrogenation catalyst Cp2TiCl2-MMAO-3A

[0146]

[0147] When hydrogen is added to the reaction, including the hydrogenation catalyst (Cp2TiCl2-MMAO-3A or Cp2TiCl2-Al), i The polymers produced by the catalyst systems IE13, IE14, IE15, and IE16 (Bu)3) and the post-metallocene pre-catalyst (PCAT-3) that does not produce hydrogen have larger molecular weights than those produced by catalyst systems lacking hydrogenation catalysts (e.g., CE18).

[0148] Table 7: Cp2TiCl2-Al with and without pre-hydrogenation catalyst ( iBu)3's aggregation PCAT-4

[0149]

[0150] In Examples IE17 and IE18, the catalyst system comprised a hydrogenation catalyst (Cp2TiCl2-MMAO-3A) and a post-metallocene pre-catalyst that did not produce hydrogen (PCAT-4). When hydrogen was added to the reaction, the polymers produced by the catalyst systems of Examples IE17 and IE18 had larger molecular weights compared to polymers produced by catalyst systems lacking a hydrogenation catalyst (e.g., CE19).

[0151] To obtain the results in Table 8, the polymerization temperature and the amount of comonomer were varied, and the polymerization reaction was carried out without the addition of hydrogen.

[0152] Table 8: Cp2TiCl2-Al with and without pre-hydrogenation catalyst (without H2 addition) i Bu)3's aggregation PCAT-4

[0153]

[0154] When polymerization is carried out without the addition of hydrogen, the molecular weight of polymers produced by catalyst systems including a pre-hydrogenation catalyst and a post-metallocene pre-catalyst (e.g., PCAT-4) is smaller than that of polymers produced by catalyst systems lacking a pre-hydrogenation catalyst, regardless of temperature and comonomer content. This observation further confirms that the post-metallocene pre-catalyst PCAT-4 does not generate enough H2 to significantly reduce the molecular weight of the polymer.

[0155] All references described in the Test Methods and Examples sections are incorporated herein by reference in their entirety.

Claims

1. A catalyst system, said catalyst system comprising: A non-hydrogen-producing post-metallocene pre-catalyst, wherein the non-hydrogen-producing post-metallocene pre-catalyst is a bis(phenylphenoxy) group IV pre-catalyst, and the bis(phenylphenoxy) group IV pre-catalyst is a metal-ligand complex according to formula (I): in: M is a metal selected from titanium, zirconium, or hafnium, said metal being in an oxidation state of +2, +3, or +4; n is 0, 1, or 2; When n is 1, X 1 It is either a monodentate ligand or a bidentate ligand; When n is 2, each X 1 It is a monodentate ligand on its own; Each X, as a monodentate ligand 1 Independently halogenated, unsubstituted C1-C 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; L is a bibase selected from the following groups: C1-C 40 Hydroxyl group, C1-C 40 Heteroalkyl groups, -O-, -S-, -S(O)- and -S(O)2-; Each Z is independently selected from -O- and -S-; R 1 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 R 15 and R 16 Choose independently from the following groups: -H, C1-C 40 Hydrocarbon group, C1-C 40 Heteroalkyl groups, -NO2, and halogens; Co-catalyst; and Having the formula Cp2TiX2TiCp2 or Cp2TiX n’ Pre-hydrogenation catalyst, in: Each Cp is optionally divided by at least one C1-C 10 Alkyl-substituted cyclopentadienyl; Each X is independently either a monoanion or neutral, wherein each X is independently C1-C. 40 Hydrocarbon group, C1-C 40 heterohydrocarbon groups or halogen atoms; and n' is 1 or 2; The post-metallocene pre-catalyst that does not produce hydrogen is unsupported and the pre-hydrogenation catalyst is unsupported.

2. A catalyst system, said catalyst system comprising: A non-hydrogen-producing post-metallocene pre-catalyst, wherein the non-hydrogen-producing post-metallocene pre-catalyst is a bis(phenylphenoxy) group IV pre-catalyst, and the bis(phenylphenoxy) group IV pre-catalyst is a metal-ligand complex according to formula (I): in: M is a metal selected from titanium, zirconium, or hafnium, said metal being in an oxidation state of +2, +3, or +4; n is 0, 1, or 2; When n is 1, X 1 It is either a monodentate ligand or a bidentate ligand; When n is 2, each X 1 It is a monodentate ligand on its own; Each X, as a monodentate ligand 1 Independently halogenated, unsubstituted C1-C 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; L is a bibase selected from the following groups: C1-C 40 Hydroxyl group, C1-C 40 Heteroalkyl groups, -O-, -S-, -S(O)- and -S(O)2-; Each Z is independently selected from -O- and -S-; R 1 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 R 15 and R 16 Choose independently from the following groups: -H, C1-C 40 Hydrocarbon group, C1-C 40 Heteroalkyl groups, -NO2, and halogens; and The pre-hydrogenation catalyst of Cp2TiX2 treated with alkylaluminum materials, wherein: Each Cp is subjected to at least one C1-C 10 Alkyl-substituted cyclopentadienyl; Each X is independently either a monoanion or neutral, wherein each X is independently C1-C. 40 Hydrocarbon anions, C1-C 40 Negative hydrocarbon anions or halogen atoms; and The post-metallocene pre-catalyst that does not produce hydrogen is unsupported and the pre-hydrogenation catalyst is unsupported.

3. The catalyst system according to claim 2, wherein the alkylaluminum material comprises alkylaluminoxane, modified alkylaluminoxane, or alkylaluminum having the formula AlR3, wherein each R is independently C1-C2. 40 Hydrocarbon group, C1-C 40 heterohydrocarbon groups or halogen atoms.

4. The catalyst system according to claim 2, wherein the alkylaluminum substance is the reaction product of AlR3 and a Lewis base.

5. The catalyst system according to claim 4, wherein the Lewis base is pyridine or a monosubstituted alkylamine, a disubstituted alkylamine, or a trisubstituted alkylamine.

6. The catalyst system according to claim 2, wherein the alkylaluminum substance is diisobutylalumina or isobutylaluminoxane.

7. The catalyst system according to claim 1 or 2, wherein the catalyst system further comprises an impurity scavenger.

8. The catalyst system according to claim 1 or 2, wherein each X is a substituted benzyl or a substituted heteroarylbenzyl.

9. The catalyst system according to claim 1 or 2, wherein X is... .

10. The catalyst system according to claim 1 or 2, wherein the non-hydrogen-producing post-metallocene pre-catalyst produces less than or equal to 1 ppm of hydrogen under polymerization conditions.

11. The catalyst system according to claim 1 or 2, wherein L is a bimolecular group selected from the group consisting of -C(O)O-, -OC(O)-, and -(CH2). x GeR G 2(CH2) x -, where x is 1 and R G It is isopropyl.

12. The catalyst system according to claim 1 or 2, Where R 1 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 R 15 and R 16 Independently selected from the following groups: -CN, -CF3, groups having formula (XI), groups having formula (XII), and groups having formula (XIII): in: 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 Heterohydric groups, -NO2, or halogens.

13. The catalyst system according to claim 12, wherein R 31 - R 35 R 41 - R 48 and R 51 - R 59 Each of them is independently selected from -CN and -CF3.

14. The catalyst system according to claim 2, wherein the alkylaluminum substance is a reaction product of AlR3 and water or alcohol.

15. The catalyst system according to claim 14, wherein the alcohol is a silanol.

Images