Polymerization process of ethylene in solution using Ziegler-Natta catalyst and hydrogenated procatalyst

Abstract

A process for polymerizing olefin monomers and a catalyst system comprising a non-hydrogen-producing post-metallocene procatalyst, a cocatalyst, and a catalyst of the formula CpTiX n TiCp2 or Cp2TiX n and a hydrogenation procatalyst having the formula: 10 ) alkyl-substituted cyclopentadienyl, each X is independently monoanionic or neutral, and each X is independently (C-C 40 ) hydrocarbons, (C1-C 40 ) heterohydrocarbons, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, or a halogen atom, and n is 1 or 2.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS 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.

[0002] FIELD OF THE DISCLOSURE Embodiments of the present disclosure generally relate to catalyst compositions for polymerizing ethylene or copolymerizing ethylene with one or more α-olefins, and polymerization processes utilizing such catalyst compositions. [Background technology]

[0003] Olefin-based polymers, such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers, are produced by various catalyst systems. The selection of such catalyst system used in the polymerization process of an olefin-based polymer is an important factor that contributes to the characteristics and properties of such an olefin-based polymer.

[0004] Ethylene-based and propylene-based polymers are produced for a wide variety of articles. Polyethylene and polypropylene polymerization processes can be modified in several ways to produce a wide variety of resulting polyethylene resins with different physical properties that make the various resins suitable for use in different applications. Ethylene monomer and, optionally, one or more comonomers are present in a liquid diluent (e.g., solvent), such as an alkane or isoalkane, e.g., isobutene. Hydrogen can also be added to the reactor. Catalyst systems for producing ethylene-based polymers typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (either metallocene or non-metallocene) catalyst systems. The diluent and the reactants in the catalyst system are circulated in the reactor at elevated polymerization temperatures, thereby producing an ethylene-based homopolymer or copolymer. Either periodically or continuously, a portion of the reaction mixture, including the polyethylene product dissolved in the diluent, is removed from the reactor along with unreacted ethylene and one or more optional comonomers. Once removed from the reactor, the reaction mixture may be treated to remove the polyethylene product from the diluent and unreacted reactants, which are typically recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, where a second polyethylene fraction may be produced.

[0005] Titanocene hydrogenation procatalysts have been used (1) in metallocene-catalyzed polymerization reactions to remove H2 produced by the metallocene polymerization catalyst, and (2) in one reactor of a series of connected reactors to remove H2 carried over from the previous reactor. Removing H2 from the catalyst system prevents the H2 from terminating the polymerization chain, thereby allowing for an increase in the molecular weight of the polymer produced. However, these applications of titanocene catalysts for removing H2 are limited to gas-phase and slurry-phase polymerization reactions, where reaction temperatures typically range from 60°C to 120°C. Summary of the Invention

[0006] There is a continuing need to create catalyst systems or procatalysts that produce high molecular weight polymers at high polymerization temperatures (temperatures between 120°C and 250°C). In addition, the catalyst systems should have high efficiency, high reactivity, and the ability to produce high molecular weight (greater than 100,000 g / mol) polymers.

[0007] Embodiments of the present disclosure include a catalyst system comprising a non-hydrogen-producing post-metallocene procatalyst, a cocatalyst, and a catalyst of the formula Cp2TiX2 or Cp2TiX n and hydrogenation procatalysts having the formula Cp2TiX2 and Cp2TiX n In TiCp2, each Cp is at least one (C1-C 10 ) alkyl-substituted cyclopentadienyl, and each X is independently a halogen atom.

[0008] Some embodiments of the present disclosure include a polymerization process. The polymerization process for producing a polyolefin polymer comprises the step of reacting a (C2-C3) olefin in solution in the presence of a catalyst system of the present disclosure. 12 ) α-olefins. DETAILED DESCRIPTION OF THE INVENTION

[0009] Embodiments of the present disclosure include a catalyst system. In one or more embodiments, the catalyst system comprises a non-hydrogen-producing post-metallocene procatalyst, a cocatalyst, and a catalyst of the formula CpTiX n and hydrogenation procatalysts having the formula Cp2TiX2 and Cp2TiX n In TiCp2, each Cp is a group consisting of at least one (C1-C 10 ) alkyl-substituted cyclopentadienyl, each X is independently monoanionic or neutral, and each X is independently (C-C 40 ) hydrocarbons, (C1-C 40 ) heterohydrocarbons, (C1-C 40 ) hydrocarbyl, (C1-C 40) heterohydrocarbyl, or a halogen atom, and n is 1 or 2.

[0010] In various embodiments, the catalyst system comprises a non-hydrogen-producing post-metallocene procatalyst and Cp2TiX2 treated with an alkylaluminum species. In the formula Cp2TiX2, each Cp is selected from the group consisting of at least one (C1-C 10 cyclopentadienyl optionally substituted with alkyl, each X is independently monoanionic or neutral, and each X is independently (C-C 40 ) hydrocarbons, (C1-C 40 ) heterohydrocarbons, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, or a halogen atom, and n is 1 or 2.

[0011] In an embodiment of the catalyst system, the hydrogenation procatalyst has the formula Cp2TiX2. n In TiCp2, each Cp has at least one R 1 is a cyclopentadienyl substituted with R 1 is (C1-C 10 ) alkyl, and each X is independently (C-C 40 ) hydrocarbons, (C1-C 40 ) Heterohydrocarbons, halogen atoms, (C1-C 40 ) heterohydrocarbyl, or (C-C 40 ) hydrocarbyl, and n is 1 or 2.

[0012] In one or more embodiments, the formulas Cp2TiX2 and Cp2TiX n In TiCp2, each Cp is at least one R selected from methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, iso-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, tert-octyl, n-nonyl, or n-decyl. 1In one or more embodiments, the hydrogenation procatalyst is selected from ethylated-Cp2TiCl2, butylated-Cp2TiCl2, and ethylated-Cp2TiCl2.

[0013] In one or more embodiments, the hydrogenation procatalyst is selected from bis(cyclopentadienyl)titanium chloride, bis(methylcyclopentadienyl)titanium chloride, bis(ethylcyclopentadienyl)titanium chloride, bis(butylcyclopentadienyl)titanium chloride.

[0014] In some embodiments, in the formula Cp2TiX2, each X is substituted benzyl or substituted heteroarylbenzyl. In other embodiments, X is selected from the group consisting of: [ka]

[0015] In one or more embodiments of the catalyst system, the hydrogenation procatalyst is unsupported.

[0016] In one of more embodiments, the alkylaluminum species comprises an alkylaluminoxane, a modified alkylaluminoxane, or an alkylaluminum having the formula AlR, where each R is independently (C-C 40 ) Hydrocarbons (C1-C 40 ), heterohydrocarbons, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, or a halogen atom. In various embodiments, the aluminum species is the reaction product of AlR3 with water, an alcohol, a silanol, or a Lewis base, such as pyridine or an alkylamine (mono-, di-, or trisubstituted). A non-limiting list of AlR3 with water, an alcohol, a silanol, or a Lewis base includes diisobutylaluminum oxide (DIBAO or DIBAL-O) or isobutylaluminoxane (IBAO).

[0017] In some embodiments, the alkylaluminum species is triisobutylaluminum (TiBAl) or an aluminoxane. The alkylaluminoxane is a (C-C 10 ) alkylaluminoxane or the polymeric form of polymethylaluminoxane (PMAO). The PMAO may be performance-improved polymethylaluminoxane (PMAO-IP) commercially available from AkzoNobel. (C1-C 10 The alkylaluminoxane can be methylaluminoxane (MAO), modified methylaluminoxane (MMAO), such as modified methylaluminoxane, type 3A (MMAO-3A), type 7 (MMAO-7), or type 12 (MMAO-12), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, or 1-methylcyclopentylaluminoxane. The arylaluminoxane can be (C6-C 10 ) arylaluminoxane, which may be phenylaluminoxane, 2,6-dimethylphenylaluminoxane, or naphthylaluminoxane.

[0018] Modified methylaluminoxanes are aluminoxane structures with a mixture of methyl or longer alkyl substituents, which are generally believed to aid in the solubility of hydrocarbon or other materials and increase their stability against gelation or other precipitation events that may occur on long-term storage.

[0019] Non-hydrogen-producing post-metallocene procatalysts of the present disclosure include non-metallocene procatalysts that produce no H2 or produce less than 1 ppm (parts per million) H2, less than 0.5 ppm H2, or less than 0.1 ppm H2 under solution polymerization conditions. Polymerization conditions can include polymerization temperatures of 90°C to 250°C and pressures of 25 psig to 650 psig.

[0020] In one or more embodiments of the catalyst system, the non-hydrogen-producing post-metallocene procatalyst is unsupported.

[0021] In one or more embodiments, the ratio of moles of aluminum in the alkylaluminum species to moles of titanium in the hydrogenation procatalyst is from 2:1 to 20:1. In some embodiments, the ratio of moles of aluminum to moles of titanium is from 2.2:1 to 15:1 or from 2.5:1 to 8:1.

[0022] In one or more embodiments, the non-hydrogen-producing post-metallocene procatalyst comprises a bis(phenylphenoxy) Group IV procatalyst or a constrained geometry Group IV procatalyst.

[0023] According to some embodiments, the bis(phenylphenoxy) metal-ligand complex has a structure according to formula (I): [ka]

[0024] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4. (X) n The subscript n in 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 a monodentate ligand.

[0025] In formula (I), L is (C1-C 40 ) hydrocarbylene, (C1-C 40 ) heterohydrocarbylene, -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(R N )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)—.

[0026] In formula (I), each Z is independently —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 are independently -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -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(RC )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, a halogen, a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII). [ka]

[0027] In formulas (XI), (XII), and (XIII), R 31 ~R 35 , R 41 ~R 48 , and R 51 ~R 59 each independently represents -H, (C-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -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 )NC(O)-, or halogen, with the proviso that R 1 or R 16 is a radical having formula (XI), a radical having formula (XII), or a radical having formula (XIII).

[0028] The group R in the metal-ligand complex of formula (I) 1 and R 16 are selected independently of each other. For example, R 1may be selected from radicals having formula (II), (III), or (IV), and R 16 However, (C1-C 40 ) hydrocarbyl, or R 1 may be selected from radicals having formula (II), (III), or (IV), and R 16 But R 1 R may be selected from radicals having formula (II), (III), or (IV) which are the same as or different from those of 1 and R 16 may both be radicals of formula (II), in which case the group R 31~35 is R 1 and R 16 In other examples, R 1 and R 16 may both be radicals of formula (III), in which case the group R 41~48 is R 1 and R 16 are the same or different in 1 and R 16 may both be radicals of formula (IV), in which case the group R 51~59 is R 1 and R 16 are the same or different in

[0029] In some embodiments, R 1 or R 16 at least one of which is a radical having formula (II), wherein R 32 and R 34 is tert-butyl.

[0030] In some embodiments, R 1 or R 16 is a radical having the formula (III), 43 and R 46 one or both of R 41~42 , R 44-~45 , and R 47~48Each of R is -H. 42 and R 47 one or both of R 41 , R 43~46 , and R 48 is —H. In some embodiments, R 42 and R 47 Both are -H.

[0031] In some embodiments, R 3 and R 14 is tert-octyl, n-octyl, methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl). 6 and R 11 is halogen. In some embodiments, R 3 and R 14 is methyl and R 6 and R 11 is a halogen.

[0032] In some embodiments of the metal-ligand complex of formula (I), R 5~7 is fluorine, R 10~12 In other embodiments, not more than one of R 10~12 is fluorine, R 5~7 In other embodiments, not more than one of R 5~7 and R 10~12 In one or more embodiments, less than four of R 7 , R 8 , R 9 , and R 10 is —H. In some embodiments, R 7 and R 10 is halogen. In some embodiments, R 5~7 Two of the are fluorine, and R 10~12 Two of them are fluorine.

[0033] In one or more embodiments, in formula (I), L is -CHCHCH-, -(CH) x GeR G 2(CH2) x - or -(CH2) x SiR2(CH2) x -, wherein each x is independently 1, 2, or 3.

[0034] M in the metal-ligand complex of formula (I) can be a transition metal such as titanium (Ti), zirconium (Zr), or hafnium (Hf), and the transition metal can have a formal oxidation state of +2, +3, or +4. (X) n The subscript n in refers to the number of ligands X bound to or associated with the metal M, and is 1, 2, or 3.

[0035] In one or more embodiments, in formula (I), each X, independently of any other ligand X, is selected from halogen, unsubstituted (C-C 20 ) hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O-, or R K R L N-, where R K and R L each independently is unsubstituted (C-C 20 ) hydrocarbyl.

[0036] 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 chloro. In some embodiments, each X is the same. In other embodiments, at least two X are different from each other. In embodiments where at least two X are different from at least one X, X is a different one of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0037] In an exemplary embodiment, the catalyst system comprises a metal-ligand complex according to formula (I) having the structure PCAT-1, PCAT-2, or PCAT-3: [ka]

[0038] (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)dimethyl-hafnium (Procatalyst 1A),

[0039] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-chloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 2A),

[0040] (2',2"-(propane-1,3-diylbis(oxy))bis(3'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 3A),

[0041] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 4A),

[0042] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-cyano-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 5A),

[0043] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-dimethylamino-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 6A),

[0044] (2',2"-(propane-1,3-diylbis(oxy))bis(3',5'-dimethyl-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 7A),

[0045] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-ethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 8A),

[0046] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5'-tert-butyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 9A),

[0047] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 10A),

[0048] (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)dimethyl-hafnium (Procatalyst 11A),

[0049] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 12A),

[0050] (2',2"-(2,2-dimethyl-2-silapropane-l,3-diylbis(oxy))bis(3',5'-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 13A),

[0051] (2'2"-(2,2-dimethyl-2-silapropane-1-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 14A),

[0052] (2',2"-(propane-1,3-diylbis(oxy))bis(3'-bromo-5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 15A),

[0053] (2',2"-(propane-l,3-diylbis(oxy))-(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(3",5"-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 16A),

[0054] (2',2"-(propane-l,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 17A),

[0055] (2',2"-(butane-1,4-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 18A),

[0056] (2',2"-(ethane-l,2-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium (Procatalyst 19A),

[0057] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-zirconium (Procatalyst 20A),

[0058] (2',2"-(propane-l,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3',5'-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium (Procatalyst 24), and

[0059] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium (Procatalyst 21A).

[0060] According to some embodiments, the non-hydrogen producing post-metallocene procatalyst is a metal-ligand complex according to formula (II). [ka]

[0061] In formula (II), M is a metal selected from any of the metals in Groups 3-13 of the Periodic Table, the lanthanides, and the actinides, and the metal is in the +2, +3, or +4 formal oxidation state.

[0062] In formula (II), each R A , R B , R C , and R D is -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(RP )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, or halogen. A , R B , R C , and R D Any two of may be joined to form a non-aromatic or aromatic ring. Q is boron, nitrogen, phosphorus, sulfur, oxygen, carbon, silicon, or germanium.

[0063] In formula (II), each X 2 are independently monodentate ligands, and the monodentate ligands may be monoanionic or dianionic, halogen, unsubstituted (C1-C 20 ) hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O-, or R K R L N- and R K and R L each independently is unsubstituted (C-C 20 ) hydrocarbyl. (X 2 ) p The subscript p in is 1, 2, or 3. In some embodiments, (1) X 2 When X is an anionic ligand, p is two less than the formal oxidation state of M, or (2) X 2 is a dianionic ligand group, p is 1.

[0064] In an exemplary embodiment, the catalyst system may include a metal-ligand complex according to formula (II) having the structure of PCAT-4. [ka]

[0065] Co-catalyst component Catalyst systems containing metal-ligand complexes of formula (I) or (II) can be made catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, procatalysts based on metal-ligand complexes of formula (I) or (II) can be made catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. In addition, metal-ligand complexes based on formula (I) or (II) include both neutral procatalyst forms and catalyst forms that can be positively charged by loss of a monoanionic ligand, such as benzyl or phenyl. Activating cocatalysts suitable for use herein include alkylaluminum; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds 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 a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, methylalumoxane modified with triisobutylaluminum, and isobutylalumoxane.

[0066] The Lewis acid activating cocatalyst may be any of the compounds described herein (C1-C 20 In some embodiments, the Group 13 metal compound includes a tri((C-C) hydrocarbyl substituent. 20 )hydrocarbyl)-substituted aluminum or tri((C-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C-C 20)hydrocarbyl)-boron compounds, tri((C-C 10 ) alkyl) aluminum, tri((C6-C 18 )aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C-C 20 ) hydrocarbyl borates (e.g., trityl tetrafluoroborate) or tri((C-C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)boranes (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a ((C-C 20 ) Hydrocarbyl) 4N + , ((C1-C 20 )hydrocarbyl)3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + means a nitrogen cation, each (C1-C 20 ) hydrocarbyls, when present in two or more instances, may be the same or different.

[0067] The combination of neutral Lewis acid activating cocatalysts is tri((C1-C4) alkyl)aluminum and tri((C6-C 18(aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments include mixtures containing such neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane)] is 1:1:1 to 1:10:30, and in other embodiments, 1:1:1.5 to 1:5:10.

[0068] A catalyst system comprising a metal-ligand complex of Formula (I) or Formula (II) can be activated to form an active catalyst composition by combining it with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, and combinations thereof.

[0069] In some embodiments, two or more of the aforementioned activating cocatalysts may be used in combination with one another. A specific example of a cocatalyst combination is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of one or more metal-ligand complexes of Formula (I) or Formula (II) to the total number of moles of one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, the ratio is 1:5000 or 1:1000 to 10:1 or 1:1. When alumoxane is used alone as the activating cocatalyst, preferably the number of moles of alumoxane used is at least 100 times the number of moles of the metal-ligand complex of Formula (I) or Formula (II). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of one or more metal-ligand complexes of Formula (I) or Formula (II) is from 0.5:1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of Formula (I) or Formula (II).

[0070] Some embodiments of the present disclosure include a polymerization process for producing a polyolefin polymer, comprising reacting ethylene and optionally one or more α-olefin monomers in solution in the presence of a catalyst system of the present disclosure, the catalyst system comprising a heterogeneous procatalyst and a hydrogenation procatalyst as previously disclosed.

[0071] In one or more embodiments of the polymerization process, the one or more α-olefins are (C-C 12 In some embodiments, only a single type of olefin, ethylene, is present in the polymerization process. In some embodiments, the polymerization process is 12 In various embodiments, the comonomer is selected from (C-C) α-olefins. 12) α-olefin comonomers 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, the one or more α-olefin comonomers can 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.

[0072] In one or more embodiments of the polymerization process, (C2-C 12 ) The α-olefin is reacted in a solution in a reactor at a reaction temperature of 150°C to 350°C.

[0073] Examples of polymerization processes include, but are not limited to, solution polymerization processes using one or more conventional reactors, such as loop reactors, isothermal reactors, stirred tank reactors, batch reactors, etc., in parallel, series, or any combination thereof. In one embodiment, the polymerization process can include solution polymerization in a dual reactor system, such as a dual loop reactor system, in which ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and, optionally, one or more cocatalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be present in the first reactor or the second reactor. In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, such as a dual loop reactor system, in which ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of a catalyst system described herein.

[0074] In another embodiment, the polymerization process may comprise a solution polymerization in a single reactor system, for example, a single loop reactor system or a single stirred tank reactor system, in which ethylene, optionally in combination with one or more α-olefin comonomers, is polymerized in the presence of a catalyst system described within this disclosure, optionally one or more cocatalysts described in the preceding paragraph, and optionally in combination with one or more other catalysts.

[0075] Test Method Gel Permeation Chromatography (GPC) Method For gel permeation chromatography (GPC), the chromatographic system included a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) coupled to a Precision Detectors (now Agilent Technologies) two-angle laser light scattering (LS) detector model 2040. The autosampler oven compartment was set to 160 °C, and the column compartment was set to 150 °C. The columns were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatographic solvent was 1,2,4 trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was sparged with nitrogen. The injection volume was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0076] The GPC column set is calibrated with 21 narrow molecular weight distribution polystyrene standards ranging from 580 g / mol to 8,400,000 g / mol, arranged in six "cocktail" mixtures with at least 10 intervals between each molecular weight. The standards are purchased from Agilent Technologies. The polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000 g / mol, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards are dissolved at 80°C with gentle stirring for 30 minutes. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 1 (described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A×(M ポリスチレン ) B (Equation 1) where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0077] A fifth-order polynomial is used to fit each polyethylene-equivalent calibration point. A minor adjustment (approximately 0.405-0.440) may be made to A to correct for column resolution and band-broadening effects to obtain NIST standard NBS 1475 at 52,000 MW.

[0078] Total plate counts for a GPC column set can be performed using decane (prepared at 0.04 g in 50 milliliters of TCB). Plate counts (Equation 2) and symmetry (Equation 3) are determined in a 200 microliter injection according to the following equations:

number

number

[0079] Samples can be prepared semi-automatically using the PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / ml, and the solvent (containing 200 ppm) added via the PolymerChar high-temperature autosampler to a pre-nitrogen-flushed septa-capped vial. Samples are dissolved at 160 degrees Celsius with "slow" shaking for 2 hours.

[0080] Calculations of Mn, Mw, and Mz are based on GPC results using the PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from a narrow standard calibration curve at point (i), according to Equations 4-6, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph.

number

[0081] To monitor deviations over time, a flow marker (decane) is introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow marker (FM) is used to linearly correct the pump flow rate (Flow Rate (Nominal)) for each sample by aligning the RV of each decane peak within the sample (RV (FM Sample)) with the RV of the decane peak within the narrow standard calibration (RV (Calibrated FM)). Any time change in the decane marker peak is assumed to be related to a linear shift in flow rate across the run (Flow Rate (Effective)). To facilitate the highest accuracy in measuring the RV of the flow marker peak, a least-squares fitting routine is used to fit the peaks in the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to determine the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated as per Equation 7 (Equation 7). Processing of the flow marker peaks is performed via PolymerChar GPCOne™ software. The allowable flow correction is that the effective flow should be within + / - 2% of the nominal flow. Flow Rate (Effective) = Flow Rate (Nominal) * (RV(Calibrated FM) / RV(FM Sample)) (Equation 7)

[0082] Short chain branching measurement. The short chain branches per 1000 total C (SCDB / 1000TC) are measured according to the method described in the "Molecular Weight Comonomer Distribution Index (MWCDI)" section of WO2015 / 200743(A1).

[0083] Catalytic efficiency Catalyst efficiency is calculated based on the amount of ethylene consumed during polymerization per gram of metal in the polymerization procatalyst (g ethylene / g metal). The grams of metal refer to the grams of metal contributed by the polymerization procatalyst and do not include Ti in the alkylated titanocene hydrogenation procatalyst.

[0084] Solution Batch Reactor Copolymerization Test Method A batch reactor is charged with the specified amounts of 1-octene and Isopar E, totaling 1580 g. The reactor contents are heated to the desired polymerization temperature, and then saturated with ethylene in the presence of the specified amount of molecular hydrogen (H). A solution of a non-hydrogen-producing postmetallocene procatalyst and cocatalyst is mixed in a cocatalyst to procatalyst molar ratio of 1.2:1. MMAO-3A is then added to the mixture in a MMAO-3A to procatalyst molar ratio of 50:1. An alkylated titanocene hydrogenation procatalyst (CpTiCl-TiBAl or CpTiCl-MMAO-3A) is added to the mixture. The contents are immediately injected into the reactor. The amount of procatalyst is adjusted to maintain ethylene consumption within approximately 10-30 g during polymerization to avoid large temperature spikes in the reactor at the start of polymerization. The pressure in the reactor is maintained at 3100 kilopascals (kPa, equivalent to 450 pounds per square inch (psi)) with ethylene flow to compensate for the pressure drop due to ethylene consumption during the polymerization. After a 10-minute reaction time, the bottom valve is opened and the reactor contents are transferred to a glass kettle. The kettle contents are poured onto a Mylar-lined tray, allowed to cool completely, and dried at standard temperature and pressure. The dried contents are further dried under reduced pressure to obtain the product poly(ethylene-co-1-octene) copolymer.

[0085] Catalytic efficiency. Catalyst efficiency is calculated based on the amount of ethylene consumed during polymerization per gram of metal in the polymerization procatalyst (g ethylene / g metal). The grams of metal refer to the grams of metal contributed by the polymerization procatalyst and do not include Ti in the alkylated titanocene hydrogenation procatalyst. [Example]

[0086] The following examples are provided to illustrate embodiments described in this disclosure and are not intended to limit the scope of this disclosure or its appended claims.

[0087] Preparation of postmetallocene procatalysts that do not produce hydrogen. PCAT-1 was synthesized generally according to Example I4 of WO2017 / 058981, substituting an equimolar amount of ZrCl4 for HfCl4 in Example I4.

[0088] PCAT-2. PCAT-2 was synthesized according to Example A11 of WO2007 / 136494.

[0089] PCAT-3. PCAT-3 was synthesized according to Example 23 of WO2018 / 183700(A1).

[0090] PCAT-4. PCAT-4 was synthesized according to Example 7 of US Pat. No. 6,268,444 (B1). [Table 1]

[0091] Cocatalyst (Co-Cat.1). Co-Cat.1 is a methyldi((C 14 -C 18) alkyl) ammonium salt, which can be prepared by the reaction of a long-chain trialkylamine (Armeen™ M2HT available from Akzo Nobel, Inc.), HCl, and Li[B(CF)]. Such a preparation is disclosed in Example 2 of U.S. Pat. No. 5,919,983. Co-Cat. 1 is purchased from Boulder Scientific.

[0092] Preparation of modified hydrogenation catalysts Alkylated titanocene hydrogenation procatalyst Cp2TiCl2-Al( i Bu). A 4 oz bottle was charged with 0.544 g of CpTiCl, 4 mL of Isopar E solvent, and a stir bar to form a mixture. To this mixture was added 1.0 M triisobutylaluminum (Al( i A 38.0 mL solution of Al(Bu)3) was added slowly over 10 minutes with stirring. The solid Cp2TiCl2 became soluble, forming a blue solution. i The molar ratio of Al from Bu)3 to Ti from Cp2TiCl2 in the solution was 17.4.

[0093] Alkylated titanocene hydrogenation procatalyst Cp2TiCl2-MMAO-3A. 50.0 mmol of MMAO-3A in a 7 wt% aluminum solution in heptane (27 mL) was added to 1.0 mmol of Cp2TiCl2 with stirring. The solid Cp2TiCl2 became soluble, forming a blue solution. The molar ratio of Al from MMAO-3A to Ti from Cp2TiCl2 in the solution was 50.

[0094] MMAO-3A has the approximate molecular formula [(CH3) 0.7 (iso-C4H9) 0.3 AlO, CAS Registry Number 146905-79-5] and is obtained as a solution in heptane from Akzo Nobel NV.

[0095] Polymerization of ethylene and α-olefins, specifically ethylene and 1-octene, was carried out in the presence of different amounts of H2 to establish the relationship between (1) polymer weight-average molecular weight (Mw) and H2 content, (2) change in molecular weight, and (3) level of short-chain branching, and the properties of the resulting polymers and catalyst systems are recorded in Tables 1-8.

[0096] Solution Batch Reactor Polymerization experiments, the data of which are provided in Tables 1-8, were carried out using the solution batch reactor method described above. [Table 2]

[0097] Δ(Mw) (%) was calculated as the percentage increase in polymer Mw relative to the Mw of a polymer obtained under the same polymerization conditions without the use of a hydrogenated procatalyst. In IE1 and IE2, each Δ(Mw) (%) was calculated based on the molecular weight of the polymer produced in CE1.

[0098] 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 comprised PCAT-1 and hydrogenated procatalyst CpTiCl-Al ( i The catalyst system for CE1 contained Br, Br, and Bu. The catalyst system for CE1 lacked a hydrogenation procatalyst. The polymers produced in IE1 and IE2 had higher molecular weights than the polymer produced in CE1. In addition, the polymers produced in IE1 and IE2 had similar amounts of short chain branches per 1000 total carbon atoms (SCB / 1000TC) as the polymer in CE1.

[0099] The polymerization reaction conditions for Comparative Example 2 (CE2) and Comparative Example 3 (CE3) were devoid of hydrogen. In the absence of H, the hydrogenated procatalyst CpTiCl-Al ( iThe catalyst system containing (Bu) produced polymers with molecular weights lower than those produced by the catalyst system of CE3, which lacked the hydrogenation procatalyst. The low molecular weight of the polymers of CE2 indicated that the postmetallocene procatalyst PCAT-1 did not produce H or did not produce enough H to significantly reduce the molecular weight of the polymer. Instead, the molecular weight of the polymers of CE2 was higher than that of the polymers produced by the alkylated titanocene hydrogenation procatalyst CpTiCl-Al( i It is believed that the molecular weight of the polymer in CE2 was lower than that of the polymer in CE3 due to the addition of Al(Bu). Without intending to be bound by theory, the involvement of alkylAl species in the hydrogenation procatalyst of the polymer led to chain transfer reactions, which resulted in the polymer in CE2 having a lower molecular weight. [Table 3]

[0100] For each of the examples in Table 2, the hydrogenation procatalyst used in the polymerization reaction was Cp2TiCl2-MMAO-3A. In each of the examples in Table 2, the temperature, ethylene pressure, and octene starting amount were identical, and the ratio of moles of PCAT-1 to moles of Cp2TiCl2 varied. The molecular weight of the polymer produced in the examples in Table 2 increased with the amount of hydrogenation procatalyst present in the system. [Table 4]

[0101] When hydrogen gas is in the reactor system, PCAT-2 and the hydrogenation catalyst Cp2TiCl2-Al( i The molecular weight of the polymer produced by the catalyst system with Bu)3 was higher than that of the polymer produced by the comparative catalyst system of CE5.

[0102] PCAT-1 and Cp2TiCl2-Al( i Compared with the catalytic system containing PCAT-2 and CpTiCl-Al( iCatalyst systems containing Bu)3 produced polymers with greater amounts of short chain branching (comonomer incorporation). [Table 5]

[0103] Examples CE9 (without a hydrogenation catalyst) and IE11 and IE12 (containing a hydrogenation catalyst and a post-metallocene procatalyst that does not produce hydrogen) were all carried out in the presence of hydrogen. The catalyst systems of IE11 and IE12 produced polymers with molecular weights greater than that of the polymer produced in CE9.

[0104] In Examples CE10 and CE11, the polymerization reaction was carried out without added hydrogen. Example CE10, which contained a hydrogenated procatalyst and a post-metallocene procatalyst, produced a polymer with a lower molecular weight than the polymer produced by catalyst system CE11, which lacked a hydrogenated procatalyst. This indicates that the post-metallocene procatalyst PCAT-3 does not produce H2 or does not produce a significant amount of H2 to reduce the molecular weight of the polymer.

[0105] To obtain the results in Table 5, the polymerization temperature and comonomer amount were varied and the polymerization reaction was carried out without added hydrogen. [Table 6]

[0106] When the polymerization reaction was carried out without added hydrogen, the molecular weight of the polymer produced by the catalyst system containing the hydrogenated procatalyst and the postmetallocene procatalyst (PCAT-3) was lower than the molecular weight of the polymer produced by the catalyst system lacking the hydrogenated procatalyst, regardless of the temperature and comonomer amount. This observation further confirms that the postmetallocene procatalyst PCAT-3 does not produce sufficient amounts of H to significantly reduce the molecular weight of the polymer. [Table 7]

[0107] When hydrogen was added to the reaction, the hydrogenation catalyst (Cp2TiCl2-MMAO-3A or Cp2TiCl2-Al( i The catalyst systems IE13, IE14, IE15, and IE16, which contained Bu)3) and a non-hydrogen-producing postmetallocene procatalyst (PCAT-3), produced polymers with higher molecular weights when compared to polymers produced by catalyst systems lacking a hydrogenation catalyst, such as CE18. [Table 8]

[0108] In Examples IE17 and IE18, the catalyst system included a hydrogenation catalyst (CpTiCl-MMAO-3A) and a post-metallocene procatalyst (PCAT-4) that does not produce hydrogen. When hydrogen was added to the reaction, the catalyst systems of Examples IE17 and IE18 produced polymers with higher molecular weights when compared to polymers produced by catalyst systems lacking a hydrogenation catalyst, such as CE19.

[0109] To obtain the results in Table 8, the polymerization temperature and comonomer amount were varied and the polymerization reaction was carried out without added hydrogen. [Table 9]

[0110] When the polymerization reaction was carried out without added hydrogen, the molecular weight of the polymer produced by the catalyst system containing the hydrogenated procatalyst and the post-metallocene procatalyst, e.g., PCAT-4, was lower than the molecular weight of the polymer produced by the catalyst system lacking the hydrogenated procatalyst, regardless of the temperature and comonomer amount. This observation further confirms that the post-metallocene procatalyst, PCAT-4, does not produce sufficient amounts of H to significantly reduce the molecular weight of the polymer.

[0111] All references cited within the Test Methods and Examples sections are incorporated by reference in their entirety. The present invention includes the following aspects. Section 1. 1. A catalyst system comprising: a post-metallocene procatalyst that does not produce hydrogen; A co-catalyst; Formula Cp2TiX2TiCp2 or Cp2TiX n and a hydrogenation procatalyst having During the ceremony, Each Cp must be at least one (C1-C 10 ) cyclopentadienyl optionally substituted with alkyl; Each X is independently monoanionic or neutral, and each X is independently (C-C 40 ) hydrocarbons, (C1-C 40 ) heterohydrocarbons, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, or halogen atom; A catalytic system wherein n is 1 or 2. Section 2. 1. A catalyst system comprising: a post-metallocene procatalyst that does not produce hydrogen; Cp2TiX2 treated with alkylaluminum species, During the ceremony, Each Cp must be at least one (C1-C 10 ) cyclopentadienyl substituted with alkyl; Each X is independently monoanionic or neutral, and each X is independently (C-C 40 ) hydrocarbons, (C1-C 40 ) heterohydrocarbons, (C1-C 40 ) hydrocarbon anions, (C1-C 40 ) a heterohydrocarbon anion, or a halogen atom; A catalytic system wherein n is 1 or 2. Section 3. The aluminum species comprises an alkylaluminoxane, a modified alkylaluminoxane, or an alkylaluminum having the formula AlR3, where each R is independently: (C1-C 40) hydrocarbons, (C1-C 40 ) heterohydrocarbons, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, or a halogen atom. Section 4. Item 4. The catalyst system of item 2 or 3, wherein the aluminum species is the reaction product of AlR3 with water, an alcohol, a silanol, or a Lewis base. Section 5. Item 5. The catalyst system of item 4, wherein the Lewis base is pyridine, or a mono-, di-, or tri-substituted alkylamine. Section 6. Item 6. The catalyst system according to any one of Items 2 to 5, wherein the aluminum species is diisobutylaluminum oxide (DIBAO or DIBAL-O) or isobutylaluminoxane (IBAO). Section 7. 10. The catalyst system of any one of the preceding claims, wherein the catalyst system further comprises an impurity scavenger. Section 8. 4. The catalyst system of any one of the preceding claims, wherein each X is substituted benzyl or substituted heteroarylbenzyl. Section 9. 5. The catalyst system of any one of the preceding claims, wherein X is selected from the group consisting of: [ka] Section 10. Item 11. The catalyst system of any one of the preceding items, wherein the non-hydrogen-producing post-metallocene procatalyst produces 1 ppm or less of hydrogen under polymerization conditions. Section 11. 8. The catalyst system of any one of the preceding claims, wherein the non-hydrogen-producing post-metallocene procatalyst is unsupported and the hydrogenation catalyst is unsupported. Section 12. the non-hydrogen-producing post-metallocene procatalyst is a metal-ligand complex according to formula (I): [ka] During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, said metal being in a +2, +3, or +4 formal oxidation state; n is 0, 1, or 2; When n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is independently a monodentate ligand; Each X is a monodentate ligand 1 are independently halogen, unsubstituted (C1-C 20 ) hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O-, or R K R L N- and R K and R L each independently is unsubstituted (C-C 20 ) hydrocarbyl, L is (C1-C 40 ) hydrocarbylene, (C1-C 40 ) heterohydrocarbylene, -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(R N )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(RC )-, -C(O)O-, -OC(O)-, -C(O)N(R)-, and -N(R C )C(O)—, Each Z is independently -O-, -S-, -N(R N )-, or -P(R P )-selected from 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 However, independently, -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -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 )NC(O)—, halogen, a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII), [ka] During the ceremony, R 31 ~R 35 , R 41 ~R 48 , and R 51 ~R59 each independently represents -H, (C-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -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 )NC(O)-, or halogen. Section 13. the non-hydrogen-producing post-metallocene procatalyst is a metal-ligand complex according to formula (II): [ka] During the ceremony, M is a metal selected from any of Groups 3-13 of the Periodic Table of the Elements, the lanthanides, and the actinides, said metal being in a +2, +3, or +4 formal oxidation state; Each R A , R B , R C , and R D But -H, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R C )2, -N(R C )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=(R C )2, R C C(O)O-, RC OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, or halogen, optionally R A , R B , R C , and R D any two of R may be joined to form a non-aromatic or aromatic ring, and each R C But independently, (C1-C 18 ) hydrocarbons or (C5-C 18 ) aryl, Q is boron, nitrogen, phosphorus, sulfur, oxygen, carbon, silicon, or germanium; each X 2 are independently a monodentate ligand, and the monodentate ligand is monoanionic or dianionic and is selected from the group consisting of halogen, unsubstituted (C-C 20 ) hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O-, or R K R L N- and R K and R L each independently is unsubstituted (C-C 20 ) hydrocarbyl, 8. The catalyst system according to any one of items 1 to 7, wherein p is 1, 2, or 3.

Claims

1. 1. A catalyst system comprising: a non-hydrogen-producing post-metallocene procatalyst which is a bis(phenylphenoxy) Group IV procatalyst, the post-metallocene procatalyst being a metal-ligand complex according to formula (I): 【Chemistry 2】 During the ceremony, M is a metal selected from titanium, zirconium, or hafnium, said metal being in a +2, +3, or +4 formal oxidation state; n is 0, 1, or 2; When n is 1, X １ is a monodentate or bidentate ligand, When n is 2, each X １ are independently monodentate ligands; Each X is a monodentate ligand １ are independently halogen, unsubstituted (C １ -C ２０ ) hydrocarbyl, unsubstituted (C １ -C ２０ ) hydrocarbyl C(O)O—, or R Ｋ R Ｌ N- and R Ｋ and R Ｌ each independently is unsubstituted (C １ -C ２０ ) hydrocarbyl, L is (C １ -C ４０ ) hydrocarbylene, (C １ -C ４０ ) heterohydrocarbylene, —O—, —S—, —S(O)—, —S(O) ２ -, -C(O)O-, -OC(O)-, and -(CH ２ ) ｘ GeR Ｇ ２ (CH ２ ) ｘ -, where x is 1, R Ｇ is isopropyl, each Z is independently selected from —O—, or —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 are independently -H, (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —NO ２ , -CN, -CF ３ , a halogen, a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII), 【Chemistry 3】 During the ceremony, R ３１ ~R ３５ , R ４１ ~R ４８ , and R ５１ ~R ５９ each independently represents —H, (C １ -C ４０ ) hydrocarbyl, (C １ -C ４０ ) heterohydrocarbyl, —NO ２ , -CN, -CF ３ or halogen; A co-catalyst; Treated with alkylaluminum species, of formula Cp ２ TiX ２ TiCp ２ or Cp ２ TiX ｎ and a hydrogenation procatalyst having During the ceremony, Each Cp is at least one (C １ -C １０ ) cyclopentadienyl optionally substituted with alkyl; each X is independently monoanionic or neutral, and each X is independently (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, or a halogen atom; n is 1 or 2; A catalyst system wherein said non-hydrogen-producing post-metallocene procatalyst is unsupported and said hydrogenation procatalyst is unsupported.

2. The catalyst system of claim 1, wherein the hydrogenation procatalyst has the formula Cp 2 TiX 2 .

3. The alkylaluminum species may be an alkylaluminoxane, a modified alkylaluminoxane, or a compound of the formula AlR ３ 3. The catalyst system of claim 1 or 2, comprising an alkylaluminum having the formula: wherein each R is independently a (C 1 -C 40 )hydrocarbyl, a (C 1 -C 40 )heterohydrocarbyl, or a halogen atom.

4. The alkyl aluminum species is AlR ３ 3. The catalyst system of claim 1, wherein the catalyst system is a reaction product of a hydroxybenzoate with water, an alcohol, a silanol, or a Lewis base.

5. 5. The catalyst system of claim 4, wherein the Lewis base is pyridine, or a mono-, di-, or tri-substituted alkylamine.

6. 3. The catalyst system of claim 1 or 2, wherein the alkylaluminum species is diisobutylaluminum oxide (DIBAO or DIBAL-O) or isobutylaluminoxane (IBAO).

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

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

9. 3. The catalyst system of claim 1, wherein X is selected from the group consisting of: 【Chemical 1】

10. 3. The catalyst system of claim 1 or 2, wherein said non-hydrogen-producing post-metallocene procatalyst produces 1 ppm or less of hydrogen under polymerization conditions.

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