Multimodal polymerization processes using multiple catalyst systems

Abstract

1. A process for polymerizing olefin monomers to produce polyolefins, the process comprising reacting ethylene and, optionally, one or more olefin monomers in a reactor or multiple reactors in the presence of a catalyst system, the catalyst comprising two or more catalysts, at least one of which is derived from a bis-phenylphenoxy procatalyst according to formula (I) and at least one of which is derived from a phosphinimine procatalyst according to formula (V): [Formula 1] JPEG2025529053000035.jpg82170

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 401,901, filed August 29, 2022, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more specifically to olefin polymerization catalyst systems including bis-phenylphenoxy Group IV transition metal catalysts and PN catalysts, and polymerization processes incorporating the catalyst systems to produce bimodal polymers. [Background technology]

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

[0004] Ethylene- and propylene-based polymers are produced for a wide variety of products. Polyethylene and polypropylene polymerization processes can be modified in several ways to produce a wide variety of 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 may also be added to the reactor. Catalyst systems for producing ethylene-based homopolymers or copolymers typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (either metallocene or nonmetallocene) catalyst systems. The diluent and the reactants in the catalyst system are circulated in the reactor at elevated polymerization temperatures, thereby producing the ethylene-based homopolymer or copolymer. 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. The reaction mixture, upon removal from the reactor, 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, producing a second polyethylene fraction. Despite research efforts to develop catalyst systems suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, there remains a need for improved efficiency of catalyst systems capable of producing polymers whose molecular weight can be controlled during the polymerization process. Summary of the Invention

[0005] There is a continuing need to produce multimodal polyethylene polymers, specifically LLDPE resins, using flexible catalyst systems compatible with high temperature solution processing.

[0006] Combining catalysts from two different classes, bis-phenylphenoxy metal-ligand complex catalyst (BPP catalyst) and phosphinimine complex catalyst (PN catalyst), allows for the production of multimodal polyethylene resins by taking advantage of the catalysts' different properties.

[0007] PN catalysts are much more sensitive to hydrogen than BPP catalysts; therefore, the molecular weight of the polymer produced by PN catalysts may be altered based on the amount of hydrogen in the reactor system. As a result, the molecular weight split (the difference in molecular weight of polyethylene produced by the two catalysts) can be easily adjusted by adjusting the hydrogen level without significantly changing other conditions. Small changes in hydrogen level result in large differences in the molecular weight of the polymer produced by PN catalysts. In comparison, the same increase in H2 results in a smaller change in the polymer produced by BPP catalysts. Figures 1A, 1B, and 1C show the change in molecular weight of polyethylene produced by BPP and PN catalysts.

[0008] Embodiments of the present disclosure include a process for polymerizing olefin monomers to produce polyolefins. The method includes reacting ethylene and, optionally, one or more olefin monomers in a reactor or reactors in the presence of a catalyst system and, optionally, hydrogen gas. The catalyst includes two or more catalysts, at least one of which is derived from a bis-phenylphenoxy procatalyst according to formula (I) and at least one of which is derived from a phosphinimine procatalyst according to formula (V). The amount of hydrogen gas may be adjusted to control the molecular weight of the polyolefin.

[0009] Formula (I) and Formula (V) have the structure according to the following:

[0010] [ka]

[0011] In formula (I), M1 is titanium, zirconium, hafnium, scandium, or yttrium.

[0012] In formula (I) and formula (V), each X is (C1 to C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C )3, -OC(O)R C , -C(O)OR C , -N(RC )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C )2, -C(O)NHR C , -C(O)NH2, halogen, B(R Y )4, Al(R Y )4, or Ga(R Y ) 4, or hydrogen, and each R C are independently (C1~C 30 ) hydrocarbyl, or (C1-C 30 ) heterohydrocarbyl, each Q is 0, 1, 2, or 3, each W is 0, 1, or 2, and each R Y is -H, (C1~C 30 ) hydrocarbyl, or halogen atom, and two X ligands may be linked to form a metallacycle ring.

[0013] In formulas (I) and (V), each Y is independently a Lewis base, and optionally, X and Y can be joined to form a ring. Each subscript m is independently 0, 1, or 2, and each subscript n is independently 0, 1, or 2.

[0014] In formula (I), R 1 and R 16 are independently -H, (C1 to 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)2NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

[0015] [ka]

[0016] In formula (II), formula (III), and formula (IV), R 31-35 , R 41-48 , and R 51-59 Each of the groups independently represents -H, (C1 to 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 )2NC(O)-, or halogen.

[0017] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently -H, (C1 to 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)-, (R C )2NC(O)-, or halogen.

[0018] In formula (I), L is (C1 to C 40 ) hydrocarbylene or (C2-C 40 ) heterohydrocarbylene.

[0019] In formula (I), each R C , R P , and R N are independent, (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H.

[0020] In formula (V), M2 is titanium, zirconium, or hafnium, and R 61 , R 62 , R 63 , R 64 , and R 65 are independently (C1~C 50 ) hydrocarbyl, or (C1-C 50 ) heterohydrocarbyl, and R 62 , R 63 , R 64 , and R 65 are optionally joined to form a ring structure, and R 66 , R 67 , and R 68 are independently (C1~C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, (C6-C 30) Aryl, (C5-C 30 ) heteroaryl, and R 66 , R 67 , and R 68 two of which are optionally joined to form a ring. [Brief explanation of the drawings]

[0021] [Figure 1A] 1 shows two theoretical molecular weight distribution curves of two unimodal polymer compositions produced by a bis-phenylphenoxy catalyst and by a phosphinimine catalyst in the absence of hydrogen gas in the reactor chamber. [Figure 1B] 1 shows two theoretical molecular weight distribution curves for two unimodal polymer compositions produced by a bis-phenylphenoxy catalyst and by a phosphinimine catalyst with a small amount of hydrogen gas in the reactor chamber. [Figure 1C] 1 shows two theoretical molecular weight distribution curves for two unimodal polymer compositions produced by a bis-phenylphenoxy catalyst and by a phosphinimine catalyst with a higher amount of hydrogen gas in the reactor chamber. [Figure 2] 1 is a graph of the molecular weight of polymers produced by three different phosphinimine catalysts as a function of the amount of hydrogen (mmol) in the reactor. [Figure 3] Molecular weight distribution curves obtained by gel permeation chromatography (GPC) of bimodal polymer compositions produced by bis-phenylphenoxy catalyst (BPP-1) and phosphinimine catalyst (PN-1) with varying amounts of hydrogen gas in the reactor chamber: 0 mmol H2, 5 mmol H2, 20 mmol H2, and 40 mmol H2. [Figure 4] 1 is a GPC trace with monomer distribution for copolymerization of polyethylene produced by dual catalysts (BPP-1 and PN-1). [Figure 5]1 is a GPC trace of the monomer distribution for copolymerization of PE produced with a dual catalyst having PN-1 and BPP-2 at a temperature of 160° C. and three hydrogenation amounts. [Figure 6] 1 is a GPC trace of copolymerization monomer distribution of PE produced with a dual catalyst. [Figure 7] Improved Comonomer Composition Distribution (iCCD) data for PE produced with a dual catalyst. [Figure 8] 1 is a GPC trace of the monomer distribution for copolymerization of PE produced with a dual catalyst having PN-1 and BPP-3 at a temperature of 160° C. and three hydrogenation amounts. [Figure 9] 1 is a GPC trace of the monomer distribution for copolymerization of PE produced with a dual catalyst having PN-1 and BPP-4 at a temperature of 160° C. and three hydrogenation amounts. [Figure 10] 1 is a GPC trace of the monomer distribution for copolymerization of PE produced with a dual catalyst having PN-1 and BPP-5 at a temperature of 160° C. and three hydrogenation amounts. DETAILED DESCRIPTION OF THE INVENTION

[0022] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0023] The term "independently selected" followed by multiple options is 1 , R 2 , R 3 , R 4 and R 5 is used herein to indicate that the individual R groups appearing before the term, such as may be the same or different, and there is no dependency on the identity of other groups appearing before the term.

[0024] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst to convert the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0025] When used to describe certain carbon atom-containing chemical groups, the term "(C x ~C y A parenthetical expression having the form "(C1-C )" means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, (C1-C 50 ) Alkyl, in its unsubstituted form, is an alkyl group having 1 to 50 carbon atoms. In some embodiments and general structures, certain chemical groups are R S The parenthesized "(C x ~C y )" for the chemical group R S The substituted form can be any group R S For example, "R S exactly one group R is phenyl (-C6H5) S (C1~C 50 The "(C ) alkyl" may contain from 7 to 56 carbon atoms. Therefore, the parenthesized "(C x ~C y )" is a group defined using one or more carbon atom-containing substituents R S When substituted by x and y, the minimum and maximum total number of carbon atoms in the chemical group is determined by the presence of all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0026] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R SThe term "persubstituted" means that all hydrogen atoms (H) bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are substituted with a substituent (e.g., R S ) The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group are replaced by a substituent. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0027] "(C1~C 50 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical of 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 50 carbon atoms, each hydrocarbon radical and each hydrocarbon diradical being aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and containing one or more R S is or is not replaced by

[0028] In this disclosure, (C1 to C 50 ) Hydrocarbyl is unsubstituted or substituted (C1-C 50 ) Alkyl, (C3-C 50 ) cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 ) alkylene (benzyl (—CH2 to C6H5) etc.).

[0029] "(C1~C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an unsubstituted or alkyl group containing one or more R Sand saturated straight-chain or branched-chain hydrocarbon radicals of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively, substituted by unsubstituted (C1 to C 50 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" refers to a group having up to 45 carbon atoms in the radical, including the substituents, e.g., one R S replaced by (C 27 ~C 40 ) alkyl, and R S means (C1-C5) alkyl. Each (C1-C5) alkyl may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0030] "(C6~C 50 The term "aryl" refers to an unsubstituted or (one or more R)aryl group of 6 to 40 carbon atoms. S "Aromatic hydrocarbon radicals" refers to monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radicals substituted (by C6-C), where at least 6 to 14 of the carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. 50 Examples of aryl include unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18)aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 40 Examples of aryl include substituted (C1-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0031] "(C3~C 50 The term "cycloalkyl" refers to a group that is unsubstituted or has one or more R S means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms substituted with other cycloalkyl groups, such as (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S is defined in a similar manner as either being replaced by

[0032] (C1~C 50 Examples of hydrocarbylenes include substituted or unsubstituted (C6-C 50 )Arylene, (C3-C 50 ) cycloalkylene, (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). Diradicals can be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include 1,2-diradicals. α,ω-diradicals are diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH 2- ), 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH 2- ) are listed. (C6~C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0033] "(C1~C 50 The term "alkylene" refers to a group that is unsubstituted or has one or more R S means a saturated straight or branched chain diradical of 1 to 50 carbon atoms (i.e., the radical is not on a ring atom) substituted with unsubstituted (C1-C 50 Examples of alkylene are unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3 and -(CH2)4C * Unsubstituted (C1-C, including (H)(CH3) 20 ) alkylene, wherein "C * " denotes a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl group. 50 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, the two R S are combined together (C1~C 18 ) alkylene, so that the substituted (C1-C 50Examples of )alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0034] "(C3~C 50 The term "cycloalkylene" may be unsubstituted or may contain one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms substituted with

[0035] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O), Si(R C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )-, and each R C and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or —H, and each R N is unsubstituted (C1 to C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 50 The term "(C1-C)heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 ) heterohydrocarbyl or (C1-C 50The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The heterohydrocarbyl radical may be present on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be present on a single carbon atom or a single heteroatom. Additionally, one of the two radicals of the diradical may be present on a carbon atom and the other radical may be present on a different carbon atom; one of the two radicals may be present on a carbon atom and the other on a heteroatom; or one of the two radicals may be present on a heteroatom and the other radical on a different heteroatom. Each (C1-C 50 ) heterohydrocarbyl and (C1-C 50 ) heterohydrocarbylene is unsubstituted or (one or more R S and may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0036] (C1~C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heterohydrocarbyls include (C1-C 50 ) heteroalkyl, (C1-C 50 ) hydrocarbyl-O-, (C1-C 50 ) hydrocarbyl-S-, (C1-C 50 ) hydrocarbyl-S(O)-, (C1-C 50 ) hydrocarbyl-S(O)2-, (C1-C 50 ) Hydrocarbyl-Si(R C )2-, (C l ~C 50 )hydrocarbyl-N(R N )-, (C l ~C 50 ) hydrocarbyl-P(R P )-, (C2~C 50 ) heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20)Cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 50 ) heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0037] "(C4~C 50 The term "heteroaryl" refers to an unsubstituted or heteroaryl group having a total of 1 to 50 carbon atoms and 1 to 10 heteroatoms (one or more R S (by) a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical. A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring(s) of the heteroaromatic radical may independently be fused or non-fused, and aromatic or non-aromatic. Other heteroaryl groups (e.g., generally (C4-C 12 ) heteroaryl, etc. x ~C y ) heteroaryl) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or has one or more R S The monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as being substituted with . The monocyclic heteroaromatic hydrocarbon radical is a 5- or 6-membered ring. A 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms, which may be 1, 2, 3, or 4, and each heteroatom may be O, S, N, or P.

[0038] "(C1~C 50 The term "(C1-C)heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms, or fewer, and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or contains one or more R S has been replaced by

[0039] The term "halogen atom" or "halogen" refers to the radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom (fluoride (F) - ), chloride (Cl - ), bromide (Br - ), or iodide (I - )) means.

[0040] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be substituted by a substituent R SThe term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds, and may or may not be present in the substituent R S , or may be absent, but does not include double bonds which may be present in (hetero)aromatic rings.

[0041] Embodiments of the present disclosure include a process for polymerizing olefin monomers to produce polyolefins. The method comprises reacting ethylene and, optionally, one or more olefin monomers in a reactor or reactors in the presence of a catalyst system. The catalyst comprises two or more catalysts, at least one of which is derived from a bis-phenylphenoxy procatalyst according to formula (I) and at least one of which is derived from a phosphinimine procatalyst according to formula (V). The amount of hydrogen gas is adjusted to control the molecular weight of the polyolefin.

[0042] Hydrogen gas may be added to the polymerization process. The amount of hydrogen gas may be 0 mmol in the reactor at any given time during the polymerization reaction. The amount of hydrogen may be increased or decreased as the reaction progresses. In a semi-batch polymerization process, the amount of hydrogen may decrease if the polymerization reactants consume hydrogen gas and no additional hydrogen gas is added.

[0043] The catalyst comprises one or more bis-phenylphenoxy procatalysts according to formula (I) and one or more phosphinimine procatalysts according to formula (V).

[0044] Embodiments of the present disclosure include catalyst systems comprising one or more bis-phenylphenoxypro catalysts according to formula (I):

[0045] [ka]

[0046] In formula (I), M1 is titanium, zirconium, hafnium, scandium, or yttrium.

[0047] In formula (I), each X is (C1 to C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C )3, -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C, -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C )2, -C(O)NHR C , -C(O)NH2, halogen, B(R Y )4, Al(R Y )4, or Ga(R Y ) 4, or hydrogen, and each R C are independently (C1~C 30 ) hydrocarbyl, or (C1-C 30 ) heterohydrocarbyl, each Q is 0, 1, 2, or 3, each W is 0, 1, or 2, and each R Y is -H, (C1~C 30 ) hydrocarbyl, or halogen atom, and two X ligands may be linked to form a metallacycle ring.

[0048] In formula (I), each Y is independently a Lewis base, and optionally, X and Y can be joined to form a ring. Subscript m is 1 or 2, and subscript n is 0, 1, or 2.

[0049] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently -H, (C1 to 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)-, RC S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, or halogen.

[0050] In formula (I), R 1 and R 16 are independently -H, (C1 to 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 )2NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

[0051] [ka]

[0052] In formula (II), R 31 , R 32 , R 33 , R 34 , R 35 are independently -H, (C1 to C 50 ) hydrocarbyl, (C1-C 50 ) 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 )2NC(O)-, or halogen.

[0053] In formula (III), R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 are independently -H, (C1 to C 50 ) hydrocarbyl, (C1-C 50 ) 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 )2NC(O)-, or halogen.

[0054] In formula (IV), R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , and R 59 are independently -H, (C1 to C 50) hydrocarbyl, (C1-C 50 ) 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 )2NC(O)-, or halogen.

[0055] The group R in the metal-ligand complex of formula (I) 1 and R 16 are selected independently of each other. For example, R 1 may be selected from radicals having formula (II), formula (III), or formula (IV), and R 16 (C4~C 50 ) heteroaryl, or R 1 may be selected from radicals having formula (II), formula (III), or formula (IV), and R 16 may be selected from radicals having formula (II), formula (III), or formula (IV), and R 1 In some embodiments, R 1 and R 16 are radicals having the formula (II), and R 1 and R 16 The group R in 31-35 are the same or different. In some embodiments, R 1 and R 16 are radicals having the formula (III), and R 1 and R 16 The group R in 41-48 are the same or different. In other embodiments, R 1 and R 16are radicals having the formula (IV), and R 1 and R 16 The group R in 51-59 are the same or different.

[0056] In some embodiments, R 1 and R 16 at least one of R is a radical having formula (II); 32 and R 34 At least one of R 1 or R 16 is a radical having the formula (III), 43 and R 46 is tert-butyl, and R 41-42 , R 44-45 , and R 47-48 is —H. In other embodiments, R 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 are both -H. In some embodiments, R 41-48 is -H.

[0057] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are independently -H, (C1 to C 50 ) hydrocarbyl, (C1-C 50 ) 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)-, (R C )2NC(O)-, or halogen.

[0058] In some embodiments, R 5 , R 6 , R 7 , and R 8 At least one of R is a halogen atom, 9 , R 10 , R 11 , and R 12 In some embodiments, at least one of R 5 , R 6 , R 7 , and R 8 At least two of R are halogen atoms, 9 , R 10 , R 11 , and R 12 At least two of R are halogen atoms. 5 , R 6 , R 7 , and R 8 At least three of R are halogen atoms, 9 , R 10 , R 11 , and R 12 At least three of the groups are halogen atoms.

[0059] In some embodiments, R 3 and R 14 is (C1~C 24 ) alkyl. In various embodiments, R 3 and R 14 is (C1~C 20) alkyl. In some embodiments, R 3 and R 14 (C4~C 24 ) alkyl. In one or more embodiments, R 3 and R 14 (C8~C 12 ) alkyl. In some embodiments, R 3 and R 14 is 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, or decyl. 3 and R 14 -OR C and R C is (C1~C 20 ) hydrocarbon, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl.

[0060] In some embodiments, R 3 and R 14 is methyl. In other embodiments, R 3 and R 14 (C4~C 24 ) alkyl. In some embodiments, R 8 and R 9 are 1-propyl, 2-propyl (also called isopropyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

[0061] In some embodiments, R 6and R 11 is halogen. In other embodiments, R 6 and R 11 is (C1~C 24 ) alkyl. In some embodiments, R 6 and R 11 is independently selected from methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, or decyl. 6 and R 11 is tert-butyl. In some embodiments, R 6 and R 11 -OR C and R C is (C1~C 20 ) hydrocarbyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl. 6 and R 11 -SiR C 3, and each R C are independently (C1~C 20 ) hydrocarbyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl), or 1,1-dimethylethyl.

[0062] In some embodiments, R 3 and R 14 is methyl and R 6 and R 11 is halogen. In other embodiments, R 6 and R 11 is tert-butyl. In other embodiments, R 3 and R 14is tert-octyl or n-octyl.

[0063] In one or more embodiments, in formula (I), R 1 and R 16 At least one of R is a radical having formula (III). 1 and R 16 is a radical having the formula (III), then R 42 and R 47 is (C1~C 20 ) hydrocarbyl or -Si[(C 20 )hydrocarbyl]3. In various embodiments, R 1 and R 16 is a radical having the formula (III), then R 43 and R 46 is (C1~C 20 ) hydrocarbyl or -Si[(C 20 ) hydrocarbyl]3.

[0064] In some embodiments, in Formula (I), R 1 and R 16 at least one of R is a group having formula (II) 32 and R 34 is (C1~C 12 ) hydrocarbyl or -Si[(C 20 ) hydrocarbyl]3.

[0065] In various embodiments, in formula (I), R 1 and R 16 at least one of R is a radical having formula (IV) 52 , R 53 , R 55 , R 57 , and R 58 At least two of them (C1~C 20 ) hydrocarbyl or -Si[(C 20 ) hydrocarbyl]3.

[0066] In one or more embodiments, R 8 and R 9 is independently (C1-C4) alkyl.

[0067] In some embodiments, R 3 and R 14 is (C1~C 20 ) alkyl. In various embodiments, R 3 and R 14 is methyl and R 6 and R 11 is halogen. In one or more embodiments, R 6 and R 11 is tert-butyl. In some embodiments, R 3 and R 14 is tert-octyl or n-octyl.

[0068] In some embodiments, L is -CH2(CH2) m CH2-, -CH2Si(R C (R D )CH2-, -CH2Ge(R C (R D )CH2-, -CH2(CH3)CH2CH * (CH3), bis(methylene)cyclohexane-1,2-diyl, -CH2CH(R C )CH2- or -CH2C(R C )2CH2-, and each R in L C (C1~C 20 ) hydrocarbyl, and R in L D (C1~C 20 ) hydrocarbyl.

[0069] Embodiments of the present disclosure include catalyst systems comprising one or more phosphinimine procatalysts according to formula (V):

[0070] [ka]

[0071] In formula (V), M2 is titanium, zirconium, or hafnium.

[0072] In formula (V), each X is (C1 to C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -NH(R C ), -N(Si(R C )3)2, -NR C Si(R C )3, -NHSi(R C )3, -OR C , -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C , -S(O)2R C , -OS(O)2R C , -N=C(R C )2, -N=CH(R C ), -N=CH2, -N=P(R C )3, -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C)C(O)H, -NHC(O)R C , -C(O)N(R C )2, -C(O)NHR C , -C(O)NH2, halogen, B(R Y )4, Al(R Y )4, or Ga(R Y ) 4, or hydrogen, and each R C are independently (C1~C 30 ) hydrocarbyl, or (C1-C 30 ) heterohydrocarbyl, each Q is 0, 1, 2, or 3, each W is 0, 1, or 2, and each R Y is -H, (C1~C 30 ) hydrocarbyl, or halogen atom, and two X ligands may be linked to form a metallacycle ring.

[0073] In formula (V), each Y is independently a Lewis base, and optionally, X and Y can be joined to form a ring. The subscript m is 1 or 2, and the subscript n is 0, 1, or 2.

[0074] In formula (V), R 61 , R 62 , R 63 , R 64 , and R 65 are independently (C1~C 50 ) hydrocarbyl, wherein R 61 and R 62 are optionally joined to form a ring, or R 62 and R 63 are optionally joined to form a ring, and R 63 and R 64 are optionally joined to form a ring, and R 64 and R 65 are optionally joined to form a ring.

[0075] In formula (V), R 66 , R 67 , and R 68 are independently (C1~C 20 ) hydrocarbyl, (C1-C20 ) heterohydrocarbyl, (C6-C 30 ) Aryl, (C5-C 30 ) heteroaryl, and R 66 , R 67 , and R 68 two of which are optionally joined to form a ring.

[0076] In formula (I), formula (II), formula (III), formula (IV), and formula (V), each R in formula (I) C , R P , and R N are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H.

[0077] In one or more embodiments, in formula (V), R 66 , R 67 , R 68 are independently (C1~C 20 ) alkyl.

[0078] In some embodiments, in formula (V), R 66 , R 67 , R 68 are independently selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

[0079] In various embodiments, in formula (V), where R 64 and R 65 are bonded to form an aromatic ring.

[0080] In some embodiments, the monodentate ligands, X and Y of Formula (I) and Formula (V), may be monoanionic ligands. The monoanionic ligands have a net formal oxidation state of -1. Each monoanionic ligand may independently be a hydride, (C1-C 40 ) hydrocarbyl carbanions, (C1-C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, carbonates, phosphates, sulfates, HC(O)O - , HC(O)N(H) - , (C1~C 40 ) Hydrocarbyl C(O)O - , (C1~C 40 ) Hydrocarbyl C(O)N((C1-C 20 )hydrocarbyl) - , (C1~C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B--, R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L Si - Each R may be K , R L , and R M are independently hydrogen, (C1 to C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R K and R L together (C2~C 40 ) hydrocarbylene or (C1-C 20 ) form a heterohydrocarbylene, and R M is as defined above.

[0081] In other embodiments, at least one of the monodentate ligands X and Y may be a neutral ligand, independent of the other ligands X and the other ligands Y. In certain embodiments, the neutral ligand is R Q NR K R L , R K OR L , R K SR L , or R Q PR K R L and each R is a neutral Lewis base such as Q are independently hydrogen, [(C1-C 10 )hydrocarbyl]3Si(C1-C 10 ) hydrocarbyl, (C1-C 40 ) hydrocarbyl, [(C1-C 10 )hydrocarbyl]Si, or (C1-C 40 ) heterohydrocarbyl, and each R K and R L are independently as defined above.

[0082] In the metal-ligand complex according to Formula (I), each Y is bonded to M through a dative or ionic bond. In one or more embodiments, Y is a Lewis base. A Lewis base can be a compound or ionic species capable of donating an electron pair to an acceptor compound. For purposes of this description, the acceptor compound is M, the metal of the metal-ligand complex of Formula (I). A Lewis base can be neutral or anionic. In some embodiments, a Lewis base can be a heterohydrocarbon or unsaturated hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. Examples of anionic hydrocarbons include, but are not limited to, cyclopentadienyl. Examples of neutral hydrocarbon Lewis bases include, but are not limited to, 1,3-butadiene.

[0083] In some embodiments, the Lewis base is an unsaturated (C1-C 20In some embodiments, the Lewis base is cyclopentadiene or 1,3-butadiene. In various embodiments, the Lewis base is a (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, Y is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0084] Further, each X and each Y may be independently selected from any other ligands X and Y, including halogen, unsubstituted (C1-C 20 ) Hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbyl C(O)O—, or R K R L R may be a monodentate ligand that is N- K and R L Each of is independently unsubstituted (C1 to C 20 In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10 ) hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) hydrocarbyl C(O)O—, or R K R L N- and R K and R L Each of is independently unsubstituted (C1 to C 10 In one or more embodiments of formula (I) and formula (V), X is benzyl, chloro, —CH 2 SiMe 3 , or phenyl.

[0085] In some embodiments, m+n is 2 or 3.

[0086] In further embodiments, each X and / or each Y is independently 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 groups are different from at least one X when m is 3, X is different from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In further embodiments, the X ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0087] In some embodiments, the chemical groups (e.g., X and R) of the metal-ligand complex of formula (I) 1 -R 4 In other embodiments, any or all of the chemical groups X and R of the metal-ligand complex of formula (I) may be unsubstituted. 1 -R 4 Any of the above may contain one or more R S or any or all of them are substituted with one or more R S Two or more R S are attached to the same chemical group in the metal-ligand complex of formula (I), the individual R S may be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, the chemical groups X and R 1 -R 4 Both of these are R S or any or all of them are R S May be oversubstituted with R S In chemical groups that are over-substituted with S may all be the same or may be independently selected.

[0088] In some embodiments, the ratio of the hydrogen chain transfer constant of the procatalyst of Formula (V) to the procatalyst of Formula (I) is 3 or greater at 160° C. In other embodiments, the ratio of the hydrogen chain transfer constant of the procatalyst of Formula (V) to the procatalyst of Formula (I) is 5 or greater at 160° C., 7 or greater at 160° C., or 10 or greater at 160° C., or 20 or greater at 160° C.

[0089] In an exemplary embodiment, the catalyst system comprises a metal-ligand complex according to formula (I) having the structure of any of procatalysts BPP-1 through BPP-10, and procatalysts PN-1 through PN-3;

[0090] [ka]

[0091] [ka] The metal-ligand complex may comprise a metal-ligand complex according to formula (V) having any of the structures:

[0092] Co-catalyst component Catalyst systems containing metal-ligand complexes of formula (I) may be catalytically activated 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) may be catalytically activated by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. It should be noted that metal-ligand complexes based on formula (I) 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 may include alkylaluminums, 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 foregoing 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, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0093] In some embodiments, the catalyst system does not include an additive. An additive is a chemical agent present during the polymerization reaction that does not inhibit olefin chain transfer reactions. In one or more embodiments, the catalyst system further includes an additive. In some embodiments, the additive functions as a co-catalyst. In other embodiments, the additive functions as a scavenger or scavenger. A co-catalyst is a reagent that cooperates with the catalyst to catalyze a reaction or improve the catalytic activity of the catalyst. Without being bound by theory, when M in formula (I) is scandium or yttrium, the ligand Y dissociates without the presence of a co-catalyst. However, it is also believed that the co-catalyst may facilitate the dissociation of any Lewis base present coordinated to the metal center of the metal-ligand complex.

[0094] The scavenger can sequester impurities in the reactor and therefore may not constitute an activator. In some cases, low alumoxane loadings do not act as a cocatalyst but rather function as a scavenger.

[0095] Suitable additives may include alkylaluminums, 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). Combinations of one or more of the foregoing additives and techniques are also contemplated. The term "alkylaluminum" refers to monoalkylaluminum dihydrides or dihalides, dialkylaluminum hydrides or halides, or trialkylaluminums. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0096] Lewis acid activating cocatalysts are described herein (C1-C 20 In some embodiments, the Group 13 metal compounds include tri((C1-C) hydrocarbyl substituents. 20 )hydrocarbyl)-substituted-aluminum or tri((C1-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C1-C 20 )hydrocarbyl)-boron compounds, tri((C1-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((C1-C 20) hydrocarbyl borate (e.g., trityl tetrafluoroborate) or tri((C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borane (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a ((C1-C 20 )hydrocarbyl) 4N+, ((C1-C 20 )hydrocarbyl)N(H)+, ((C1-C 20 )hydrocarbyl)2N(H)2+, (C1-C 20 ) hydrocarbyl N(H)3+, or N(H)4+, each (C1 to C 20 ) When two or more hydrocarbyls are present, they may be the same or different.

[0097] A 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 of 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.

[0098] A catalyst system comprising a metal-ligand complex of formula (I) may 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.

[0099] 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 the one or more metal-ligand complexes of Formula (I) to the total number of moles of the one or more activating cocatalysts is from 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000; in other embodiments, it is at least 1:1000 and no more than 10:1; and in other embodiments, it is no more than 1:1. When alumoxane is used alone as the activating cocatalyst, it is preferred that the number of moles of alumoxane used be at least 100 times the number of moles of the metal-ligand complex of Formula (I). 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 the one or more metal-ligand complexes of Formula (I) 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 the one or more metal-ligand complexes of Formula (I).

[0100] Polymerization Process Any conventional polymerization process may be used to produce the polyolefin compositions according to the present disclosure, including, but not limited to, solution polymerization processes, particle-forming polymerization processes, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed reactors, stirred tank reactors, batch reactors in parallel, in series, and / or any combination thereof.

[0101] In one embodiment, the polyolefin composition according to the present disclosure may be produced by a solution phase polymerization process using, for example, one or more loop reactors, isothermal reactors, and combinations thereof.

[0102] Generally, solution-phase polymerization processes are carried out in one or more well-stirred reactors, such as one or more loop reactors or one or more spherical isothermal reactors, at temperatures ranging from 120°C to 300°C, 120°C to 250°C, 150°C to 300°C, 150°C to 250°C, or 160°C to 215°C, and at pressures ranging from 300 to 1500 psi, e.g., 400 to 750 psi. The residence time in a solution-phase polymerization process is typically in the range of 2 to 30 minutes, e.g., 5 to 15 minutes. Ethylene, one or more solvents, one or more high-temperature olefin polymerization catalyst systems, one or more cocatalysts and / or scavengers, and optionally one or more comonomers are continuously fed to one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available from ExxonMobil Chemical Co. (Houston, Texas) under the name ISOPAR E. The resulting mixture of ethylene-based polymer and solvent is then removed from the reactor and the ethylene-based polymer is isolated. The solvent is typically recovered via a solvent recovery unit, i.e., a heat exchanger and a gas-liquid separator drum, and then recycled to the polymerization system.

[0103] In one embodiment, an ethylene-based polymer may be produced by solution polymerization in a single reactor system, e.g., a single loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of one or more high-temperature olefin polymerization catalyst systems, optionally one or more other catalysts, and optionally one or more co-catalysts. In one embodiment, an ethylene-based polymer may be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of one or more olefin polymerization catalyst systems, optionally one or more other catalysts, and optionally one or more co-catalysts. In one embodiment, an ethylene-based polymer may be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of one or more high-temperature olefin polymerization catalyst systems, as described herein.

[0104] Polyolefin The catalyst system described in the previous paragraph is utilized for the polymerization of olefins, primarily ethylene and propylene. In some embodiments, there is only one type of olefin or α-olefin in the polymerization scheme, resulting in the production of a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin copolymerizing monomer typically has 20 or fewer carbon atoms. For example, the α-olefin copolymerizing monomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin copolymerizing monomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more α-olefin copolymerizing monomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0105] Ethylene-based polymers, e.g., homopolymers and / or interpolymers (including copolymers) of ethylene, and optionally one or more comonomers such as α-olefins, may comprise from at least 50 weight percent ethylene-derived monomer units. All individual values ​​and subranges encompassed by "from at least 50 weight percent" are disclosed herein as separate embodiments; for example, an ethylene-based polymer, homopolymer, and / or interpolymer (including copolymer) of ethylene and, optionally, one or more comonomers such as α-olefins may comprise at least 60 weight percent ethylene-derived monomer units, at least 70 weight percent ethylene-derived monomer units, at least 80 weight percent ethylene-derived monomer units, or from 50 to 100 weight percent ethylene-derived monomer units, or from 80 to 100 weight percent ethylene-derived monomer units.

[0106] In some embodiments, the ethylene-based polymer may comprise at least 90 mole percent units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may comprise at least 93 mole percent units derived from ethylene, at least 96 mole percent units, at least 97 mole percent units derived from ethylene, or alternatively, from 90 to 100 mole percent units derived from ethylene, from 90 to 99.5 mole percent units derived from ethylene, or from 97 to 99.5 mole percent units derived from ethylene.

[0107] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50%, other embodiments include at least 0.5 mole percent (mol %) to 25 mol %, and in further embodiments, the amount of additional α-olefin is at least 5 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0108] Any conventional polymerization process may be used to produce the ethylene-based polymers, including, but not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, and the like, in parallel, series, or any combination thereof.

[0109] In one embodiment, an ethylene-based polymer may be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, an ethylene-based polymer may be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system of the present disclosure and described herein and, optionally, one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, may be used in the first reactor or the second reactor. In one embodiment, an ethylene-based polymer may be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of the catalyst system described herein.

[0110] In another embodiment, the ethylene-based polymer may be produced by solution polymerization in a single reactor system, for example, a single loop reactor system, where ethylene, and optionally one or more α-olefins, are polymerized as described in the previous paragraph in the presence of a catalyst system described within this disclosure and optionally one or more cocatalysts.

[0111] The ethylene-based polymer may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer may comprise any amount of additives. The ethylene-based polymer may comprise from about 0 to about 10 percent by combined weight of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, including, but not limited to, an organic filler or an inorganic filler. The ethylene-based polymer may comprise from about 0 to about 20 percent by weight of a filler, such as calcium carbonate, talc, or Mg(OH)2, based on the combined weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer may be further compounded with one or more polymers to form a blend.

[0112] In some embodiments, a polymerization process for producing an ethylene-based polymer may comprise polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, the catalyst system incorporating at least one metal-ligand complex of Formula (I). Polymers obtained from such catalyst systems incorporating a metal-ligand complex of Formula (I) may have a molecular weight of, for example, 0.850 g / cm or less according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.960g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm 3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density may be

[0113] In another embodiment, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a melt flow ratio (I 10 / I2), where the melt index I2 is measured at 190°C and a load of 2.16 kg according to ASTM D1238 (which is incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 190°C and a load of 10 kg. In other embodiments, the melt flow ratio (I 10 / I2) is 5-10, and in other embodiments the melt flow ratio is 5-9.

[0114] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 1 to 25, where MWD is M w / M n is defined as M w is the weight average molecular weight, and M n is the number average molecular weight. In other embodiments, the polymer resulting from the catalyst system has an MWD of 1 to 6. Another embodiment has an MWD of 1 to 3, and another embodiment has an MWD of 1.5 to 2.5.

[0115] Embodiments of the catalyst systems described in this disclosure result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0116] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passage through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glovebox were further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware was dried overnight in an oven before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis was performed using a Waters e2695 separations module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a 5:95 to 100:0 gradient of acetonitrile and water (containing 0.1% formic acid as the ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 H NMR data are reported as follows: chemical shifts (multiplicities (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integrals, and assignments). 1 Chemical shifts for H NMR data are reported in ppm downfield from internal tetramethylsilane (tetramethylsilane, TMS, δ scale) using residual protons in the deuterated solvent as the reference. 13 C NMR data is 1 Determined using H decoupling, chemical shifts are reported in ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

[0117] Conventional composition GPC The chromatography system consisted of a PolymerChar (Valencia, Spain) GPC-IR high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160 °C, and the column compartment was set to 150 °C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0118] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 g / mol, arranged in six "cocktail" mixtures with at least one decade between individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. The polystyrene standards were predissolved at 80°C with gentle agitation for 30 minutes, then cooled, and the room temperature solution was transferred to an autosampler dissolving oven at 160°C for 30 minutes to cool. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). 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.

[0119] A fifth-order polynomial was used to fit each polyethylene-equivalent calibration point. A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band-broadening effects for a linear homopolymer polyethylene standard obtained at 120,000 MW.

[0120] The total plate count for the GPC column set was performed using decane introduced into the blank sample via a micropump controlled using a PolymerChar GPC-IR system. The plate count for the chromatography system should exceed 18,000 for four Agilent "Mixed A" 30 cm 20 micron linear mixed-bed columns.

[0121] Samples were prepared in a semi-automated fashion using PolymerChar's "Instrument Control" software, with a target sample weight of 2 mg / mL, and solvent (containing 200 ppm BHT) was added via a PolymerChar high-temperature autosampler to a pre-nitrogen-sparged, septum-capped vial. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0122] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on GPC results using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph according to Equations 2-4 using PolymerChar's GPCOne™ software, baseline-subtracted IR chromatograms at each equally spaced data collection point (i), and polyethylene equivalent molecular weights obtained from a narrow standard calibration curve for point (i) of Equation 1.

[0123]

number

[0124] 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 calibrate the pump flow rate (Flow Rate (Nominal)) for each sample by RV-aligning the respective decane peak in the sample (RV (FM Sample)) with the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. After calibrating the system based on the flow rate marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated as per Equation 5. Processing of the flow rate marker peak was performed via PolymerChar GPCOne™ software. An acceptable flow rate correction is such that the effective flow rate should be within ±0.5% of the apparent flow rate. Flow rate (effective) = Flow rate (nominal) * (RV(FM calibrated) / RV(FM sample)) (Equation 5)

[0125] Conventional UHMW-GPC composition The chromatography system consisted of a PolymerChar (Valencia, Spain) GPC-IR high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 165 °C, and the column compartment and detector were set to 155 °C. The columns used were four TOSOH TSKgel GMHHR-H(30)HT 30-micron particle size, mixed-pore size columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0126] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 g / mol, arranged in six "cocktail" mixtures with at least one decade between each molecular weight. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. Individually prepared polystyrene standards of 10,000,000 g / mol and 15,000,000 g / mol, both from Agilent Technologies, were also prepared at 0.5 and 0.3 mg / mL, respectively. The polystyrene standards were predissolved at 80 °C with gentle agitation for 30 minutes, then cooled, and the room temperature solutions were transferred to an autosampler dissolving oven at 160 °C for 30 minutes to cool. 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)).

[0127] A third-order polynomial was used to fit each polyethylene-equivalent calibration point. A small adjustment to A (approximately 0.375 to 0.445) was made to correct for column resolution and band-broadening effects for a linear homopolymer polyethylene standard obtained at 120,000 MW.

[0128] The total plate count of the GPC column set was performed using decane as a blank sample introduced via a micropump controlled using a PolymerChar GPC-IR system. The plate count of the chromatography system should exceed 12,000 for four TOSOH TSKgel GMHHR-H(30)HT 30 micron particle size, mixed pore size columns.

[0129] Samples were prepared in a semi-automated fashion using PolymerChar's "Instrument Control" software, with a target sample weight of 2 mg / mL, and solvent (containing 200 ppm BHT) was added via a PolymerChar high-temperature autosampler to a pre-nitrogen-sparged, septum-capped vial. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0130] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on GPC results using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph according to Equations 2-4 using PolymerChar's GPCOne™ software, baseline-subtracted IR chromatograms at each equally spaced data collection point (i), and polyethylene equivalent molecular weights obtained from a narrow standard calibration curve for point (i) of Equation 1.

[0131] To monitor deviations over time, a flow marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow marker (FM) was used to linearly calibrate the pump flow rate (Flow Rate (Nominal)) for each sample by RV-aligning the respective decane peak in the sample (RV (FM Sample)) with the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. 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 5. Processing of the flow marker peak was performed via PolymerChar GPCOne™ software. An acceptable flow rate correction is such that the effective flow rate should be within ±0.5% of the apparent flow rate.

[0132] IR5 GPC Octene Composition Calibration The quantitative calibration of the IR5 detector was performed using a narrow SCB distribution ranging from a single polymer (0 SCB / 1000 total carbons) to approximately 40 SCB / 1000 total carbons (where total C = carbons in the main chain + carbons in the branches) and a known copolymerization monomer content ( 13 The analysis was carried out using at least 10 ethylene-based polymer standards (octene as the comonomer) produced by single-site metallocene catalysis from a single reactor (polyethylene homopolymer and ethylene / octene copolymer) in a solution process (measured by C NMR Method, Qiu et al., Anal. Chem. 2009, 81, 8585-8589). Each standard had a weight average molecular weight (Mw) of 36,000 g / mol to 126,000 g / mol as measured by GPC. Each standard had a molecular weight distribution (Mw / Mn) of 2.0 to 2.5. The polymer properties of the SCB standards are listed in Table A.

[0133] [Table 1]

[0134] The "IR5 area ratio" (or "IR5 area ratio") of the "baseline-subtracted area response of the IR5 methyl channel sensor" to the "baseline-subtracted area response of the IR5 measurement channel sensor" メチルチャネル面積 / IR5 測定チャネル面積 ")" (Standard filters and filter wheel supplied by PolymerChar: Part Number IR5_FWM01 is included as part of the GPC-IR instrument) were calculated for each of the "copolymer" standards. A linear fit of wt% copolymerizing monomer frequency versus "IR5 area ratio" was constructed in the form of the following Equation 6: Weight % Comonomer = A0 + [A1 × (IR5 メチルチャネル面積 / IR5 測定チャネル面積 )](Equation 6) where A0 is the "wt% comonomer" at an "IR5 area ratio" of zero, and A1 is the slope of "wt% comonomer" vs. "IR5 area ratio," representing the increase in wt% comonomer as a function of "IR5 area ratio." The IR5 area ratio is equal to the IR5 height ratio for the narrow PDI and narrow SCBD standard material.

[0135] Improved Method for Monomer Content Analysis for Copolymerization (iCCD) (Cong and Parrott et al., WO 2017040127(A1)). iCCD experiments were performed using a Crystallization Elution Fractionation instrument (CEF) (PolymerChar, Spain) equipped with an IR-5 detector (PolymerChar, Spain) and a two-angle light scattering detector model 2040 (Precision Detectors, now Agilent Technologies). A 5 cm or 10 cm (length) x 1 / 4 inch (inner diameter) guard column packed with 20-27 micron glass (MoSCi Corporation, USA) on stainless steel was placed immediately before the IR-5 detector in the detector oven. Ortho-dichlorobenzene (ODCB, 99% anhydrous grade or technical grade) was used. Silica gel 40 (particle size 0.2-0.5 mm, catalog number 10181-3) was obtained from EMD Chemicals (which may be used to dry the ODCB solvent prior). The CEF instrument is equipped with an autosampler with N2 purge capability. Before use, the ODCB is sparged with dry nitrogen (N2) and agitated for 1 hour. Samples were prepared at 4 mg / ml (unless otherwise specified) using the autosampler at 160 °C for 1 hour with shaking. The injection volume was 300 pL. The temperature profile for the iCCD was: crystallization from 105 °C to 30 °C at 3 °C / min, thermal equilibration at 30 °C for 2 minutes (including a soluble fraction elution time of 2 minutes), and elution from 30 °C to 140 °C at 3 °C / min. The flow rate during crystallization is 0.0 ml / min. The flow rate during elution is 0.50 ml / min. Data is collected at 1 data point per second.

[0136] The iCCD column was packed with gold-coated nickel particles (Bright 7GNM8-NiS, Nippon Chemical Industrial Co.) in a 15 cm (length) × ¼ inch (inner diameter, ID) stainless steel tube. Column packing and conditioning were performed using a slurry method according to reference (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. International Publication No. 2017040127(A1)). The final pressure using TCB slurry packing was 150 bar.

[0137] Column temperature calibration was performed using a linear homopolymer polyethylene (comonomer content: zero, melt index (I2) 1.0, polydispersity M) reference material in ODCB. w / M n was performed using a mixture of 1.0 mg / ml (approximately 2.6 mg / ml) and eicosane (2 mg / ml) by conventional gel permeation chromatography. iCCD temperature calibration consisted of four steps: (1) calculating the delay volume, defined as the temperature offset between the measured peak elution temperatures of eicosane minus 30.00°C; and (2) subtracting the temperature offset of the elution temperature from the iCCD raw temperature data. Note that this temperature offset is a function of experimental conditions such as elution temperature, elution flow rate, etc.; (3) creating a linear calibration line converting elution temperatures over the range of 30.00°C to 140.00°C, such that the linear monopolymer polyethylene reference material has a peak temperature at 101.0°C and eicosane has a peak temperature of 30.0°C; and (4) linearly extrapolating elution temperatures below 30.0°C for soluble fractions measured isothermally at 30°C by using an elution heating rate of 3°C / min according to reference (Cerk and Cong et al., U.S. Pat. No. 9,688,795).

[0138] Comonomer content versus iCCD elution temperature was constructed using 12 reference materials (ethylene homopolymers and single-site metallocene-catalyzed ethylene-octene random copolymers, with ethylene equivalent weight average molecular weights ranging from 35,000 to 128,000). All of these reference materials were analyzed at 4 mg / mL using the same methodology as previously specified. The reported elution peak temperatures were linearly fit to the linear equation y = -6.3515x + 101.00, where y represents the iCCD elution temperature, x represents octene mole %, and R 2 was 0.978.

[0139] The molecular weights of the polymer and polymer fractions were determined directly from the LS detector (at a 90-degree angle) and the concentration detector (IR-5) according to the Rayleigh-Gans-Debys approximation (Striegel and Yau, "Modern Size Exclusion Liquid Chromatogram," pp. 242 and 263) by assuming a form factor of 1 and all virial coefficients of zero. An integration window was set to integrate all chromatograms over the elution temperature range of 23.0–120 °C (temperature calibration specified above).

[0140] Calculating molecular weight (Mw) from iCCD involves four steps: (1) Step of measuring the inter-detector offset. The offset is defined as the geometric volume offset between the LS detector and the concentration detector. It is calculated as the difference in elution volume (mL) of the polymer peak between the concentration detector and the LS chromatogram. This is converted to a temperature offset by using the elution heat rate and elution flow rate. A linear high-density polyethylene (comonomer content: zero, melt index (I2): 1.0, polydispersity M w / M nConventional gel permeation chromatography (GPC) uses approximately 2.6. The experimental conditions are the same as those for the conventional iCCD method described above, except for the following parameters: crystallization from 140°C to 137°C at 10°C / min, soluble fraction elution time at 137°C for 1 minute, soluble fraction (SF) time of 7 minutes, and elution from 137°C to 142°C at 3°C / min. The flow rate during crystallization is 0.0 ml / min. The flow rate during elution is 0.80 ml / min. The sample concentration is 1.0 mg / ml. (2) Shift each LS data point in the LS chromatogram to correct for inter-detector offset before integration. (3) The baseline-subtracted LS and concentration chromatograms are integrated over the entire elution temperature range of step (1). The MW detector constant is calculated using HDPE samples of known MW in the range of 100,000-140,000 MW and the area ratio of the LS and concentration integrated signals. (4) The Mw of the polymer was calculated by using the ratio of the integrated light scattering detector (at a 90-degree angle) to the concentration detector and the MW detector constant.

[0141] The half-width calculation is defined as the temperature difference between the front and rear temperatures at half the maximum peak height, where the front temperature at half the maximum peak is searched forward from 35.0°C, while the rear temperature at half the maximum peak is searched backward from 119.0°C.

[0142] Chain transfer constant calculation The chain transfer constant was calculated using a version of the Mayo equation shown in Equation 7, where Mn0 is the Mn with no hydrogen added to the reactor, H2 and ethylene concentrations are liquid phase concentrations, and c CTHis the ratio of the hydrogenolysis rate constant to the rate constant for the chain transfer reaction. The reactor volume was 3.414 L, the liquid phase ethylene concentration was estimated to be 0.539 M, and the estimated hydrogen concentrations were 1.17 mM, 2.31 mM, 4.53 mM, 8.74 mM, and 16.3 mM for 10 mmol, 20 mmol, 40 mmol, 80 mmol, and 160 mmol H2, respectively. Mn values ​​were calculated for each hydrogen charge using Equation 7. The Solver function in MS Excel was used to calculate the c CTH The value of was varied to minimize the sum of the squared deviations of the calculated Mn values ​​versus the experimental Mn values ​​simultaneously for all hydrogen loading amounts.

[0143]

number

[0144] Batch Reactor Polymerization Procedure The feedstocks (ethylene, 1-octene) and process solvent (a narrow-boiling range, high-purity isoparaffinic solvent commercially available from ExxonMobil Chemical Co. under the trademark ISOPAR E) were purified with molecular sieves before being introduced into the reaction environment. A 1-gallon (3.79 L) stirred autoclave reactor was charged with ISOPAR E and 1-octene. The reactor was then heated to the desired temperature and charged with ethylene to reach the desired pressure. If desired, hydrogen was also added at this point. The catalyst composition was prepared in a dry box under an inert atmosphere by mixing the desired procatalyst and, optionally, one or more additives, if desired, with additional solvent to achieve a total volume of approximately 15-20 mL. The activated catalyst mixture was then rapidly injected into the reactor. The reactor pressure and temperature were maintained constant by feeding ethylene during the polymerization and cooling the reactor as needed. After 10 minutes, the ethylene feed was stopped, and the solution was transferred to a nitrogen-purged resin kettle. The polymer was thoroughly dried in a vacuum oven and the reactor was thoroughly rinsed with hot ISOPAR E between polymerization runs.

[0145] Procedure A for Polymerization in a Continuous Reactor The feedstocks (ethylene, 1-octene) and process solvent (high-purity narrow-boiling isoparaffin solvent commercially available from ExxonMobil Chemical Co. under the trademark Isopar E) were purified with molecular sieves before being introduced into the reaction environment. Hydrogen was supplied as a high-purity grade in a pressurized cylinder without further purification. The reactor monomer feed (ethylene) stream was pressurized via a mechanical compressor to a pressure above the reaction pressure of 525 psig. The solvent and copolymerization monomer (1-octene) feed were pressurized via a mechanical positive displacement pump to a pressure above the reaction pressure of 525 psig. MMAO-3A, ​​commercially available from Nouryon, was used as an impurity scavenger. Individual catalyst components (procatalyst or cocatalyst) were manually batch diluted to specific component concentrations with purified solvent (Isopar E) and pressurized to a pressure above the reaction pressure of 525 psig. The cocatalyst was [HNMe(C)], commercially available from Boulder Scientific. 18 H 37 )2][B(CF)4] was used in a 1.2 molar ratio relative to the metal-ligand complex of formula (I), the metal-ligand complex of formula (V), or the sum of both complexes of formula (I) and formula (V). All reaction feed streams were measured by mass flow meters and independently controlled by computerized automated valve control systems.

[0146] Continuous solution polymerizations were conducted in one or more of a 5 liter (L) continuously stirred-tank reactor (CSTR), a 5.7 L CSTR, and / or a plug flow reactor. The CSTR reactor has independent control of all fresh solvent, monomer, copolymerization monomer, hydrogen, and catalyst component feeds. The plug flow reactor has independent control of the catalyst component feeds. The combined solvent, monomer, copolymerization monomer, and hydrogen feed to the reactor is temperature controlled anywhere between 5°C and 50°C, typically at 25°C. The fresh copolymerization monomer feed to the polymerization reactor is fed along with the solvent feed. The fresh solvent feed is typically controlled by each injector receiving half of the total fresh feed mass flow rate. The cocatalyst is fed to the procatalyst based on a calculated specific molar ratio (1.2 molar equivalents). Immediately after each fresh injection point, the feed stream is mixed with the contents of the circulating polymerization reactor using a static mixing element. The effluent from the polymerization reactor system (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a control valve (responsible for maintaining the reactor system pressure at a specified target). As the stream exits the reactor, it is contacted with water to quench the reaction. Various additives, such as antioxidants, could be added at this point. The stream then passes through another set of static mixing elements to uniformly distribute the catalyst kill and additives.

[0147] Following additive addition, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passed through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from other low-boiling reaction components. The stream then entered a two-stage separation and devolatilization system, where the polymer was stripped from the solvent, hydrogen, and unreacted monomer and comonomer. The separated, devolatilized polymer melt was pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transported to boxes for storage.

[0148] Procedure B for polymerization in a continuous reactor The feedstocks (ethylene, 1-octene, 1-hexene) and process solvent (Isopar-E™, a narrow-boiling, high-purity isoparaffinic solvent commercially available from ExxonMobil Corporation) are purified with molecular sieves before being introduced into the reaction environment. Hydrogen is supplied as a high-purity grade in a pressurized cylinder without further purification. The reactor monomer feed (ethylene) stream is pressurized via a mechanical compressor to a pressure above the reaction pressure of 725 psig. The solvent and copolymerization monomer (1-hexene or 1-octene) feed are pressurized via a mechanical positive displacement pump to a pressure above the reaction pressure of 725 psig. MMAO-3A, ​​commercially available from AkzoNobel, was used as an impurity scavenger. Individual catalyst components (procatalyst cocatalysts) were manually batch diluted to specific component concentrations with purified solvent (Isopar E) and pressurized above the reaction pressure at 725 psig. The cocatalyst was [HNMe(C)], commercially available from Boulder Scientific. 18 H 37 )2][B(CF5)4] was used in a 1.2 molar ratio relative to the procatalyst. All reaction feed streams were measured using mass flow meters and independently controlled by computer-automated valve control systems.

[0149] Continuous solution polymerization is carried out in a 5-liter (L) continuously stirred tank reactor (CSTR). The reactor independently controls all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. The combined solvent, monomer, comonomer, and hydrogen feeds to the reactor are temperature controlled anywhere between 5°C and 50°C, typically at 25°C. Fresh comonomer feed to the polymerization reactor is fed along with the solvent feed. The fresh solvent feed is typically controlled by each injector receiving half of the total fresh feed mass flow rate. Cocatalyst is fed to the procatalyst components based on a calculated specific molar ratio (1.2 molar equivalents). Immediately after each fresh injection point, the feed stream is mixed with the contents of the circulating polymerization reactor using a static mixing element. The effluent from the polymerization reactor (including solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the first reactor loop and passes through a control valve (responsible for maintaining the reactor pressure at a specified target). As the stream exits the reactor, it is contacted with water to quench the reaction. Various additives, such as antioxidants, can be added at this point. The stream then passes through another set of static mixing elements to uniformly distribute the catalyst kill and additives.

[0150] Following additive addition, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passed through a heat exchanger to increase the stream temperature in preparation for separation of the polymer from other lower-boiling reaction components. The stream then entered a two-stage separation and devolatilization system, where the polymer was stripped of solvent, hydrogen, and unreacted monomer and comonomer. The separated, devolatilized polymer melt was pumped to a devolatilizing extruder. The polymer strands exited the extruder and entered a cold water bath where the polymer crystallized before entering a strand chopper for pelletization. [Example]

[0151] The results of polymerization reactions of procatalysts PN-1, PN-2, or PN-3 in combination with BPP-1, BPP-2, BPP-3, BPP-4, BPP-5, BPP-6, BPP-7, BPP-8, BPP-9, or BPP-10 are tabulated and discussed. One or more features of the present disclosure are illustrated in view of the following examples.

[0152] [ka]

[0153] Polymerization conditions: 3.79 L (1 Gal) batch reactor, 1250 g of Isopar-E, precatalyst:activator=1:1.2, activator=[HNMe(C 18 H 37 )2][B(C6F5)4], 50 equivalents of MMAO-3A, ​​10 minute reaction time. 160°C: 60g 1-octene, ethylene, pressure reached 320 psi. 190°C: 65g 1-octene, ethylene, pressure reached 410 psi.

[0154] [Table 2]

[0155] [Table 3]

[0156] [Table 4]

[0157] [Table 5]

[0158] [Table 6]

[0159] [Table 7]

[0160] [Table 8]

[0161] [Table 9]

[0162] [Table 10]

[0163] Some BPP catalysts have larger Mz / Mn values, such as in C9 and C10. For example, BPP-8 produces polymers with a low molecular weight tail resulting in a larger Mz / Mn, as tabulated in C10. However, an increase in Mz / Mn beyond this starting value is still observed when this catalyst is combined with a PN catalyst, as shown in results I21-I23 and I24-I27.

[0164] [Table 11]

[0165] [Table 12]

[0166] [Table 13]

[0167] [Table 14]

[0168] [Table 15]

[0169] [Table 16]

[0170] [Table 17-1]

[0171] [Table 17-2]

[0172] [Table 18]

[0173] [Table 19] * Calculated at 190°C

[0174] Figure 3 shows GPC traces of polyethylene produced with a dual catalyst, as well as PN-1 and BPP-1. As the amount of hydrogen gas increases, the molecular weight of the produced polyethylene splits into two distinct peaks. Varying the level of hydrogen significantly affects the molecular weight of PN-produced PE, while the MW of BPP-1-produced PE changes little. At 0H2, the molecular weights of PN-1-produced PE and BPP-1-produced PE are very similar and overlap. However, as the level of H2 increases from 5 mmol to 20 mmol and then to 40 mmol, the MW of PN-1-produced PE drops significantly, while the MW of BPP-1-produced PE remains nearly unchanged, resulting in a bimodal GPC trace in Figure 3.

[0175] The inherent difference in comonomer incorporation between the PN-1 and BPP-1 catalysts results in dual catalyst-produced resins with significant density splitting between low molecular weight segmented polyethylene and higher molecular weight segmented polyethylene, as shown in Figure 4. The low molecular weight segmented polyethylene shown in Figure 4 has a lower level of comonomer incorporation (about 3 wt%) than the high molecular weight segmented polyethylene (about 18 wt%) due to the different catalysts producing each portion of the material.

[0176] Figures 5 and 6 show similar behavior between other BPP catalysts and phosphinimine catalysts. For example, Figures 5 and 6 show GPC data for the PN-1 / BPP-2 catalyst pair. These GPC curves are similar to the GPC data for the PN-1 / BPP-1 catalyst pair shown in Figures 3 and 4. Here, the same trend is observed: the molecular weights of the polymers produced by PN-1 and BPP-2 are similar without hydrogen, but when hydrogen is introduced, the molecular weight of the polyethylene produced by PN-1 decreases significantly, while the molecular weight of the polyethylene produced by BPP-2 remains largely unchanged. Figures 8, 9, and 10 also show similar trends.

Claims

1. 1. A process for producing polyolefins, said process comprising reacting ethylene and optionally one or more olefin monomers in a reactor or reactors in the presence of a catalyst system and optionally hydrogen gas, said catalyst comprising two or more catalysts, at least one of which is derived from a bis-phenylphenoxy procatalyst according to formula (I) and at least one of which is derived from a phosphinimine procatalyst according to formula (V); 【Chemical 1】 In formula (I), M １ is titanium, zirconium, hafnium, scandium, or yttrium; Each X is independently selected from the group consisting of (C １ ~C ５０ ) hydrocarbyl, (C １ ~C ５０ ) heterohydrocarbyl, —CH ２ Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -OSi(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -CH ２ Ge(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -Ge(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -P(R Ｃ ) ２－Ｗ (OR Ｃ ) Ｗ , -P(O)(R Ｃ ) ２－Ｗ (OR Ｃ ) Ｗ , -N(R Ｃ ) ２ , -NH(R Ｃ ), —N(Si(R Ｃ ) ３ ) ２ , -NR Ｃ Si(R Ｃ ) ３ , -NHSi(R Ｃ ) ３ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , -OCF ３ , -S(O)R Ｃ , -S(O) ２ R Ｃ , -OS(O) ２ R Ｃ , -N=C(R Ｃ ) ２ , -N=CH(R Ｃ ), -N=CH ２ , -N=P(R Ｃ ) ３ , -OC(O)R Ｃ , -C(O)OR Ｃ , -N(R Ｃ ) C(O)R Ｃ , -N(R Ｃ )C(O)H, -NHC(O)R Ｃ , -C(O)N(R Ｃ ) ２ , —C(O)NHR Ｃ , —C(O)NH ２ , halogen, B(R Ｙ ) ４ , Al(R Ｙ ) ４ , or Ga(R Ｙ ) ４ or hydrogen, and each R Ｃ are independently １ ~C ３０ ) hydrocarbyl, or (C １ ~C ３０ ) heterohydrocarbyl, each Q is 0, 1, 2, or 3, each W is 0, 1, or 2, and each R Ｙ is -H, (C １ ~C ３０ ) a hydrocarbyl, or halogen atom, and two X ligands may be linked to form a metallacycle ring; each Y is independently a Lewis base; optionally, X and Y can be linked to form a ring or a bidentate ligand; m is 0, 1, or 2; n is 0, 1, and 2; R １ and R １６ are independently —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , 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 ) ２ is selected from the group consisting of NC(O)—, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV); 【Chemistry 2】 In the formula, R ３１－３５ , R ４１－４８ , and R ５１－５９ Each of the groups independently represents —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ ) -, (R Ｃ ) ２ NC(O)—, or halogen; R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , and R １５ are independently —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S (O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)— and halogen; L is (C １ ~C ４０ ) hydrocarbylene or (C ２ ~C ４０ ) heterohydrocarbylene; In formula (I), each R Ｃ , R Ｐ , and R Ｎ are independently １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ ) heterohydrocarbyl, or —H; M ２ is titanium, zirconium, or hafnium; R ６１ , R ６２ , R ６３ , R ６４ , and R ６５ are independently H, (C １ ~C ５０ ) hydrocarbyl, (C １ ~C ５０ ) heterohydrocarbyl, R ６２ , R ６３ , R ６４ , and R ６５ are optionally joined to form a ring or polycyclic structure; R ６６ , R ６７ , and R ６８ are independently １ ~C ２０ ) hydrocarbyl, (C １ ~C ２０ ) heterohydrocarbyl, (C ６ ~C ３０ ) aryl, (C ５ ~C ３０ ) heteroaryl, and R ６６ , R ６７ , and R ６８ two of which are optionally joined to form a ring.

2. 10. The polymerization process of claim 1, wherein the ratio of the hydrogen chain transfer constants of the procatalyst of formula (V) to the procatalyst of formula (I) is 3 or greater at 160°C.

3. R １ and R １６ 10. The polymerization process of claim 1, wherein at least one of is a radical having formula (II):

4. R １ and R １６ 10. The polymerization process of claim 1, wherein at least one of: is a radical having formula (III):

5. R ８ and R ９ are independently １ ~C ４ 5. The polymerization process of claim 1, wherein the alkyl is 2-(2-methyl-2-propanol).

6. R ３ and R １４ is (C １ ~C ２０ 6. The polymerization process of claim 1, wherein the alkyl is 2-(2-methyl-2-propanol).

7. R ３ and R １４ The polymerization process of any one of claims 1 to 6, wherein is tert-octyl or n-octyl.

8. L is -CH ２ (CH ２ ) ｍ CH ２ -, -CH ２ Si(R Ｃ ) (R Ｄ ) CH ２ -, -CH ２ Ge(R Ｃ ) (R Ｄ ) CH ２ -, -CH ２ (CH ３ ) CH ２ CH ＊ (CH ３ ), bis(methylene)cyclohexane-1,2-diyl and —CH ２ CH (R Ｃ ) CH ２ -, -CH ２ C (R Ｃ ) ２ CH ２ - and each R in L is selected from Ｃ (C １ ~C ２０ ) hydrocarbyl, and R in L Ｄ (C １ ~C ２０ 8. The polymerization process of claim 1, wherein the alkyl group is a methyl group.

9. R ６６ , R ６７ , R ６８ are independently １ ~C ２０ 9. The polymerization process of claim 1, wherein the alkyl is .

10. R ６６ , R ６７ , R ６８ are independently selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), 1,1-dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

11. R ６１ , R ６２ , R ６３ , R ６４ , and R ６５ is H, or (C １ ~C ３ ) alkyl, or R ６１ , R ６２ , and R ６４ (C １ ~C ３ ) alkyl, and R ６３ , R ６５ is H, or R ６１ and R ６３ (C １ ~C ３ ) alkyl, and R ６２ , R ６４ , R ６５ The polymerization process of any one of claims 1 to 10, wherein

12. R ６１ , R ６２ , R ６３ , R ６４ , and R ６５ One of the groups is -OMe and -NMe. ２ The polymerization process according to any one of claims 1 to 11, wherein the polymerization is selected from

13. (A)R ６１ and R ６２ are joined to form a ring, and optionally one or more R Ｓ and R Ｓ is (C １ ~C ３０ ) hydrocarbyl; or (B) R ６３ and R ６４ are joined to form a ring, and optionally one or more R Ｓ and R Ｓ is (C １ ~C ３０ ) hydrocarbyl; or (C) both (A) and (B); 11. The polymerization process of any one of claims 1 to 10, wherein (A), (B), or (C), and the cyclopentadienyl of formula (V) have a structure selected from the group consisting of: 【Chemistry 3】

14. The polymerization process according to any one of claims 1 to 13, wherein the polymerization process is a solution polymerization process.

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