Multimodal polymerization processes using multiple catalyst systems

Abstract

The present disclosure relates to a process for polymerizing olefin monomers to produce polyolefins. The process comprises reacting ethylene and, optionally, one or more olefin monomers in a reactor or reactors in the presence of a catalyst system. The catalyst system comprises two or more catalysts, at least one of which is derived from a constrained geometry procatalyst according to formula (I) and at least one of which is derived from a phosphinimine procatalyst according to formula (V):(I)(V).

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 401,909, filed August 29, 2022, and U.S. Provisional Patent Application No. 63 / 516,725, filed July 31, 2023, which are incorporated by reference in their entireties.

[0002] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more specifically to olefin polymerization catalyst systems comprising one or more constrained geometry procatalysts and one or more phosphinimine procatalysts, 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 that contributes to the characteristics and properties of such an olefin-based polymer.

[0004] Ethylene-based polymers and propylene-based polymers are produced for a wide variety of articles. Polyethylene and polypropylene polymerization processes can be varied in several ways to produce a wide variety of resulting polyethylene resins with different physical properties that make the various resins suitable for use in different applications. Ethylene monomer and, optionally, one or more comonomers are present in a liquid diluent (e.g., solvent), such as an alkane or isoalkane, e.g., isobutene. Hydrogen may also be added to the reactor. Catalyst systems for producing ethylene-based polymers typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (either metallocene or non-metallocene) catalyst systems. The diluent and reactants in the catalyst system are circulated in the reactor at elevated polymerization temperatures, thereby producing an 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. Upon removal from the reactor, the reaction mixture may be treated to remove the polyethylene product from the diluent and unreacted reactants, which are typically recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, where a second polyethylene fraction may be produced. 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 with high molecular weights and narrow molecular weight distributions. 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] By combining catalysts from two different classes, constrained geometry metal-ligand complexes (CGC catalysts) and phosphinimine complex catalysts (PN catalysts), it is possible to take advantage of the different properties of the catalysts and create multimodal polyethylene resins.

[0007] The molecular weight of the polymer produced by the PN catalyst is much more sensitive to hydrogen than that of the polymer produced by the CGC catalyst. As a result, the molecular weight split (the difference in molecular weight of the 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 the PN catalyst. In comparison, the same increase in H2 results in a smaller change in the polymer produced by the CGC catalyst. Figures 1A, 1B, and 1C show the change in molecular weight of the polyethylene produced by the CGC 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 constrained geometry procatalyst according to formula (I) and at least one of which is derived from a phosphinimine catalyst 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) and formula (V), each of X1 and X2 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)NHRC , -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 X1 ligands may be joined to form a metallacycle ring, and two X2 ligands may be joined to form a metallacycle ring.

[0012] In Formula (I) and Formula (V), each Y1 and Y2 is independently a Lewis base, and optionally, X1 and Y1 can be joined to form a ring, and optionally, X2 and Y2 can be joined to form a ring.

[0013] In formula (I) and formula (V), each subscript m1 and m2 is 1 or 2, and each subscript n1 and n2 is 0, 1, and 2. The metal-ligand complex is overall charge neutral, In formula (I), M1 is titanium, zirconium, hafnium, or scandium. In formula (I), N is nitrogen, and T is carbon, silicon, or germanium. R 1 and R 2 are independently -H, (C1 to C 40 ) hydrocarbyl, and (C1-C 40 ) heterohydrocarbyl, R 3 are independently (C1~C 40 ) hydrocarbyl, and (C1-C 40 ) heterohydrocarbyl.

[0014] In formula (V), M2 is titanium, zirconium, or hafnium, and R 51 , R 52 , R 53 , R54 , and R 55 are independently (C1~C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, and R 52 , R 53 , R 54 , and R 55 are optionally joined to form a ring structure, and R 56 , R 57 , and R 58 are independently (C1~C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, (C6-C 30 ) Aryl, (C5-C 30 ) heteroaryl, and R 56 , R 57 , and R 58 two of which are optionally joined to form a ring. [Brief explanation of the drawings]

[0015] [Figure 1A] 1 shows two theoretical molecular weight distribution curves for two unimodal polymer compositions produced by a constrained geometry 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 constrained geometry 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 constrained geometry 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]1 shows molecular weight distribution curves for bimodal polymer compositions produced by CGC-1 and PN-1 with varying amounts of hydrogen gas in the reactor chamber, with the amounts being 0 mmol, 5 mmol, 20 mmol, and 40 mmol. DETAILED DESCRIPTION OF THE INVENTION

[0016] 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.

[0017] 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.

[0018] 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.

[0019] When used to describe certain carbon atom-containing chemical groups, x ~C y A bracketed expression having the form "(C1-C)" means that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive, including 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 version can be any group R S may contain more than y carbon atoms depending on what "R" is. For example, S exactly one group R is phenyl (-C6H5) S (C1~C 50 A "(C ) alkyl" can contain 7 to 56 carbon atoms. Thus, in general, the parenthesized "(C x ~C y )" is a group defined using one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is the sum of all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0020] 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 S The term "hypersubstituted" means that all hydrogen atoms (H) bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by 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 substituents. 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.

[0021] "(C1~C 50The 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

[0022] 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, such as benzyl (—CH2—C6H5).

[0023] "(C1~C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an unsubstituted or alkyl group containing one or more R S and 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 that is (C1-C5) alkyl. S replaced by (C 27 ~C 40 Each (C1-C5) alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0024] "(C6~C 50 The term "aryl" refers to an aryl group having 6 to 40 carbon atoms, of which at least 6 to 14 carbon atoms are aromatic ring carbon atoms, unsubstituted or (one or more R S "Aromatic hydrocarbon radicals" refers to monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radicals substituted (by) a cyclic or cyclic aromatic hydrocarbon radical. 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. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may independently be fused or non-fused, and aromatic or non-aromatic. Unsubstituted (C6-C 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.

[0025] "(C3~C 50 The term "cycloalkyl" refers to an unsubstituted or substituted group having 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 Unsubstituted (C3 to C 40 Examples of cycloalkyl are unsubstituted (C-C 20 ) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0026] (C1~C 50 Examples of hydrocarbylene include unsubstituted or substituted (C-C 50 ) arylene, (C3-C 50 ) cycloalkylene, and (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 three 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-C 20Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH-), and 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (C6-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0027] "(C1~C 50 The term "alkylene" refers to an unsubstituted or substituted group having 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 by 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 radical. 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 50 Examples 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.

[0028] "(C3~C 50 The term "cycloalkylene" refers to an unsubstituted or substituted group having one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms substituted by

[0029] 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 )-, wherein each R C and each R P is a non-substituted (C 1~ C 18 ) hydrocarbyl or —H, wherein 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 can be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene can be on a single carbon atom or a single heteroatom. Additionally, one of the two radicals of the diradical can be on a carbon atom and the other radical can be on a different carbon atom; one of the two radicals can be on a carbon atom and the other on a heteroatom; or one of the two radicals can be 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.

[0030] (C1~C 50 ) Heterohydrocarbyl can 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-C19 ) 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.

[0031] "(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 SThe 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 and can be 1, 2, or 3, and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. A 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2, and the heteroatoms may be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon radicals may be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon radicals may be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0032] "(C1~C 50The 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

[0033] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0034] 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.

[0035] 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 S The 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 This does not include double bonds which may be present in, or may be absent from, (hetero)aromatic rings.

[0036] Embodiments of the present disclosure include a process for polymerizing olefin monomers to produce polyolefins, which process comprises reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system and adjusting the hydrogen gas to control the molecular weight of the polyolefin.

[0037] The amount of hydrogen gas may comprise 0 mmol of hydrogen gas 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.

[0038] The catalyst system comprises one or more constrained geometry procatalysts according to formula (I) and one or more phosphinimine procatalysts according to formula (V).

[0039] An embodiment of the present disclosure is a compound of formula (I):

[0040] [ka] The present invention also includes a catalyst system comprising one or more constrained geometry procatalysts according to the present invention.

[0041] In formula (I), M1 is titanium, zirconium, hafnium, or scandium; the subscript n1 is 0, 1, 2, or 3; the subscript m1 is 0, 1, or 2; and each X1 is independently selected from the group consisting of (C1 to C 50 ) Hydrocarbons, (C1-C 50 ) Heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C6-C 50 ) Aryl, (C6-C 50 ) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) dienes, halogens, hydrogen, -N(R N )2, and -NCOR C The metal-ligand complex is generally charge neutral.

[0042] In formula (I), N is nitrogen, T is carbon or silicon and is covalently bonded to Cp, and R 1 and R 2 are independently -H, (C1 to C 40 ) hydrocarbyl, and (C1-C 40 ) heterohydrocarbyl, R 3 are independently (C1~C 40 ) hydrocarbyl, and (C1-C 40 ) heterohydrocarbyl.

[0043] In formula (I), R 4 , R 5 , R 6 , and R 7 are independently (C1~C 50 ) hydrocarbyl, (C1-C 50 ) heterohydrocarbyl, and R 4 , R 5 , R 6 , and R 7 are optionally joined to form a ring structure.

[0044] In one or more embodiments, in formula (I), R 1 and R 2 is methyl, ethyl, propyl, or phenyl. In some embodiments, R 3 are independently (C1~C 12 ) alkyl. In various embodiments, R 3 is independently tert-butyl, tert-octyl, or n-octyl.

[0045] In some embodiments, R 6 is -OMe, or R 5 is -NMe2.

[0046] In some embodiments, in Formula (I), (A)R 4 and R 5 are connected and contain one or more R S or (B) R 6 and R 7 are combined to form one or more R S or (C) both (A) and (B). Thus, when (A), (B), or (C) occurs, the cyclopentadienyl of formula (I) has a structure selected from the group consisting of:

[0047] [ka]

[0048] An embodiment of the present disclosure is a compound of formula (V):

[0049] [ka] The catalyst system includes one or more phosphinimine procatalysts according to the present invention.

[0050] In formula (V), the subscript m2 is 0, 1, or 2, the subscript n2 is 0, 1, and 2, and each Y2 is independently selected from the group consisting of (C1 to C 20 ) hydrocarbyl, (C6-C 50 ) Aryl, (C6-C 50 ) heteroaryl, halogen, -N(R N )2, and -NCOR C is a monodentate ligand selected from

[0051] In formula (IV), each X2 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 is independently selected from (C 30 )hydrocarbyl, or (C1-C30)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 X2 ligands may be linked to form a metallacycle ring.

[0052] In formula (V), each Y2 is independently a Lewis base, and optionally, X2 and Y2 can be joined to form a ring. Subscript m2 is 0, 1, and 2, and subscript n2 is 0, 1, and 2.

[0053] In formula (V), R 51 , R 52 , R 53 , R 54 , and R 55 are independently (C1~C 50 ) hydrocarbyl, wherein R 51 and R 52 are optionally joined to form a ring, or R 52 and R 53 are optionally joined to form a ring, and R 53 and R 54 are optionally joined to form a ring, and R 54 and R55 are optionally joined to form a ring.

[0054] In formula (V), R 56 , R 57 , and R 58 are independently (C1~C 20 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl, (C6-C 30 ) Aryl, (C5-C 30 ) heteroaryl, and R 56 , R 57 , and R 58 two of which are optionally joined to form a ring.

[0055] 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.

[0056] In one or more embodiments, in formula (V), R 66 , R 67 , R 68 are independently (C1~C 20 ) alkyl.

[0057] 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.

[0058] In various embodiments, in formula (V), where R 54 and R 55 are bonded to form an aromatic ring.

[0059] In one or more embodiments, in formula (V), R 51 , R 52 , R 53 , R 54 , and R 55 is (C1-C3) alkyl, or R 51 , R 52 , and R 54 is (C1-C3) alkyl, or R 51 and R 53 is (C1-C3) alkyl.

[0060] In some embodiments, in formula (V), R 51 , R 52 , R 53 , R 54 , and R 55 is selected from -OMe and -NMe2.

[0061] In various embodiments, in formula (V), (A)R 51 and R 52 are bonded to form a ring, and one or more R S or (B) R 53 and R 54 are bonded to form a ring, and one or more R S or (C) both (A) and (B). Thus, when (A), (B), or (C) occurs, the cyclopentadienyl of formula (V) has a structure selected from the group consisting of:

[0062] [ka]

[0063] In some embodiments, the monodentate ligands, X1 of Formula (I) and X2 of 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.

[0064] In other embodiments, at least one monodentate ligand X1 is independent of any other ligand X1, and X2 of formula (V) may be a neutral ligand, independent of any other ligand X2. 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 wherein each R 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.

[0065] In the metal-ligand complexes according to Formula (I) and Formula (V), each Y1 may be bonded to M1 through a dative or ionic bond, and each Y2 may be bonded to M2 through a dative or ionic bond. In one or more embodiments, Y1 or Y2 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 M1 or M2, the metal of the metal-ligand complexes of Formula (I) and Formula (V). 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.

[0066] In some embodiments, the Lewis base is (C1-C 20 In 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, Y1 or Y2 is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0067] Further, each X and each Y may be independently selected from any other ligands X and Y, and may be selected from 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 independently is unsubstituted (C1 to C 20 In some embodiments, each monodentate ligand X1 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 ) hydrocarbyl.

[0068] In one or more embodiments of formula (I) and formula (V), X1 and X2 are each selected from the group consisting of (C1-C 20 ) hydrocarbyl or (C1-C 10 ) hydrocarbyl, (C1-C 20 ) heterohydrocarbyl or (C1-C 10 In some embodiments, in Formula (I) and Formula (V), X1 and X2 are (C1-C20 ) aryl or (C1-C 20 ) heteroaryl.

[0069] In one or more embodiments in Formula (I) and Formula (V), X1 and X2 are benzyl, chloro, -CH2SiMe3, or phenyl.

[0070] In various embodiments, each X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. In some embodiments, each X is the same. In other embodiments, at least two Xs are different from each other. In embodiments where at least two Xs are different from at least one X, Xs are methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0071] In further embodiments, each X2 is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. In some embodiments, each X2 is the same. In other embodiments, at least two X2 are different from each other. In embodiments where at least two X2 are different from at least one X2, X2 is methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, trimethylsilylmethyl, phenyl, benzyl, and chloro. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

[0072] In some embodiments, the chemical groups (e.g., X, X, and R) of the metal-ligand complex of formula (I) 1 -R 4In other embodiments, any or all of the chemical groups X, X, and R of the metal-ligand complex of formula (I) may be unsubstituted. 1 -R 4 Any of the above has 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 different carbon atoms or heteroatoms. In some embodiments, any of the chemical groups X, X, and R-R may be attached to R S are not over-substituted with, 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.

[0073] In some embodiments, the ratio of the hydrogen chain transfer constant of the procatalyst for Formula (V) to the procatalyst of Formula (I) is 3 or greater at 160° C. In some embodiments, the ratio of the hydrogen chain transfer constant of the procatalyst for 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.

[0074] In an exemplary embodiment, the catalyst system comprises a metal-ligand complex according to formula (I) having the structure of any of procatalysts CGC-1, CGC-2, CGC-3, CGC-4, CGC-5, CGC-6, CGC-7, CGC-8, CGC-9, CGC-10, CGC-11, CGC-12, CGC-13, CGC-14, CGC-15, CGC-16, CGC-17, CGC

[0075] [ka]

[0076] promoter component Catalyst systems containing metal-ligand complexes of formula (I) can 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) can be catalytically activated by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. In addition, metal-ligand complexes based on formula (I) include both neutral procatalyst forms and catalyst forms that can be positively charged by loss of a monoanionic ligand such as benzyl or phenyl. Activating cocatalysts suitable for use herein include 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 aforementioned activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0077] 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.

[0078] The scavenger is not activator in nature, as it sequesters impurities in the reactor before the precatalyst is added. At low loadings of alumoxane, it does not act as a cocatalyst, but rather as a scavenger.

[0079] Suitable additives 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.

[0080] The Lewis acid activating cocatalyst may be any of the compounds 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)3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + Each of the nitrogen cations (C1 to C 20 ) When two or more hydrocarbyls are present, they may be the same or different.

[0081] The combination of neutral Lewis acid activating cocatalysts is tri((C1-C4) alkyl)aluminum and tri((C6-C 18 )aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments include such neutral Lewis acid mixtures in combination 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(pentafluorophenylborane):(alumoxane) [e.g., Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane)] is from 1:1:1 to 1:10:30, and in other embodiments, from 1:1:1.5 to 1:5:10.

[0082] 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.

[0083] 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 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 one or more metal-ligand complexes of Formula (I).

[0084] 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.

[0085] 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.

[0086] 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 into one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available under the name ISOPAR E from ExxonMobil Chemical Co. (Houston, Texas). 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.

[0087] 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.

[0088] 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.

[0089] 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 at least 50 weight percent ethylene-derived monomeric units. All individual values ​​and subranges encompassed by "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 monomeric units, at least 70 weight percent ethylene-derived monomeric units, at least 80 weight percent ethylene-derived monomeric units, or from 50 to 100 weight percent ethylene-derived monomeric units, or from 80 to 100 weight percent ethylene-derived units.

[0090] In some embodiments, the ethylene-based polymer can comprise at least 90 mol percent units derived from ethylene. All individual values ​​and subranges from at least 90 mol percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may comprise at least 93 mol percent units derived from ethylene, at least 96 mol percent units, at least 97 mol percent units derived from ethylene, or alternatively, 90 to 100 mol percent units derived from ethylene, 90 to 99.5 mol percent units derived from ethylene, or 97 to 99.5 mol percent units derived from ethylene.

[0091] 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.

[0092] 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.

[0093] In one embodiment, an ethylene-based polymer can 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 a catalyst system described herein and optionally one or more cocatalysts. In another embodiment, an ethylene-based polymer can 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 a catalyst system described herein and herein and optionally one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be used in the first reactor or the second reactor. In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, 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 a catalyst system described herein.

[0094] In another embodiment, ethylene-based polymers can be produced via solution polymerization in a single reactor system, for example a single loop reactor system, in which 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.

[0095] 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% of such additives by weight, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may comprise from about 0 to about 20% by weight of a filler, such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the total 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.

[0096] In some embodiments, a polymerization process for producing an ethylene-based polymer comprises polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one metal-ligand complex of Formula (I). Polymers obtained from such catalyst systems incorporating a metal-ligand complex of Formula (I) 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

[0097] 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.

[0098] In some embodiments, the polymers obtained from the catalyst system comprising the metal-ligand complex of Formula (I) have a molecular weight distribution (MWD) of 1 to 25, where MWD is defined as Mw / Mn, where Mw is the weight average molecular weight and Mn is the number average molecular weight. In other embodiments, the polymers obtained from the catalyst system have a MWD of 1 to 6. Another embodiment has a MWD of 1 to 3, and another embodiment has a MWD of 1.5 to 2.5.

[0099] 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.

[0100] 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. Glassware for moisture-sensitive reactions was dried overnight in an oven before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analyses were 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.

[0101] 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.

[0102] 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)):

[0103]

number

[0104] 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.

[0105] A total plate count for 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 for the chromatography system should exceed 18,000 for four Agilent "Mixed A" 30 cm 20 micron linear mixed-bed columns.

[0106] 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.

[0107] Mn (GPC) , Mw (GPC) , and Mz (GPC) was calculated based on GPC results using the internal IR5 detector (measurement channel) of the 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.

[0108]

number

[0109] To monitor deviations over time, a flow marker (decane) was introduced into each sample via a micropump controlled by the 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 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 peaks was performed via PolymerChar GPCOne™ software. 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)

[0110] 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.

[0111] 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)).

[0112] 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.

[0113] 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.

[0114] 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.

[0115] Mn (GPC) , Mw (GPC) , and Mz (GPC) was calculated based on GPC results using the internal IR5 detector (measurement channel) of the 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.

[0116] 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 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 peaks was performed via PolymerChar GPCOne™ software. Acceptable flow rate correction is such that the effective flow rate should be within ±0.5% of the apparent flow rate.

[0117] 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) ranging from 36,000 g / mol to 126,000 g / mol as measured by GPC. Each standard had a molecular weight distribution (Mw / Mn) ranging from 2.0 to 2.5. The polymer properties of the SCB standards are listed in Table A.

[0118] [Table 1]

[0119] Chain transfer constant calculation The chain transfer constant was calculated using a version of the Meiot 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 CTH is 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, 20, 40, 80, and 160 mmol of H, 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.

[0120]

number

[0121] Batch Reactor Polymerization Procedure The feedstocks (ethylene, 1-octene) and process solvent (a high-purity isoparaffin solvent with a narrow boiling range, commercially available from ExxonMobil Corporation under the trademark ISOPAR E) were purified with molecular sieves. 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, if desired, optionally one or more additives with additional solvent to obtain 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. [Example]

[0122] The results of polymerization reactions of procatalysts PN-1, PN-2, or PN-3 in combination with CGC-1 are tabulated and discussed. One or more features of the present disclosure are illustrated in view of the following examples.

[0123] [ka]

[0124] 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, ​​160 °C: 60 g of 1-octene, ethylene, pressure reaching 320 psi (reaction time 10 min).

[0125] [Table 2]

[0126] [Table 3]

[0127] [Table 4]

[0128] Figure 2 demonstrates the concept that varying the hydrogen level in the polymerization reactor alters the molecular weight of the polymer produced by the phosphinimine procatalyst, thus enabling the production of bimodal polyethylene as shown in Figures 1A, 1B, and 1C.

[0129] In Figure 3, as the amount of hydrogen in the reactor increased, the molecular weight of the polyethylene produced by PN-1 decreased significantly, while the molecular weight of the polyethylene produced by CGC-1 was affected to a much lesser extent. At 0 H2, the molecular weights of the PN-1 and CGC-1 produced polyethylenes were very similar and overlapped. However, as the level of H2 increased from 5 mmol to 20 mmol to 40 mmol, the molecular weight of the PN-1 produced polyethylene decreased significantly, while the molecular weight of the CGC-1 produced polyethylene decreased only slightly, resulting in a bimodal GPC trace in Figure 3.

Claims

1. 1. A process for polymerizing olefin monomers to produce 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, wherein the catalyst system comprises two or more catalysts, at least one of which is derived from a constrained geometry procatalyst according to formula (I), at least one of which is a constrained geometry procatalyst according to formula (V): 【Chemical 1】 Derived from a phosphinimine procatalyst by During the ceremony, M １ is titanium, zirconium, hafnium, or scandium; each X １ is (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 RC, -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, -NH Ｃ (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 ) hydrocarbyl or halogen atom, and two X １ the ligands may be linked to form a metallacycle ring; Each Y １ are independently a Lewis base, and optionally, X １ and Y １ can be linked to form a ring, m １ is 1 or 2, n １ is 0, 1, or 2, Procatalysts (I) and (V) are overall charge neutral; N is nitrogen; T is carbon, silicon, or germanium; R １ and R ２ are independently —H, (C １ ~C ４０ ) hydrocarbyl, and (C １ ~C ４０ ) heterohydrocarbyl; R １ and R ２ are optionally joined to form a ring structure; R ３ are independently １ ~C ４０ ) hydrocarbyl, and (C １ ~C ４０ ) heterohydrocarbyl; R ４ , R ５ , R ６ , and R ７ are independently H, (C １ ~C ５０ ) hydrocarbyl, or (C １ ~C ５０ ) heterohydrocarbyl, R ４ , R ５ , R ６ , and R ７ are optionally joined to form a ring or multiple ring structures; M ２ is titanium, zirconium, or hafnium; each X ２ is (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 , -O Ｃ (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 ) hydrocarbyl or halogen atom, and two X ２ the ligands may be linked to form a metallacycle ring; Each Y ２ are independently a Lewis base, and optionally, X ２ and Y ２ can be linked to form a ring, m ２ is 1 or 2, n ２ are 0, 1, and 2, R ５１ , R ５２ , R ５３ , R ５４ , and R ５５ are independently H, (C １ ~C ５０ ) hydrocarbyl, (C １ ~C ５０ ) heterohydrocarbyl, where R ５２ , R ５３ , R ５４ , and R ５５ are optionally joined to form a ring or multiple ring structures; R ５６ , R ５７ , and R ５８ are independently １ ~C ２０ ) hydrocarbyl, (C １ ~C ２０ ) heterohydrocarbyl, (C ６ ~C ３０ ) aryl, (C ５ ~C ３０ ) heteroaryl, and R ５６ , R ５７ , and R ５８ 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 ２ The polymerization process of claim 1, wherein is methyl, ethyl, propyl, isopropyl, isobutyl, phenyl, para-tolyl.

4. R ３ are independently １ ~C １２ 4. The polymerization process of claim 1, wherein the alkyl is 2-(2-methyl-2-propanol).

5. R ４ , R ５ , R ６ , and R ７ 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, dimethylamino, pyrrolidino, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

6. R ６ is -OMe, or R ５ is -NMe ２ The polymerization process according to any one of claims 1 to 5, wherein

7. (A)R ４ and R ５ are bonded to one or more R Ｓ or forming a ring optionally substituted by (B) R ６ and R ７ are bonded to one or more R Ｓ or forming a ring optionally substituted by (C) both (A) and (B); 5. The polymerization process of any one of claims 1 to 4, wherein (A), (B), or (C), and the cyclopentadienyl of formula (I) have a structure selected from the group consisting of: 【Chemistry 2】

8. R ５１ , R ５２ , R ５３ , R ５４ , and R ５５ One of the groups is -OMe and -NMe. ２ The polymerization process according to any one of claims 1 to 7, wherein the polymerization is selected from

9. (A)R ５１ and R ５２ are bonded to form a ring, and these are one or more R Ｓ or optionally replaced by (B) R ５３ and R ５４ are bonded to form a ring, and these are one or more R Ｓ or (C) both (A) and (B); 8. The polymerization process of any one of claims 1 to 7, wherein (A), (B), or (C), and the cyclopentadienyl of formula (V) have a structure selected from the group consisting of: 【Chemistry 3】

10. R ５６ , R ５７ , R ５８ are independently １ ~C ２０ 10. The polymerization process of claim 1, wherein the alkyl is .

11. R ５６ , R ５７ , R ５８ 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, dimethylamino, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

12. R ５１ , R ５２ , R ５３ , R ５４ , and R ５５ 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, dimethylamino, pyrrolidino, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl.

12. The polymerization process according to any one of claims 1 to 11, wherein the polymerization process is a solution polymerization reaction.

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