Multimodal polymerization process using multiple catalyst systems

Abstract

The present disclosure relates to processes for polymerizing olefin monomers to produce polyolefins. The process comprises reacting ethylene and optionally one or more olefin monomers in one or more reactors in the presence of a catalyst system. The catalyst system comprises two or more catalysts wherein at least one catalyst is derived from a defined geometry procatalyst according to formula (I), and wherein at least one catalyst is derived from a phosphinimine procatalyst according to formula (V): (I) (V). # imgabs0 #

Description

[0001] Cross-references to related patent applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 401,909 filed on August 29, 2022 and U.S. Provisional Patent Application No. 63 / 516,725 filed on July 31, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more particularly to olefin polymerization catalyst systems including one or more constrained geometry procatalysts and one or more phosphinimine procatalysts, and polymerization processes incorporating the catalyst systems to produce bimodal polymers. Background Art

[0004] Olefin-based polymers such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers are produced by various catalyst systems. The selection of such catalyst systems used in the polymerization process of olefin-based polymers is an important factor contributing to the characteristics and properties of such olefin-based polymers.

[0005] Ethylene-based polymers and propylene-based polymers are manufactured for various articles. Polyethylene and polypropylene polymerization processes can differ in many aspects to produce various resulting polyethylene resins having different physical properties, which make the various resins suitable for different applications. Ethylene monomer and optionally one or more comonomers are present in a liquid diluent (such as a solvent), such as an alkane or isoalkane, for example isobutylene. Hydrogen can also be added to the reactor. Catalyst systems for producing ethylene-based products can generally include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (metallocene or non-metallocene (molecular)) catalyst systems. The diluent and the reactants in the catalyst system are circulated around the reactor at an elevated polymerization temperature to produce ethylene-based homopolymers or copolymers. A portion of the reaction mixture containing the polyethylene product dissolved in the diluent and unreacted ethylene and one or more optional comonomers is periodically or continuously removed from the reactor. The reaction mixture can be processed to remove the polyethylene product from the diluent and unreacted reactants when removed from the reactor, wherein the diluent and unreacted reactants are generally recycled back to the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series with the first reactor, in which a second polyethylene fraction may be produced.Despite research efforts devoted to developing catalyst systems suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, there remains a need to improve the efficiency of catalyst systems capable of producing polymers having high molecular weight and narrow molecular weight distribution. Summary of the invention

[0006] There is a continuing need to produce multimodal polyethylene polymers. In particular, to synthesize LLDPE resins using flexible catalyst systems that are compatible with high temperature solution processes.

[0007] By combining catalysts derived from two different classes—constrained geometry metal-ligand complexes (CGC catalysts) and phosphinimine complexes (PN catalysts)—multimodal polyethylene resins can be prepared taking advantage of the different properties of the catalysts.

[0008] The molecular weight of the polymer produced by the PN catalyst is much more sensitive to hydrogen than the molecular weight of the polymer produced by the CGC catalyst. Therefore, the molecular weight distribution (the difference in molecular weight of the polyethylene produced by the two catalysts) can be easily tailored 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 smaller changes in the polymer produced by the CGC catalyst. Figure 1A , Figure 1B and Figure 1C show the molecular weight changes of polyethylene produced by CGC catalyst and PN catalyst.

[0009] Embodiments of the present disclosure include methods for polymerizing olefin monomers to produce polyolefins. The method includes reacting ethylene and optional one or more olefin monomers in one reactor or multiple reactors in the presence of a catalyst system and optional hydrogen. The catalyst includes two or more catalysts, wherein at least one catalyst is derived from a restricted geometry procatalyst according to formula (I), and wherein at least one catalyst is derived from a phosphinimine procatalyst according to formula (V). The amount of hydrogen can be adjusted to customize the molecular weight of the polyolefin.

[0010] Formula (I) and Formula (V) have structures according to the following formula:

[0011]

[0012] In formula (I) and formula (V), each X1 and X2 is independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -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 a monodentate ligand of hydrogen, wherein each R C Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each R Y =–H, (C1-C 30 ) a hydrocarbon group or a halogen atom, wherein two X1 ligands can be linked to form a metal cyclize ring; and wherein two X2 ligands can be linked to form a metal cyclize ring.

[0013] In formula (I) and formula (V), each Y1 and Y2 is independently a Lewis base; optionally, X1 and Y1 can be linked to form a ring; optionally, X2 and Y2 can be linked to form a ring.

[0014] 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 electrically neutral as a whole;

[0015] In formula (I), M1 is titanium, zirconium, hafnium or scandium. In formula (I), N is nitrogen; T is carbon, silicon or germanium. R 1 and R 2 are independently selected from -H, (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl; R 3 Independently selected from (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl.

[0016] In formula (V), M2 is titanium, zirconium or hafnium; R 51 , R 52 , R 53 , R 54 and R 55 Independently (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, wherein R 52 , R 53 , R 54 and R 55 Any of are optionally linked to form a ring structure; R 56 , R 57 and R 58 Independently (C1-C 20 ) hydrocarbon group, (C1-C 20 ) heteroalkyl, (C6-C 30 ) aryl, (C5-C 30 ) heteroaryl, wherein R 56 , R 57 and R 58 Two of are optionally linked to form a ring; and BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1A Two theoretical molecular weight distribution curves are shown for two unimodal polymer compositions produced by a constrained geometry catalyst and by a phosphinimine catalyst in the absence of hydrogen in the reactor chamber.

[0018] Figure 1B Two theoretical molecular weight distribution curves are shown for two unimodal polymer compositions produced by a constrained geometry catalyst and by a phosphinimine catalyst with a small amount of hydrogen in the reactor chamber.

[0019] Figure 1C 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 relatively large amount of hydrogen in the reactor chamber.

[0020] Figure 2 is a graph of the molecular weight of the polymers produced by three different phosphinimine catalysts as a function of the amount of hydrogen (mmol) in the reactor.

[0021] Figure 3] are molecular weight distribution curves of bimodal polymer compositions produced by CGC-1 and PN-1 with different amounts of hydrogen in the reactor chamber. The amounts of hydrogen are 0 mmol, 5 mmol, 20 mmol and 40 mmol. DETAILED DESCRIPTION

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

[0023] The term "independently selected from" is used herein to refer to each of the R groups that precede the term, such as R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different and is not dependent on the identity of any other groups that precede 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 the procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms "procatalyst" and "activator" are interchangeable terms.

[0025] When used to describe certain chemical groups containing carbon atoms, the form "(C x -C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms (including x and y). For example, (C1-C 50 ) alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be replaced by, for example, R S etc. is substituted with one or more substituents. x -C y )" The chemical group defined in brackets is R S The substitution pattern may be based on any group R S The property contains more than y carbon atoms. For example, "exactly one group R S Substituted (C1-C 50 ) alkyl, wherein R S The phenyl group (-C6H5)" may contain from 7 to 56 carbon atoms. Therefore, in general, when the parenthetical phrase "(C x -Cy )" is replaced by one or more carbon-containing substituents R S When substituted, both x and y are added to the substituent R from all carbon atoms. S The combined sum of the number of carbon atoms is used to determine the minimum and maximum total number of carbon atoms in a chemical group.

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

[0027] The term "(C1-C 50 )hydrocarbyl" means a hydrocarbon group having 1 to 50 carbon atoms, and the term "(C1-C 50 )alkylene group" means a hydrocarbon diradical having 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (having three carbons or more, and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and is substituted by one or more R S Substituted or unsubstituted.

[0028] In the present disclosure, (C1-C 50 The hydrocarbon group may be 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)).

[0029] The term "(C1-C 50 )alkyl" and "(C1-C 18 )alkyl" refers to unsubstituted or substituted with one or more R SSubstituted saturated straight chain or branched hydrocarbon groups having 1 to 50 carbon atoms and saturated straight chain or branched hydrocarbon groups having 1 to 18 carbon atoms. 50 Examples of alkyl groups are unsubstituted (C1-C 20 ) alkyl; unsubstituted (C1-C 10 ) alkyl; unsubstituted (C 1- 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. Substituted (C1-C 40 Examples of alkyl groups are substituted (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl and [C 45 ] alkyl. The term "[C 45 "] alkyl" means that there are up to 45 carbon atoms in the group (including substituents), and is, for example, (C 27 -C 40 ) alkyl, each of which is replaced by an R S (which is a (C1-C5) alkyl) substituted. Each (C1-C5) alkyl may be a methyl group, a trifluoromethyl group, an ethyl group, a 1-propyl group, a 1-methylethyl group or a 1,1-dimethylethyl group.

[0030] The term "(C6-C 50 ) aryl means an unsubstituted or (substituted by one or more R S ) substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon groups, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. Monocyclic aromatic hydrocarbon groups include one aromatic ring; bicyclic aromatic hydrocarbon groups have two rings; and tricyclic aromatic hydrocarbon groups have three rings. When bicyclic or tricyclic aromatic hydrocarbon groups are present, at least one of the rings of the group is aromatic. The other one or more rings of the aromatic group may independently be fused or non-fused and be aromatic or non-aromatic. Unsubstituted (C 6- C 50 Examples of aryl groups include: unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 40 Examples of aryl groups 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] The term "(C3-C 50 "Cycloalkyl" means a saturated cyclic hydrocarbon group having 3 to 50 carbon atoms, which is unsubstituted or substituted by one or more R S Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) is defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C3-C 40 Examples of cycloalkyl groups are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. 40 Examples of cycloalkyl groups are substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 )cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

[0032] (C 1- C 50 Examples of the alkylene group include unsubstituted or substituted (C6-C 50 ) arylene, (C3-C 50 )cycloalkylene and (C1-C 50 ) alkylene (e.g., (C 1- C 20 ) alkylene). The 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 than two intermediate carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-diradicals, 1,3-diradicals, 1,4-diradicals, or α,ω-diradicals and other 1,2-diradicals. α,ω-diradicals are diradicals with the largest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diyl radicals include ethane-1,2-diyl (ie, -CH2CH2-), propane-1,3-diyl (ie, -CH2CH2CH2-), 2-methylpropane-1,3-diyl (ie, -CH2CH(CH3)CH2-). (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] The term "(C1-C 50 ) Alkylene means a group having 1 to 50 carbon atoms which is unsubstituted or substituted with one or more R S Substituted saturated straight or branched chain diradicals (i.e., the groups are not on ring atoms). Unsubstituted (C1-C 50 Examples of alkylene groups are unsubstituted (C 1- C 20 )alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), wherein "C*" represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. Substituted (C1-C 50 Examples of alkylene groups are substituted (C1-C 20 )alkylene, -CF2-, -C(O)- and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosene). As mentioned above, the two R S can form together (C1-C 18 ) alkylene, substituted (C1-C 50 Examples of the alkylene group 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] The term "(C3-C 50 ) Cycloalkylene means a cycloalkylene having 3 to 50 carbon atoms which is unsubstituted or substituted with one or more R S Substituted cyclic diradicals (ie, the groups are on ring atoms).

[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)2, Si(R C )2. P(R P )、N(R N )、-N=C(R C )2、-Ge(R C )2- or -Si(R C )-, where each R C and each R P For unsubstituted (C1-C 18 )alkyl or -H, and each R NFor unsubstituted (C1-C 18 ) hydrocarbon group. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. 50 )heteroalkyl" means a heteroalkyl group having 1 to 50 carbon atoms, and the term "(C1-C 50 "Heteroalkylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 )heteroalkyl or (C1-C 50 ) The heteroalkylene group has one or more heteroatoms. The radicals of the heteroalkylene group can be on carbon atoms or heteroatoms. The two radicals of the heteroalkylene group can be on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of the diradical can be on a carbon atom and the other can be on a different carbon atom; one of the two radicals can be on a carbon atom and the other can be on a heteroatom; or one of the two radicals can be on a heteroatom and the other can be on a different heteroatom. Each (C1-C 50 ) heteroalkyl and (C1-C 50 ) heteroalkylene may be unsubstituted or (substituted by one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0036] (C1-C 50 )Heteroalkyl may be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heteroalkyl groups include (C1-C 50 ) heteroalkyl, (C1-C 50 )alkyl-O-, (C 1- C 50 )alkyl-S-, (C1-C 50 )alkyl-S(O)-, (C1-C 50 )alkyl-S(O)2-, (C1-C 50 )alkyl-Si(R C )2-、(C l -C 50 )alkyl-N(R N )-、(C l -C 50 )alkyl-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] The term "(C4-C 50 ) heteroaryl" means an unsubstituted or (substituted by one or more R S ) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups. Monocyclic heteroaromatic hydrocarbon groups include one heteroaromatic ring; bicyclic heteroaromatic hydrocarbon groups have two rings; and tricyclic heteroaromatic hydrocarbon groups have three rings. When a bicyclic heteroaromatic hydrocarbon group or a tricyclic heteroaromatic hydrocarbon group is present, at least one of the rings in the group is heteroaromatic. The other one or more rings of the heteroaromatic group may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., typically (C x -C y ) heteroaryl, such as (C4-C 12 )heteroaryl) is defined as having x to y carbon atoms (such as 4 to 12 carbon atoms) and is unsubstituted or substituted by one or more than one R SSubstituted. The monocyclic heteroaromatic hydrocarbon group is a 5-membered ring or a 6-membered ring. The 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 groups include: pyrrol-1-yl; piperidin-2-yl; furan-3-yl; thien-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazole-1-yl; 1,3,4-oxadiazole-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon groups include pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon group can be a fused 5,6- or 6,6-ring system. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl; and isoquinolin-1-yl. The bicyclic heteroaromatic hydrocarbon group can be a fused 5,6,5-ring system; 5,6,6-ring system; 6,5,6-ring system; or 6,6,6-ring system. 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 acridin-9-yl.

[0038] The term "(C1-C 50 ) heteroalkyl" means a saturated straight or branched chain group containing one to fifty carbon atoms or less and one or more heteroatoms. The term "(C1-C 50 ) "heteroalkylene" means a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of heteroalkyl or heteroalkylene may 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, SR C , S(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or substituted with one or more RS replace.

[0039] Unsubstituted (C2-C 40 Examples of the heterocycloalkyl group include unsubstituted (C2-C 20 )heterocycloalkyl, unsubstituted (C2-C 10 )heterocycloalkyl, aziridine-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxy-2-yl, morpholin-4-yl, 1,4-dioxane-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thioxo-cyclononyl and 2-aza-cyclodecyl.

[0040] The term "halogen atom" or "halogen" refers to a 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: a fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) or iodide ion (I - ).

[0041] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. S In the case of substitution, one or more double bonds and / or triple bonds may or may not be present in the substituent R S The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds or (in a group containing heteroatoms) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds or carbon-silicon double bonds, excluding those that may be present in the substituent R S double bonds in aromatic rings (if any) or (hetero)aromatic rings (if any).

[0042] Embodiments of the present disclosure include a method for polymerizing olefin monomers to produce polyolefins. The method includes reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system and adjusting the hydrogen to tailor the molecular weight of the polyolefin.

[0043] At any given time during the polymerization reaction, the amount of hydrogen in the reactor may include 0 mmol of hydrogen. The amount of hydrogen may increase or decrease as the reaction proceeds. In a semi-batch polymerization process, the amount of hydrogen may decrease when the polymerization reactants consume hydrogen and no additional hydrogen is added.

[0044] The catalyst system comprises one or more constrained geometry procatalysts according to formula (I) and one or more phosphinimine procatalysts according to formula (V).

[0045] Embodiments of the present disclosure include catalyst systems comprising one or more constrained geometry procatalysts according to formula (I):

[0046]

[0047] In formula (I), M1 is titanium, zirconium, hafnium or scandium; subscript n1 is 0, 1, 2 or 3; subscript m1 is 0, 1 or 2, and each X1 is independently selected from (C1-C 50 ) hydrocarbons, (C1-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C6-C 50 ) aryl, (C6-C 50 ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )diene, halogen, hydrogen, -N(R N )2 and -NCOR C The metal-ligand complex is electrically neutral as a whole.

[0048] 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 selected from -H, (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl; and R 3 Independently selected from (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl.

[0049] In formula (I), R 4 , R 5 , R 6 and R 7 Independently (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, wherein R 4 , R 5 , R 6 and R 7 Any of are optionally linked to form a ring structure.

[0050] In one or more embodiments, in formula (I), R 1 and R 2 is methyl, ethyl, propyl or phenyl. 3 Independently (C1-C 12 ) alkyl. In various embodiments, R 3 are independently tert-butyl, tert-octyl or n-octyl.

[0051] In some embodiments, R 6 is –OMe; or R 5 for –NMe2.

[0052] In some embodiments, in Formula (I), (A) R 4 and R 5 connected and formed by one or more R S substituted ring; or (B) R 6 and R 7 connected and formed by one or more R S substituted ring; or (C) (A) and (B) both. Therefore, when (A), (B) or (C) occurs, the cyclopentadienyl group of formula (I) has a structure selected from the group consisting of:

[0053]

[0054]

[0055] Embodiments of the present disclosure include catalyst systems comprising one or more phosphinimine procatalysts according to formula (V):

[0056]

[0057] In formula (V), subscript m2 is 0, 1 or 2; subscript n2 is 0, 1 and 2, and each Y2 is independently selected from (C1-C 20 ) hydrocarbon group, (C6-C 50 ) aryl, (C6-C 50 )heteroaryl, halogen, -N(R N )2 and -NCOR C of monodentate ligands.

[0058] In formula (IV), each X2 is independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -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 (ORC ) 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 a monodentate ligand of hydrogen, wherein each R C Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each R Y =–H, (C1-C 30 ) a hydrocarbon group or a halogen atom, wherein two X2 ligands can be linked to form a metal cyclize ring.

[0059] In formula (V), each Y2 is independently a Lewis base; optionally, X2 and Y2 can be linked to form a ring. Subscript m2 is 0, 1, and 2; and subscript n2 is 0, 1, and 2.

[0060] In formula (V), R 51 , R 52 , R 53 , R 54 and R 55 Independently (C1-C 50 ) alkyl, wherein R 51 and R 52 Optionally connected to form a ring, or R 52 and R 53 Optionally connected to form a ring, R 53 and R 54 Optionally connected to form a ring, R 54 and R 55 optionally linked to form a ring;

[0061] In formula (V), R 56 , R 57 and R 58 Independently (C1-C 20 ) hydrocarbon group, (C1-C 20 ) heteroalkyl, (C6-C 30 ) aryl, (C5-C 30 ) heteroaryl, wherein R 56 , R 57 and R 58 Two of are optionally linked to form a ring.

[0062] In formula (I), (II), (III), (IV) and (V), each R in formula (I) C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

[0063] In one or more embodiments, in Formula (V), R 66 , R 67 , R 68 Independently (C1-C 20 )alkyl.

[0064] In some embodiments, in Formula (V), R 66 , R 67 , R 68are independently selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl and decyl.

[0065] In various embodiments, in Formula (V), wherein R 54 and R 55 connected to form an aromatic ring.

[0066] In one or more embodiments, in Formula (V), R 51 , R 52 , R 53 , R 54 and R 55 are independently (C1-C3) alkyl; or R 51 , R 52 and R 54 is (C1-C3) alkyl, or R 51 and R 53 It is (C1-C3) alkyl.

[0067] In some embodiments, in Formula (V), R 51 , R 52 , R 53 , R 54 and R 55 One of the compounds is selected from -OMe and -NMe2.

[0068] In various embodiments, in Formula (V), (A) R 51 and R 52 connected to form a ring, and optionally one or more R S Replace; or (B) R 53 and R 54 connected to form a ring, and optionally one or more R S or (C) (A) and (B). Thus, when (A), (B) or (C) occurs, the cyclopentadienyl group of formula (V) has a structure selected from the group consisting of:

[0069]

[0070] In some embodiments, the monodentate ligand X1 of formula (I) and the monodentate ligand X2 of formula (V) can be a monoanionic ligand. The net formal oxidation state of the monoanionic ligand is -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) Hydrocarbyl carbon anion, (C1-C 40) Heteroalkyl carbon anions, halides, nitrates, carbonates, phosphates, sulfates, HC(O)O - 、HC(O)N(H) - 、(C1-C 40 )C(O)O - 、(C1-C 40 )alkylC(O)N((C1-C 20 )alkyl) - 、(C1-C 40 )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 - , where each R K , R L and R M are independently hydrogen, (C1-C 40 )alkyl or (C1-C 40 ) heteroalkyl, or R K and R L Together they form (C2-C 40 )alkylene or (C1-C 20 )heteroalkylene and R M As defined above.

[0071] In other embodiments, at least one monodentate ligand X1 independent of any other ligand X1 and X2 of formula (V) independent of other ligands X2 can be a neutral ligand. In a specific embodiment, the neutral ligand is a neutral Lewis base group, such as R Q NR K R L , R K OR L , R K SR L or R Q PR K R L , where each R Q are independently hydrogen, [(C1-C 10 )alkyl]3Si(C1-C 10) hydrocarbon group, (C1-C 40 )alkyl, [(C1-C 10 )alkyl]3Si or (C1-C 40 ) heteroalkyl, and each R K and R L Independently as defined previously.

[0072] In the metal-ligand complex according to formula (I) and (V), each Y1 can be bonded to M1 by a coordination bond or an ionic bond, and each Y2 can be bonded to M2 by a coordination bond or an ionic bond. In one or more embodiments, Y1 or Y2 is a Lewis base. The Lewis base can be a compound or an ionic substance that can donate electron pairs to the acceptor compound. For the purpose of this specific embodiment, the acceptor compound is M1 or M2, which is the metal of the metal-ligand complex of formula (I) and (V). The Lewis base can be neutral or anionic. In some embodiments, the Lewis base can be a heterohydrocarbon or an unsaturated hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cyclic ethers, or sulfides. Examples of anionic hydrocarbons include, but are not limited to, cyclopentadienyl. Examples of neutral hydrocarbon Lewis bases include, but are not limited to, 1,3-butadiene.

[0073] In some embodiments, the Lewis base is (C1-C 20 ) hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene or 1,3-butadiene. In various embodiments, the Lewis base is (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).

[0074] In addition, each X2 and each Y2 can be a monodentate ligand, which is independent of any other ligands X2 and Y2 and is a halogen, an unsubstituted (C1-C 20 ) alkyl, unsubstituted (C1-C 20 )C(O)O– or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 20 In some embodiments, each monodentate ligand X1 is a chlorine atom, (C1-C 10 ) hydrocarbon group (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 )C(O)O– or R K R L N-, where R K and R LEach of which is independently unsubstituted (C1-C 10 ) hydrocarbon group.

[0075] In one or more embodiments of formula (I) and (V), X1 and X2 are (C1-C 20 ) alkyl or (C1-C 10 ) hydrocarbon group, (C1-C 20 )heteroalkyl or (C1-C 10 In some embodiments, in formula (I) and (V), X1 and X2 are (C1-C 20 )aryl or (C1-C 20 ) heteroaryl.

[0076] In one or more embodiments, in formula (I) and (V), X1 and X2 are benzyl, chloro, -CH2SiMe3 or phenyl.

[0077] In various embodiments, each X1 is selected from: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. In some embodiments, each X1 is the same. In other embodiments, at least two X1 are different from each other. In embodiments in which at least two X1 are different from at least one X1, X1 is a different one of the following: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine. In other embodiments, the bidentate ligand is 2,2-dimethyl-2-dimethylsilane-1,3-diyl or 1,3-butadiene.

[0078] In other embodiments, each X2 is selected from: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. In some embodiments, each X2 is the same. In other embodiments, at least two X2 are different from each other. In embodiments in which at least two X2 are different from at least one X2, X2 is a different one of the following: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine. In other embodiments, the bidentate ligand is 2,2-dimethyl-2-dimethylsilane-1,3-diyl or 1,3-butadiene.

[0079] In some embodiments, the chemical groups (e.g., X, X2, and R) of the metal-ligand complex of formula (I) 1 -R 4 ) may be unsubstituted. In other embodiments, the chemical groups X1, X2 and R of the metal-ligand complex of formula (I)1 -R 4 None, any, or all of them may be represented by one or more R S When two or more R S When the same chemical group of the metal-ligand complex of formula (I) is bonded, each R S can be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. 1 -R 4 None, any, or all of them can be R S Completely replaced. S In a fully substituted chemical group, each R S They may all be the same or may be independently selected.

[0080] In some embodiments, the ratio of the hydrogen chain transfer constant of the procatalyst of formula (V) to the procatalyst of formula (I) is greater than or equal to 3 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 greater than or equal to 5 at 160°C; greater than or equal to 7 at 160°C; or greater than or equal to 10 at 160°C; or greater than or equal to 20 at 160°C.

[0081] In an exemplary embodiment, the catalyst system may include a metal-ligand complex according to formula (I) having a structure of any one of the procatalysts CGC-1 and a metal-ligand complex according to formula (V) having a structure of any one of the procatalysts PN-1 to PN-3:

[0082]

[0083] Co-catalyst component

[0084] Catalyst systems comprising the metal-ligand complex of formula (I) can be rendered catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the main catalyst of the metal-ligand complex of formula (I) can be rendered catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. In addition, the metal-ligand complex according to formula (I) comprises both a neutral main catalyst form and a catalytic form that may be positively charged due to the loss of a monomeric ionic ligand (such as a benzyl or phenyl group). Activating cocatalysts suitable for use herein include alkylaluminums; polymeric or oligomeric aluminoxanes (also referred to 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 a monoalkylaluminum dihalide, a dialkylaluminum hydride or a dialkylaluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0085] In some embodiments, the catalyst system does not include additives. Additives are chemical reagents present during the polymerization reaction that do not prevent olefin growth. In one or more embodiments, the catalyst system also includes additives. In some embodiments, the additive is used as a co-catalyst. In other embodiments, the additive is used as a scavenger or scavenger. A co-catalyst is a reagent that reacts in conjunction with the catalyst to catalyze the reaction or increase the catalytic activity of the catalyst.

[0086] The scavengers sequester impurities in the reactor prior to the addition of the procatalyst and therefore do not constitute an activator. Lower loadings of aluminoxanes do not act as cocatalysts, instead they act as scavengers.

[0087] Suitable additives may include, but are not limited to, aluminum alkyls; polymeric or oligomeric aluminoxanes (also referred to as alumoxanes); 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 "aluminum alkyl" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0088] The Lewis acid activated cocatalyst comprises a (C1-C 20 )hydrocarbyl substituent. In some embodiments, the Group 13 metal compound is tri((C1-C 20) alkyl) substituted aluminum or tri((C1-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)substituted aluminum, a tri((C1-C 20 )alkyl)-boron compounds, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 ) aryl) boron compounds and their halogenated (including perhalogenated) derivatives. In other embodiments, the Group 13 metal compound is tri(fluoro-substituted phenyl) borane, tri(pentafluorophenyl) borane. In some embodiments, the activating cocatalyst is tri((C1-C 20 ) alkyl borate (e.g., trityl tetrafluoroborate) or tris((C1-C 20 )alkyl)ammonium tetra((C1-C 20 )alkyl)borane (e.g., bis(octadecyl)methylammoniumtetra(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a nitrogen cation, which is ((C1-C 20 )alkyl)4N + 、((C1-C 20 )alkyl)3N(H) + 、((C1-C 20 )alkyl)2N(H)2 + 、(C1-C 20 )Hydrocarbon N(H)3 + or N(H)4 + , where there are two or more (C1-C 20 ) hydrocarbon groups, they may be the same or different.

[0089] The combination of a neutral Lewis acid activated cocatalyst comprises a tri((C1-C4)alkyl)aluminum and a tri((C6-C 18 In some embodiments, the present invention provides a mixture of a combination of a (pentafluorophenyl)borane and a (pentafluorophenyl)borane. Other embodiments are combinations of such neutral Lewis acid mixtures with polymeric or oligomeric aluminoxanes and combinations of a single neutral Lewis acid (especially tris(pentafluorophenyl)borane) with polymeric or oligomeric aluminoxanes. The molar ratio of (metal-ligand complex): (tris(pentafluorophenyl)borane): (aluminoxane) [e.g., (Group 4 metal-ligand complex): (tris(pentafluorophenyl)borane): (aluminoxane)] is 1:1:1 to 1:10:30, and in other embodiments is 1:1:1.5 to 1:5:10.

[0090] The catalyst system comprising the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining with one or more cocatalysts (e.g., a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof). Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes (especially methylaluminoxane) and 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.

[0091] In some embodiments, one or more of the previously mentioned activating co-catalysts may be used in combination with one another. A specific example of a co-catalyst combination is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane or ammonium borate with an oligomeric or polymeric aluminoxane compound. The ratio of the total number of moles of the metal-ligand complex of one or more formula (I) to the total number of moles of the one or more activating co-catalysts in the activating co-catalyst is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, at least 1:1000 in some other embodiments; and 10:1 or less, and 1:1 or less in some other embodiments. When aluminoxane is used alone as an activating co-catalyst, preferably, the number of moles of aluminoxane employed is at least 100 times the number of moles of the metal-ligand complex of formula (I). In some other embodiments, when tri(pentafluorophenyl)borane is used alone as an activating co-catalyst, the ratio of the number of moles of tri(pentafluorophenyl)borane employed to the total number of moles of the one or more metal-ligand complexes of formula (I) is 0.5: 1 to 10: 1, 1: 1 to 6: 1, or 1: 1 to 5: 1. The remaining activating co-catalyst is typically employed in a molar amount approximately equal to the total molar amount of the one or more metal-ligand complexes of formula (I).

[0092] Aggregation methods

[0093] Any conventional polymerization process may be employed to produce the polyolefin compositions according to the present disclosure. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, particle forming polymerization processes, and combinations thereof using one or more conventional reactors such as loop reactors in parallel or in series, isothermal reactors, fluidized bed reactors, stirred tank reactors, batch reactors, and / or any combination thereof.

[0094] In one embodiment, the polyolefin composition according to the present disclosure may be produced, for example, via a solution phase polymerization process using one or more loop reactors, isothermal reactors, and combinations thereof.

[0095] Generally speaking, the solution phase polymerization process is carried out in one or more well-stirred reactors such as one or more loop reactors or one or more spherical isothermal reactors at a temperature in the range of 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 a pressure in the range of 300 psi to 1500 psi; for example, at a pressure in the range of 400 psi to 750 psi. The residence time in the solution phase polymerization process is generally in the range of 2 minutes to 30 minutes; for example, in the range of 5 minutes to 15 minutes. Ethylene, one or more solvents, one or more high temperature olefin polymerization catalyst systems, one or more cocatalysts and / or scavengers, and optionally one or more comonomers are continuously fed to one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents can be purchased 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 separated.The solvent is typically recovered via a solvent recovery unit (ie, heat exchanger and vapor liquid separator drum) and subsequently recycled back into the polymerization system.

[0096] In one embodiment, ethylene-based polymers can be produced via solution polymerization in a single reactor system (e.g., a single loop reactor system), wherein ethylene and optionally one or more alpha-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, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-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, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in both reactors in the presence of one or more high temperature olefin polymerization catalyst systems as described herein.

[0097] Polyolefins

[0098] The catalytic system described in the preceding paragraph is utilized to polymerize olefins, mainly ethylene and propylene. In some embodiments, there is only a single type of olefin or alpha-olefin in the polymerization scheme, thereby forming a homopolymer. However, additional alpha-olefins can be incorporated into the polymerization procedure. Additional alpha-olefin comonomers generally have no more than 20 carbon atoms. For example, alpha-olefin comonomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary alpha-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more alpha-olefin comonomers may be selected from the group consisting of: propylene, 1-butene, 1-hexene, and 1-octene; or in an alternative, selected from the group consisting of: 1-hexene and 1-octene.

[0099] Ethylene-based polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, can contain at least 50 weight percent of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 weight percent" are disclosed herein as separate embodiments; for example, ethylene-based polymers, i.e. homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, can contain at least 60 weight percent of monomer units derived from ethylene; at least 70 weight percent of monomer units derived from ethylene; at least 80 weight percent of monomer units derived from ethylene; or 50 weight % to 100 weight percent of monomer units derived from ethylene; or 80 weight % to 100 weight percent of units derived from ethylene.

[0100] In some embodiments, the ethylene-based polymer may include at least 90 mole percent of units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed as separate embodiments herein. For example, the ethylene-based polymer may include at least 93 mole percent of units derived from ethylene; at least 96 mole percent of units; at least 97 mole percent of units derived from ethylene; or alternatively, 90 mole percent to 100 mole percent of units derived from ethylene; 90 mole percent to 99.5 mole percent of units derived from ethylene; or 97 mole percent to 99.5 mole percent of units derived from ethylene.

[0101] 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 other embodiments, the amount of additional α-olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0102] Any conventional polymerization process may be employed to produce ethylene polymers. Such conventional polymerization processes include, but are not limited to, for example, solution polymerization, gas phase polymerization, slurry phase polymerization, 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 in parallel or series, or any combination thereof.

[0103] In one embodiment, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more cocatalysts. In another embodiment, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha olefins are polymerized in the presence of a catalyst system in the present disclosure and as described herein and optionally one or more other catalysts. The catalyst system as described herein can be optionally used in the first reactor or the second reactor in combination with one or more other catalysts. In one embodiment, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha olefins are polymerized in the presence of a catalyst system as described herein in these two reactors.

[0104] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system (e.g., a single loop reactor system) wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described within the present disclosure and optionally one or more cocatalysts as described in the preceding paragraphs.

[0105] Ethylene-based polymers may further include one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. Ethylene-based polymers may contain any amount of additives. Ethylene-based polymers may include a combined weight of such additives of about 0 to about 10% based on the weight of the ethylene-based polymer and one or more additives. Ethylene-based polymers may further include fillers, which may include, but are not limited to, organic or inorganic fillers. Based on the combined weight of ethylene-based polymers and all additives or fillers, ethylene-based polymers may contain fillers of about 0 to about 20 weight percent, such as calcium carbonate, talcum powder, or Mg(OH)2. Ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0106] 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, wherein the catalyst system incorporates at least one metal-ligand complex of formula (I). The density of a polymer produced by such a catalyst system incorporating a metal-ligand complex of formula (I) may be, for example, 0.850 g / cm according to ASTM D792 (incorporated herein by reference in its entirety). 3 Up to 0.960g / cm 3 、0.880g / cm 3 Up to 0.920g / cm 3 、0.880g / cm 3 Up to 0.910g / cm 3 or 0.880g / cm 3 Up to 0.900g / cm 3 .

[0107] In another embodiment, the melt flow ratio (I) of the polymer produced by the catalyst system comprising the metal-ligand complex of formula (I) is 10 / I2) is 5 to 20, wherein the melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190°C and a load of 2.16 kg, and the melt index I 10 Measured according to ASTM D1238 at 190°C and 10 kg load. In other embodiments, the melt flow ratio (I 10 / I2) is 5 to 10, and in other embodiments, the melt flow ratio is 5 to 9.

[0108] In some embodiments, the polymer produced by the catalyst system including the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 1 to 25, wherein MWD is defined as M w / M n , where M w is the weight average molecular weight, and M n is the number average molecular weight. In other embodiments, the polymer produced by the catalyst system has an MWD of 1 to 6. Another embodiment includes an MWD of 1 to 3; and other embodiments include an MWD of 1.5 to 2.5.

[0109]

[0013] Embodiments of the catalyst systems described in this disclosure produce unique polymer properties due to the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0110] Unless otherwise noted, all solvents and reagents were obtained from commercial sources and used as received. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing through activated alumina and, in some cases, through Q-5 Reactants. Solvents used for experiments performed in a nitrogen-filled glove box were obtained by purifying the solvents in an activated The HPLC-MS / MS spectra were recorded on a Varian 400-MR and VNMRS-500 spectrometer. The HPLC-MS / MS spectra were analyzed by using a Waters e2695 Separations Module coupled to a Waters 2424ELS detector, a Waters 2998PDA detector, and a Waters 3100ESI mass detector. The LC-MS separation was performed on an XBridge C18 3.5 μm 2.1 x 50 mm column using a gradient of 5:95 to 100:0 of ​​acetonitrile to water and 0.1% formic acid as an ionizer. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax EclipsePlus C18 1.8 μm 2.1 x 50 mm column coupled to an Agilent 6230 TOF Mass Spectrometer with electrospray ionization. 1 H NMR data are reported as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integration and assignment). The values ​​are reported downfield from internal tetramethylsilane (TMS, scale δ) using residual protons in the deuterated solvent as reference. 1 Chemical shifts (in ppm) for H NMR data were obtained using 1 H decoupling method was used to determine 13 C NMR data and chemical shifts are reported in ppm downfield from tetramethylsilane (TMS, scale δ) compared to the reference using the residual protons in the deuterated solvent.

[0111] Composition Conventional GPC

[0112] Chromatographic system is composed of PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with internal IR5 infrared detector (IR5). The automatic sampler oven chamber is set to 160 degrees Celsius, and the column chamber is set to 150 degrees Celsius. The column used is 4 Agilent "Mixed A" 30cm 20 micron linear mixed bed columns. The chromatographic solvent used is 1,2,4 trichlorobenzene and contains 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0113] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards ranging from 580 g / mol to 8,400,000 g / mol and arranged in 6 "cocktail" mixtures with at least ten times intervals between individual molecular weights. Standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standards were prepared in 50 ml of solvent, and for molecular weights less than 1,000,000, 0.05 g of polystyrene standards were prepared in 50 ml of solvent. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes, then cooled and the room temperature solution transferred to a 160°C autosampler dissolution oven to cool for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0114] M 聚乙烯 =A×(M 聚苯乙烯 ) B (Equation 1)

[0115] Where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0116] A fifth order polynomial was used to fit the calibration points to the corresponding polyethylene equivalents.A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band broadening effects such that a linear homopolymer polyethylene standard was obtained at 120,000 Mw.

[0117] Total plate counts for the GPC column set were performed with decane, which was introduced into the blank sample via a micro pump controlled by the PolymerChar GPC-IR system. The plate count of the chromatography system should be greater than 18,000 for 4 Agilent "Mixed A" 30 cm 20 micron linear mixed bed columns.

[0118] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set to 2 mg / ml, and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen via the PolymerChar high temperature autosampler. The samples were dissolved at 160 degrees Celsius for 2 hours under "slow" shaking.

[0119] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer, according to equations 2-4, the PolymerChar GPCOne TM The software was used to calculate the Mn value of the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation.

[0120]

[0121] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate for each sample (Flow Rate (Nominal)) by comparing the RV of the corresponding decane peak in the sample (RV (FM Sample)) with the retention volume of the decane peak in the narrow standard calibration (RV (FM Calibration)). It was then assumed that any changes in the decane marker peak time were related to a linear change in the 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) was calculated as Equation 5. By PolymerCharGPCOne TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.5% of the nominal flow rate.

[0122] Flow rate (effective) = flow rate (nominal) * (RV (FM calibration) / RV (FM sample)) (Equation 5)

[0123] Composition Conventional UHMW GPC

[0124] Chromatographic system is composed of PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with internal IR5 infrared detector (IR5). The automatic sampler oven chamber is set to 165 degrees Celsius, and the column chamber and detector are set to 155 degrees Celsius. The column used is a mixed pore size column of 4TOSOH TSKgel GMHHR-H (30) HT 30-micron particle size. The chromatographic solvent used is 1,2,4 trichlorobenzene and contains 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0125] The calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards, with molecular weights ranging from 580 g / mol to 8,400,000 g / mol, and arranged in 6 "mixed liquid" mixtures, with at least ten times of spacing between individual molecular weights. Standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standards were prepared in 50 ml of solvent, and for molecular weights less than 1,000,000, 0.05 g of polystyrene standards were prepared in 50 ml of solvent. Separately 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 mg / mL and 0.3 mg / mL, respectively. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes, then cooled and the room temperature solution transferred to a 160°C autosampler dissolution oven to cool for 30 minutes. The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).

[0126] A third order polynomial was used to fit the corresponding polyethylene equivalent calibration points. A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band broadening effects, resulting in a linear homopolymer polyethylene standard at 120,000 Mw.

[0127] Total plate counts for the GPC column set were performed with decane, which was introduced into the blank sample via a micropump controlled by the PolymerChar GPC-IR system. For a 4TOSOH TSKgel GMHHR-H(30)HT 30 micron particle size mixed pore size column, the plate count of the chromatography system should be greater than 12,000.

[0128] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set to 2 mg / ml, and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen via the PolymerChar high temperature autosampler. The samples were dissolved at 160 degrees Celsius for 2 hours under "slow" shaking.

[0129] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer, according to equations 2-4, the PolymerChar GPCOne TM The software was used to calculate the Mn value of the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation.

[0130] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate for each sample (Flow Rate (Nominal)) by comparing the RV of the corresponding decane peak in the sample (RV (FM Sample)) with the retention volume of the decane peak in the narrow standard calibration (RV (FM Calibration)). It was then assumed that any changes in the decane marker peak time were related to a linear change in the 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) was calculated as Equation 5. By PolymerCharGPCOne TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.5% of the nominal flow rate.

[0131] IR5 GPC Octene Composition Calibration

[0132] Calibration for IR5 detector dosing was performed using at least ten ethylene-based polymer standards (octene as comonomer) produced in a solution process (polyethylene homopolymer and ethylene / octene copolymer) from a single reactor over a single site metallocene catalyst, with narrow SCB distribution and known comonomer content (e.g., by 13C NMR method, Qiu et al., Anal. Chem., 2009, 81, 8585-8589) in a solution process (polyethylene homopolymer and ethylene / octene copolymer) from a single reactor over a single-site metallocene catalyst, the known monomer content is in the range of from homopolymer (0 SCB / 1000 total C) to about 40 SCB / 1000 total C, where total C = carbon in the main chain + carbon in the branch chain. Each standard has a weight average molecular weight of 36,000 g / mole to 126,000 g / mole, as measured by GPC. The molecular weight distribution (Mw / Mn) of each standard is 2.0 to 2.5. The SCB standard polymer properties are shown in Table A.

[0133] Table A: Copolymer Standards

[0134] Comonomer weight % IR5 Area Ratio SCB / 1000Total C M Mw / Mn 23.1 0.2411 28.9 37,300 2.22 14.0 0.2152 17.5 36,000 2.19 0.0 0.1809 0.0 38,400 2.20 35.9 0.2708 44.9 42,200 2.18 5.4 0.1959 6.8 37,400 2.16 8.6 0.2043 10.8 36,800 2.20 39.2 0.2770 49.0 125,600 2.22 1.1 0.1810 1.4 107,000 2.09 14.3 0.2161 17.9 103,600 2.20 9.4 0.2031 11.8 103,200 2.26

[0135] Chain transfer constant calculation

[0136] The chain transfer constant was calculated using the Mayo equation shown in Equation 7, where Mn0 is the Mn without any 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 growth rate constant. 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. For each hydrogen loading, the Mn value was calculated using Equation 7. The Solver feature of MS Excel was used to vary c CTH The value of is chosen to simultaneously minimize the sum of the squared deviations of the calculated Mn values ​​from the experimental Mn values ​​for all hydrogen loadings.

[0137]

[0138] Batch Reactor Polymerization Procedure

[0139] The raw materials (ethylene, 1-octene) and process solvent (narrow boiling range high purity isoparaffin solvent, commercially available from ExxonMobil Corporation under the trademark ISOPAR E) were purified with molecular sieves and then introduced into the reaction environment. ISOPAR E and 1-octene were charged to a one gallon (3.79 L) stirred autoclave reactor. The reactor was then heated to the desired temperature and charged with ethylene to reach the desired pressure. If necessary, hydrogen was also added at this time. In a dry box under an inert atmosphere, the catalyst composition was prepared by mixing the desired precatalyst and one or more optional additives as required with additional solvent to obtain a total volume of about 15 mL-20 mL. The activated catalyst mixture was then rapidly injected into the reactor. The reactor pressure and temperature were kept constant by feeding ethylene during the polymerization reaction and cooling the reactor as required. After 10 minutes, the ethylene feed was turned off and the solution was transferred to a resin pot purged with nitrogen. The polymer was thoroughly dried in a vacuum oven and the reactor was thoroughly rinsed with hot ISOPAR E between each polymerization run.

[0140] Example

[0141] The results of the polymerization reactions of the main catalysts 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 according to the following examples:

[0142]

[0143] Polymerization conditions: 3.79L (1Gal) batch reactor, 1250g Isopar-E; main catalyst: 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 reached 320 psi, reaction time 10 min.

[0144] Table 1: Changes in weight average molecular weight when hydrogen is introduced at 160°C

[0145]

[0146] Table 2: Polymer compositions produced from PN-1 and CGC-1 at four different hydrogen loadings at 160 °C

[0147]

[0148] Table 3: Chain transfer constants to hydrogen (cH2) for selected catalysts at 160°C

[0149] catalyst cH2 PN-1 0.53 PN-2 2.23 PN-3 1.27 CGC-1 0.027 CGC-2 0.040

[0150] Figure 2 The concept of varying the hydrogen level in the polymerization reactor to vary the molecular weight of the polymer produced by the phosphinimine procatalyst was demonstrated. Figure 1A , Figure 1B and bimodal polyethylene as shown in Figure 1C.

[0151] exist Figure 3 In the results, the molecular weight of the polyethylene produced by PN-1 decreased significantly when the amount of hydrogen in the reactor increased; while the molecular weight of the polyethylene produced by CGC-1 was affected to a much lesser extent. At 0H2, the molecular weight of the polyethylene produced by PN-1 was very similar and overlapping with that of the polyethylene produced by CGC-1. However, when the H2 level was increased from 5mmol to 20mmol and then to 40mmol, the molecular weight of the polyethylene produced by PN-1 decreased significantly, while the molecular weight of the PE produced by CGC-1 decreased only slightly, resulting in Figure 3 Double peaks in the GPC trace.

Claims

1. A process for polymerizing olefin monomers to produce polyolefins, the process comprising reacting ethylene and optionally one or more olefin monomers in one or more reactors in the presence of a catalyst system and optionally hydrogen; the catalyst system comprising two or more catalysts, wherein at least one catalyst is derived from a constrained geometry procatalyst according to formula (I), and wherein at least one catalyst is derived from a phosphinimine procatalyst according to formula (V): in: M1 is titanium, zirconium, hafnium or scandium; Each X1 is independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -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 a monodentate ligand of hydrogen, wherein each R C Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each R Y =–H, (C1-C 30 ) a hydrocarbon group or a halogen atom, wherein two X1 ligands can be linked to form a metal cyclize ring; Each Y1 is independently a Lewis base; optionally, X1 and Y1 can be linked to form a ring; m1 is 1 or 2; n1 is 0, 1 or 2; The main catalysts (I) and (V) are electrically neutral as a whole; N is nitrogen; T is carbon, silicon or germanium; R 1 and R 2 are independently selected from -H, (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl; R 1 and R 2 optionally linked to form a ring structure; R 3 Independently selected from (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl; R 4 , R 5 , R 6 and R 7 are independently H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, wherein R 4 , R 5 , R 6 and R 7 Any of are optionally linked to form a ring structure or multiple ring structures; M2 is titanium, zirconium or hafnium; Each X2 is independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -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 a monodentate ligand of hydrogen, wherein each R C Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each R Y =–H, (C1-C 30 ) a hydrocarbon group or a halogen atom, wherein two X2 ligands can be linked to form a metal cyclize ring; Each Y2 is independently a Lewis base; optionally, X2 and Y2 can be linked to form a ring. m2 is 1 or 2; n2 is 0, 1, and 2; R 51 , R 52 , R 53 , R 54 and R 55 are independently H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, wherein R 52 , R 53 , R 54 and R 55 Any of are optionally linked to form a ring structure or multiple ring structures; R 56 , R 57 and R 58 Independently (C1-C 20 ) hydrocarbon group, (C1-C 20 ) heteroalkyl, (C6-C 30 ) aryl, (C5-C 30 ) heteroaryl, wherein R 56 , R 57 and R 58 Two of are optionally linked to form a ring.

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

3. The polymerization process according to claim 1, wherein R 1 and R 2 Methyl, ethyl, propyl, isopropyl, isobutyl, phenyl, p-tolyl 4. The polymerization process according to any one of the preceding claims, wherein R 3 Independently (C1-C 12 )alkyl.

5. The polymerization process according to any one of the preceding claims, wherein R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, dimethylamino, pyrrolidinyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl and decyl.

6. The polymerization process according to any one of the preceding claims, wherein R 6 is -OMe; or R 5 for –NMe2.

7. The polymerization process according to any one of claims 1 to 4, wherein: (A)R 4 and R 5 connected and formed by one or more R S a substituted ring; or (B)R 6 and R 7 connected and formed by one or more R S a substituted ring; or (C) both (A) and (B); wherein (A), (B) or (C) and the cyclopentadienyl group of formula (I) has a structure selected from the group consisting of:

8. The polymerization process according to any one of the preceding claims, wherein R 51 , R 52 , R 53 , R 54 and R 55 One of the compounds is selected from -OMe and -NMe2.

9. The polymerization process according to any one of claims 1 to 7, wherein: (A)R 51 and R 52 connected to form a ring, and optionally one or more R S replace; or (B)R 53 and R 54 connected to form a ring, and optionally one or more R S replace; or (C) both (A) and (B); wherein (A), (B) or (C) and the cyclopentadienyl group of formula (V) has a structure selected from the group consisting of:

10. The polymerization process according to any one of the preceding claims, wherein R 56 , R 57 , R 58 Independently (C1-C 20 )alkyl.

11. The polymerization process according to any one of the preceding claims, wherein R 56 , R 57 , R 58 Independently selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, dimethylamino, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl and decyl.

12. The polymerization process according to any one of the preceding claims, wherein 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 known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, dimethylamino, pyrrolidinyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl and decyl.

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

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