Process for producing multimodal polyethylene using at least one group III-or lanthanide-based biphenyl phenoxy catalyst

Abstract

Embodiments of the present disclosure relate to a catalyst system comprising a metal-ligand complex according to formula (I): # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 401,924, filed on August 29, 2022, the entire disclosure of which is hereby incorporated by reference into this document. Technical Field

[0003] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more particularly to bisphenylphenoxy metal-ligand complexes having a Group III or lanthanide metal center. 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 ways to produce various resulting polyethylene resins with different physical properties that make the various resins suitable for different applications. Ethylene monomer and optionally one or more comonomers are present in a liquid diluent or solvent, such as an alkane or isoalkane, with specific examples being hexane and isobutane. Hydrogen may also be added to the reactor. Catalyst systems for producing ethylene-based polymers can typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (metallocene or non-metallocene (molecular)) catalyst systems. The reactants and diluents in the catalyst system are circulated in the reactor at an elevated polymerization temperature to produce ethylene-based homopolymers or copolymers. Periodically or continuously, a portion of the reaction mixture is removed from the reactor, including the polyethylene product dissolved in the diluent, as well as unreacted ethylene and one or more optional comonomers. The reaction mixture can be processed after being removed from the reactor to remove the polyethylene product and unreacted reactants in the diluent, wherein the diluent and unreacted reactants are usually recycled back to the reactor. Alternatively, the reaction mixture can be sent to a second reactor connected in series with the first reactor, in which a second polyethylene fraction can be produced. Although research is devoted to developing catalyst systems suitable for olefin polymerizations such as polyethylene polymerization, it is still necessary to improve the efficiency of catalyst systems with high selectivity to ethylene. Summary of the invention

[0006] There is a continuing need to produce catalyst systems or metal-ligand complexes that have high selectivity for ethylene during copolymerization of ethylene and α-olefins. In addition, the metal-ligand complex should have high catalyst efficiency and the general ability to produce polymers with high or low molecular weight at high temperatures (such as greater than 140° C. or about 190° C.).

[0007] Embodiments of the present disclosure include polymerization methods. The polymerization method includes polymerizing ethylene and optionally one or more olefins in the presence of a catalyst system. The catalyst system includes at least one metal-ligand complex of formula (I), at least one Group IV catalyst, at least one additive, and an optional Lewis acid. The polymerization method is carried out in a solution polymerization reactor under olefin polymerization conditions to form an ethylene-based polymer.

[0008] In one or more embodiments, the metal-ligand complex of formula (I) has a structure according to:

[0009]

[0010] In formula (I), M is scandium, yttrium, a lanthanide metal or an actinide metal. n The subscript n is 0, 1 or 2. T is a Lewis base. k The subscript k is 1 or 2. X is selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) 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 or hydrogen ligands, wherein each R C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbon or substituted or unsubstituted (C1-C 30 ) heteroalkyl. The subscript Q is 0, 1, 2 or 3, and the subscript W is 0, 1 or 2. When T n When the subscript n of is 1, X and T are optionally linked to form a bidentate ligand. n The subscript n is 1 and X k When k is 2, each X and T are optionally linked to form a bidentate ligand or a tridentate ligand. The metal-ligand complex is electrically neutral as a whole.

[0011] In formula (I), R 1 and R 16 Independently selected from the group consisting of: –H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、RC S(O)2-, -N=C(R C 2. R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)-, halogen, a group having the formula (II), a group having the formula (III) and a group having the formula (IV):

[0012]

[0013] In formula (II), (III) and (IV), R 31-35 , R 41-48 and R 51-59 Each of the following is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen;

[0014] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(RP )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen.

[0015] In formula (I), L is (C1-C 40 )alkylene or (C1-C 40 ) heteroalkylene; and each Z is independently selected from -O-, -S-, -N(R N )-or-P(R P )-.

[0016] In formulas (I), (II), (III) and (IV), each R C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H. DETAILED DESCRIPTION

[0017] 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 limited to the specific embodiments set forth in the present disclosure.

[0018] Common abbreviations are listed below:

[0019] R, Z, M, X and n: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; i-Pr: isopropyl; t-Bu: tert-butyl; t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl); Tf: trifluoromethanesulfonate; CV: column volume (used in column chromatography); EtOAc: ethyl acetate; TEA: triethylaluminum; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; LiCH2TMS: (trimethylsilyl)methyllithium; TMS: trimethylsilyl; Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II) dichloride; Pd(AmPhos): chloro(crotyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II); Pd(dppf)Cl2: [1, 1'-bis(diphenylphosphino)ferrocene]palladium(II) chloride; ScCl3: scandium(III) chloride; PhMe: toluene; THF: tetrahydrofuran; CH2Cl2: dichloromethane; DMF: N,N-dimethylformamide; EtOAc: ethyl acetate; Et2O: diethyl ether; MeOH: methanol; NH4Cl: ammonium chloride; MgSO4: magnesium sulfate; Na2SO4: sodium sulfate; NaOH: sodium hydroxide; brine: saturated aqueous sodium chloride solution; SiO2: silicon dioxide; CDCl3: chloroform-D; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimole; mL: milliliter; M: mole; min or mins: minutes; h or hrs: hours; d: day; TLC: thin layer chromatography; rpm: revolutions per minute; rt: room temperature.

[0020] The term "independently selected from" is used herein to indicate that, for example, R 1 , R 2 , R 3 , R 4 and R 5 The R groups may be the same or different (e.g., R 1 , R 2 , R 3 , R 4 and R 5 can be substituted alkyl, or R 1 and R 2 may be a substituted alkyl group, and R 3 The chemical names associated with the R groups are intended to convey chemical structures recognized in the art as corresponding to the chemical structures of the chemical names. Therefore, the chemical names are intended to supplement and illustrate rather than exclude structural definitions known to those skilled in the art.

[0021] When used to describe certain chemical groups containing carbon atoms, the form "(C x -Cy )" 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 substituted with one or more substituents such as RS. The parenthetical phrase "(C x -C y )” defined by R S The substituted chemical group may contain more than y carbon atoms, depending on the number of carbon atoms in any group R. S 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 -C y )" 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.

[0022] 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.

[0023] 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 group 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.

[0024] 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)).

[0025] The term "(C1-C 50 )alkyl" and "(C1-C 18 )alkyl" means unsubstituted or substituted with one or more R S Substituted 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 (C 1- 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 for example, one R is respectively (C1-C5) alkyl S Replaced (C 27 -C 40 Each (C1-C5)alkyl group 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.

[0026] The term "(C6-C 50 ) aryl" means an unsubstituted or substituted aryl having 6 to 40 carbon atoms (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 a bicyclic or tricyclic aromatic hydrocarbon group is 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.

[0027] The term "(C3-C 50 ) Cycloalkyl refers to 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.

[0028] (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.

[0029] The term "(C1-C 50 ) Alkylene means an unsubstituted or substituted group having 1 to 50 carbon atoms. 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]octene.

[0030] 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 radical is on a ring atom).

[0031] 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-、-Si(R C )-, boron (B), aluminum (Al), gallium (Ga) or indium (In), wherein each R C and each R P is unsubstituted (C1-C 18 )alkyl or -H, and each R N is 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 heteroalkyl 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 with (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.

[0032] (C1-C 50 )Heteroalkyl may be unsubstituted or substituted. 50Non-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.

[0033] The term "(C1-C 50 ) heteroaryl" means an unsubstituted or substituted (one or more R S ) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon radicals. 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 or 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 (C1-C 12) heteroaryl) is defined in a similar manner as having x to y carbon atoms (such as 1 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one R S substituted. The monocyclic heteroaromatic hydrocarbon group is a 5-membered ring or a 6-membered ring. The 5-membered ring monocyclic heteroaromatic hydrocarbon group has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3 or 4, and each heteroatom can be O, S, N or P. Examples of 5-membered ring 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-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. The 6-membered ring monocyclic heteroaromatic hydrocarbon group 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 bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring 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; a 5,6,6-ring system; a 6,5,6-ring system; or a 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 6,6,6-ring system is acridin-9-yl.

[0034] The term "(C1-C 50 ) heteroalkyl" means a saturated straight or branched chain group containing from one to fifty carbon atoms 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, SRC , S(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or substituted with one or more R S replace.

[0035] 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.

[0036] 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 - ).

[0037] 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 optionally be present in the substituent R S The term "unsaturated" means containing one or more carbon-carbon double bonds or 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 (if any) or double bonds (if any) in an aromatic ring or a heteroaromatic ring.

[0038] The term "lanthanide metal" includes elements 57 to 71 (lanthanum (La) to lutetium (Lu)).

[0039] Embodiments of the present disclosure include polymerization methods. The polymerization method includes polymerizing ethylene and optionally one or more olefins in the presence of a first catalyst system and a second catalyst system. The catalyst system includes at least one metal-ligand complex of formula (I), at least one Group IV catalyst, at least one additive, and optionally a Lewis acid. The polymerization method is carried out in a solution polymerization reactor under olefin polymerization conditions to form an ethylene-based polymer,

[0040] In one or more embodiments, the metal-ligand complex of formula (I) has a structure according to:

[0041]

[0042] In formula (I), M is scandium, yttrium, a lanthanide metal or an actinide metal. n The subscript n is 0, 1, or 2, X k The subscript k is 1 or 2, and X is selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) 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)RC 、-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 or hydrogen ligand. Each R C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C 30 ) heteroalkyl. Subscript Q is 0, 1, 2 or 3, and subscript W is 0, 1 or 2. T is a Lewis base. When T n When the subscript n of is 1, X and T are optionally linked to form a bidentate ligand. n The subscript n is 1 and X k When k is 2, each X and T are optionally linked to form a bidentate ligand or a tridentate ligand. The metal-ligand complex is electrically neutral as a whole.

[0043] In formula (I), R 1 and R 16 Independently selected from the group consisting of: –H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-, -N=C(R C 2. R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)-, halogen, a group having the formula (II), a group having the formula (III) and a group having the formula (IV):

[0044]

[0045] In some embodiments, in the metal-ligand complex of formula (I), R 1 or R 16 Any of, or R 1 and R16 Both are selected from groups having formula (II), formula (III) or formula (IV). Provided that when M is yttrium or a lanthanide metal, R 1 is not -H, phenyl or tert-butyl; and R 16 Not –H, phenyl or tert-butyl.

[0046] When present in the metal-ligand complex of formula (I) as part of a group having formula (II), formula (III) or formula (IV), the group R of the metal-ligand complex of formula (I) 31-35 , R 41-48 and R 51-59 Each independently selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, Si(R C )3. P(R P )2、N(R N 2. OR C , SR C 、NO2、CN、CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R N )2NC(O)-, halogen, hydrogen (-H) or a combination thereof. Each R C , R P and R N are independently unsubstituted (C1-C 18 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

[0047] The group R in the metal-ligand complex of formula (I) 1 and R 16 are chosen independently of each other. For example, R 1 can be selected from a group having formula (II), (III) or (IV), and R 16 It can be (C1-C 40 ) a hydrocarbon group; or R 1 can be selected from a group having formula (II), (III) or (IV), and R 16 Can be selected from R 1 The same or different groups having the formula (II), (III) or (IV). 1 and R 16Both may be groups having formula (II) wherein the group R 31-35 In R 1 and R 16 In other examples, R 1 and R 16 Both may be groups having formula (III) wherein the group R 41-48 In R 1 and R 16 the same or different in R 1 and R 16 Both may be groups having the formula (IV) wherein the group R 51-59 In R 1 and R 16 The same or different.

[0048] In some embodiments, R 1 and R 16 At least one of them is a group having formula (II), wherein R 32 and R 34 In one or more embodiments, R 32 and R 34 is (C1-C 16 )alkyl, -Si[(C1-C 16 )hydrocarbon group]3.

[0049] In some embodiments, when R 1 or R 16 When at least one of them is a group having formula (III), R 43 and R 46 One or both of them are tert-butyl, and R 41-42 , R 44-45 and is -H. In other embodiments, R 42 and R 47 One or both of them are tert-butyl, and R 41 , R 43-46 and is -H. In some embodiments, R 42 and R 47 Both are -H. In various embodiments, R 42 and R 47 is (C1-C 20 )alkyl or -Si[(C1-C 16 )alkyl]3. In other embodiments, R 43 and R 46 is (C1-C 20 ) alkyl or –Si(C1-C 16 )alkyl]3. In some embodiments, R42 and R 43 connected to form a ring structure, and R 46 and R 47 connected to form a ring structure.

[0050] In an embodiment, when R 1 or R 16 When at least one of them is a group having formula (IV), each R 52 , R 53 , R 55 , R 57 and R 58 =–H, (C1-C 20 )alkyl, -Si[(C1-C 20 )alkyl]3 or -Ge[(C1-C 20 )alkyl]3. In some embodiments, R 52 , R 53 , R 55 , R 57 and R 58 At least one of (C3-C 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10 )alkyl]3. In one or more embodiments, R 52 , R 53 , R 55 , R 57 and R 58 At least two of them are (C3-C 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10 )alkyl]3. In various embodiments, R 52 , R 53 , R 55 , R 57 and R 58 At least three of them are (C3-C 10 )alkyl, -Si[(C3-C 10 )alkyl]3 or -Ge[(C3-C 10 )alkyl]3.

[0051] In some embodiments, when R 1 or R 16 When at least one of them is a group having formula (IV), R 52 , R 53 , R 55 , R 57 and R 58 At least two of them are (C1-C20 )alkyl or -C(H)2Si[(C1-C 20 )hydrocarbon group]3.

[0052] (C3-C 10 Examples of alkyl groups include, but are not limited to, 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.

[0053] In some embodiments of the metal-ligand catalyst according to formula (I), R 1 and R 16 Selected from 3,5-di-tert-butylphenyl; 2,4,6-trimethylphenyl; 2,4,6-triisopropylphenyl; 3,5-diisopropylphenyl; carbazolyl; carbazole-9-yl, 1,2,3,4-tetrahydrocarbazolyl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl; 3,6-bis-(3,5-di-tert-butylphenyl)carbazole-9-yl; 3,6-bis-(2,4,6-trimethylphenyl)carbazole-9-yl); 3,6-bis-( 2,4,6-triisopropylphenyl)carbazole-9-yl; 2,7-di(tert-butyl)-carbazole-9-yl; 2,7-di(tert-octyl)-carbazole-9-yl; 2,7-diphenylcarbazole-9-yl; 2,7-bis(2,4,6-trimethylphenyl)-carbazole-9-ylanthracenyl; 2,7-bis(triisobutylsilyl)-carbazole-9-yl; 2,7-bis(dimethylphenylsilyl)-carbazole-9-yl; 2,7-di(methyldiphenyl) 2,7-bis(diisopropyl-n-octylsilyl)-carbazole-9-yl; 1,2,3,4-tetrahydroanthracenyl; 1,2,3,4,5,6,7,8-octahydroanthracenyl; phenanthrene; 1,2,3,4,5,6,7,8-octahydrophenanthrene; 1,2,3,4-tetrahydronaphthyl; 2,6-dimethylphenyl; 2,6-diisopropylphenyl; 3,5-diphenylphenyl; 1-naphthyl; 2-methyl-1-naphthyl; 2-naphthyl; 1,2,3,4-tetrahydronaphthalen-5-yl; 1,2,3,4-tetrahydronaphthalen-6-yl; anthracen-9-yl; 1,2,3,4-tetrahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydrophenanthracen-9-yl; indolyl; dihydroindolyl; quinolyl; 1,2,3,4-tetrahydroquinolyl; isoquinolyl; or 1,2,3,4-tetrahydroisoquinolyl.

[0054] In formula (I), R 2 , R 3 , R 4 , R 5, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen.

[0055] In one or more embodiments, R 2 , R 4 , R 5 , R 12 , R 13 and R 15 is hydrogen; and each Z is oxygen.

[0056] In embodiments, the dashed lines are optionally coordination bonds between the metal center M and the group Z. In some embodiments, one of the dashed lines connecting Z and M is coordination, while the other dashed line does not form a coordination bond between Z and M. In various embodiments, both dashed lines form a coordination bond between the group Z and M.

[0057] In various embodiments, R 3 and R 14 Yes (C1-C 24 ) alkyl. In one or more embodiments, R 3 and R 14 Yes (C4-C 24 In some embodiments, R 3 and R 14is 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In an embodiment, R 3 and R 14 For-OR C , where R C is (C1-C 20 ) hydrocarbon, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0058] In one or more embodiments, R 8 and R 9 In various embodiments, R 8 and R 9 At least one of (C1-C 24 In some embodiments, R 8 and R 9 Both are (C1-C 24 In some embodiments, R 8 and R 9 In other embodiments, R 8 and R 9 It is a halogen.

[0059] In some embodiments, R 3 and R 14 is methyl; in one or more embodiments, R 3 and R 14 Yes (C4-C 24 In some embodiments, R 8 and R 9 are 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl and decyl.

[0060] In various embodiments, in the metal-ligand complex of formula (I), R 6 and R 11 In some embodiments, R 6 and R 11 is (C1-C 24 ) alkyl. In various embodiments, R6 and R 11 R is independently selected from 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-trimethylpentan-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 In the embodiment, R 6 and R 11 For-OR C , where R C is (C1-C 20 ) alkyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl) or 1,1-dimethylethyl. In other embodiments, R 6 and R 11 -SiR C 3, where each R C Independently (C1-C 20 ) alkyl, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0061] In some embodiments, the chemical groups (e.g., X and R) of the metal-ligand complex of formula (I) 1-59 ) may be unsubstituted. In other embodiments, the chemical groups X and R of the metal-ligand complex of formula (I) 1-59 None of them are covered by one or more R S or any or all of them are replaced by one or more than one 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 The chemical groups X and R may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. 1-59 None of them were R S All of them can be replaced by R S Completely replaced. S In a fully substituted chemical group, each R S Can all be the same or can be independently selected. In one or more embodiments, R S Selected from (C1-C 20 ) hydrocarbon group, (C1-C 20)alkyl, (C1-C 20 )heteroalkyl or (C1-C 20 ) heteroalkyl.

[0062] In formula (I), L is (C1-C 40 )alkylene or (C1-C 40 ) heteroalkylene; and each Z is independently selected from -O-, -S-, -N(R N )-or-P(R P )-. In one or more embodiments, L comprises 1 to 10 atoms.

[0063] In formulas (I), (II), (III) and (IV), each R C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

[0064] In some embodiments of formula (I), L can be selected from (C3-C7) alkyl 1,3-diradicals, such as -CH2CH2CH2-, -CH(CH3)CH2C*H(CH3), -CH(CH3)CH(CH3)C*H(CH3), -CH2C(CH3)2CH2-, cyclopentane-1,3-diyl or cyclohexane-1,3-diyl. In some embodiments, L can be selected from (C4-C 10 ) alkyl 1,4-diradicals, such as -CH2CH2CH2CH2-, Cyclohexane-1,2-diyldimethyl and bicyclo[2.2.2]octane-2,3-diyldimethyl. In some embodiments, L can be selected from (C5-C 12 ) alkyl 1,5-diradicals, such as -CH2CH2CH2CH2CH2- and 1,3-bis(methylene)cyclohexane. In some embodiments, L may be selected from (C6-C 14 )alkyl 1,6-diradicals such as -CH2CH2CH2CH2CH2CH2- or, for example, 1,2-bis(ethylene)cyclohexane.

[0065] In one or more embodiments, L is (C2-C 40 )heteroalkylene, and at least one of the 2 to 10 atoms comprises a heteroatom. In some embodiments, L is -CH2Ge(R C )2CH2-, where each R C is (C1-C 30In some embodiments, L is -CH2Ge(CH3)2CH2-, -CH2Ge(ethyl)2CH2-, -CH2Ge(2-propyl)2CH2-, -CH2Ge(tert-butyl)2CH2-, -CH2Ge(cyclopentyl)2CH2-, or -CH2Ge(cyclohexyl)2CH2-.

[0066] In one or more embodiments, L is selected from -CH2-; -CH2CH2-; -CH2(CH2) m CH2-, where m is 1 to 3; –CH2Si(R C )2CH2-; -CH(CH3)CH2CH*(CH3), where C* represents the position of the group (the group can also be written as: -CH(CH3)CH2CH(CH3)-); and -CH2(phenyl-1,2-diyl)CH2-; where each R in L C is (C1-C 20 ) hydrocarbon group.

[0067] This type (C1-C 12 Examples of alkyl groups include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl, cyclopentyl, or cyclohexyl, butyl, tert-butyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, decyl, undecyl, and dodecyl.

[0068] In some embodiments, in the metal-ligand complex according to formula (I), R 8 and R 9 In other embodiments, R 8 and R 9 One of them is methyl, and R 8 and R 9 The other one is –H.

[0069] In the metal-ligand complex according to formula (I), X is bonded to M by a covalent bond or an ionic bond. In some embodiments, X can be a monoanionic ligand with a net formal oxidation state of -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-C20 )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.

[0070] In some embodiments, X is 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 X is a chlorine atom, a (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 L Each of which is independently unsubstituted (C1-C 10 ) hydrocarbon group.

[0071] In some embodiments, n is 1, and X is linked to T and is selected from the group consisting of:

[0072]

[0073] In other embodiments, X is selected from: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. In one embodiment, k is 2. In a specific embodiment, when k is 2, two X groups are linked to form a bidentate ligand.

[0074] In one or more embodiments, each X is independently -(CH2)SiR X 3, where each R X Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, and at least one R X is (C1-C 30 In some embodiments, when R X One of them is (C1-C 30 ) is a heteroalkyl group, the heteroatom is a silicon dioxide or oxygen atom. X It is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl or nonyl.

[0075] In one or more embodiments, X is –(CH2)Si(CH3)3, –(CH2)Si(CH3)2(CH2CH3); –(CH2)Si(CH3)(CH2CH3)2, –(CH2)Si(CH2CH3)3, –(CH2)Si(CH3)2(n-butyl), –(CH2)Si(CH3)2(n-hexyl), –(CH2)Si(CH3)(n-octyl)R X 、–(CH2)Si(n-octyl)R X 2, -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), -CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as -CH2Si(CH3)2CH2TMS). Optionally, in some embodiments, according to the metal-ligand complex of formula (I), exactly two R X Covalently linked or exactly three R X Covalently linked.

[0076] In some embodiments, X is -CH2Si(R C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C )Q 、-OSi(R C ) 3-Q (OR C ) Q , where subscript Q is 0, 1, 2, or 3, and each R C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbon group, or substituted or unsubstituted (C1-C 30 ) heteroalkyl.

[0077] In some embodiments, X is B(R Y )4、Al(R Y )4 or Ga(R Y )4, where each R Y =–H, (C1-C 30 In one embodiment, when k is 2, two X groups are linked to form a bidentate ligand such that R Y Both of them are independently connected to metal M.

[0078] In the metal-ligand complex according to formula (I), each T is bonded to M by a coordination bond or an ionic bond. In one or more embodiments, T is a Lewis base. A Lewis base can be a compound or an ionic substance that can donate an electron pair to an acceptor compound. For the purposes of this embodiment, the acceptor compound is M, which is the metal of the metal-ligand complex of formula (I). The Lewis base can be neutral or anionic. In some embodiments, the Lewis base can be a heterohydrocarbon or a 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, cyclopentadiene. Examples of neutral hydrocarbons include, but are not limited to, 1,3-butadiene.

[0079] In one or more embodiments, the Lewis base can be a monodentate ligand, which can be a neutral ligand. In some embodiments, the neutral ligand can contain a heteroatom. In a specific embodiment, the neutral ligand is a neutral group, such as R T NR K R L , R K OR L , R K SR L or R T PR K R L , where each R T 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.

[0080] In some embodiments, the Lewis base is (C1-C 20 In some embodiments, the Lewis base is cyclopentadiene or 1,3-butadiene.

[0081] In various embodiments, the Lewis base is (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, T is tetrahydrofuran, diethyl ether or methyl tert-butyl ether (MTBE).

[0082] In the metal-ligand complex of formula (I), each Z is independently O, S, N (C1-C 40 ) alkyl or P(C1-C 40 ) alkyl. In some embodiments, each Z is different. For example, one Z is O and the other Z is NCH3. In some embodiments, one Z is O and one Z is S. In another embodiment, one Z is S and one Z is N(C1-C 40 )alkyl (e.g., NCH3). In another embodiment, each Z is the same. In yet another embodiment, each Z is O. In another embodiment, each Z is S.

[0083] In formula (I), each Z is connected to M by a dotted line. The dotted line defines an optional coordination bond. In some embodiments, one of these dotted lines forms a coordination bond between Z and M, and the second dotted line does not directly connect or bond Z to M. In various embodiments, each Z forms a coordination bond with M. In other embodiments, each Z is not directly connected or bonded to M. In the case of not intended to be bonded by theory, it is believed that the number of ZM coordination bonds depends on the atomic radius of the metal as defined by M.

[0084] In a specific embodiment of the catalyst system, the metal-ligand complex according to formula (I) may include, but is not limited to, a complex having the structure of any one of metal-ligand complexes 1 to 3 (US2021 / 015723):

[0085]

[0086] Olefin Growth

[0087] Although no cocatalyst is required to initiate olefin propagation on the metal-ligand complex of formula (I), it is believed that the metal-ligand complex is not efficient when the Lewis base T coordinates to the metal center M of formula (I). Therefore, without intending to be bound by theory, it is believed that during the olefin propagation process, the Lewis base dissociates from the metal center M and the metal-ligand complex has a structure according to formula (Ia):

[0088]

[0089] In formula (Ia), R 1 To R 16 , M, Z and L are as defined in formula (I). p is a hydrocarbon group, wherein the hydrocarbon group is branched or unbranched, and has at least 30 carbon atoms. More specifically, X p It is a growing olefin chain.

[0090] Additive components

[0091] Additives are chemical agents present during the polymerization reaction that do not prevent olefin growth. In one or more embodiments, the catalyst system further comprises an additive. In some embodiments, the additive is used as a co-catalyst. In other embodiments, the additive is used as a scavenger or a scavenger. In some embodiments, the additive is used as an alkylating agent. In one or more embodiments, the additive may have more than one function or may be used as a scavenger, an alkylating agent, and a co-catalyst.

[0092] A cocatalyst is a reagent that reacts with the primary catalyst to form an active catalyst. Without being bound by theory, it is believed that the Lewis base T of formula (I) dissociates in the absence of a cocatalyst. However, it is also believed that a cocatalyst can promote the dissociation of the Lewis base and the metal center of the metal-ligand complex.

[0093] 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.

[0094] In some embodiments, the additive is a compound containing (C1-C 20 ) hydrocarbyl substituent Lewis acid Group 13 metal compound. In some embodiments, the additive includes tri((C1-C 20) alkyl) substituted aluminum or tri((C1-C 20 In other embodiments, the additive is selected from tri(hydrocarbyl)substituted aluminum, 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.

[0095] In one or more embodiments, the polymerization method further comprises a borate-based additive. In some embodiments, the borate-based additive is selected from tri(fluoro-substituted phenyl)borane, tri(pentafluorophenyl)borane. In some embodiments, the cocatalyst is tri((C1-C 20 )alkyl)ammonium tetra((C1-C 20 )alkyl) borate (e.g., bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borate). 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 each (C1-C 20 ) The hydrocarbon groups may be the same or different (when there are two or more).

[0096] In one or more embodiments, the additive can be selected from polymeric or oligomeric aluminoxanes, especially methylaluminoxane, and inert, compatible, non-coordinating ion-forming compounds. Exemplary suitable additives include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1-)ammonium, triethylaluminum, butylated hydroxytoluene diethylaluminum, bis-(butylated hydroxytoluene)ethylaluminum, tri-(butylated hydroxytoluene)aluminum, and combinations thereof.

[0097] Additives such as aluminoxanes and aluminum alkyls can have multiple functions. Aluminoxanes and aluminum alkyls can be used as cocatalysts, scavengers, and alkylating agents in the polymerization process.

[0098] In some embodiments, the additive is of the formula AlR A1 R B1 R C1 Alkyl aluminum, where R A1 , R B1 and R C1Independently (C1-C 40 ) alkyl. In one or more embodiments, R A1 , R B1 and R C1 Independently (C1-C 10 ) alkyl. In one or more embodiments, R A1 , R B1 and R C1 R is independently methyl, ethyl, propyl, 2-propyl, butyl, tert-butyl or octyl. A1 , R B1 and R C1 In other embodiments, R A1 , R B1 and R C1 At least one of the R A1 , R B1 and R C1 .

[0099] In some embodiments, the alkyl aluminum material is triisobutyl aluminum (TiBAl) or aluminoxane. The alkyl aluminoxane can be (C1-C 10 ) alkylaluminoxane or a polymeric form of polymethylaluminoxane (PMAO). PMAO may be polymethylaluminoxane with improved performance (PMAO-IP), which is commercially available from Nouryon. (C1-C 10 The alkylaluminoxane may be methylaluminoxane (MAO), modified methylaluminoxane (MMAO) (e.g., 3A type (MMAO-3A), 7 type (MMAO-7), or 12 type (MMAO-12) modified methylaluminoxane), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, or 1-methylcyclopentylaluminoxane. The arylaluminoxane may be (C6-C 10 ) Aryl aluminoxane, which may be phenyl aluminoxane, 2,6-dimethylphenyl aluminoxane, or naphthyl aluminoxane.

[0100] In some embodiments, one or more co-catalysts may be used in combination with one another. Specific examples of co-catalyst combinations are tri((C1-C8)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, tri((C6 ... 18) aryl) borane or ammonium borate and a mixture of oligomeric or polymeric aluminoxane compounds. The ratio of the total moles of one or more metal-ligand complexes of formula (I) to the total moles of one or more co-catalysts in the co-catalyst is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When aluminoxane is used alone as a co-catalyst, preferably, the ratio of Al of aluminoxane to the metal of the metal-ligand complex of formula (I) (Al / M) is at least 20. In some other embodiments, when tris(pentafluorophenyl)borane is used alone as a co-catalyst, the ratio of the moles of tris(pentafluorophenyl)borane used to the total moles of 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.

[0101] Catalyst system components

[0102] In an embodiment, the second catalyst system includes at least one Group IV catalyst. The at least one Group IV catalyst may be selected from a Group IV metal-ligand complex, such as a titanium (Ti) metal-ligand complex, a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) metal-ligand complex. In one or more embodiments, the Group IV metal-ligand complex comprises a bis-biphenylphenoxy Group IV metal-ligand complex, a procatalyst, which may impart catalytic activity when contacted with an activator of the present disclosure.

[0103] In one or more embodiments, the Group IV metal-ligand complex can include a -biphenylphenoxy Group IV metal-ligand complex, a constrained geometry catalyst, or a phosphinimidite Group IV complex.

[0104] According to some embodiments, the bis-biphenylphenoxy Group IV metal-ligand complex has a structure according to Formula (X):

[0105]

[0106] In formula (X), M 1 is a metal selected from titanium, zirconium or hafnium, said metal being in a formal oxidation state of +2, +3 or +4. x ) n The subscript n is 1, 2, or 3. When the subscript n is 1, X x is a monodentate ligand or a bidentate ligand, and when the subscript n is 2, each X is a monodentate ligand. In formula (X), each Z is independently selected from -O-, -S-, -N(R N )-or-P(R P )-;L xis (C1-C 40 )alkylene or (C1-C 40 ) heteroalkylene, R 2x-4x , R 5x-8x , R 9x-12x and R 13x-15x Independently selected from the group consisting of: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-, -N=C(R C 2. R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen. 1x and R 16x is selected from a group having formula (XI), a group having formula (XII) and a group having formula (XIII):

[0107]

[0108] In formulae (XI), (XII) and (XIII), R 31 To R 35 , R 41 To R 48 and R 51 To R 59 Each of which is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R CC(O)N(R N )-、(R C )2NC(O)- or halogen.

[0109] In some embodiments of Formula (X), for example, L x It can be selected from (C3-C7) alkyl 1,3-diradicals, such as -CH2CH2CH2-, -CH(CH3)CH2C*H(CH3), -CH(CH3)CH(CH3)C*H(CH3), -CH2C(CH3)2CH2-, cyclopentane-1,3-diyl or cyclohexane-1,3-diyl. In some embodiments, for example, L x Can be selected from (C4-C 10 ) alkyl 1,4-diradicals, such as -CH2CH2CH2CH2-, Cyclohexane-1,2-diyldimethyl and bicyclo[2.2.2]octane-2,3-diyldimethyl. In some embodiments, L can be selected from (C5-C 12 ) alkyl 1,5-diradicals, such as -CH2CH2CH2CH2CH2- and 1,3-bis(methylene)cyclohexane. In some embodiments, for example, L x Can be selected from (C6-C 14 )alkyl 1,6-diradicals such as -CH2CH2CH2CH2CH2CH2- or 1,2-bis(ethylene)cyclohexane.

[0110] In one or more embodiments, L is (C2-C 40 )heteroalkylene, and at least one of the 2 to 10 atoms comprises a heteroatom. In some embodiments, L is -CH2Ge(R C )2CH2-, where each R C is (C1-C 30 In some embodiments, L is -CH2Ge(CH3)2CH2-, -CH2Ge(ethyl)2CH2-, -CH2Ge(2-propyl)2CH2-, -CH2Ge(tert-butyl)2CH2-, -CH2Ge(cyclopentyl)2CH2-, or -CH2Ge(cyclohexyl)2CH2-.

[0111] In one or more embodiments, in Formula (X), each X x It can be a monodentate ligand that is independent of any other ligand X x , is halogen, unsubstituted (C1-C 20 ) alkyl, unsubstituted [(C1-C 20 )alkyl]C(O)O– or R K R L N-, where RK and R L Each of which is independently unsubstituted (C1-C 20 In some embodiments, X x is benzyl, phenyl, chlorine, (C 1- C 10 )alkyl or -CH2Si(R x ), where each R x is (C1-C 20 )alkyl.

[0112] Illustrative metal-ligand complexes according to formula (X) include, for example:

[0113]

[0114] Other bis-biphenylphenoxy Group IV metal-ligand complexes that can be used in combination with the additives in the catalyst systems of the present disclosure will be apparent to those skilled in the art.

[0115] In one or more embodiments, the Group IV metal-ligand complex comprises a constrained geometry Group IV complex having a structure according to Formula (XV):

[0116]

[0117] In formula (XV), M 2 Titanium, hafnium or zirconium. (X) b The subscript b is 1, 2, or 3. Each X C are independently selected from unsaturated (C2-C 50 ) hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, saturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C6-C 50 ) aryl, (C6-C 50 ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )diene, halogen, -N(R N )2. AND-NCOR C The metal-ligand complex is electrically neutral as a whole.

[0118] In one or more embodiments, in Formula (XV), each X C It can be a monodentate ligand that is independent of any other ligand X C , is halogen, unsubstituted (C1-C 20 ) alkyl, unsubstituted [(C1-C 20 )alkyl]C(O)O– or RK R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 20 In some embodiments, X C benzyl, phenyl, chlorine, (C 1- C 10 )alkyl or -CH2Si(R x ), where each R x is (C1-C 20 )alkyl.

[0119] In formula (XV), Cp is selected from the group consisting of cyclopentadienyl and R S The group consisting of substituted cyclopentadienyl groups, the Cp is η 5 The bonding mode of M is combined with R S Independently selected from the group consisting of: (C1-C 20 )alkyl, (C1-C 20 ) heteroalkyl, (C1-C 20 ) aryl or R S Substituents (C1-C 20 ) aryl, (C1-C 20 ) heteroaryl or R S Substituents (C1-C 20 ) heteroaryl, wherein two adjacent R S The groups are optionally linked to form a ring.

[0120] In Formula (XV), N is nitrogen; Y is carbon or silicon; wherein Y 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.

[0121] Other catalysts, especially catalysts comprising one or more other Group IV metal-complexes not specifically listed above, will be apparent to those skilled in the art.

[0122] Catalyst system characteristics

[0123] As described herein, the reactivity ratio r1 (as further defined below) of the procatalyst comprising a metal-ligand complex of formula (I) and one or more cocatalysts is in the range of greater than 100, for example, greater than 150, greater than 200, greater than 300, or greater than 500.

[0124] A terminal copolymerization model is used for random copolymers in which the properties of the last monomer inserted determine the rate of subsequent monomer insertion. In this model, the type of insertion reaction is

[0125]

[0126] Among them, C * Represents catalyst, M i represents monomer i, and k ij is the rate constant with the following rate equation:

[0127]

[0128] The comonomer mole fraction (i=2) in the reaction medium is defined by the following equation:

[0129]

[0130] A simplified equation for comonomer composition can be derived as disclosed in George Odian, Principles of Polymerization, 2nd Edition, John Wiley and Sons, 1970, as follows:

[0131]

[0132] For this equation, the mole fraction of comonomer in the polymer depends only on the mole fraction of comonomer in the reaction medium and two temperature-dependent reactivity ratios defined in terms of the insertion rate constant as follows:

[0133]

[0134] Alternatively, in the penultimate copolymerization model, the properties of the last two monomers inserted into the growing polymer chain determine the rate of subsequent monomer insertion. The polymerization reaction takes the form

[0135]

[0136] And the individual rate equations are:

[0137]

[0138] The comonomer content can be calculated (again as disclosed in George Odian, Supra.) as:

[0139]

[0140] where X is defined as:

[0141]

[0142] And the reactivity ratio is defined as:

[0143]

[0144] Also for this model, the polymer composition is simply a function of the temperature-dependent reactivity ratio and the mole fraction of the comonomer in the reactor. This is also true when reverse comonomer or monomer insertion may occur, or in cases where more than two monomers are copolymerized.

[0145] The reaction rates used in the aforementioned models can be predicted using well-known theoretical techniques, or empirically derived from actual polymerization data. Suitable theoretical techniques have been disclosed, for example, in BG Kyle, "Chemical and Process Thermodynamics", 3rd edition, Prentice-Hall, 1999, and in the Redlich-Kwong-Soave (RKS) Equation of State, Chemical Engineering Science, 1972, pp. 1197-1203. Commercially available software programs can be used to help derive the reactivity ratio from experimentally derived data. An example of such software is Aspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, Massachusetts 02141-2201.

[0146] Thus, the method for producing ethylene-based polymers according to the present invention selectively produces polyethylene-rich (e.g., high density polyethylene) or polyethylene-rich segments of poly(ethylene alpha-olefin) copolymers in the presence of alpha-olefins, which are therefore substantially unpolymerized. The method for producing ethylene-based polymers employs olefin polymerization conditions. In some embodiments, the olefin polymerization conditions independently produce an in-situ catalyst formed by reacting a primary catalyst comprising a metal-ligand complex of formula (I) with one or more co-catalysts in the presence of one or more other ingredients. Such other ingredients include, but are not limited to, (i) an olefin monomer; (ii) another metal-ligand complex of formula (I); (iii) one or more of the catalyst system; (iv) one or more chain shuttling agents; (v) one or more catalyst stabilizers; (vi) one or more solvents; and (vii) a mixture of any two or more of them.

[0147] In particular, the catalyst of the present invention is useful in a process for producing ethylene-based polymers in (C3-C 40 ) α-olefins, wherein the high selectivity is characterized by the reactivity ratio r1 described previously. Preferably, for the process of the present invention, the reactivity ratio r1 is greater than 50, more preferably greater than 100, even more preferably greater than 150, even more preferably greater than 200. When the reactivity ratio r1 of the process of the present invention approaches infinity, the incorporation of α-olefins in (or on) the resulting polyethylene-enriched polyethylene approaches 0 mole percent (mol%).

[0148] Polyolefins

[0149] The catalytic system described in the present disclosure can be used for polymerizing olefins, mainly ethylene, propylene, α-olefins, such as octene and diene. In some embodiments, there is only a single type of olefin or α-olefin in the polymerization scheme, thereby forming a homopolymer. However, other α-olefins can be incorporated into the polymerization process. Other α-olefin comonomers generally have no more than 20 carbon atoms. For example, α-olefin comonomers can have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-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 α-olefin comonomers can 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.

[0150] Ethylene-based polymers, e.g., homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers (such as α-olefins), can contain at least 50 mole % (mol%) of monomeric units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 mole %" 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 mole % (mol %) of monomeric units derived from ethylene; at least 70 mole % of monomeric units derived from ethylene; at least 80 mole % of monomeric units derived from ethylene; or 50 to 100 mole % of monomeric units derived from ethylene; or 80 to 100 mole % of monomeric units derived from ethylene.

[0151] In some embodiments, the catalyst system can produce an ethylene-based polymer comprising at least 90 mol % 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, an ethylene-based polymer may include at least 93 mol % of units derived from ethylene; at least 96 mol % of units; at least 97 mol % of units derived from ethylene; or alternatively, 90 mol % to 100 mol % of units derived from ethylene; 90 mol % to 99.5 mol % of units derived from ethylene; or 97 mol % to 99.5 mol % of units derived from ethylene.

[0152] In some embodiments, the amount of additional α-olefins in the ethylene-based polymer produced by the catalyst system is less than 50 mole percent (mol%); in other embodiments, the amount of additional α-olefins comprises at least 0.01 mol% to 25 mol%; and in other embodiments, the amount of additional α-olefins comprises at least 0.1 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0153] Ethylene-based polymers can be produced by other conventional polymerization processes that include catalyst systems according to embodiments of the present disclosure. 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 in series, or any combination thereof.

[0154] In one embodiment, ethylene-based polymers can be produced by 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 by 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 other catalysts in the present disclosure. The catalyst system as described herein can be optionally used in combination with one or more other catalysts for the first reactor or the second reactor. In one embodiment, ethylene-based polymers can be produced by 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.

[0155] 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.

[0156] Ethylene-based polymers may also 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. Based on the weight of the polymer of ethylene and one or more additives, the polymer based on ethylene may contain about 0% to about 10% of such additives by combined weight. 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 the polymer of ethylene and all additives or fillers, the polymer based on ethylene may contain about 0% by weight to about 20% by weight of fillers, 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.

[0157] In some embodiments, a polymerization process for producing an ethylene-based polymer may include 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 0.970g / cm 3 、0.870g / cm 3 Up to 0.950g / cm 3 、0.870g / cm 3 Up to 0.920g / cm 3 , or 0.870g / cm 3 Up to 0.900g / cm 3 .

[0158] In an 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 15, 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 10It is 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.

[0159] In some embodiments, the melt index (I2) of the polymer produced by the catalyst system comprising the metal-ligand complex of formula (I) is from 0.1 to 100, wherein the melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190°C and 2.16 kg load.

[0160] 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 1.0 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 1.5 to 6. Another embodiment includes an MWD of 1.5 to 3; and other embodiments include an MWD of 2 to 2.5.

[0161] SymRADHT-GPC analysis

[0162] Molecular weight data were determined by analysis on a hybrid robotic-assisted dilution high temperature gel permeation chromatograph (Sym-RAD-GPC) built by Symyx / Dow. Polymer samples were dissolved in 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL stabilized by 300 ppm of butylated hydroxytoluene (BHT) by heating at 160°C for 120 minutes. Each sample was diluted to 1 mg / mL immediately before injecting a 250 μL aliquot of the sample. The GPC was equipped with two Polymer Labs PLgel 10 μm MIXED-B columns (300 × 10 mm) with a flow rate of 2.0 mL / min at 160°C. Sample detection was performed using a PolyChar IR4 detector in concentrated mode. Conventional calibration with narrow polystyrene (PS) standards was employed, adjusted to apparent units of homopolymer polyethylene (PE) using the known Mark-Houwink coefficients of PS and PE in TCB at this temperature.

[0163] IR Analysis of 1-Octene Incorporation

[0164] Samples for HT-GPC analysis were run prior to IR analysis. For IR analysis, 48-well HT silicon wafers were utilized to deposit and analyze samples for 1-octene incorporation. For this analysis, the samples were heated to 160°C for less than or equal to 210 minutes; the samples were reheated to remove the magnetic GPC stir bar and oscillated with a glass stir bar on a J-KEM Scientific heated mechanical oscillator. The samples were deposited while heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene was evaporated from the deposited wafer holes at 160°C under a nitrogen purge. Analysis of 1-octene was performed on HT silicon wafers using a NEXUS 670E.SPFT-IR.

[0165] Example

[0166] Examples 1 to 5 are synthetic procedures for intermediates for ligands, for the ligands themselves, and for isolated metal-ligand complexes containing these ligands. It should be understood that the synthetic procedures for catalysts 1 to 5 are provided to illustrate the embodiments described in the present disclosure and are not intended to limit the scope of the present disclosure or the claims thereto.

[0167] The synthesis procedure of Catalyst 1 (Cat-1) is disclosed in WO 2021 / 155158.

[0168] The synthesis procedure of Catalyst 2 (Cat-2) is disclosed in WO 2021 / 155158.

[0169] The synthesis procedure of Catalyst 3 (Cat-3) is disclosed in WO 2021 / 155158.

[0170] The synthesis procedure of catalyst 4 (Cat-4) is disclosed in WO / 2021243213.

[0171] The synthesis procedure of Catalyst 5 (Cat-5) is presented in International Application US11208503B2 and is disclosed as WO2018 / 183056.

[0172] Example 1 - Continuous Process Polymerization Results

[0173] Preparation of Examples

[0174] Before being introduced into the reaction environment, all raw materials (monomers and comonomers) and process solvents (narrow boiling range high purity paraffin solvents and cycloparaffin solvents) are purified with molecular sieves. High purity hydrogen is supplied through a common pipeline and dried with molecular sieves. The reactor monomer feed stream is pressurized to greater than the reaction pressure via a mechanical compressor. The solvent feed is pressurized to greater than the reaction pressure via a pump. The comonomer feed is pressurized to greater than the reaction pressure via a pump. Each catalyst component is manually diluted in batches to a specified component concentration with a purified solvent and pressurized to greater than the reaction pressure. All reaction feed flows are measured with mass flow meters and independently controlled with metering pumps.

[0175] The comonomer feed is mechanically pressurized and can be injected into the process at several potential locations depending on the reactor configuration, including: feed stream for the first reactor only, feed stream for the second reactor only, or both separate first and second reactor feed streams. Some comonomer injection combinations are only possible when running a dual feed reactor configuration.

[0176] Reactor configuration options include single reactor operation, dual series reactor operation, or dual parallel reactor operation.

[0177] A continuous solution polymerization reactor consists of a full liquid, adiabatic, and continuously stirred tank reactor (CSTR). All solvent, monomer, comonomer, hydrogen, and catalyst component feeds can be controlled independently. The temperature of the total feed stream (solvent, monomer, comonomer, and hydrogen) entering the reactor is controlled by passing the feed stream through a heat exchanger. All feeds to the polymerization reactor are injected into the reactor from one location. The catalyst components are injected into the polymerization reactor separately from the other feeds. The agitator in the reactor is responsible for the continuous mixing of the reactants. An oil bath provides some fine-tuning of the reactor temperature control.

[0178] In a dual series reactor configuration, the effluent from the first polymerization reactor exits the first reactor and is added to the second reactor separately from the other feeds added to the second reactor.

[0179] In a dual parallel reactor configuration, the effluent streams from the first and second polymerization reactors are combined prior to any further processing.

[0180] In all reactor configurations, the final reactor effluent (the effluent of the second reactor in dual series, the combined effluent of dual parallel, or the effluent of a single reactor) enters a zone where a suitable reagent (usually water) is added and reacted to deactivate the final reactor effluent. At this same reactor outlet location, other additives may also be added for polymer stabilization (octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane, and tris(2,4-di-tert-butyl-phenyl)phosphite).

[0181] After catalyst deactivation and addition of any additives, the reactor effluent enters a devolatilization system where the polymer is removed from the non-polymer stream. The non-polymer stream is removed from the system. The separated polymer melt is pelletized and collected.

[0182] Table 1. Dual-material reactor with two catalysts and dual-material reactor with three catalyst configurations

[0183]

[0184]

[0185] H2 (mol%) is defined as the mole fraction of hydrogen fed to the reactor relative to ethylene. Ethylene conversion is measured as the difference between the ethylene fed to the reactor relative to the amount leaving the reactor, expressed as a percentage. C8 / Olefins is the fresh C8 feed divided by the sum of the fresh C8 and fresh C2 feeds. Cocatalyst ratio is the total molar ratio of Al from MMAO or MMAO-3a / to the total catalyst A and B metal or C metal or the molar ratio of bis(hydrogenated tallow alkyl)methyl, tetra(pentafluorophenyl)borate (1-)ammonium (RIBS-2) to catalyst A metal. Catalyst A / B ratio is the metal molar ratio of the two catalysts in the same reactor.

[0186] MMAO-3a is commercially available from Nouryon and has a CAS# of 146905-79-5. MMAO-B is modified with n-octyl substituents such that the ratio of methyl:n-octyl is about 6:1.

[0187] Equipment Standards

[0188] 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 samples were further dried by storing over 100% 1% zeolite. Glassware used for moisture-sensitive reactions was dried in an oven overnight before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. The residual protons in the deuterated solvent were used as reference and reported downfield from internal tetramethylsilane (TMS, scaled δ). 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.

Claims

1. A polymerization method comprising: Ethylene and optionally one or more olefins are polymerized in a solution polymerization reactor under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based polymer, the catalyst system comprising at least one metal-ligand complex of formula (I), at least one Group IV procatalyst, at least one additive, and optionally a Lewis acid, wherein the metal-ligand complex of formula (I) (precatalyst) has a structure according to the following formula: in: M is scandium, yttrium or a lanthanide metal; Each X is selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) 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 And(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、B(R Y )4、Al(R Y )4 or Ga(R Y )4 or hydrogen ligand, wherein each R C are independently substituted or unsubstituted (C1-C 30 ) hydrocarbon group, or substituted or unsubstituted (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; k is 1 or 2; Each T is independently a Lewis base; n is 0, 1 or 2, when n is 1, X and T are optionally connected, when n is 2, X and one of T are optionally connected; The metal-ligand complex is electrically neutral as a whole; Each Z is independently selected from -O-, -S-, -N(R N )-or–P(R P )-, wherein the dashed line optionally defines a coordination bond; R 1 and R 16 Independently selected from the group consisting of: (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-, -N=C(R C 2. R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- or halogen; R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 and R 15 are independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3. -Ge(R C )3、-P(R P )2、-N(R N )2-OR C 、-SR C 、-NO2、-CN、-CF3、 R C S(O)-、R C S(O)2-、(R C )2C=N-、(R C )2P=N-、R C C(O)O-、 R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen; The prerequisite is that when M is yttrium or a lanthanide metal, R 1 is not -H, phenyl or tert-butyl; and R 16 is not –H, phenyl or tert-butyl; L is (C1-C 40 )alkylene or (C1-C 40 )heteroalkylene; and Each R in formula (I) C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

2. The polymerization process according to claim 1, wherein the polymerization reactor is a single reactor.

3. The polymerization process according to claim 1, wherein the polymerization reactor is a dual-material reactor; and: The metal-ligand catalyst of formula (I) is located in the first reactor and the Group (IV) catalyst is located in the second reactor; or The Group (IV) catalyst is located in a first reactor and the metal-ligand catalyst of formula (I) is located in a second reactor; or The metal-ligand catalyst of formula (I) and the Group (IV) catalyst are located in the first reactor, and a second metal-ligand catalyst of formula (I) or a second Group (IV) catalyst is located in the second reactor; or The metal-ligand catalyst of formula (I) and the Group (IV) catalyst are located in the second reactor, and a second metal-ligand catalyst of formula (I) or a second Group (IV) catalyst is located in the first reactor.

4. The polymerization process according to claim 1, wherein the polymerization reactor is a multi-zone reactor.

5. The polymerization process according to any one of the preceding claims, wherein the additive is an alkylating agent, a cocatalyst or a scavenger.

6. The polymerization process according to any one of the preceding claims, wherein the additive is an alkylaluminoxane compound, an alkyl-modified aluminoxane or an aluminum alkyl.

7. The polymerization process according to any one of the preceding claims, wherein the Lewis acid is an alkyl-modified aluminoxane.

8. A polymerization process according to any one of the preceding claims, wherein the Lewis acid is a A 3 alkylaluminum, wherein each R A Independently (C1-C 40 ) hydrocarbon group.

9. The polymerization process according to claim 9, wherein each R A Independently (C1-C 40 )alkyl.

10. The polymerization process according to any one of claims 1 to 4, wherein the additive comprises (A) at least one cocatalyst selected from the group consisting of aluminoxanes or (B) at least one cocatalyst selected from the group consisting of AlR A1 R B1 R C1 or (C) at least one cocatalyst selected from aluminoxanes and at least one activator selected from the group consisting of an alkyl aluminum of the formula AlR 1 R 2 R 3 The group consisting of alkyl aluminum, wherein R A1 , R B1 and R C1 Independently (C1-C 40 )alkyl.

11. The polymerization process according to any one of the preceding claims, wherein the additive is a borate compound.

12. The polymerization process of claim 1, wherein the at least one Lewis acid is selected from a mixture of an alkyl aluminum compound and a boryl Lewis acid.

13. A polymerization process according to any one of the preceding claims, wherein R 1 and R 16 is selected from a group having formula (II), a group having formula (III) and a group having formula (IV): Where R 31-35 , R 41-48 and R 51-59 Each of the following is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen; provided that when R 1 and R 16 When it is formula (II), R 31 To R 35 At least one of them is not -H.

14. A polymerisation process according to any one of the preceding claims, wherein M is scandium.

15. A polymerization process according to any one of the preceding claims, wherein when M is yttrium or a lanthanide metal, R 5-8 At least one of is not -H, and R 9-12 At least one of them is not –H.

16. A polymerization process according to any one of the preceding claims, wherein R 1 and R 16 At least one of them is a group having formula (III), wherein: R 42 and R 47 is (C1-C 20 )alkyl, –Si[(C1-C 20 )alkyl]3 or –Ge[(C1-C 20 )alkyl]3; or R 43 and R 46 is (C1-C 20 )alkyl, –Si[(C1-C 20 )alkyl]3 or –Ge[(C1-C 20 )hydrocarbon group]3.

17. The polymerization process according to any one of claims 1 to 15, wherein R 1 and R 16 At least one of them is a group having formula (II), wherein: R 31 To R 35 At least one of is not –H; or R 32 and R 34 is (C1-C 20 )alkyl, –Si[(C1-C 20 )alkyl]3 or –Ge[(C1-C 20 )hydrocarbon group]3.

18. The polymerization process according to any one of claims 1 to 15, wherein R 1 and R 16 At least one of them is a group having formula (IV), wherein: R 52 , R 53 , R 55 , R 57 and R 58 At least two of them are (C1-C 20 )alkyl, –Si[(C1-C 20 )alkyl]3 or –Ge[(C1-C 20 )alkyl]3; and Optionally, R 52 and R 53 connected to form a ring structure, and optionally, R 57 and R 58 connected to form a ring structure.

19. The polymerization process according to any one of the preceding claims, wherein L is selected from -CH2-, -CH2(CH2) m CH2-, –CH2Si(R C )2CH2-、-CH2Ge(R C )2CH2-、 -CH(CH3)CH2CH(CH3), and -CH2(benzene-1,2-diyl)CH2-, wherein m is 0 to 3, wherein each R in L C is (C1-C 20 ) hydrocarbon group.

20. The polymerization process according to any one of the preceding claims, wherein X is (C6-C 20 )aryl, benzyl, -CH2Si[(C1-C 20 )alkyl]3, (C1-C 12 )alkyl.

21. The polymerization process according to any one of the preceding claims, wherein n is 1 or 2; and At least one T is (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen.

22. The polymerization process according to any one of the preceding claims, wherein n is 1 or 2; and At least one T is tetrahydrofuran, diethyl ether or methyl tert-butyl ether (MTBE).

23. A polymerization process according to any one of the preceding claims, wherein: R 2 , R 4 , R 5 , R 12 , R 13 and R 15 is hydrogen; and Each Z is oxygen.

24. The polymerization process according to any one of the preceding claims, wherein the Group (IV) metal-ligand complex is a bis-biphenylphenoxy Group IV metal-ligand complex having a structure according to formula (X): Among them, M 1 is a metal selected from titanium, zirconium or hafnium; Each X x are independently selected from unsaturated (C2-C 50 ) hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, saturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C6-C 50 ) aryl, (C6-C 50 ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )diene, halogen, -N(R N )2. AND-NCOR C A monodentate ligand or a bidentate ligand; n is 1, 2 or 3; when n is 1, X x is a monodentate ligand or a bidentate ligand, and when the subscript n is 2, each X x It is a monodentate ligand; The metal-ligand complex is electrically neutral as a whole; Each Z is independently selected from -O-, -S-, -N(R N )-or-P(R P )-; L x is (C1-C 40 )alkylene or (C1-C 40 ) heteroalkylene; R 2x-4x , R 5x-8x , R 9x-12x and R 13x-15x Independently selected from the group consisting of: –H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2. -N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-, -N=C(R C 2. R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen; R 1x and R 16x is selected from a group having formula (XI), a group having formula (XII) and a group having formula (XIII): Where R 31-35 , R 41-48 and R 51-59 Each of the following is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen.

25. The polymerization process of any one of claims 1 to 23, wherein the Group (IV) metal-ligand complex is a constrained geometry Group IV complex having a structure according to formula (XV): M 2 is titanium, hafnium or zirconium; b is 1, 2, or 3; Each X is independently selected from unsaturated (C2-C 50 ) hydrocarbons, unsaturated (C2-C 50 ) heterohydrocarbons, saturated (C2-C 50 ) heterohydrocarbons, (C1-C 50 ) hydrocarbon group, (C6-C 50 ) aryl, (C6-C 50 ) heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 )diene, halogen, -N(R N )2 and -NCOR C A monodentate ligand or a bidentate ligand; The metal-ligand complex is electrically neutral as a whole; Cp is selected from the group consisting of cyclopentadienyl and R S The group consisting of substituted cyclopentadienyl groups, wherein Cp is η 5 To M 2 The bonding mode of R S Independently selected from the group consisting of: (C1-C 20 )alkyl, (C1-C 20 )heteroalkyl, (C1-C 20 ) aryl, or R S Substituents (C1-C 20 ) aryl, (C1-C 20 ) heteroaryl or R S Substituents (C1-C 20 ) heteroaryl, wherein two adjacent R S The groups are optionally linked to form a ring; N is nitrogen; Y is carbon or silicon; wherein Y 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.

26. A polymerization method comprising: Ethylene and optionally one or more olefins are polymerized in a solution polymerization reactor under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based polymer, the catalyst system comprising at least one olefin growth catalytic material according to formula (Ia): at least one olefin growth catalytic material of a Group IV catalyst, at least one additive, and optionally a Lewis acid, wherein the olefin growth catalytic material of (Ia) has a structure according to the following formula: in: M is scandium, yttrium or a lanthanide metal; X p is a ligand selected from a hydrocarbon group, wherein the hydrocarbon group is branched or unbranched and has at least 30 carbon atoms; Each Z is independently selected from -O-, -S-, -N(R N )-or–P(R P )-, wherein the dashed line optionally defines a coordination bond; R 1 and R 16 Independently selected from the group consisting of: (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-, -N=C(R C 2. R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- or halogen; R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 and R 15 are independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3. -Ge(R C )3、-P(R P )2、-N(R N )2-OR C 、-SR C 、-NO2、-CN、-CF3、 R C S(O)-、R C S(O)2-、(R C )2C=N-、(R C )2P=N-、R C C(O)O-、 R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen; The prerequisite is that when M is yttrium or a lanthanide metal, R 1 is not -H, phenyl or tert-butyl; and R 16 is not –H, phenyl or tert-butyl; L is (C1-C 40 )alkylene or (C1-C 40 )heteroalkylene; and Each R in formula (I) C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

27. The polymerization process of claim 26, wherein M is yttrium or a lanthanide metal, R 5-8 At least one of is not -H, and R 9-12 At least one of them is not –H.

28. The olefin growth catalytic substance according to claim 26 or claim 27, wherein R 1 and R 16 is selected from a group having formula (II), a group having formula (III), and a group having formula (IV): Where R 31-35 , R 41-48 and R 51-59 Each of the following is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen; provided that when R 1 and R 16 When it is formula (II), R 31 To R 35 At least one of them is not -H.

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