Bis(phosphino)-phenoxynickel(II) catalysts for the copolymerization of ethylene and acrylate monomers

Abstract

A process for polymerizing olefin monomers using a catalyst system and a catalyst system comprising a procatalyst having a structure according to formula (I): [Formula 1] JPEG2022544936000012.jpg132170

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 889,249, filed Aug. 20, 2019, the disclosure of which is incorporated herein by reference in its entirety.

[0002] Embodiments of the present disclosure relate generally to ethylene and acrylate polymerization catalyst systems and processes, and more specifically to ethylene and acrylate polymerization catalyst systems including bis(phosphino)-phenoxynickel(II) complexes and olefin polymerization processes incorporating these catalyst systems. [Background technology]

[0003] Ethylene / acrylate copolymers are formed through high pressure and / or high temperature radical processes and have a highly branched microstructure similar to low density polyethylene (LDPE). Coordination catalysis offers a route to highly linear ethylene / acrylate copolymers, similar to linear low density polyethylene (LLDPE). These linear copolymers exhibit higher crystallinity and higher thermal resistance than existing materials formed through radical processes. Unfortunately, most organometallic coordination catalysts are not compatible with acrylic acid or acrylates.

[0004] The Group IV metal catalysts (Ti, Zr, Hf) used in the industrial production of LLDPE (ethylene / α-olefin copolymers) are incompatible with polar olefin monomers such as acrylates: the oxygen atoms of the acrylates strongly coordinate with Lewis acidic Group IV metals which block the active sites of the metal, effectively preventing further olefin polymerization.

[0005] Therefore, more electron-rich later metal catalysts containing group 10 metals (Pd, Ni) are utilized for the copolymerization reaction of ethylene with acrylate monomers. However, many reported Ni- and Pd-containing metal catalysts a) have slow polymerization rates and / or b) provide low incorporation of the desired polar monomers. Summary of the Invention

[0006] There is a continuing need to create new ligand frameworks for Ni catalysts that promote both high rates of ethylene copolymerization activity and high incorporation of acrylate comonomers. With the new ligand frameworks for Ni, ethylene and polar monomers may be copolymerized via coordination catalysis to form highly linear LLDPE-like copolymers. The new highly linear copolymers are expected to exhibit improved creep resistance and dimensional stability at higher application temperatures.

[0007] Embodiments of the present disclosure include a catalyst system comprising a procatalyst having a structure according to formula (I): [ka]

[0008] In formula (I), M is nickel(II) or palladium(II) and X is (C 1 -C 40 ) hydrocarbyl, (C 1 -C 40 ) heterohydrocarbyl, -CH 2 Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(RC ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C ) 2 , -NH(R C ), -N(Si(R C ) 3 ) 2 , -NR C Si(R C ) 3 , -NHSi(R C ) 3 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , -OCF 3 , -S(O)R C , -S(O) 2 R C , -OS(O) 2 R C , -N=C(R C ) 2 , -N=CH(R C ), -N=CH 2 , -N=P(R C ) 3、 -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C ) 2 , -C(O)NHR C , -C(O)NH 2 , halogen, or hydrogen; C are independently substituted or unsubstituted (C 1 -C 30 ) hydrocarbyl, or substituted or unsubstituted (C 1 -C 30) heterohydrocarbyl, where the subscript Q is 0, 1, 2, or 3, and the subscript W is 0, 1, or 2. Each Y is a Lewis base, and X and Y are optionally linked.

[0009] In some embodiments, Y is an organic Lewis base.

[0010] In formula (I), Z 1 , Z 2 , Z 3 are independent, C(R Z ) or nitrogen, and each R Z are independently substituted (C 1 -C 30 ) hydrocarbyl, unsubstituted (C 1 -C 30 ) hydrocarbyl, substituted (C 1 -C 30 ) Heterohydrocarbyl, unsubstituted (C 1 -C 30 ) heterohydrocarbyl, -CH 2 Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C ) 2 , -NH(R C ), -N(Si(R C ) 3 ) 2 , -NR C Si(R C) 3 , -NHSi(R C ) 3 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , -OCF 3 , -S(O)R C , -S(O) 2 R C , -OS(O) 2 R C , -N=C(R C ) 2 , -N=CH(R C ), -N=CH 2 , -N=P(R C ) 3 , -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C ) 2 , -C(O)NHR C , -C(O)NH 2 , halogen, or hydrogen; the subscript Q is 0, 1, 2, or 3; the subscript W is 0, 1, or 2; R C is (C 1 -C 18 ) hydrocarbyl, wherein Z 1 , Z 2 and Z 3 At least one of C(R Z ) is the condition.

[0011] In formula (I), R 1 , R 2 , R 3 , and R 4 are independent, (C 1 -C 50 ) hydrocarbyl and (C 1 -C 50 ) heterohydrocarbyl.

[0012] In formula (I), Z 1 and Z 2 Both are C(R Z ), optionally each group R Z are linked to form a ring structure. 2 and Z 3 Both are C(R Z ), optionally each group R Z are linked to form a ring structure. 1 , Z 2 , and Z 3 All of the above are C(R Z ), optionally each group R Z are linked to form a multiple ring structure. 1 and R 2 are linked to form a ring structure, and R 3 and R 4 are optionally linked to form a ring structure.

[0013] An embodiment of the present disclosure includes a polymerization process comprising polymerizing ethylene and one or more polar monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based copolymer. The catalyst system comprises a metal-ligand complex according to formula (I) of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Specific embodiments of the catalyst system are described below. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as being limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0015] Common abbreviations are listed below.

[0016] R C , R Z , R 1 , R 2 , R 3 , R4 , Z 1 , Z 2 , Z 3 , X, Y, Q, and W: 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), THF: tetrahydrofuran, Et 2 O: Diethyl ether, CH 2 Cl 2 : dichloromethane, EtOAc: ethyl acetate, C 6 D 6 : Deuterated benzene or benzene-d 6 , CDCl 3 : Deuterated chloroform, Na 2 SO 4 : Sodium sulfate, MgSO 4 : Magnesium sulfate, HCl: Hydrogen chloride, n-BuLi: Butyl lithium, t-BuLi: tert-Butyl lithium, K 2 CO 3 : Potassium carbonate, N 2 : nitrogen gas, PhMe: toluene, PPR: parallel pressure reactor, MAO: methylalumoxane, MMAO: modified methylalumoxane, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: mole, min or mins: minute, h or hrs: hour, d: day, R f : retention factor, TLC: thin layer chromatography, rpm: revolutions per minute.

[0017] The term "independently selected" followed by multiple options is 1 , R 2 , R 3 , R 4 , and R C etc. are used herein to indicate that the individual groups appearing before the term may be the same or different and there is no dependency as to the identity of any other group appearing before the term.

[0018] The term "procatalyst" refers to a compound that has catalytic activity after activation, for example, upon removal of a Lewis base coordinated to a Ni or Pd metal center.

[0019] When used to describe a chemical group that contains a particular carbon atom, "(C x -C y A bracketed expression having the form "(C)" means that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive. For example, (C 1 -C 50 ) Alkyl, in its unsubstituted form, is an alkyl group having 1 to 50 carbon atoms. In some embodiments and general structures, certain chemical groups are R S and R S Generally represents any of the substituents defined herein. x -C y ) for the chemical group R S The substituted version can be any group R S Depending on the identity of R, R may contain more than y carbon atoms. For example, S is phenyl (-C 6 H 5 ) exactly one group R S Replaced by (C 1 -C 50 "(C)alkyl" can contain from 7 to 56 carbon atoms. Thus, the parenthetical "(C)alkyl" is generally used. x -C y )" is a group defined as one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group are both x and y, respectively, all the carbon atom-containing substituents R S The total number of carbon atoms derived from the aryl group is determined by adding the total number of carbon atoms derived from the aryl group.

[0020] The term "substituted" refers to the replacement of at least one hydrogen atom (-H) bonded to a carbon or heteroatom or functional group of the corresponding unsubstituted compound with a substituent (e.g., R SThe prefix "per" has its ordinary meaning of "completely" or "totally," and for example, the term "persubstituted" or "persubstituted" means that all of the hydrogen atoms (H) attached to the carbon or heteroatoms of the corresponding unsubstituted compound or functional group have been replaced by a substituent (e.g., R S ), and similarly, in the case of "perfluorinated alkyl," all of the hydrogens in the alkyl group are replaced by fluorine atoms. The term "polysubstituted" means that at least two, but fewer than all, of the hydrogen atoms bonded to carbon or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0021] "(C 1 -C 50 The term "(C)hydrocarbyl" means a hydrocarbon radical of 1 to 50 carbon atoms. 1 -C 50 The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 50 carbon atoms, each of which may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and which may contain one or more R S or not replaced by

[0022] In this disclosure, 1 -C 50 ) hydrocarbyl is unsubstituted or substituted (C 1 -C 50 ) alkyl, (C 3 -C 50 ) cycloalkyl, (C 3 -C 20 )Cycloalkyl-(C 1 -C 20 ) alkylene, (C6 -C 40 ) aryl, or (C 6 -C 20 )Aryl-(C 1 -C 20 ) alkylene (benzyl (-CH 2 -C 6 H 5 ) etc.

[0023] "(C 1 -C 50 ) alkyl" and "(C 1 -C 18 The term "alkyl" refers to an unsubstituted or alkyl group having one or more R S and saturated linear or branched hydrocarbon radicals of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively. 1 -C 50 Examples of alkyl groups include unsubstituted (C 1 -C 20 ) Alkyl, unsubstituted (C 1 -C 10 ) Alkyl, unsubstituted (C 1 -C 5 ) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 2,2-dimethylpropyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 1 -C 40 Examples of substituted (C 1 -C 20 ) Alkyl, Substituted (C 1 -C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" means that there are up to 45 carbon atoms in the radical, including the substituents, e.g., (C 1 -C 5 ) one R that is alkyl S is replaced by (C 27 -C 40 ) alkyl.1 -C 5 ) Alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, 2,2-dimethylpropyl, or 1,1-dimethylethyl.

[0024] "(C 6 -C 50 The term "aryl" refers to an unsubstituted or substituted (one or more R) aryl group having 6 to 40 carbon atoms, at least 6 to 14 of which are aromatic ring carbon atoms. S A monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical is intended to mean a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical, according to the formula (I) (C 1 -C 2 -C 3 -C 4 -C 5 -C 6 -C 7 -C 8 -C 9 -C 10 -C 11 -C 12 -C 13 -C 14 -C 15 -C 16 -C 17 -C 18 -C 19 -C 20 -C 21 -C 22 -C 23 -C 24 -C 25 -C 26 -C 27 -C 28 -C 29 -C 30 -C 31 -C 32 -C 33 -C 34 -C 35 -C 36 -C 37 -C 38 -C 39 -C 40 -C 41 -C 42 -C 43 -C 44 -C 50 -C 51 -C 52 -C 53 -C 54 -C 55 -C 66 -C 67 -C 70 -C 71 -C 72 -C 73 -C 74 -C 75 -C 76 -C 77 -C 88 -C 99 -C 100 -C 111 -C 121 -C 132 -C 142 -C 153 -C 163 -C 174 -C 185 -C 196 -C 197 -C 198 -C 199 -C 199 -C 199 -C 199 -C 199 -C 199 6 -C 50 Examples of aryl include unsubstituted (C 6 -C 20 )Aryl, unsubstituted (C 6 -C 18 )aryl, 2-(C 1 -C 5 ) alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrenyl. 6 -C 40 Examples of aryl include substituted (C 1 -C 20 ) Aryl, Substituted (C 6 -C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, 3,5-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-one-l-yl.

[0025] "(C 3 -C 50 The term "cycloalkyl" means unsubstituted or substituted with one or more R S means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms, substituted by other cycloalkyl groups, such as (C x -C y )Cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S The unsubstituted (C 3 -C 40 Examples of cycloalkyl are unsubstituted (C 3 -C 20 ) Cycloalkyl, unsubstituted (C 3 -C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 3 -C 40 Examples of cycloalkyl are substituted (C 3 -C 20 ) Cycloalkyl, substituted (C 3 -C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0026] (C 1 -C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C 6 -C 50 ) arylene, (C 3 -C 50 ) cycloalkylene, and (C 1 -C 50 ) alkylene (e.g., (C 1 -C 20 ) alkylene). Diradicals are groups on the same carbon atom (e.g., -CH 2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include 1,2-diradicals. α,ω-diradicals are the diradicals with the greatest carbon backbone spacing between the radical carbons. (C 2 -C 20 Some examples of alkylene α,ω-diradicals are ethane-1,2-diyl (i.e., -CH 2 CH 2 -), propane-1,3-diyl (i.e., -CH 2 CH 2 CH 2 -), 2-methylpropane-1,3-diyl (i.e., -CH 2 CH(CH 3 )CH 2 -) is one of them. (C 6 -C 50 ) Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0027] "(C 1 -C 50 The term "alkylene" refers to a group that is unsubstituted or has one or more R S means a saturated straight or branched diradical of 1 to 50 carbon atoms (i.e., the radicals are not on ring atoms) substituted by 1 -C 50 Examples of alkylenes are unsubstituted (C 1 -C 20 ) alkylene and unsubstituted —CH 2 CH 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -(CH 2 ) 5 -, -(CH 2 )6 -, -(CH 2 ) 7 -, -(CH 2 ) 8 -, -CH 2 C*HCH 3 , and -(CH 2 ) 4 C*(H)(CH 3 ), and "C*" indicates a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 1 -C 50 Examples of alkylenes are substituted (C 1 -C 20 ) alkylene, -CF 2 -, -C(O)-, and -(CH 2 ) 14 C(CH 3 ) 2 (CH 2 ) 5 - (i.e., 6,6-dimethyl-substituted 1,20-eicosylene). As mentioned above, the two R S Together (C 1 -C 18 ) alkylene, so that the substitution (C 1 -C 50 Examples of alkylenes also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

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

[0029] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include -O-, -S-, -S(O)-, -S(O) 2 -, -Si(RC ) 2 -, -P(R P )-, -P(R P ) 2 , -N(R N )-, -N(R N ) 2 -N=C(R C ) 2 , -N=C(NR 2 N )(R C ) 、 -Ge(R C ) 2 - or -Si(R C ) 3 Each R C and each R P is a non-substituted (C 1 -C 18 ) hydrocarbyl or -H, and each R N is non-substituted (C 1 -C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 1 -C 50 The term "heterohydrocarbyl" means a heterohydrocarbon radical of 1 to 50 carbon atoms, and 1 -C 50 The term "heterohydrocarbylene" means a heterohydrocarbon diradical of 1 to 50 carbon atoms. 1 -C 50 )heterohydrocarbyl or (C 1 -C 50The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be present on a carbon atom or on a heteroatom. The two radicals of the heterohydrocarbylene may be present on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of the diradical may be present on a carbon atom and the other radical on a different carbon atom, or one of the two radicals may be present on a carbon atom and the other on a heteroatom, or one of the two radicals may be present on a heteroatom and the other radical on a different heteroatom. Each (C 1 -C 50 ) heterohydrocarbyl and (C 1 -C 50 ) Heterohydrocarbylene is unsubstituted or substituted (one or more R S The aromatic ring may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0030] (C 1 -C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. 1 -C 50 Non-limiting examples of heterohydrocarbyls include (C 1 -C 50 )heteroalkyl, (C 1 -C 50 ) hydrocarbyl-O-, (C 1 -C 50 ) hydrocarbyl-S-, (C 1 -C 50 ) hydrocarbyl-S(O)-, (C 1 -C 50 ) Hydrocarbyl-S(O) 2 -, (C 1 -C 50 ) Hydrocarbyl-Si(R C ) 2 -, (C l -C 50 )hydrocarbyl-N(RN )-, (C l -C 50 ) hydrocarbyl-P(R P )-, (C 2 -C 50 )heterocycloalkyl, (C 2 -C 19 )Heterocycloalkyl-(C 1 -C 20 ) alkylene, (C 3 -C 20 )Cycloalkyl-(C 1 -C 19 ) heteroalkylene, (C 2 -C 19 )Heterocycloalkyl-(C 1 -C 20 ) heteroalkylene, (C 1 -C 50 ) heteroaryl, (C 1 -C 19 )Heteroaryl-(C 1 -C 20 ) alkylene, (C 6 -C 20 )Aryl-(C 1 -C 19 ) heteroalkylene, or (C 1 -C 19 )Heteroaryl-(C 1 -C 20 )heteroalkylene. Additional examples include -Si(R C ) 3-Q (OR C ) Q , -OSi(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(RC ) 2 , -OR C , -SR C , --NO 2 , -CN, -CF 3 , -OCF 3 , -S(O)R C , -S(O) 2 R C , -OS(O) 2 R C , -N=C(R C ) 2 , -N=P(R C ) 3 , -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , and -C(O)N(R C ) 2 These include, but are not limited to:

[0031] "(C 4 -C 50 The term "heteroaryl" refers to unsubstituted or substituted (one or more R) heteroaryls having a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms. S (C) means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical. A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., generally (C) x -C y ) heteroaryl, (C 4 -C 12 ) heteroaryl, etc., has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or substituted with one or more R SThe monocyclic heteroaromatic hydrocarbon radical is a 5- or 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, 3, or 4, and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. The six-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and the heteroatoms can be N or P. Examples of six-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, pyrazin-2-yl, and 1,3,5-triazin-2-yl. The bicyclic heteroaromatic hydrocarbon radicals can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radicals can be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0032] "(C 1 -C 50The term "(C)heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms or fewer and one or more heteroatoms. 1 -C 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene include Si(R C ) 3 , Ge(R C ) 3 , Si(R C ) 2 , Ge(R C ) 2 , P(R P ) 2 , P(R P ), N(R N ) 2 , N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O) 2 and each of the heteroalkyl and heteroalkylene groups can be unsubstituted or can include one or more R S has been replaced by

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

[0034] The term "halogen atom" or "halogen" refers to 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: fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I - ).

[0035] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be replaced by a substituent R S The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, or carbon-silicon double bonds, and the substituent R S or absent, but does not include double bonds which may be present in (hetero)aromatic rings.

[0036] Embodiments of the present disclosure include a catalyst system comprising a procatalyst having a structure according to formula (I): [ka]

[0037] In formula (I), M is nickel(II) or palladium(II) and X is (C 1 -C 40 ) hydrocarbyl, (C 1 -C 40 ) heterohydrocarbyl, -CH 2 Si(R C ) 3-Q (OR C ) Q , -Si(RC ) 3-Q (OR C ) Q 、-OSi(R C ) 3-Q (OR C ) Q 、-Ge(R C ) 3-Q (OR C ) Q 、-P(R C ) 2-W (OR C ) W 、-P(O)(R C ) 2-W (OR C ) W 、-N(R C ) 2 、-NH(R C )、-N(Si(R C ) 3 ) 2 、-NR C Si(R C ) 3 、-NHSi(R C ) 3 、-OR C 、-SR C 、-NO 2 、-CN、-CF 3 、-OCF 3 、-S(O)R C 、-S(O) 2 R C 、-OS(O) 2 R C 、-N=C(R C ) 2 、-N=CH(R C )、-N=CH 2 、-N=P(R C ) 3、 -OC(O)R C 、-C(O)OR C 、-N(R C )C(O)R C 、-N(R C )C(O)H、-NHC(O)R C 、-C(O)N(R C ) 2 、-C(O)NHR C 、-C(O)NH 2, halogen, or hydrogen; C are independently substituted or unsubstituted (C 1 -C 30 ) hydrocarbyl, or substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl, where the subscript Q is 0, 1, 2, or 3, and the subscript W is 0, 1, or 2. Each R C is (C 1 -C 18 ) hydrocarbyl. Each Y is a Lewis base, and X and Y are optionally linked.

[0038] In formula (I), Z 1 , Z 2 , Z 3 are independent, C(R Z ) or nitrogen, and each R Z are independently hydrogen, substitution (C 1 -C 30 ) hydrocarbyl, substituted (C 1 -C 30 ) Heterohydrocarbyl, unsubstituted (C 1 -C 30 ) hydrocarbyl, unsubstituted (C 1 -C 30 ) heterohydrocarbyl, -CH 2 Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C )W , -N(R C ) 2 , -NH(R C ), -N(Si(R C ) 3 ) 2 , -NR C Si(R C ) 3 , -NHSi(R C ) 3 , -OR C , -SR C , --NO 2 , -CN, -CF 3 , -OCF 3 , -S(O)R C , -S(O) 2 R C , -OS(O) 2 R C , -N=C(R C ) 2 , -N=CH(R C ), -N=CH 2 , -N=P(R C ) 3 , -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C ) 2 , -C(O)NHR C , -C(O)NH 2 , halogen, or hydrogen, but Z 1 , Z 2 , and Z 3 At least one of C(R Z ), where the subscript Q is 0, 1, 2, or 3, and the subscript W is 0, 1, or 2. Each R C is hydrogen or (C 1 -C 18 ) hydrocarbyl. In some embodiments, each R C is hydrogen or (C 1 -C 18 ) alkyl.

[0039] In formula (I), R 1 , R 2 , R 3 , and R 4 are independent, (C 1 -C 50 ) hydrocarbyl and (C 1 -C 50 ) heterohydrocarbyl.

[0040] Optionally, in formula (I), Z 1 and Z 2 Both are C(R Z ), each group R Z are linked to form a ring structure, and Z 2 and Z 3 Both are C(R Z ), each group R Z are linked to form a ring structure, and Z 1 , Z 2 , and Z 3 All of the above are C(R Z ), each group R Z are linked to form a multi-ring structure, and R 1 and R 2 are linked to form a ring structure, and R 3 and R 4 are linked to form a ring structure.

[0041] In some embodiments, in the procatalyst of formula (I), Z 1 and Z 2 is C(R Z ) and each group R Z are linked to form a six-membered ring structure. The procatalyst has a structure according to formula (II): [ka]

[0042] In formula (II), R Z1 , R Z2 , R Z3 , and R Z4are independently -H, (C 1 -C 20 ) hydrocarbyl, or (C 1 -C 40 ) heterohydrocarbyl, and Ni; R 1 , R 2 , R 3 , R 4 、 Z 3 , X, and Y are as defined in formula (I).

[0043] In some embodiments, in the procatalyst of formula (I), Z 2 and Z 3 is C(R Z ) and each group R Z are linked to form a six-membered ring structure, and the procatalyst has a structure according to formula (III): [ka]

[0044] In formula (III), R Z5 , R Z6 , R Z7 , and R Z8 are independently -H, (C 1 -C 20 ) hydrocarbyl, or (C 1 -C 40 ) heterohydrocarbyl, and Ni; R 1 , R 2 , R 3 , R 4 、 Z 1 , X, and Y are as defined in formula (I).

[0045] In various embodiments, R 1 , R 2 , R 3 , and R 4 is independently unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, or substituted anthracenyl. In some embodiments, R 1 , R 2 , R 3, and R 4 are independently 2,6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-diphenoxyphenyl, 2,4,6-triethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-phenylphenyl, and 2,6-diisopropoxyphenyl. 1 , R 2 , R 3 , and R 4 is (C 1 -C 18 ) alkyl. In some embodiments, R 1 , R 2 , R 3 , and R 4 is (C 1 -C 18 ) cycloalkyl.

[0046] In one or more embodiments, R 1 and R 2 are linked to form a five-membered ring structure, and / or R 3 and R 4 are linked to form a five-membered ring structure. In other words, in one or more embodiments, R 1 and R 2 are linked to form a five-membered ring structure, and R 3 and R 4 are linked together to form a five-membered ring structure, or R 1 and R 2 are linked to form a five-membered ring structure, and R 3 and R 4 are not linked together to form a five-membered ring structure, or R 1 and R 2 are not linked to form a five-membered ring structure, and R 3 and R 4 are linked to form a five-membered ring structure.

[0047] In some embodiments, Z 1 is N. In other embodiments, Z 2 is N. In some embodiments, Z 3 is N. In one or more embodiments, Z 1and Z 3 is N.

[0048] In various embodiments, Z 1 and Z 3 is C(R Z ) and each R Z is -H, Z 2 is C(R Z ) and each R Z is -H, substitution (C 1 -C 20 ) Alkyl, unsubstituted (C 1 -C 20 ) Alkyl, Substituted (C 6 -C 18 )Aryl, unsubstituted (C 6 -C 18 ) Aryl, -OR N , -SR N , -SO 3 R N , -SiR N 3 , halogen, -N(R N ) 2 , -P(R P ) 2 , or -P(O)(R P ) 2 Each R N are independently substituted and unsubstituted (C 6 -C 18 ) aryl or (C 1 -C 18 ) alkyl or halogen. P are independently substituted (C 6 -C 18 )Aryl, unsubstituted (C 6 -C 18 ) Aryl, Substituted (C 6 -C 18 ) Heteroaryl, unsubstituted (C 6 -C 18 ) Heteroaryl, substituted (C 1 -C 18 ) Alkyl, unsubstituted (C 1 -C 18 ) alkyl, or -OR P Optionally, two R Pcan be linked together to form a ring structure, and optionally two R N can be linked together to form a ring structure.

[0049] In one or more embodiments, in the procatalyst of formula (I), Z 1 and Z 3 is C(R Z ) and each R Z is -H, Z 2 is C(R Z ) and each R Z is phenyl, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, -CF 3 , -NMe 2 , -PPh 2 , -P(O)Ph 2 , -OMe, -SiMe 3 , -SiPh 3 , carbazole, di-tert-butyl-carbazole, anthracenyl, di-tert-butyl-anthracenyl, fluorine, or chlorine.

[0050] In one or more embodiments, in the procatalyst of formula (I), Z 1 and Z 3 is C(R Z ) and each R Z is -H, Z 2 is C(R Z ) and each R Z are methyl, ethyl, 2-propyl, n-propyl, n-butyl, tert-butyl, 2-methylpropyl, pentyl, hexyl, heptyl, octyl, n-octyl, tert-octyl, nonyl, decyl, undecyl, and dodecyl.

[0051] In the procatalyst according to formula (I), formula (II), or formula (III), X is bonded to M through a covalent bond and Y is bonded to M through a coordinate bond. The procatalysts of formula (I), (II), and (III) can be overall charge neutral. In some embodiments, the catalyst system includes a procatalyst of formula (I), (II), and (III), where X is independently a substituent (C 1 -C 30 ) hydrocarbyl, unsubstituted (C 1 -C 30 ) hydrocarbyl, substituted (C 1 -C 30 ) Heterohydrocarbyl, unsubstituted (C 1 -C 30 ) heterohydrocarbyl, (C 1 -C 20 ) alkyl, (C 1 -C 20 )heteroalkyl, (C 6 -C 20 ) aryl, (C 4 -C 20 ) heteroaryl, or halogen. In one or more embodiments, each X is independently selected from -CH 2 Si(CH 3 ) 3 , methyl, benzyl, phenyl, or chloro. In further embodiments, each X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethylpropyl, (n-butyl)dimethylsilylmethyl, (n-hexyl)dimethylsilylmethyl, (n-octyl)dimethylsilylmethyl.

[0052] In some embodiments, X is halogen, unsubstituted (C 1 -C 20 ) hydrocarbyl, unsubstituted (C 1 -C 20 ) hydrocarbyl-C(O)O-, or R K R L N- and R K and R L Each of the is independently unsubstituted (C 1 -C 20In some embodiments, each monodentate ligand X is a chlorine atom, (C 1 -C 10 ) hydrocarbyl (e.g., (C 1 -C 6 ) alkyl or benzyl), unsubstituted (C 1 -C 10 ) hydrocarbyl-C(O)O-, or R K R L N- and R K and R L Each of the is independently unsubstituted (C 1 -C 10 ) hydrocarbyl.

[0053] In one or more embodiments, Y is a Lewis base. In some embodiments, Y is an organic Lewis base. In various embodiments, the organic Lewis base is 1 -C 30) heterohydrocarbyl, provided that the heteroatom of the heterohydrocarbyl is capable of forming a coordinate bond with M. The organic Lewis base may be a sulfoxide, a trihydrocarbyl phosphine, such as a trialkyl phosphine, a dialkylaryl phosphine, an alkyl diaryl phosphine, or a triaryl phosphine, a trialkyl, triaryl phosphine, an olefin or cyclic olefin, a substituted or unsubstituted heterocycle, an alkyl ester of an aliphatic or aromatic carboxylic acid, an aliphatic ketone, an aliphatic amine, an aliphatic alcohol, an alkyl or cycloalkyl ether, or mixtures thereof, each electron donor having 2 to 20 carbon atoms. In various embodiments, the organic Lewis base is selected from alkyl ethers and cycloalkyl ethers having 2 to 20 carbon atoms, dialkyl, diaryl, and alkylaryl ketones having 3 to 20 carbon atoms, and alkyl, alkoxy, and alkylalkoxy esters of alkyl and aryl carboxylic acids having 2 to 20 carbon atoms. Specific examples of organic Lewis bases include, but are not limited to, methyl formate, ethyl acetate, butyl acetate, ethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethanol, 1-butanol, ethyl formate, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, tetrahydrofuran, ethyl propionate, pyridine, substituted pyridine, lutidine, picoline, dimethyl sulfoxide, trimethylphosphine, triphenylphosphine, cyclooctadiene, cyclopentene, ethylene, propylene, tert-butylethylene, trimethylamine, 1-methylimidazole, or 1-methylpyrazole. In some embodiments, the Lewis base is pyridine.

[0054] In some embodiments, X and Y are covalently linked. Specific examples of organic Lewis bases Y that are covalently linked together with the X groups include, but are not limited to, 4-cycloocten-1-yl, 2-dimethylaminobenzyl, and 2-dimethylaminomethylphenyl.

[0055] In some embodiments, the chemical groups (e.g., X and R 1 -R 4 In other embodiments, any or all of the chemical groups X and R of the metal-ligand complex of formula (I) may be unsubstituted. 1 -R 4 Any of the following has one or more R S or any or all of them are substituted with one or more R S Two or more R S are attached to the same chemical group of the procatalyst of formula (I), the individual R S may be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, the chemical groups X and R 1 -R 4 Both of these are R S may not be over-substituted, and any or all of S It may be oversubstituted with R S In chemical groups that are over-substituted with S may all be the same or may be independently selected.

[0056] Some embodiments of the present disclosure include a polymerization process. In some embodiments, the polymerization process includes polymerizing ethylene and one or more olefin monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based copolymer, the catalyst system including a metal-ligand complex according to formula (I) as described in the present disclosure. The olefin monomers include propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, styrene, alkyl acrylates, glycidyl acrylate, CH 2 =C(H)(CH 2 ) n C(O)(OR), CH 2 =C(H)C(O)(OR), CH 2 =CHC(O)R,,CH 2=C(H)-OC(O)R,,CH 2 =CH(OR), CH 2 =CHSi(R) 3-T (OR) T , or C.H. 2 Each R is an integer from 1 to 5, including, but not limited to, -H, substituted (C 1 -C 30 ) hydrocarbyl, unsubstituted (C 1 -C 30 ) hydrocarbyl, substituted (C 1 -C 30 ) heterohydrocarbyl, or unsubstituted (C 1 -C 30 ) heterohydrocarbyl. The subscript T is 0, 1, 2, or 3. The subscript n is 1 to 10.

[0057] In various embodiments of the polymerization process, the polar comonomers include alkyl acrylates, glycidyl acrylates, CH 2 =C(H)(CH 2 ) n C(O)(OR), CH 2 =C(H)C(O)(OR), CH 2 =CHC(O)R, CH 2 =C(H)-OC(O)R, CH 2 =CH(OR), CH 2 =CHSi(R) 3-T (OR) T , or C.H. 2 Each R is -H, a substituent (C 1 -C 30 ) hydrocarbyl, unsubstituted (C 1 -C 30 ) hydrocarbyl, substituted (C 1 -C 30 ) heterohydrocarbyl, or unsubstituted (C 1 -C 30 ) heterohydrocarbyl. The subscript T is 0, 1, 2, or 3. The subscript n is 1 to 10. In embodiments where the polar monomer is an alkyl acrylate, the polar ethylene-based copolymer may be deesterified to form an acrylic acid ethylene-based copolymer.

[0058] In some embodiments of the polymerization process, the alkyl acrylate monomer can be, by way of example and not limitation, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, or combinations thereof. In various embodiments, the alkyl acrylate has an alkyl group having 1 to 8 carbons. This includes C 2 -C 8 -alkyl acrylate. In certain embodiments, the alkyl acrylate is methyl acrylate, t-butyl acrylate, or n-butyl acrylate.

[0059] In some embodiments of the polymerization process, the optional α-olefin monomer can be, by way of example and not limitation, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, styrene, or combinations thereof.

[0060] In an exemplary embodiment, the catalyst system can include a procatalyst according to Formula (I), having the structure of Procatalyst 1 listed below. [ka]

[0061] Acid component A catalyst system including a procatalyst of formula (I) can be made catalytically active by removing the Lewis base coordinated to the Ni center. For example, a procatalyst with a procatalyst of formula (I) can be made catalytically active by contacting the complex with a Lewis acid or combining the complex with a Lewis acid. In some embodiments, the catalyst system may not include an acid component. Suitable acids for use herein include, for example, alkyl / aryl aluminum, polymeric or oligomeric alumoxanes (also known as aluminoxanes), or alkyl zincs. Combinations of one or more of the foregoing acids are also contemplated. The term "alkyl aluminum" refers to monoalkyl aluminum dihydrides or dihalides, dialkyl aluminum hydrides or halides, or trialkyl aluminum, or mixtures thereof. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum modified methylalumoxane, and isobutylalumoxane.

[0062] Suitable acids include those described herein (C 1 -C 20 In some embodiments, the Group 13 metal compound includes a tri((C 1 -C 20 )hydrocarbyl)-substituted aluminum or tri((C 1 -C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C 1 -C 20 )hydrocarbyl)-boron compounds, tri((C 1 -C 10 ) alkyl) aluminum, tri((C 6 -C 18)aryl)boron compounds, and their halogenated (including perhalogenated, particularly fluorinated or perfluorinated) derivatives. In a further embodiment, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, or tris(pentafluorophenyl)borane.

[0063] As a combination of neutral Lewis acids, tri((C 1 -C 4 ) alkyl) aluminum and tri((C) halide 6 -C 18 )aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments are such neutral Lewis acid mixtures in combination with polymeric or oligomeric alumoxanes, and a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, in combination with polymeric or oligomeric alumoxanes. The molar ratio of (procatalyst):(tris(pentafluorophenyl)borane):(alumoxane is from 1:1:1 to 1:10:30, and in other embodiments is from 1:1:1.5 to 1:5:10.

[0064] Ethylene / Acrylate Copolymer In various embodiments, the polymerization process of the present disclosure may produce an ethylene-based copolymer, where the polar ethylene-based copolymer contains at least 50 weight percent (wt%) ethylene, based on the weight of the polar ethylene-based copolymer. In some embodiments, the polar ethylene-based copolymer is the reaction product of 70 to 99.9 wt% ethylene units and 0.1 wt% to 30 wt% polar comonomer units, based on the total of the ethylene units and the polar comonomer units.

[0065] In one or more embodiments, the polymerization process of the present disclosure may include ethylene monomer, alkyl acrylate monomer, and optionally one or more α-olefins. In some embodiments of the polymerization process including α-olefins, the α-olefins may be incorporated into the produced polymer in an amount of 0.01 to 45 weight percent, based on the weight of the ethylene-based acid copolymer.

[0066] In various embodiments, the polymerization process of the present disclosure may produce ethylene-based acid copolymers having a molecular weight of 5,000 g / mol to 1,000,000 g / mol. In some embodiments, the polymers produced have a molecular weight of 25,000 g / mol to 900,000 g / mol, 30,000 g / mol to 800,000 g / mol, or 10,000 g / mol to 300,000 g / mol.

[0067] General procedure for PPR screening experiments Polyolefin catalysis screening was carried out in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consisted of an array of 48 single-cell (6 × 8 matrix) reactors in an inert atmosphere glove box. Each cell was equipped with a glass insert (reactor tube) with an internal working liquid volume of approximately 5 mL. Each cell had independent pressure control and was continuously stirred at 500 Hz. Catalyst, ligand, and metal precursor solutions, as well as optional activator solutions (if used), were prepared in toluene unless otherwise noted. Ligands were metallated at a 1:1 ligand:metal (L:M) ratio by premixing a solution of metal precursor with a solution of ligand, unless otherwise specified. All liquids (i.e., solvent, t-butyl acrylate, and catalyst solutions, as well as optional activator solutions (if used)) were added via robotic syringes. Gas reagents (i.e., ethylene) were added via a gas inlet. Before each run, the reactor was heated to 50° C., purged with ethylene, and vented. Tert-butyl acrylate was filtered through a short column of activated alumina to remove any polymerization inhibitors (e.g., 4-methoxyphenol) before use.

[0068] All desired cells were injected with t-butyl acrylate, followed by a portion of toluene. The reactor was heated to the run temperature and then pressurized with ethylene to the appropriate psig. The isolated catalyst complex or in situ metallated ligand and optional activator solution (if used) were then added to the cells. Each catalyst addition was chased with a small amount of toluene to bring the total reaction volume to 5 mL after the final addition. As the catalyst was added, the PPR software began monitoring the pressure of each cell. The desired pressure (within approximately 2-6 psig) was maintained by opening the valve at the set point minus 1 psi, closing the valve when the pressure reached 2 psi higher, and adding make-up ethylene gas. All pressure drops were recorded cumulatively as ethylene "uptake" or "conversion" for the duration of the run or until the uptake or conversion requirement was reached, whichever occurred first. Each reaction was then quenched by adding 1% oxygen in nitrogen for 30 seconds at 40 psi above the reactor pressure. The shorter the "quench time" (the time elapsed from the addition of the catalyst until the reaction was quenched), the more active the catalyst. To prevent the formation of excess polymer in any given cell, the reaction was quenched when a preset uptake level of 80 psig was reached. All reactors were quenched and then cooled to about 60°C. They were then vented and the reactor tubes were removed and placed in a centrifugal evaporator. The polymer samples were then dried in a centrifugal evaporator for 12 hours at 60°C and weighed to determine the polymer yield and were subjected to IR (t-butyl acrylate incorporation), GPC (molecular weight, polydispersity (PDI)), and DSC (melting point) analysis.

[0069] General procedure for batch reactor experiments Under a nitrogen atmosphere, 640 g of dry toluene was introduced into a 2 L stainless steel Parr reactor equipped with a rotating stirring shaft. Before being introduced into the reactor, tert-butyl acrylate was filtered through a short column of activated alumina to remove any polymerization inhibitors (e.g., 4-methoxyphenol). Tert-butyl acrylate was added to the reactor in neat form (see Table 2 for amounts) by a nitrogen pressurized shot tank. The shot tank was rinsed twice with toluene, and the rinse was also transferred to the reactor. The reactor was heated to the desired temperature and pressure, and then a toluene solution of the catalyst was added to the reactor by a nitrogen pressurized shot tank. The shot tank was rinsed twice with toluene, and the rinse was also transferred to the reactor. Ethylene was continuously fed to the reactor to maintain a pressure of 400 psi. After the desired uptake of ethylene was achieved, or otherwise after the set reaction time, the ethylene feed was stopped. The reactor contents were then dumped into a covered dump pot containing Irganox as a quenching agent. The contents of the dump pot were placed into an open stainless steel tray in a fume hood and the volatiles were allowed to evaporate for 2 days. The tray was then transferred to a vacuum oven for further drying. Polymer samples were scraped from the tray, weighed, and submitted for further analysis.

[0070] GPC procedure High temperature GPC analysis was performed using a Dow Robot Assisted Delivery (RAD) system equipped with a Polymer Char infrared detector (IR5) and an Agilent PLgel Mixed A column. Decane (10 μL) was added to each sample for use as an internal flow marker. Samples were first diluted to a concentration of 10 mg / mL in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxyltoluene (BHT) and dissolved by stirring at 160 °C for 120 min. Prior to injection, samples were further diluted to a concentration of 3 mg / mL in TCB stabilized with BHT. Samples (250 μL) were eluted through one PL-gel 20 μm (50 mm x 7.5 mm) guard column followed by two PL-gel 20 μm (300 mm x 7.5 mm) Mixed-A columns, maintained at 160 °C in TCB stabilized with BHT at a flow rate of 1.0 mL / min. The total run time was 24 minutes. To calibrate the molecular weight (MW), Agilent EasiCal polystyrene standards (PS-1 and PS-2) were dissolved by diluting with 1.5 mL of TCB stabilized with BHT and stirring at 160° C. for 15 minutes. These standards were analyzed to generate a third-order MW calibration curve. The molecular weight units were converted from polystyrene (PS) to polyethylene (PE) units using a 1-day Q factor calculated to be approximately 0.4 using an average of five Dowlex 2045 reference samples.

[0071] FT-IR procedure A 10 mg / mL sample prepared for GPC analysis was also utilized to quantify t-butyl acrylate (tBA) incorporation by Fourier transform infrared spectroscopy (FTIR). The Dow robotic preparation station heated and stirred the sample at 160 °C for 60 min, then deposited 130 μL portions into stainless wells promoted on silicon wafers. The TCB was evaporated at 160 °C under a nitrogen purge. Resolution 4 cm -1 4000~400cm using 128 scans -1IR spectra were collected using a Nexus 6700 FT-IR equipped with a DTGS KBr detector. tBA (C=O: 1762–1704 cm -1 ) of ethylene (CH 2 :736~709cm -1 ) was calculated and fitted to a linear calibration curve to determine total tBA.

[0072] DSC procedure The melting temperature (Tm), glass transition temperature (Tg), crystallization temperature (Tc), and heat of solution were measured by differential scanning calorimetry (DSC Q2000, TA Instruments, Inc.) using a heat-cool-heat temperature profile. Open-pan DSC samples of 3–6 mg of polymer were subjected to the following temperature profile and traces were analyzed individually using TA Universal analysis software or TA Instruments TRIOS software. Equilibrate at 175.00°C Isothermal for 3 minutes Rise to 0.00°C at 30.00°C / min Rise to 175.00°C at 10.00°C / min The present invention includes the following aspects. Section 1. A catalyst system comprising a procatalyst having a structure according to formula (I): [ka] During the ceremony, M is nickel(II) or palladium(II); X is (C 1 -C 40 ) hydrocarbyl, (C 1 -C 40 ) heterohydrocarbyl, -CH 2 Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C )3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C ) 2 , -NH(R C ), -N(Si(R C ) 3 ) 2 , -NR C Si(R C ) 3 , -NHSi(R C ) 3 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , -OCF 3 , -S(O)R C , -S(O) 2 R C , -OS(O) 2 R C , -N=C(R C ) 2 , -N=CH(R C ), -N=CH 2 , -N=P(R C ) 3、 -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C ) 2 , -C(O)NHR C , -C(O)NH 2 , halogen, or hydrogen; C are independently substituted or unsubstituted (C 1 -C 30) hydrocarbyl, or substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl, Q is 0, 1, 2, or 3, and W is 0, 1, or 2; each Y is a Lewis base; and X and Y are optionally linked; Z 1 , Z 2 , Z 3 is independent, C(R Z ) or nitrogen, and each R Z are independent, and the substitution (C 1 -C 30 ) hydrocarbyl, unsubstituted (C 1 -C 30 ) hydrocarbyl, substituted (C 1 -C 30 ) Heterohydrocarbyl, unsubstituted (C 1 -C 30 ) heterohydrocarbyl, -CH 2 Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C ) 2 , -NH(R C ), -N(Si(R C ) 3 ) 2 , -NR C Si(R C ) 3 , -NHSi(R C ) 3, -OR C , -SR C , -NO 2 , -CN, -CF 3 , -OCF 3 , -S(O)R C , -S(O) 2 R C , -OS(O) 2 R C , -N=C(R C ) 2 , -N=CH(R C ), -N=CH 2 , -N=P(R C ) 3 , -OC(O)R C , -C(O)OR C , -N(R C )C(O)R C , -C(O)N(R C ) 2 , -N(R C )C(O)H, -NHC(O)R C , -C(O)N(R C ) 2 , -C(O)NHR C , -C(O)NH 2 , halogen, or hydrogen; Q is 0, 1, 2, or 3; W is 0, 1, or 2; and each R C are independently substituted or unsubstituted (C 1 -C 30 ) hydrocarbyl, or substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl, or hydrogen, but Z 1 , Z 2 , and Z 3 At least one of C(R Z ), R 1 , R 2 , R 3 , and R 4 is independent, (C 1 -C 50 ) hydrocarbyl and (C 1 -C 50 ) heterohydrocarbyl; Z 1 and Z2 Both are C(R Z ), optionally each group R Z are linked to form a ring structure, Z 2 and Z 3 Both are C(R Z ), optionally each group R Z are linked to form a ring structure, Z 1 , Z 2 , and Z 3 All of the above are C(R Z ), optionally each group R Z are linked to form a multiple ring structure, Optionally, R 1 and R 2 are linked to form a ring structure, Optionally, R 3 and R 4 are linked to form a ring structure, a catalytic system. Section 2. Z 1 and Z 2 But, C(R Z ) and each group R Z are linked to form a six-membered aromatic ring structure, and the procatalyst has a structure according to formula (II): [ka] During the ceremony, M, R 1 , R 2 , R 3 , R 4 , Z 3 , X, and Y are as defined in formula (I); R Z1 , R Z2 , R Z3 , and R Z4 are independently -H, (C 1 -C 20 ) hydrocarbyl, or (C 1 -C 40 Item 2. The catalyst system according to item 1, wherein the heterohydrocarbyl is a heterohydrocarbyl. Section 3. Z 2 and Z 3 But, C(R Z ) and each group R Z are linked to form a six-membered aromatic ring structure, and the procatalyst has a structure according to formula (III): [ka] During the ceremony, M, R 1 , R 2 , R 3 , R 4 , Z 1 , X, and Y are as defined in formula (I); R Z5 , R Z6 , R Z7 , and R Z8 are independent, -H, (C 1 -C 40 ) hydrocarbyl, or (C 1 -C 40 Item 2. The catalyst system according to item 1, wherein the heterohydrocarbyl is a heterohydrocarbyl. Section 4. R 1 , R 2 , R 3 , and R 4 Item 4. The catalyst system according to any one of items 1 to 3, wherein each is independently substituted phenyl, unsubstituted phenyl, substituted naphthyl, unsubstituted naphthyl, substituted anthracenyl, or unsubstituted anthracenyl. Section 5. R 1 , R 2 , R 3 , and R 4 5. The catalyst system according to any one of items 1 to 4, wherein is 2,6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-diphenoxyphenyl, 2,4,6-triethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-phenylphenyl, or 2,6-diisopropoxyphenyl. Section 6. R 1 , R 2 , R 3 , and R 4 However, (C 1 -C18 4. The catalyst system according to any one of items 1 to 3, wherein R is an alkyl group. Section 7. R 1 and R 2 are linked to form a five-membered ring structure, and / or R 3 and R 4 are linked to form a five-membered ring structure. Section 8. Z 1 The catalyst system according to any one of items 1 and 3 to 7, wherein is N. Section 9. Z 2 The catalyst system according to any one of items 1 and 3 to 7, wherein is N. Section 10. Z 3 The catalyst system according to any one of items 1 or 2 and 4 to 7, wherein is N. Section 11. Z 1 and Z 3 The catalyst system according to any one of items 1 and 4 to 8, wherein is N. Section 12. Z 1 and Z 3 But, C(R Z ) and each R Z is -H and Z 2 But, C(R Z ) and each of the R Z -H, substitution (C 1 -C 20 ) Alkyl, unsubstituted (C 1 -C 20 ) Alkyl, Substituted (C 6 -C 18 )Aryl, unsubstituted (C 1 -C 20 ) Heteroalkyl, substituted (C 6 -C 18 ) Heteroaryl, unsubstituted (C 6 -C 18 ) Aryl, -OR N , -SR N , -SO 3 R N , -SiRN 3 , halogen, -N(R N ) 2 , -P(R P ) 2 , or -P(O)(R P ) 2 Each R N are independently substituted and unsubstituted (C 6 -C 18 ) aryl or (C 1 -C 18 ) alkyl or halogen, and each R P are independently substituted or unsubstituted (C 6 -C 18 ) aryl or substituted or unsubstituted (C 1 -C 18 ) alkyl, -OR P The catalyst system according to any one of items 1 and 4 to 7, Section 13. Z 1 and Z 3 But, C(R Z ) and each R Z is -H and Z 2 But, C(R Z ) and each of the R Z phenyl, pentafluorophenyl, 3,5-di-trifluoromethylphenyl, -CF 3、 -NMe 2 , -PPh 2、 -P(O)Ph 2 -OMe, -SiMe 3 , -SiPh 3 Item 8. The catalyst system according to any one of items 1 and 4 to 7, wherein the aryl group is selected from the group consisting of aryl, aryl, di-tBu-aryl, anthracenyl, di-tBu-anthracenyl, -F, and -Cl. Section 14. Z 1 and Z 3 But, C(R Z ) and each R Z is -H and Z 2 But, C(R Z ) and each of the R ZItem 1 and any one of items 4 to 6, wherein is methyl, ethyl, 2-propyl, n-propyl, n-butyl, tert-butyl, 2-methylpropyl, pentyl, hexyl, heptyl, octyl, n-octyl, tert-octyl, nonyl, decyl, undecyl, dodecyl. Section 15. X may be substituted or unsubstituted (C 1 -C 30 ) hydrocarbyl, substituted or unsubstituted (C 1 -C 30 Item 2. The catalyst system according to item 1, wherein the heterohydrocarbyl is a heterohydrocarbyl. Section 16. Item 2. The catalyst system of item 1, wherein X is methyl, 2,2-dimethylpropyl, trimethylsilylmethyl, (n-butyl)dimethylsilylmethyl, (n-hexyl)dimethylsilylmethyl, (n-octyl)dimethylsilylmethyl, or benzyl. Section 17. 1. A polymerization process comprising: 10. A polymerization process comprising polymerizing ethylene and optionally an olefin monomer under olefin polymerization conditions in the presence of a catalyst system to form an ethylene-based copolymer, said catalyst system comprising a metal-ligand complex according to formula (I) as defined in any one of the preceding claims. Section 18. The olefin monomer is propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, styrene, alkyl acrylate, glycidyl acrylate, CH 2 =C(H)(CH 2 ) n C(O)(OR), CH 2 =C(H)C(O)(OR), CH 2 =CHC(O)R, CH 2 =C(H)-OC(O)R, CH 2 =CH(OR), CH 2 =CHSi(R) 3-T (OR) T , or C.H. 2 =CHCl, R is -H, substituted (C 1-C 30 ) hydrocarbyl, unsubstituted (C 1 -C 30 ) hydrocarbyl, substituted (C 1 -C 30 ) heterohydrocarbyl, or unsubstituted (C 1 -C 30 ) heterohydrocarbyl; T is 0, 1, 2, or 3; The polymerization process wherein n is 1 to 10. Section 19. A procatalyst according to any of the structures of the present disclosure. EXAMPLES

[0073] Examples 1-2 provide synthetic procedures for the ligand intermediates, ligands, and isolated procatalysts. Examples 3 and 4 tabulate and discuss the results of polymerization reactions of procatalyst 1. One or more features of the present disclosure are illustrated in view of the following examples.

[0074] Example 1 - Synthesis of 2,6-bis(bis(2',6'-dimethoxyphenyl)phosphino)-4-tert-butylphenol (POP-H). A Schlenk flask fitted with a screw-on Teflon stopper was charged with a solution of 1,3-dibromo-5-(tert-butyl)-2-(methoxymethoxy)benzene (3.52 g, 10.0 mmol) in THF (40 mL) and cooled to −78° C. under nitrogen. A solution of n-butyllithium in hexanes (4 mL, 2.5 M, 10.0 mmol) was added dropwise via syringe. After stirring for an additional 30 minutes, a solution of bis(2,6-dimethoxyphenyl)phosphine chloride (3.41 g, 10.0 mmol) in THF (20 mL) was added dropwise via cannula. After complete addition, the reaction was allowed to warm to room temperature and stirred for an additional 3 hours to give a yellow solution. The reaction mixture was then cooled to −78° C. and a solution of n-butyllithium in hexanes (4 mL, 2.5 M, 10.0 mmol) was added dropwise via syringe. After stirring for an additional 30 min, a solution of bis(2,6-dimethoxyphenyl)phosphine chloride (3.41 g, 10.0 mmol) in THF (20 mL) was added dropwise via cannula. After complete addition, the reaction was allowed to warm to room temperature and stirred for an additional 3 h to give a bright orange solution. The volatiles were then removed under vacuum. The pale yellow-white residue, CH 2 Cl 2 (20 mL) was added degassed MeOH (10 mL) and concentrated aqueous HCl (5 mL). The resulting mixture was stirred at room temperature for 8 h, then the volatiles were removed in vacuo once more. 2 The resulting orange residue was dissolved in CH 2 Cl 2 (40 mL) and K 2 CO 3 (10 mL × 3) and NH 4The solid was washed with a saturated aqueous solution of Cl (10 mL x 3). The volatiles were removed under reduced pressure. In a glove box (water and oxygen excluded), the resulting pale yellow solid was dissolved in ether and filtered through Celite. The volatiles were removed once more under vacuum, the resulting mixture was washed with hexanes (10 mL), and the solid was collected via vacuum filtration to give 2,6-bis(bis(2',6'-dimethoxyphenyl)phosphino)-4-tert-butylphenol (POP-H) (1.68 g, 2.2 mmol, 22%) as a white powder.

[0075] 1 H NMR (400 MHz, C 6 D 6 ):δ 7.56-7.54(d,2H,ArH),7.50(s,1H,OH),7.03-6.99(t,4H,ArH),6.26-6.23(dd,8H,ArH),3.13(s,24H,OCH 3 ), 1.17(s,9H,C(CH 3 ) 3 ); 13 C NMR (400 MHz, C 6 D 6 ):162.52(d,aryl-C),159.09(t,Ar-C),138.94(t,Ar-C),130.83(d,Ar-C),128 .92(s,Ar-C),121.97(d,Ar-C),115.16(d,Ar-C),104.20(s,Ar-C),55.12(s,OCH 3 ), 33.95(s,C(CH 3 ) 3 ), 31.65(s,C(CH 3 ) 3 ); 31 P NMR (400 MHz, C 6 D 6 ):-55.61(s).

[0076] Example 2 - Synthesis of POP-Ni(pyridine)(CH 2 Sim 3 ) complex, procatalyst 1 Step 1-(Pyridine) 2 Ni(CH 2 Si(CH 3) 3 ) 2 Preparation of In a nitrogen filled glove box, a reaction jar was charged with tetrakis(pyridine)nickel dichloride (1.78 g, 3.99 mmol, 1 equiv.), diethyl ether (40 mL), and pyridine (0.51 mL). The jar was chilled in a -35°C freezer for 3 days. The jar was removed from the freezer and diluted with Et 2 A 1.0 M solution of trimethylsilylmethylmagnesium chloride in 2H2O (8.0 mL, 8.0 mmol, 2 equiv.) was added slowly. During the addition, the blue solid turned blue-green and finally beige. The reaction mixture was stirred at room temperature for 15 min, after which the suspension was observed to be brown in color. The solution was concentrated in vacuo over 15 min to give a dark brown slurry. The brown slurry was triturated with pentane (20 mL) and concentrated in vacuo. A solution of pentane (120 mL) and pyridine (1.2 mL) was prepared. The brown solid was triturated with a pentane / pyridine solution (40 mL) and filtered through a pad of Celite (this process was repeated a total of three times). The combined filtrates were concentrated in vacuo to a volume of 40 mL. The red solution was placed in a -35°C freezer for 20 h to precipitate a crystalline solid. The suspension was filtered, washed with cold (-30°C) pentane (10 mL) and dried under vacuum to give a dark red crystalline solid (0.770 g, 49% yield).

[0077] Step 2 - POP-Ni(pyridine)(CH 2 Sim 3 ) Complex-Procatalyst 1 In a glove box, add (pyridine) to a 20 mL vial. 2 Ni(CH 2 Si(CH 3 ) 3 ) 2(22 mg, 0.0593 mmol) and benzene (2 mL). To this solution was added a solution of 2,6-bis(bis(2',6'-dimethoxyphenyl)phosphino)-4-tert-butylphenol (POP-H, 42.83 mg, 0.0563 mmol) in benzene (4 mL). A drop of pyridine was added to the mixture and the resulting solution was stirred in a glove box for 2 h to form a red-brown solution. All volatiles were removed under vacuum and the residue was extracted with hexane, filtered and dried in vacuum to give the complex as a dark yellow solid (44 mg, 76%).

[0078] 1 H NMR (400 MHz, C 6 D 6 ):δ 8.94-8.92(m,2H,ArH),(s,1H,OH),7.47-7.43(m,1H,ArH),7.08-7.04(t,2H,ArH),7.04-7.00(t,2H,ArH),6.95-6.92(m,1 H,ArH),6.83-6.79(m,1H,ArH),6.47-6.43(m,2H,ArH),6.34-6.32(dd,4H,ArH),6.29-6.26(dd,4H,ArH),3.36(s,12H,OCH) 3 ), 3.28(s,12H,OCH 3 ), 1.13(s,9H,C(CH 3 ) 3 ), 0.12(s,9H,Si(CH 3 ) 3 ),-0.71--0.74(s,2H,NiCH 2 Si),; 13 C NMR (400 MHz, C 6 D 6):163.54(d,Ar-C),163.42(d,Ar-C)151.15(s,Ar-C),132.93(d,Ar-C),12 9.84(m,Ar-C),129.76(s,Ar-C),128.78(d,Ar-C),128.37(s,Ar-C),128.1 9(s,Ar-C),125.05(t,Ar-C),122.69(d,Ar-C),118.20(d,Ar-C),112.32(s ,Ar-C),111.86(s,Ar-C),104.67(s,Ar-C),104.45(d,Ar-C),55.66(d,OCH 3 ),55.13(d,OCH 3 ), 33.70(s,C(CH 3 ) 3 ), 31.98(s,C(CH 3 ) 3 ), 2.15(s,Si(CH 3 ) 3 ),-18.25(d,NiCH 2 Si); 31 P NMR (400 MHz, C 6 D 6 ):-5.28,-5.35(d),-52.06,-52.13(d).

[0079] Example 3 - Polymerization reaction in parallel pressure reactors The catalytic activity (in terms of quench time and polymer yield) as well as the resulting polymer properties were evaluated for procatalyst 1. The polymerization reactions were carried out in a parallel pressure reactor (PPR) as previously described.

[0080] In these experiments, the ligand was metallized in situ by combining a 2 mM solution of the ligand in toluene with a 2 mM solution of bis(trimethylsilylmethyl)bis(pyridine)nickel(II) in toluene to form a yellow solution. The solution was stirred at room temperature for 30 min and then sent to a dry box containing a PPR reactor. Copolymerization experiments were performed at 400 psi ethylene pressure with a catalyst loading of 0.25 μmol. Reactor temperature and tert-butyl acrylate loading were varied as shown in Table 1. Each entry in Table 1 represents the average of at least two replicate runs. [Table 1]

[0081] At various reactor temperatures and acrylate loadings, catalyst systems containing procatalyst 1 produced polymers containing various amounts of t-butyl acrylate (t-BA).

[0082] Example 4 - Batch Reactor Polymerization Reaction In this experiment, the procatalyst was introduced into the reactor as a toluene solution of the isolated metal complex (see Example 2). The copolymerization experiment was carried out at 400 psi ethylene pressure with a catalyst loading of 59.2 μmol. The reactor temperature and t-butyl acrylate loading were as shown in Table 2. [Table 2]

Claims

1. A catalyst system comprising a procatalyst having a structure according to formula (I): 【Chemistry 1】 During the ceremony, M is nickel(II) or palladium(II); X is -CH ２ Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -OSi(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , and -Ge(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ and each R Ｃ is independent, (C １ -C ３０ ) hydrocarbyl or (C １ -C ３０ ) heterohydrocarbyl, Q is 0, 1, 2, or 3; Each Y is (C １ -C ３０ ) an organic Lewis base which is a heterohydrocarbyl, provided that a heteroatom of the Lewis base is capable of forming a coordinate bond with M; X and Y are optionally linked; Z １ , Z ２ , and Z ３ But C(R Ｚ ) and each group R Ｚ is independent, (C １ -C ３０ ) hydrocarbyl, (C １ -C ３０ ) heterohydrocarbyl, or hydrogen; and optionally, Z １ , Z ２ , and Z ３ Each group R Ｚ at least two of are linked to form a ring structure or multiple ring structure; R １ , R ２ , R ３ , and R ４ is independently selected from the group consisting of substituted phenyl, unsubstituted phenyl, substituted naphthyl, unsubstituted naphthyl, substituted anthracenyl, and unsubstituted anthracenyl; Catalyst system.

2. Z １ and Z ２ Each group R Ｚ are linked to form a six-membered aromatic ring structure, and the procatalyst has a structure according to formula (II): 【Chemistry 2】 During the ceremony, M.R. １ , R ２ , R ３ , R ４ , Z ３ , X, and Y are as defined in formula (I); R Ｚ１ , R Ｚ２ , R Ｚ３ , and R Ｚ４ are independently -H, (C １ -C ２０ ) hydrocarbyl, or (C １ -C ４０ 2. The catalyst system of claim 1, wherein said heterohydrocarbyl is aryl;

3. Z ２ and Z ３ Each group R Ｚ are linked to form a six-membered aromatic ring structure, and the procatalyst has a structure according to formula (III): 【Chemistry 3】 During the ceremony, M.R. １ , R ２ , R ３ , R ４ , Z １ , X, and Y are as defined in formula (I); R Ｚ５ , R Ｚ６ , R Ｚ７ , and R Ｚ８ are independently -H, (C １ -C ４０ ) hydrocarbyl, or (C １ -C ４０ 2. The catalyst system of claim 1, wherein said heterohydrocarbyl is aryl;

4. R １ , R ２ , R ３ , and R ４ 2. The catalyst system of claim 1, wherein is independently 2,6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-diphenoxyphenyl, 2,4,6-triethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-phenylphenyl, or 2,6-diisopropoxyphenyl.

5. 2. The catalyst system of claim 1 , wherein the procatalyst has the following structural formula: 【Chemistry 4】

6. Z １ and Z ３ Each group R Ｚ The catalyst system of claim 1, wherein is -H.

7. Z １ and Z ３ Each group R Ｚ is -H, and Z ２ Group R Ｚ is phenyl, pentafluorophenyl, 3,5-di-trifluoromethylphenyl, -CF ３、 -NMe ２ , -PPh ２、 -P(O)Ph ２ -OMe, -SiMe ３ , -SiPh ３ , carbazole, di-tBu-carbazole, anthracenyl, and di-tBu-anthracenyl.

8. Z １ and Z ３ Each group R Ｚ is -H, and Z ２ Group R Ｚ 2. The catalyst system of claim 1, wherein is methyl, ethyl, 2-propyl, n-propyl, n-butyl, tert-butyl, 2-methylpropyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl.

9. Z ２ Group R Ｚ 9. The catalyst system of claim 8, wherein is n-octyl or tert-octyl.

10. 2. The catalyst system of claim 1, wherein X is trimethylsilylmethyl, (n-butyl)dimethylsilylmethyl, (n-hexyl)dimethylsilylmethyl, or (n-octyl)dimethylsilylmethyl.

11. 1. A polymerization process comprising: A polymerization process comprising polymerizing ethylene and alkyl acrylate monomers, and optionally one or more α-olefin monomers, under olefin polymerization conditions in the presence of the catalyst system of any one of claims 1 to 10 to form an ethylene-based copolymer.

12. The α-olefin monomer is propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, styrene, alkyl acrylate, glycidyl acrylate, CH ２ = C(H)(CH ２ ) ｎ C(O)(OR), CH ２ =C(H)C(O)(OR), CH ２ =CHC(O)R,CH ２ =C(H)-OC(O)R, CH ２ =CH (OR), CH ２ =CHSi(R) ３－Ｔ (OR) Ｔ , or C.H. ２ =CHCl, R is -H, substituted (C １ -C ３０ ) hydrocarbyl, unsubstituted (C １ -C ３０ ) hydrocarbyl, substituted (C １ -C ３０ ) heterohydrocarbyl, or unsubstituted (C １ -C ３０ ) heterohydrocarbyl; T is 0, 1, 2, or 3; The polymerization process of claim 11, wherein n is 1 to 10.

13. A procatalyst having a structure according to formula (I): 【Chemistry 1】 During the ceremony, M is nickel(II) or palladium(II); X is -CH ２ Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , -OSi(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ , and -Ge(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ and each R Ｃ is independent, (C １ -C ３０ ) hydrocarbyl or (C １ -C ３０ ) heterohydrocarbyl, Q is 0, 1, 2, or 3; Each Y is (C １ -C ３０ ) an organic Lewis base which is a heterohydrocarbyl, provided that a heteroatom of the Lewis base is capable of forming a coordinate bond with M; X and Y are optionally linked; Z １ , Z ２ , and Z ３ But C(R Ｚ ) and each group R Ｚ is independent, (C １ -C ３０ ) hydrocarbyl, (C １ -C ３０ ) heterohydrocarbyl, or hydrogen; and optionally, Z １ , Z ２ , and Z ３ Each group R Ｚ at least two of are linked to form a ring structure or multiple ring structure; R １ , R ２ , R ３ , and R ４ is independently selected from the group consisting of substituted phenyl, unsubstituted phenyl, substituted naphthyl, unsubstituted naphthyl, substituted anthracenyl, and unsubstituted anthracenyl; Pro Catalyst.

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