Use of transition metal catalysts for the production of linear ethylene / polar copolymers in high-pressure processes

Abstract

Ethylene, and one or more polar comonomers, and optionally one or more (C3-C3) 12 A process for polymerizing α-olefins and optionally aluminum compounds in the presence of a catalyst system to form ethylene copolymers in a high-pressure reactor at a pressure greater than 1000 barg and a temperature greater than 100°C, wherein the catalyst system includes a transition metal catalyst.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the interests of U.S. Provisional Patent Application No. 63 / 511,257, filed June 30, 2023, the contents of which are incorporated herein by reference in their entirety.

[0002] (Field of Invention) Embodiments of the present disclosure generally relate to polymerization processes of ethylene and polar comonomers for producing linear ethylene copolymers, and more specifically, to polymerization processes carried out at high temperature and high pressure that incorporate a catalytic system having a transition metal catalyst. [Background technology]

[0003] Commercially, 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). Methods for copolymerizing ethylene with polar group-containing vinyl monomers (e.g., vinyl acetate and (meth)acrylate) by radical polymerization under high temperature (above 100°C) and high pressure (above 1000 barg) are well known. However, these methods result in copolymers with relatively low heat resistance (low melting temperature due to their low crystallinity and high long-chain branching).

[0004] Coordination catalysis in solution provides a route to highly linear ethylene / acrylate copolymers with a structure similar to linear low-density polyethylene (LLDPE). Linear ethylene / acrylate copolymers formed by coordination catalysis exhibit higher crystallinity and higher thermal resistance than copolymers formed by radical processes. Both Ni and Pd catalysts have been reported for copolymerization of ethylene and acrylate monomers in solution at relatively low ethylene pressures (10–50 barg). However, the reported catalytic efficiencies are typically very low. The reported Ni and Pd catalysts also exhibit significant deactivation in solution at temperatures above 120°C, and the Mw of the copolymer decreases sharply at temperatures above 90°C. [Overview of the project]

[0005] There is a continuing need to develop improved processes for the copolymerization of ethylene and acrylate comonomers to obtain highly linear copolymers. This process should promote both high ethylene copolymerization activity and high incorporation of alkyl acrylate comonomers, thereby producing highly linear copolymers. Linear ethylene / alkyl acrylate copolymers can exhibit improved molecular weight distribution and increased melting temperatures. Solution-based processes using Ni and Pd catalysts produce highly linear copolymers, but at low rates. These rates can be improved by introducing the Ni or Pd catalyst into a reactor at high pressure (over 1000 barg) and high temperature (over 100°C), where the copolymerization reaction occurs in supercritical ethylene. This leads to the production of highly linear copolymers at increased rates and higher molecular weights.

[0006] Embodiments of this disclosure include a polymerization process. This process comprises ethylene, one or more polar comonomers, and optionally one or more (C3-C3) 12)Polymerize an α-olefin and optionally an aluminum species in the presence of a catalyst system to form an ethylene-based copolymer in a high-pressure reactor at a pressure above 1000 barg and a temperature above 100 °C, the catalyst system comprising a transition metal catalyst.

[0007] In one or more embodiments, the transition metal catalyst comprises nickel(II) or palladium(II). In some embodiments, the transition metal catalyst or transition metal precatalyst comprises nickel(II) or palladium(II) and has a structure according to formula (I).

[0008]

Chemical formula

[0009] M is nickel(II) or palladium(II), and X is (C1-C 40 )hydrocarbyl, (C1-C 40 )heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q 、-OSi(R C ) 3-Q (OR C ) Q 、-Ge(R C ) 3-Q (OR C ) Q 、-P(R C ) 2-W (OR C ) W [[ID=�0]]、-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 A ligand selected from -C(O)NH2, halogens, or hydrogen, and each R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, or substituted or unsubstituted (C1~C 30 ) is a heterohydrocarbyl, where Q is 0, 1, 2, or 3, and W is 0, 1, or 2.

[0010] In formula (I), each Y is a Lewis base, and X and Y are linked together by arbitrary choice. P is phosphorus.

[0011] In formula (I), R 1 These are independently -H, (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -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(=O)(R P ) 2、 -P(R C )2-W (OR C ) W 、 -P(O)(R C ) 2-W (OR C ) W 、 -Ge(R C )3、 -P(R P )2、 -N(R N )2、 -OR C 、 -SR C 、 -NO2、 -CN、 -CF3、 R C S(O)-、 R C S(O)2-、 -N=C(R C )2、 R C C(O)O-、 R C OC(O)-、 R C C(O)N(R)-、 (R C )2NC(O)-、 halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV).

[0012] [Chemical formula]

[0013] In formula (II), (III), and (IV), each of R 31~35 , R 41~48 , and R 51~59 is independently -H, (C₁-C 40 ) hydrocarbyl, (C₁-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C [[ID=8​​​​​) Selected from 2NC(O)- or halogen.

[0014] In formula (I), R 2 , R 3 , and R 4 These are independently, substitutions (C1~C 30 ) Hydrocarbyl, unsubstituted (C1~C 30 ) Hydrocarbyl substitution (C1~C 30 ) Heterohydrocarbyl, unsubstituted (C1~C 30 ) Heterohydrocarbyl, -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 )2, -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=P(R C )3, -OC(O)R C , -C(O)OR C ,-N(R)C(O)R C ,-C(O)N(R C )2, or selected from halogen, each R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, or substituted or unsubstituted (C1~C 30 ) is a heterohydrocarbyl, where Q is 0, 1, 2, or 3, and W is 0, 1, or 2.

[0015] In formula (I), R 5 and R 6 These are independently, substitutions (C1~C 30 ) Hydrocarbyl, unsubstituted (C1~C 30 ) Hydrocarbyl substitution (C1~C 30 ) Heterohydrocarbyl, or unsubstituted (C1~C 30 ) Selected from heterohydrocarbyl.

[0016] In some embodiments, in formula (I), R is optionally replaced with 5 and R 6 However, they are linked to form a ring structure, or optionally, R 2 and R 3 However, they are linked to form a ring structure, or optionally, R 3 and R 4 However, they are connected to form a ring structure. [Brief explanation of the drawing]

[0017] [Figure 1] This is a graph of the melting temperature of acrylate / ethylene copolymers as a function of the weight percentage (W%) of polar comonomers. [Modes for carrying out the invention]

[0018] Herein, specific embodiments of the catalyst system will be described. It should be understood that the catalyst system of this disclosure may be embodied in different forms and should not be construed as being limited to the specific embodiments described herein. Rather, embodiments are provided so as to ensure that this disclosure is thorough and complete and fully conveys the scope of the subject matter to those skilled in the art.

[0019] Common abbreviations are listed below.

[0020] 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, Et2O: Diethyl ether, CH2Cl2: Dichloromethane, siRNA: Ethyl acetate, C6D6: Deuterated benzene or benzene-d6: CDCl3: Deuterated chloroform, Na2SO4: Sodium sulfate, MgSO4: Magnesium sulfate, HCl: hydrogen chloride, n-BuLi: butyllithium, t-BuLi: tert-butyllithium, K2CO3: potassium carbonate, N2: nitrogen gas, PhMe: toluene, PPR: parallel pressure reactor, MAO: methyl aluminoxane, MMAO: modified methyl aluminoxane, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimoles, mL: milliliters, M: molar concentration, min or mins: minutes, h or hrs: hours, d: days, R f : Retention factor, TLC: Thin-layer chromatography, rpm: Revolutions per minute.

[0021] The term "independently selected" and the subsequent multiple options are in R 1 , R 2 , R 3 , and R C These terms are used herein to indicate that each individual base appearing before the term may be identical or different, and that there is no dependency on the identity of any other base appearing before the term.

[0022] The term "procatalyst" refers to a compound that, after activation, exhibits catalytic activity during the removal of a Lewis base coordinated to, for example, a Ni or Pd metal center.

[0023] When used to describe a chemical group containing a specific carbon atom, use "(C x ~C y A parenthetical expression in the form of ")" means that the unsubstituted form of the chemical group has x carbon atoms 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, a particular chemical group is R S It may be substituted by one or more substituents such as R S This generally represents any substituent as defined herein. (C) x ~C y The R of the chemical group defined using ) S The substitution version is any base R S Depending on the identity, it may contain more than y carbon atoms. For example, "R S Strictly speaking, one group R is phenyl (-C6H5). S Replaced by (C1~C 50 )alkyl can contain 7 to 56 carbon atoms. Therefore, generally, the parenthetical "(C x ~C y A chemical group defined using ) is a substituent containing one or more carbon atoms R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is, respectively, all carbon-containing substituents R in both x and y. S It is determined by adding up the total number of carbon atoms from each origin.

[0024] The term "substitution" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is a substituent (e.g., R S It means that all hydrogen atoms (H) bonded to the carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents (e.g., R). SThis means that all hydrogen atoms are replaced by fluorine atoms. Therefore, "perfluorinated alkyl" is an alkyl group in which all hydrogen atoms are replaced by fluorine atoms. The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to the carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0025] (C1~C 50 The term "hydrocarbyl" refers to a hydrocarbon radical consisting of 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical having 1 to 50 carbon atoms, and each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (having 3 or more carbon atoms, including monocyclic and polycyclic, condensed and non-condensed polycyclic, and bicyclic) or acyclic, and contains 1 or more R S It is either replaced by or not replaced by.

[0026] In this disclosure, (C1~C 50 ) Hydrocarbyls include the following groups: (C1~C 50 ) alkyl, (C3~C 50 )Cycloalkyl, (C3~C 20 )Cycloalkyl-(C1~C 20 ) Alkilen, (C6~C 40 )aryl, or (C6~C 20 )aryl-(C1~C 20 Examples include, but are not limited to, unsubstituted or substituted forms of alkylenes (e.g., benzyl(-CH2-C6H5)).

[0027] (C1~C 50 )alkyl" and "(C1~C 18 The term "alkyl" refers to an unsubstituted or one or more R SThese refer to saturated linear or branched hydrocarbon radicals of 1 to 50 carbon atoms and saturated linear or branched hydrocarbon radicals of 1 to 18 carbon atoms, respectively, which are substituted by (C1-C). The radical can be located on any one carbon atom of the alkyl group. Unsubstituted (C1-C 50 Examples of alkyl groups include unsubstituted (C1~C 20 ) alkyl, unsubstituted (C1~C 10 ) Alkyl, unsubstituted (C1~C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 2,2-dimethylpropyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Substituted (C1~C 40 Examples of alkyl groups include substitutions (C1~C 20 ) alkyl, substituted (C1~C 10 ) alkyl, trifluoromethyl, and [C n It is alkyl. [C n The term "alkyl" refers to a radical that contains substituents but contains up to n carbon atoms, where n is an integer from 1 to 45. For example, [C 45 Alkyl is, for example, a (C1-C5) alkyl group. S Replaced by (C 27 ~C 40 ) are alkyl, or for example, each (C1~C 10 ) Two R's are alkyl S (C) substituted by the group 15 ~C 25 ) is an alkyl group. Examples of (C1-C5) alkyl groups include methyl, ethyl, 1-propyl, 1-methylethyl, 2,2-dimethylpropyl, or 1,1-dimethylethyl. 1,1-dimethylethyl is a four-carbon alkyl group that has its radical on a tertiary carbon. The term "tertiary carbon atom" refers to a carbon atom covalently bonded to three other carbon atoms.

[0028] (C6~C 50 The term "aryl" refers to an unsubstituted or (one or more R) having 6 to 40 carbon atoms. SThis refers to monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radicals (C6~C) that are substituted, and at least 6 to 14 of their carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical exists, at least one of the rings of the radical is aromatic. One or more other rings of an aromatic hydrocarbon radical can independently be condensed or uncondensed, and aromatic or non-aromatic. Unsubstituted (C6~C 50 Examples of aryl compounds include unsubstituted (C6~C) 20 ) Aryl, unsubstituted (C6~C 18 Examples include aryl, 2-(C1~C5) alkylphenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, anthracenyl, and phenantrenyl. Substitutions (C6~C 40 Examples of aryl substitutions include (C1~C 20 ) Aryl, substitution (C6~C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, 3,5-bis([C 20 Examples include alkyl)phenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0029] (C3~C 50 The term "cycloalkyl" refers to unsubstituted or one or more R S This refers to saturated cyclic hydrocarbon radicals of 3 to 50 carbon atoms that are substituted with (C). Other cycloalkyl groups (e.g., (C) x ~C y A cycloalkyl group has x to y carbon atoms and is either unsubstituted or has one or more R atoms. S It is defined in a similar format as either being replaced by (C3~C). 40 Examples of cycloalkyl groups include unsubstituted (C3~C) 20 ) Cycloalkyl, unsubstituted (C3~C 10)They are cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3-C 40 )Examples of cycloalkyl are substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 )cycloalkyl, cyclopentanone-2-yl, and 1-fluorocyclohexyl.

[0030] (C1-C 50 )Examples of (C1-C 50 )hydrocarbylene include unsubstituted or substituted forms of groups such as (C6-C 50 )arylene, (C3-C 50 )cycloalkylene, and (C1-C 20 )alkylene (e.g., (C1-C 20 )alkylene), but are not limited thereto. The diradicals can be on the same carbon atom (e.g., -CH2-) or adjacent carbon atoms (e.g., 1,2-diradical), or separated by one, two, or more intervening carbon atoms (e.g., 1,3-diradical, 1,4-diradical, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, and others include 1,2-diradical. The α,ω-diradical is a diradical having the maximum carbon skeleton spacing between the radical carbons. Some examples of the α,ω-diradical of (C2-C 50 )alkylene include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), and 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). Some examples of the α,ω-diradical of (C6-C

[0031] The term “(C1-C 50 )alkylene” is either unsubstituted or has one or more R Smeans a saturated straight-chain or branched-chain diradical of 1 to 50 carbon atoms (i.e., the radicals are not present on ring atoms) which is replaced by. Unsubstituted (C1-C 50 ) alkylene examples include unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3, and -(CH2)4C * (H)(CH3), which are unsubstituted (C1-C 20 ) alkylene, where "C * " indicates a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1-C 50 ) alkylene include substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted 1,20-eicosylene). Examples of substituted (C1-C 50 ) alkylene also include 1,2-cyclopentanediyldisubstituted (methylene), 1,2-cyclohexanediyldisubstituted (methylene), 7,7-dimethyl-bicyclo[2.2.1]heptane-2,3-diyldisubstituted (methylene), and bicyclo[2.2.2]octane-2,3-diyldisubstituted (methylene).

[0032] The term "(C3-C 50 ) cycloalkylene" means a cyclic diradical of 3 to 50 carbon atoms that is either unsubstituted or substituted by one or more R S (i.e., the radicals are present on ring atoms).

[0033] 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 )-, -P(R P )2, -P(O)(R P )2, -N(R N )-, -N(RN )2, -N=C(R C )2, -N=C(NR N 2)(R C ), -Ge(R C )2-, or -Si(R C )3 is given, and in the formula, each R C and each R P is non-substitutable (C1~C 18 ) Hydrocarbyl or -H, each R N is non-substitutable (C1~C 18 ) Hydrocarbyl or -H. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms. (C1~C 50 The term "heterohydrocarbyl" refers to a heterohydrocarbon radical consisting of 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" refers to a heterohydrocarbon diradical consisting of 1 to 50 carbon atoms. (C1~C 50 ) Heterohydrocarbyl or (C1~C 50 A heterohydrocarbylene heterohydrocarbon has one or more heteroatoms. The radical of a heterohydrocarbylene may reside on a carbon atom or on a heteroatom. Two radicals of a heterohydrocarbylene may reside on a single carbon atom or on a single heteroatom. Additionally, one of the two radicals of a diradical may reside on a carbon atom and the other radical on a different carbon atom, one of the two radicals may reside on a carbon atom and the other on a heteroatom, or one of the two radicals may reside on a heteroatom and the other radical on a different heteroatom. Each (C1~C 50 )heterohydrocarbyl and (C1~C 50 ) Heterohydrocarbylene may be unsubstituted, (one or more R S They may be substituted by, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, condensed and non-condensed polycyclic) or acyclic.

[0034] (C1~C 50) Heterohydrocarbyls may be unsubstituted or substituted. (C1~C 50 ) Non-limiting examples of heterohydrocarbils include (C1~C 50 ) Heteroalkyl, (C1~C 50 ) Hydrocarbyl-O-, (C1~C 50 ) Hydrocarbyl-S-, (C1~C 50 ) Hydrocarbyl-S(O)-, (C1~C 50 )hydrocarbyl-S(O)2-, (C1~C 50 ) Hydrocarbyl-Si(R C )2-, (C l ~C 50 ) Hydrocarbyl-N(R N )-, (C l ~C 50 ) Hydrocarbil-P(R P )-, (C2~C 50 ) Heterocycloalkyl, (C2~C 19 ) Heterocycloalkyl-(C1~C 20 ) Alkilen, (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 ) Alkilen, (C6~C 20 )aryl-(C1~C 19 ) Heteroalkylene, or (C1~C 19 ) Heteroaryl-(C1~C 20 ) Heteroalkylenes are an example. 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(R C )2, -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=P(R C )3, -OC(O)R C , -C(O)R C , -C(O)OR C , -N(R C )C(O)R C , and -C(O)N(R C )2 is one example, but it is not limited to these.

[0035] (C4~C 50 The term "heteroaryl" refers to a compound consisting of a total of 2 to 50 carbon atoms and 1 to 10 heteroatoms, which is unsubstituted or (one or more R) S This refers to monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radicals substituted by (C). Heteroaryl radicals can be located on carbon atoms or heteroatoms. 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. If a bicyclic or tricyclic heteroaromatic hydrocarbon radical exists, at least one of the rings in the radical is heteroaromatic. One or more other rings in the heteroaromatic radical can independently be condensed or uncondensed, and aromatic or nonaromatic. Other heteroaryl groups (e.g., generally (C)) x ~C y ) Heteroaryls, for example (C4~C 12Similarly, heteroaryl compounds have x to y carbon atoms (for example, 4 to 12 carbon atoms) and are either unsubstituted or have one or more R atoms. S It is defined as being substituted by a monocyclic heteroaromatic hydrocarbon radical. A monocyclic heteroaromatic hydrocarbon radical is a five-membered or six-membered ring. A five-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms, which can be 1, 2, 3, or 4, and each heteroatom can independently be O, S, N, or P. Examples of five-membered heteroaromatic hydrocarbon radicals include pyrrole-1-yl, pyrrole-2-yl, furan-3-yl, thiophen-2-yl, pyrazole-1-yl, isoxazole-2-yl, isothiazol-5-yl, imidazole-2-yl, oxazole-4-yl, thiazol-2-yl, 1,2,4-triazole-1-yl, 1,3,4-oxadiazole-2-yl, 1,3,4-thiadiazole-2-yl, tetrazole-1-yl, tetrazole-2-yl, and tetrazole-5-yl. A six-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms, which can be 1, 2, or 3, and the heteroatoms can be N or P. Examples of six-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl, pyrimidine-2-yl, pyrazine-2-yl, and 1,3,5-triazine-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can be condensed 5,6- or 6,6-ring systems. Examples of condensed 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indole-1-yl and benzimidazole-1-yl. Examples of condensed 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinoline-2-yl and isoquinoline-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be condensed 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a condensed 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a condensed 5,6,6-ring system is 1H-benzo[f]indole-1-yl. An example of a condensed 6,5,6-ring system is 9H-carbazole-9-yl. An example of a condensed 6,6,6-ring system is acridine-9-yl.

[0036] (C1~C50 The term "(C1-C) heteroalkyl" refers to a saturated linear or branched diradical containing 1 to 50 carbon atoms and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated linear or branched diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of 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 ), P(O)(R P )2, N(R N )2, N(R N ), N, O, OR C S, SR C Examples include, but are not limited to, S(O) and S(O)2, and each of the heteroalkyl group and heteroalkylene group may be unsubstituted or have one or more R S It has been replaced by.

[0037] Unsubstituted (C2~C 40 Examples of heterocycloalkyl groups include unsubstituted (C2~C 20 ) Heterocycloalkyl, unsubstituted (C2~C 10 Examples include heterocycloalkyls, aziridine-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidine-l-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholine-4-yl, 1,4-dioxan-2-yl, hexahydroazepine-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0038] The terms "halogen atom" or "halogen" refer to the radicals of fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). The term "halide" refers to the anionic form of the halogen atom (fluoride (F)). - ), chloride (Cl - ), bromide (Br- ), or iodide (I - It means )).

[0039] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, and carbon-silicon double or triple bonds (in heteroatom-containing groups). A saturated chemical group has one or more substituents R S When substituted by, one or more double and / or triple bonds are optionally substituted with substituent R S It may or may not be present. The term "unsaturated" means containing one or more carbon-carbon double or carbon-carbon triple bonds, or one or more carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, or carbon-silicon double or triple bonds (in heteroatom-containing groups), if present, substituent R S It does not contain any double bonds that may be present in the (hetero)aromatic ring, or if present.

[0040] Embodiments of the present disclosure include a polymerization process. The polymerization process includes ethylene, and one or more polar comonomers, and optionally one or more (C3-C3) 12 The process involves polymerizing an α-olefin in the presence of a catalyst system to form an ethylene copolymer in a high-pressure reactor at a pressure exceeding 1000 barg and a temperature exceeding 100°C, wherein the catalyst system includes a transition metal catalyst.

[0041] In one or more embodiments, the reactor temperature is 100°C to 500°C. In some embodiments, the reactor temperature is 120°C to 500°C, 140°C to 500°C, 150°C to 500°C, 160°C to 500°C, 120°C to 400°C, 130°C to 400°C, 140°C to 400°C, 150°C to 400°C, 120°C to 300°C, 130°C to 300°C, 140°C to 300°C, or 150°C to 300°C. In various embodiments, the reactor temperature is greater than 150°C.

[0042] In one or more embodiments, the reactor pressure is 1,000 barg to 10,000 barg. In some embodiments, the reactor pressure is 1,000 barg to 5,000 barg, 1,100 barg to 5,000 barg, 1,200 barg to 5,000 barg, 1,300 barg to 5,000 barg, 1,400 barg to 5,000 barg, 1,500 barg to 5,000 barg, 1,000 barg to 4,000 barg, 1,100 barg to 4,000 barg, 1,200 barg to 4,000 barg. These ranges are 00 barg, 1,300 barg-4,000 barg, 1,400 barg-4,000 barg, 1,500 barg-4,000 barg, 1,000 barg-3,000 barg, 1,100 barg-3,000 barg, 1,200 barg-3,000 barg, 1,300 barg-3,000 barg, 1,400 barg-3,000 barg, or 1,500 barg-3,000 barg.

[0043] In some embodiments, the polar comonomers include alkyl acrylates, glycidyl acrylates, vinyl acetate, CH2=C(H)C(O)(OR X ), CH2=C(H)(CH2) n C(O)(OR X ), CH2=CHC(O)R X CH2=C(H)(CH2) n C(O)OR X CH2=CH(OR X ), CH2=CH(CH2) n (OR X ), CH2=CHSi(R X ) 3-Y (OR X ) Y CH2=CH(CH2) n Si(R X ) 3-Y (OR X ) Y CH2 = CH - OSi(R X ) 3-Y (OR X ) Y CH2=CH(CH2) n -OSi(R X )3-Y (OR X ) Y , or CH2=CHCl may be mentioned, where R X -H, substitution or non-substitution (C1~C 30 ) Hydrocarbyl, or substituted or unsubstituted (C1~C 30 ) is selected from heterohydrocarbyl, where the subscript Y is 0, 1, 2, or 3 (n is 1 to 10). In various embodiments, the polar monomer comprises alkyl acrylates. In some embodiments, the alkyl acrylate is methyl acrylate, ethyl acrylate, n-butyl acrylate, or t-butyl acrylate.

[0044] Olefin monomers, for example, (C3~C 12 Examples of α-olefins include, but are not limited to, propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, styrene, cyclobutene, cyclopentene, norbornene, and ethylidenenorbornene.

[0045] In various embodiments of the polymerization procell, the polar comonomers include alkyl acrylate CH2=CHC(O)(OR), glycidyl acrylate, and CH2=CH(CH2) n C(O)(OR), CH2=CHC(O)R, CH2=CH(CH2) n C(O)R, CH2=CH-OC(O)R, CH2=CH(CH2) n -OC(O)R, CH2=CH(OR), CH2=CH(CH2) n (OR), CH2=CHSi(R) 3-T (OR) T CH2=CH(CH2) n Si(R) 3-T (OR) T, CH2=CH-OSi(R) 3-T (OR) T CH2=CH(CH2) n -OSi(R) 3-T (OR) TAlternatively, CH2=CHCl can be used. Each R is -H, substitution (C1~C 30 ) Hydrocarbyl, unsubstituted (C1~C 30 ) Hydrocarbyl substitution (C1~C 30 ) Heterohydrocarbyl, or unsubstituted (C1~C 30 ) Selected from heterohydrocarbyl. The subscript T is 0, 1, 2, or 3. The subscript n is 1 to 10. The polar monomer is alkyl acrylate, substituted (C1 to C 30 ) Hydrocarbyl acrylate, unsubstituted (C1~C 30 ) Hydrocarbyl acrylate, substitution (C1~C 30 ) Heterohydrocarbyl acrylate, or unsubstituted (C1~C 30 ) Heterohydrocarbyl acrylate, or unsubstituted (C1~C 30 In embodiments where the copolymer is a heterohydrocarbyl acrylate, the polar ethylene copolymer can be deesterified to form an acrylic acid / ethylene copolymer.

[0046] In some embodiments of the polymerization process, the alkyl acrylate monomer may be methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, or a combination thereof, but are not limited to these examples. In various embodiments, the alkyl acrylate has an alkyl group having 1 to 8 carbon atoms. This is called C1-C8 alkyl acrylate. In certain embodiments, the alkyl acrylate is t-butyl acrylate or n-butyl acrylate.

[0047] In some embodiments of the polymerization process, optional α-olefin monomers may be, but are not limited to, 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. In one or more embodiments of the polymerization process, the process involves (C1-C) at positions 5 and 6. 20The material may further contain cyclic olefins such as cyclobutene, cyclopentene, norbornene, and norbornene derivatives substituted with a hydrocarbyl group.

[0048] The polymerization process involves ethylene, one or more polar comonomers, and optionally one or more (C3-C3) 12 The process involves polymerizing α-olefins and optionally aluminum species in the presence of a catalyst system to form ethylene copolymers in a high-pressure reactor at a pressure exceeding 1000 barg and a temperature exceeding 100°C, wherein the catalyst system includes a transition metal catalyst. In some embodiments, the transition metal catalyst includes nickel(II) or palladium(II).

[0049] In various embodiments, the transition metal catalyst or transition metal procatalyst comprises nickel(II) or palladium(II) and has a structure according to formula (I).

[0050] [ka]

[0051] In formula (I), M is nickel(II) or palladium(II), and X is (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -CH2Si(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q , -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、 a ligand selected from halogen, or hydrogen, and each R C is, independently, a substituted or unsubstituted (C1 - C 30 ) hydrocarbyl, or a substituted or unsubstituted (C1 - C 30 ) heterohydrocarbyl, Q is 0, 1, 2, or 3, and W is 0, 1, or 2.

[0052] In formula (I), each Y is a Lewis base, and X and Y are optionally linked. P is phosphorus.

[0053] In formula (I), R 1 is, independently, -H, (C1 - C 40 ) hydrocarbyl, (C1 - C 40 ) heterohydrocarbyl, -Si(R C )3, -Si(R C ) 3-Q (OR C ) Q 、 -OSi(RC ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q -P(=O)(R P ) 2、 -P(R C ) 2-W (OR C ) W ,-P(O)(R C ) 2-W (OR C ), -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 ) Selected from the group consisting of 2NC(O)-, halogens, radicals having formula (II), radicals having formula (III), and radicals having formula (IV).

[0054] [ka]

[0055] In equations (II), (III), and (IV), R 31~35 , R 41~48 , and R 51~59 Each of these is independent of -H, (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, RC 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 ) Selected from 2NC(O)- or halogen.

[0056] In formula (I), R 2 , R 3 , and R 4 These are independently, substitutions (C1~C 30 ) Hydrocarbyl, unsubstituted (C1~C 30 ) Hydrocarbyl substitution (C1~C 30 ) Heterohydrocarbyl, unsubstituted (C1~C 30 ) Heterohydrocarbyl, -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 )2, -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=P(R C )3, -OC(O)R C , -C(O)OR C ,-N(R)C(O)R C ,-C(O)N(RC )2, or selected from halogens, in the formula, each R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, or substituted or unsubstituted (C1~C 30 ) is a heterohydrocarbyl, where Q is 0, 1, 2, or 3, and W is 0, 1, or 2.

[0057] In formula (I), R 5 and R 6 These are independently, substitutions (C1~C 30 ) Hydrocarbyl, unsubstituted (C1~C 30 ) Hydrocarbyl substitution (C1~C 30 ) Heterohydrocarbyl, or unsubstituted (C1~C 30 ) Selected from heterohydrocarbyl.

[0058] In formula (I), R 5 and R 6 These are optionally linked to form a ring structure, R 2 and R 3 These are optionally linked to form a ring structure. In some embodiments, R 3 and R 4 These elements are optionally linked together to form a ring structure.

[0059] In some embodiments, R 5 and R 6 (C1~C 20 ) alkyl, or (C6~C 20 ) It is Ariel.

[0060] In some embodiments, R 2 , R 3 , and R 4 (C1~C 18 ) Alkyl or -H.

[0061] In one or more embodiments, R 1 is a radical of formula (II), (III), or (IV). In some embodiments, R 1R is the radical of formula (I). In various embodiments, R 1 However, if it is a radical of formula (III), R 42 and R 47 (C1~C 12 ) is alkyl. In other embodiments, R 1 However, if it is a radical of formula (III), R 43 and R 46 (C1~C 12 It is alkyl.

[0062] In some embodiments, R 5 and R 6 These are 2,6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-diphenoxyphenyl, 2,4,6-triethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-phenylphenyl, or 2,6-diisopropoxyphenyl.

[0063] In the metal-ligand complex of formula (I), each Y is bonded to M through a donor bond or an ionic bond. In one or more embodiments, Y is a Lewis base. The Lewis base may be a compound or ionic species capable of donating an electron pair to the acceptor moiety. For the purposes of this specification, the acceptor moiety is M (the metal of the metal-ligand complex of formula (I)). In some embodiments, the Lewis base may be a heterohydrocarbon or a hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. Examples of neutral hydrocarbon Lewis bases include, but are not limited to, alkenes, alkynes, or arenes.

[0064] In one or more embodiments, Y is neutral Lewis basic aprotic (C2-C2 40 ) It is a heterohydrocarbon. Aprotic (C2~C 40 ) Heterohydrocarbons are, as defined earlier, (C2~C 40 ) All hydrogen atoms in heterohydrocarbons have a pKa greater than 30, where pKa is the logarithm of the negative base 10 of the acid dissociation constant (Ka), (C2~C40 ) is a heterohydrocarbon. In some embodiments, Y is an organic Lewis base. Examples of organic Lewis bases include pyridine or substituted pyridine, sulfoxide, trialkyl or triarylphosphine, trialkyl or triarylphosphine oxide, olefin or cyclic olefin, substituted or unsubstituted heterocycle, alkyl ester of aliphatic or aromatic carboxylic acid, aliphatic ketone, aliphatic amine, alkyl or cycloalkyl ether, or mixtures thereof, where each electron donor has 2 to 20 carbon atoms. In various embodiments, the organic Lewis base is selected from alkyl and cycloalkyl ethers having 2 to 20 carbon atoms, as well as dialkyl, diaryl, and alkylaryl ketones having 3 to 20 carbon atoms, and alkyl esters 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, ethyl formate, dimethylformamide, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, tetrahydrofuran, ethyl propionate, lutidine, picoline, pyridine, dimethyl sulfoxide, trimethylphosphine, triethylphosphine, triphenylphosphine, cyclooctadiene, cyclopentene, ethylene, propylene, tert-butylethylene, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, 1-methylimidazole, or 1-methylpyrazole.

[0065] In one or more embodiments, the Lewis base may be a monodentate ligand that can be a neutral ligand. In some embodiments, the neutral ligand may contain a heteroatom. In specific embodiments, the neutral ligand is R T NR K R L , R K Ure L , R K SR L , or R T PR K RL These are neutral groups, and each R T [(C1~C 10 ) Hydrocarbyl]3Si(C1~C 10 ) Hydrocarbylene, (C1~C 40 ) Hydrocarbyl, [(C1~C 10 ) Hydrocarbyl 3Si, or (C1~C 40 ) is a heterohydrocarbyl, and each R K and R L Independently, hydrogen, (C1~C 40 ) Hydrocarbyl, or (C1~C 40 ) It is a heterohydrocarbyl.

[0066] In some embodiments, the Lewis base is (C1~C 20 ) is a hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene, 1,3-butadiene, or cyclooctene.

[0067] In various embodiments, the Lewis base is (C1~C 20 ) is a heterohydrocarbon, and the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, Y is tetrahydrofuran, pyrene, dioxane, diethyl ether, or methyl tert-butyl ether (MTBE).

[0068] In various embodiments, the Lewis base is (C1~C 20 ) is a heterohydrocarbon, and the heteroatom of the heterohydrocarbon is nitrogen. In some embodiments, Y is pyridine, picoline, lutidine, trimethylamine, or triethylamine.

[0069] In various embodiments, the Lewis base is (C1~C 20) is a heterohydrocarbon, and the heteroatom of the heterohydrocarbon is phosphorus. In some embodiments, Y is trimethylphosphine, triethylphosphine, triphenylphosphine, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, or triphenylphosphine oxide.

[0070] In some embodiments, X and Y are covalently linked. Specific examples of organic Lewis base Y covalently linked with the X group include, but are not limited to, 4-cycloocteno-1-yl, 2-dimethylaminobenzyl, and 2-dimethylaminomethylphenyl.

[0071] In some embodiments, X and Y are connected and selected from the following group:

[0072] [ka] In the formula, R C is -H, or (C1~C 30 ) Hydrocarbyl, (C1~C 30 ) Heterohydrocarbyl, (C1~C 20 ) alkyl, or (C1~C 12 It is alkyl.

[0073] In the metal-ligand complex of formula (I), X is bonded to M through covalent or ionic bonds. In some embodiments, X may be a monoanionic ligand having a net formal oxidation state of -1. Each monoanionic ligand is independently a hydride, (C1-C 40 ) Hydrocarbyl carbanion, (C1~C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, hydrogen carbonates, dihydrogen phosphates, hydrate sulfates, HC(O)O - , HC(O)N(H) - , (C1~C 40 ) Hydrocarbyl C(O)O - , (C1~C40 ) Hydrocarbyl C(O)N((C1~C 20 (Hydrocarbyl) - , (C1~C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L Si - This is possible, and in the formula, each R K , R L , and R M Independently, hydrogen, (C1~C 40 ) Hydrocarbyl, or (C1~C 40 ) Heterohydrocarbyl or R K and R L They come together, (C2~C 40 ) Hydrocarbylene, or (C1~C 20 ) Forms heterohydrocarbylene, R M This is as defined above.

[0074] In some embodiments, X is a halogen, (C1~C 20 ) Hydrocarbyl, (C1~C 20 ) Heterohydrocarbyl, (C1~C 20 ) Hydrocarbyl C(O)O-, or R K R L N- and R K and R L Each of these is independent of (C1~C 20 ) is hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, (C1~C 10 ) Hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) Hydrocarbyl C(O)O-, or RK R L N-, and in the formula, R K and R L Each of these is independent of the non-substitutable (C1~C 10 ) It is hydrocarbyl.

[0075] In various embodiments, X is substituted or non-substituted (C1~C 30 ) Hydrocarbyl, substituted or unsubstituted (C1~C 30 ) It is a heterohydrocarbyl.

[0076] In further embodiments, X is selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2,-dimethylpropyl, trimethylsilylmethyl, dimethylphenylsilylmethyl, methyldiphenylsilylmethyl, triphenylsilylmethyl, benzyldimethylsilylmethyl, trimethylsilylmethyldimethylsilylmethyl, phenyl, benzyl, or chloro.

[0077] In one or more embodiments, X is -(CH2)SiR X 3, and in the formula, each R X (C1~C 30 ) Alkyl or (C1~C 30 ) is heteroalkyl and has at least one R X (C1~C 30 ) is alkyl. In some embodiments, R X One of them is (C1~C 30 ) If it is a heteroalkyl, the heteroatom is a silicon or oxygen atom. In some embodiments, R X These are methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0078] In one or more embodiments, X is -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(C6H5), -(CH2)Si(CH3)(C6H5)2, -(CH2)Si(C6H5)3, -(CH2)Si(CH3)2(CH2C6H5), -(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-oct)R X ,-(CH2)Si(CH3)2R X 、-(CH2)Si(n-oct)R X 2, -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), or -CH2Si(CH3)2CH2Si(CH3)3 (referred to herein as -CH2Si(CH3)2 (CH2TMS)). Optionally, in some embodiments, the metal-ligand complex of formula (I) has exactly two R X They are covalently bonded, or exactly three R X They are covalently bonded.

[0079] 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 In the formula, the subscript Q is 0, 1, 2, or 3, and each R C These can be substituted or not substituted independently (C1~C 30 ) Hydrocarbyl, or substituted or unsubstituted (C1~C 30 ) is a heterohydrocarbyl. In some embodiments, X is -CH2Si(CH3)3.

[0080] In various embodiments, X is methyl, 2,2-dimethylpropyl, trimethylsilylmethyl, (n-butyl)dimethylsilylmethyl, (n-hexyl)dimethylsilylmethyl, (n-octyl)dimethylsilylmethyl, or benzyl.

[0081] Aluminum species In one or more embodiments, aluminum species may include alkylaluminum, polymeric or oligomeric almoxanes (also known as aluminoxanes), neutral Lewis acids, and nonpolymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidative conditions). The term "alkylaluminum" means monoalkylaluminum dihydride or monoalkylaluminum dihalide, dialkylaluminum hydride or dialkylaluminum halide, or trialkylaluminum. Examples of polymeric or oligomeric almoxanes include methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, and isobutylaluminoxane.

[0082] In one or more embodiments, the aluminum species is as described herein (C1-C 20 Examples include group 13 metal compounds containing hydrocarbyl substituents. In some embodiments, the group 13 metal compound is tri((C1~C 20 ()hydrocarbyl)-substituted aluminum. In other embodiments, the aluminum species may be tri(hydrocarbyl)-substituted aluminum, tri(C1~C 10 Examples include alkylaluminum and halogenated (including perhalated) derivatives thereof.

[0083] In some embodiments, aluminum species may include polymers or oligomeric aluminoxanes, particularly methyl aluminoxanes, as well as inert, compatible, non-coordinating, and ion-forming compounds. Exemplary and preferred co-catalysts include, but are not limited to, modified methyl aluminoxane (MMAO).

[0084] The ratio of the total number of moles of one or more metal-ligand complexes in formula (I) to the total number of moles of aluminum species is between 1:10,000 and 100:1. In some embodiments, this ratio is at least 1:5000, in some other embodiments it is at least 1:1000 and 10:1 or less, and in some other embodiments it is 1:1 or less.

[0085] Ethylene / acrylate copolymer In various embodiments, the polymerization process of the present disclosure may produce a polar ethylene copolymer containing at least 50 weight percent (wt%) of ethylene, based on the weight of the polar ethylene copolymer. In some embodiments, the polar ethylene copolymer is a reaction product of 70 wt% to 99.9 wt% of ethylene units and 0.1 wt% to 30 wt% of polar comonomer units, based on the sum of the ethylene units and polar comonomer units.

[0086] In one or more embodiments, the polymerization process of the present disclosure may comprise an ethylene monomer, an alkyl acrylate monomer, and optionally one or more α-olefins. In some embodiments of the polymerization process comprising α-olefins, the α-olefins may be incorporated into the resulting polymer in an amount of 0.01% to 49.9% by weight, based on the weight of the ethylene copolymer.

[0087] In various embodiments, the polymerization process of the present disclosure can produce ethylene copolymers having molecular weights of 2,000 g / mol to 1,000,000 g / mol. In some embodiments, the resulting polymers have molecular weights 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.

[0088] GPC procedure The chromatography system consisted of a PolymerChar (Valencia, Spain) GPC-IR high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160°C, and the column compartment to 150°C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was spurged with nitrogen. The injection volume used was 200 microliters, and the flow rate was 1.0 ml / min.

[0089] Calibration of the GPC column set was performed using polystyrene standards with a narrow molecular weight distribution, ranging from 580 to a maximum of 8,400,000 g / mol. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared using 0.025 grams in 50 ml of solvent for molecular weights greater than 1,000,000, and 0.05 grams in 50 ml of solvent for molecular weights less than 1,000,000. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes, then cooled, and the room-temperature solution was transferred to an autosampler dissolution oven at 160°C for 30 minutes and cooled. The peak molecular weight of the polystyrene standards was converted to polyethylene molecular weight using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A × (M ポリエチレン ) B (Equation 1) In the formula, M is the molecular weight, A has a value of 0.4117, and B is equal to 1.0.

[0090] A quintic polynomial was used to fit each polyethylene equivalent calibration point.

[0091] The total plate count of the GPC column set was performed using decane introduced into blank samples via a micropump controlled by the PolymerChar GPC-IR system. The plate count of the chromatography system should be greater than 18,000 for four Agilent "Mixed A" 30 cm² 20 micron linear mixed-bed columns.

[0092] The sample was prepared semi-automatically using PolymerChar's "Instrument Control" software, with a target weight of 2 mg / mL. The solvent (containing 200 ppm BHT) was added to a vial with a pre-nitrogen-spurged septum cap via a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for 2 hours under "low-speed" shaking.

[0093] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculations were based on GPC results using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph, according to Equations 2-4, using PolymerChar's GPCOne® software, IR chromatograms with baselines subtracted at each equally spaced data acquisition point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for point (i) in Equation 1.

[0094]

number

[0095] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly calibrate the pump flow rate (nominal flow rate) for each sample by RV matching each decane peak in the sample (RV(FM sample)) with the decane peak in a narrow standard calibration (RV(FM calibrated)). It was then assumed that any change in the decane marker peak over time would correspond to a linear shift in the flow rate (effective flow rate) over the entire run. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) was calculated as shown in Equation 5. The processing of the flow rate marker peaks was performed via PolymerChar GPCOne® software. An acceptable flow rate correction should be such that the effective flow rate is within ±0.5% of the nominal flow rate. Effective flow rate = Apparent flow rate * (RV(FM calibrated) / RV(FM sample)) (Equation 5)

[0096] FT-IR procedure The incorporation of tert-butyl acrylate (tBA) was quantified by Fourier transform infrared spectroscopy (FTIR). Samples with varying tBA concentrations (approximately 8–28 wt%) were prepared in a high-pressure miniplant, and the tBA content was measured by NMR. The samples were compressed into thin (approximately 10 mil) films using a Carver press equipped with a platen heated to 190°C. 4 cm -1 Using 64 scans with a resolution of 4000-400cm -1 IR spectra were collected from film using a Thermo Nicolet 6700 FT-IR equipped with a DTGS KBr detector. tBA(3438cm²) -1 C=O overtone and ethylene combination band (CH2: 4253cm) -1The peak height ratio was calculated and fitted to a linear calibration curve to determine the total tBA.

[0097] For measuring tBA content 13 C nuclear magnetic resonance spectroscopy 13 Samples for 13C NMR were prepared in a 10 mm NMR tube by adding approximately 3 g of 1,1,2,2-tetrachloroethane (TCE) containing 25 wt% TCE-d2 and 0.025 M Cr(AcAc)3 to approximately 0.30 g of polymer sample. The samples were dissolved and homogenized by heating the tube and its contents to 115°C using a heating block and vortex mixer. Homogeneity was ensured by visual inspection of each dissolved sample. The samples were thoroughly mixed immediately before analysis and kept from cooling until inserted into a heated NMR sample holder.

[0098] All data were acquired using a Bruker 600MHz spectrometer equipped with a 10mm high-temperature cryoprobe. Sample temperatures of 100 or 120°C were used, with a pulse repetition delay of 7.8 seconds, a 90-degree flip angle, and decoupling with a reverse gate. 13 C data was acquired. All measurements were performed on a non-rotating sample in lock mode. The sample was thermally equilibrated before data acquisition. 13 The 30¹³C NMR chemical shift was internally referenced to a 30.0 ppm EEE triad.

[0099] t-butyl acrylate comonomers were quantified using four peak areas corresponding to approximately 176 ppm carbonyl, approximately 80 ppm CH2-O-, approximately 47 ppm quaternary carbon, and approximately 28.5 ppm t-butylmethyl.

[0100] DSC Procedure In preparation for the Differential Scanning Calorimetry (DSC) test, the pelletized sample was first filled into a 1-inch diameter, 0.13 mm thick chase and compressed into a film at 190°C for approximately 10 seconds under a pressure of 25,000 lbs. The resulting film was then cooled to room temperature. The film was then subjected to a punch press to obtain discs that fit into the aluminum DSC test pan. The sample weight was approximately 5-6 mg. The discs were then individually weighed, placed in the aluminum pan, sealed, and inserted into the DSC test chamber.

[0101] For ASTM standard D3418, the DSC test is performed using a heating-cooling-heating cycle. First, the sample is equilibrated at 180°C and held isothermally for 5 minutes to remove thermal and process history. Then, the sample is quenched to below -40°C at a rate of 10°C / min and held isothermally again for 5 minutes. Finally, for the second heating cycle, the sample is heated to 150°C at a rate of 10°C / min. For data analysis, the melting temperature and enthalpy of melting are taken from the second heating curve, while the enthalpy of crystallization is determined from the cooling curve. The enthalpies of melting and crystallization are obtained by integrating the DSC thermogram from -20°C to the end of melting and crystallization, respectively. The heat of fusion for 100% crystalline polyethylene is assumed to be 292 J / g to calculate the weight % crystallinity. The DSC test is performed using TA Instruments Discovery DSC, and data analysis is performed via TA Instruments Universal Analysis.

[0102] Calculation of catalyst efficiency Catalyst efficiency (g ポリマー / g 金属The θ was calculated by analyzing polymer samples using inductively coupled plasma atomic emission spectroscopy (ICP-AES). Samples were weighed in a quartz crucible and approximately 2 mL of sulfuric acid was added. A replica of each sample was ashed in a muffle furnace at 550°C until all organic components were removed. The ash was then dissolved in aqua regia on a hot plate. The samples were diluted to weight with deionized water and analyzed using ICP-AES.

[0103] [Table 1] [Examples]

[0104] Example 1 describes the synthesis procedure for ligand intermediate, ligand, nickel precursor, and nickel pro catalyst. Examples IE1 to IE8 are high-pressure copolymerization reactions of Ni catalyst 1, and are discussed in a table. Examples CE1 to CE7 are comparative examples. One or more features of this disclosure are illustrated by considering the following examples.

[0105] General considerations for synthesis All synthesis reactions were carried out in a nitrogen-purged glove box unless otherwise specified. All solvents and reagents were obtained from commercial sources and used as received unless otherwise specified. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing them through activated alumina and, in some cases, through the Q-5 reactant. Alumina for solvent purification was activated by passing a nitrogen stream through the alumina at 300°C for 8 hours. The Q-5 reactant was activated by heating at 200°C under a nitrogen stream for 4 hours, followed by heating at 200°C under a 5% hydrogen stream in nitrogen for 3 hours, and finally flushing with nitrogen gas. Solvents used in experiments conducted in a nitrogen-filled glove box were further dried by storing them on an activated 4 Å molecular sieve. Moisture-sensitive reaction glassware was dried in an oven overnight before use. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column, coupled with an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. NMR spectra were recorded using a Varian 400-MR and VNMRS-500 spectrometer. 1 ¹H NMR data are reported as follows: chemical shift (multiplicity (br=broadline, s=singlet, d=doublet, t=triplet, q=quadruplet, p=quintlet, sex=sextlet, sept=septuplet, and m=multitlet), integral value, and assignment). As a standard, residual protons in deuterated solvent are used. 1 We report the chemical shifts of 1H NMR data in ppm at low magnetic fields using tetramethylsilane (TMS, δ scale). 13 C NMR data, 1 The determination is made using H decoupling, and the chemical shift is reported in ppm relative to tetramethylsilane. 13 The 13C NMR spectrum was complex due to CP coupling. 31The chemical shifts of the P NMR data are reported in ppm relative to external neat H3PO4. Deuterated solvents for NMR analysis were purchased from Cambridge Isotope Laboratories and stored on activated 4 Å molecular sieves in a nitrogen-purged glove box.

[0106] Example 1 - Synthesis of Ni catalyst: Tetrahydropyran (THP) protection of 2-iodophenol

[0107] [ka]

[0108] The reaction was set up in a nitrogen-atmosphere glove box. 2-iodophenol (98.87 g, 449.38 mmol), pyridinium p-toluenesulfonate (11.29 g, 44.94 mmol), and anhydrous degassed methylene chloride (250 mL) were added to a 500 mL three-necked round-bottom flask equipped with a stirring bar, which had been oven-dried. 3,4-dihydropyran (DHP, 102.50 mL, 1123.44 mmol) was added to an addition funnel, capped, and attached to the center neck of the flask. The necks of the other flasks were capped with rubber septums, and the apparatus was moved to a fume hood. The flasks were placed under nitrogen purge, and DHP was added dropwise over 45 minutes. Exothermic reaction (16.6–40.4°C) was observed, with the temperature peaking when approximately 75% of the addition was complete, after which the temperature began to decrease. Immediately after the addition of DHP was completed, the reaction solution was sampled (at a temperature of 28.4°C) and analyzed by GC / MS and 1The completion of the reaction was confirmed by 1H NMR. After the reaction was determined to be complete (20 minutes later), the reaction solution was transferred to a separatory funnel and washed with brine (2 × 135 mL). The organic phase was dried over MgSO4 and then filtered. The solvent was removed by rotary evaporation to obtain 136.77 g of a golden oil. Analysis (NMR and GC / MS) showed trace amounts of starting phenol, so the product oil was transferred to a glove box and dissolved in 500 mL of dry THF, followed by the addition of sodium methoxide (13.11 g, 242.66 mmol) to the solution. After stirring for 10 minutes, the flask was capped, placed in a fume hood, and passed through a short column of basic alumina. The column was pre-moistened with 10% siRNA / hexane, the product solution was passed through the column, and then rinsed further with a total of 300 mL of 10% siRNA / hexane. The solvent was removed under vacuum to obtain 135.55 g of a golden oil. 1 After analysis by 1H NMR, residual THF was removed by dissolving it in dry dichloromethane (DCM) and then drying it under reduced pressure. Final product analysis of 135.20 g (98.9%) of the golden oily substance showed the desired product (GC / MS and NMR).

[0109] 1 ¹H NMR (400MHz, chloroform-d) δ 7.77 (dd, J=7.8, 1.6Hz, 1H), 7.27 (ddd, J=8.3, 7.3, 1.6Hz, 1H), 7.08 (dd, J=8.3, 1.4Hz, 1H), 6.73 (td, J=7.6, 1.4Hz, 1H), 5.54 (t, J=2.9Hz, 1H), 3 .87(td,J=11.1,2.9Hz,1H),3.60(dddd,J=11.4,4.5,3.0,1.6Hz,1H),2.26-2.09(m, 1H),2.05-1.95(m,1H),1.87(dddd,J=13.5,11.9,4.2,3.1Hz,1H),1.81-1.46(m,3H). 13 ¹³C NMR (101 MHz, chloroform-d): δ 155.55, 139.29, 129.36, 123.28, 115.17, 96.50, 87.45, 61.72, 30.21, 25.25, 18.30.

[0110] Synthesis of chlorobis(2,6-dimethoxyphenyl)phosphine

[0111] [ka]

[0112] The reaction was carried out in a nitrogen-atmosphere glove box. The solution concentration was confirmed by titration of n-BuLi before the reaction, and all glassware was oven-dried before use.

[0113] 93.23 mL of n-BuLi in hexane (2.69 M, 250.79 mmol) was added to a 1 L jar (equipped with a stirring bar) containing a -35°C solution of 1,3-dimethoxybenzene (35.00 g, 253.32 mmol) in 400 mL of THF. The solution was warmed to ambient temperature and stirred for 4 hours. The solution was cooled to -35°C, and 18.32 g of dimethylphosphoramide dichloride (125.52 mmol) in 33 mL of THF was slowly added dropwise. The reaction mixture was warmed overnight with stirring to room temperature to obtain a yellow solution containing some precipitate. 31 Aliquots were taken for 3P NMR analysis, which indicated that the starting Me2NPCl2 had been consumed. HCl (146.93 mL, 2.0 M, 293.85 mmol) in diethyl ether solution was added via syringe over 10-15 minutes. Precipitation began immediately upon addition of HCl. The reaction mixture was stirred overnight.

[0114] The solvent was removed under reduced pressure. The residue was extracted with toluene (800 mL, under vigorous stirring), filtered to obtain a slightly turbid solution, and the toluene was removed under reduced pressure. Another 800 mL of toluene was added, and the mixture was filtered through Celite® to form a clear filtrate, and the toluene was removed under reduced pressure. The resulting white solid was pulverized with 200-300 mL of hexane, filtered, washed with hexane, dried under reduced pressure, and isolated to obtain 32.60 g (75.6%) of the desired product.

[0115] 1H NMR (400MHz, benzene-d6) δ7.05 (td, J=8.3, 1.3Hz, 2H), 6.23 (dd, J=8.3, 2.8Hz, 4H), 3.26 (s, 12H). 13 ¹³C NMR (101 MHz, benzene-d6) δ 162.34, 162.22, 131.06, 116.92, 116.40, 104.31, 55.32. 31 P NMR (162 MHz, benzene-d6) δ 60.33.

[0116] Synthesis of 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole

[0117] [ka]

[0118] A 2 L two-necked round-bottom flask equipped with a stirring bar, which had been oven-dried, was transferred to a glove box. The flask was filled with 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole (69.40 g, 246.6 mmol), 2-(2-iodophenoxy)tetrahydro-2H-pyran (112.49 g, 369.88 mmol), K3PO4 (179.01 g, 843.33 mmol), and anhydrous deaerated toluene (560 mL). Copper(I) iodide (2.02 g, 10.6 mmol) and N,N'-dimethylethylenediamine (4.04 mL, 37.0 mmol) were weighed into a jar along with 65 mL of toluene. This mixture was added to the carbazole solution using a small amount of toluene, and it was confirmed that the slurry had completely moved. After adding the CuI solution, the solution turned olive green. A condenser (with a rubber septum) and the rubber septum were attached to the flask, and the other end was closed. The flask was placed in a fume hood and under a nitrogen sweep. The reaction solution was heated for a total of 19 hours (heating block temperature set to 125°C), and a sample was taken at 18 hours and analyzed by GC / MS to confirm completion of the reaction. The solution was cooled to room temperature and filtered through a short silica plug (pre-washed with THF). The silica plug was rinsed with THF (4 × 400 mL) to ensure that the product was completely washed away. The filtrate was concentrated in a rotary evaporator to obtain a dark oily substance. Acetonitrile (1 L) was added, and the mixture was vigorously stirred using an overhead stirrer until a solid was formed (this occurred almost immediately). After vigorous stirring for 30 minutes, a homogeneous, creamy-looking solution was obtained. The slurry was filtered, and the solid was rinsed with additional cold acetonitrile (3 × 300 mL). Volatile matter was removed using a rotary evaporator, followed by the addition of several hundred mL of methylene chloride, and all volatile matter was removed using the rotary evaporator. After further drying under reduced pressure, the resulting off-white solid (80.23 g, 71.1%) was obtained. 1 H and 13 Analysis was performed by 13C NMR.

[0119] 1HNMR(400MHz,chloroform-d)δ8.13(d,J=1.9Hz,2H),7.49(dt,J=7.7,1.0Hz,1H),7.46-7.38(m,4H),7.20-7.14(m,2H),7.10(dd,J=8.6,0 .6Hz,1H),5.28(t,J=2.9Hz,1H),3.71(td,J=11.2,2.9Hz,1H),3.54-3.45(m,1H),1.46(s,18H),1.43-1.36(m,1H),1.33-1.00(m,5H). 13 ¹³C NMR (101MHz, chloroform-d) δ 153.86, 142.71, 140.40, 130.01, 129.41, 127.91, 123.66, 123.61, 123.60, 123.51, 122.55, 117.55, 116.34, 116.21, 110.69, 110.07, 97.31, 62.03, 35.16, 32.51, 30.40, 25.46, 17.94.

[0120] Synthesis of 9-(3-(bis(2,6-dimethoxyphenyl)phosphanyl)-2-((tetrahydro-2H-pyran-2yl)oxy)phenyl)-3,6-di-tert-butyl-9H-carbazole

[0121] [ka]

[0122] Before the reaction, the solution concentration was confirmed by titration with n-BuLi, and all glassware was oven-dried before use. In a nitrogen-atmosphere glove box, 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole (36.50 g, 80.11 mmol) and 215 mL of anhydrous THF were placed in a glass jar equipped with a stirring bar. The solution was cooled in a dry box freezer (-35°C) for 60 minutes. The solution was removed from the freezer, and n-BuLi (28.2 mL, 81.2 mmol, 2.29 M) was added dropwise over 9 minutes. The solution was warmed to room temperature, and a sample was taken after 180 minutes to determine completion of the reaction. To prepare reaction aliquots, a small amount of the solution was quenched with CD3OD, and the THF layer was analyzed by GC / MS. During the reaction time, chlorobis(2,6-dimethoxyphenyl)phosphine (24.59 g, 72.10 mmol) was added to the jar along with 135 mL of anhydrous THF and placed in a -35°C freezer for approximately 1 hour. After GC / MS determined that lithiation was complete, the solution was returned to the freezer for 55 minutes. The reaction solution was removed from the freezer and the chlorophosphine solution was added dropwise to the reaction solution. The resulting solution was warmed to room temperature overnight. 31 ¹P NMR analysis (C6D6) indicated that the reaction was complete and all of the chlorophosphine starting material had been consumed. The solvent was removed under vacuum to obtain a dark, oily residue. To aid in the removal of residual THF, 275 mL of hexane was added to the product material, and the mixture was vigorously stirred, after which the solvent was removed under vacuum. A second round of hexane (275 mL) was added, and the slurry was filtered. The filtered solid was rinsed with further hexane and then dried overnight under vacuum to obtain 52 g of solid. The solid was mixed with approximately 175 mL of toluene and then filtered through Celite®. The solid was rinsed with further toluene and combined with the original filtrate. The filtrate was dried overnight at 50°C under vacuum. Hexane was added, and volatiles were removed under reduced pressure to remove residual toluene. The product was dried overnight under vacuum to obtain 48.44 g (88.3%) of product, verified by NMR.

[0123] 1H NMR (400MHz, benzene-d6) δ8.38(d,J=1.9Hz,2H),7.58-7.49(m,3H),7.43(d,J=8.7Hz,1H) ,7.35(d,J=8.6Hz,1H),7.17(d,J=0.9Hz,1H),6.86(td,J=7.7,0.8Hz,1H),6.37(dt,J= 8.3,2.8Hz,4H),5.37(s,1H),4.01-3.79(m,1H),3.19(d,J=2.2Hz,12H),3.12-3.02(m, 1H),1.79(dd,J=14.4,10.2Hz,1H),1.61-1.51(m,1H),1.43(s,18H),1.33-0.82(m,6H). 13 ¹³C NMR (101MHz, benzene-d6) δ 163.43, 163.37, 163.33, 163.28, 155.49, 155.28, 142.43, 142.38, 140.24, 140.19, 137.04, 136.87, 133.50, 130.34, 130.30, 130.00, 129.94, 124.15, 124.02, 12 3.89, 123.70, 122.74, 116.30, 116.25, 115.35, 115.09, 114.80, 114.53, 111.34, 104.70, 104.53, 100.21, 100.14, 61.51, 61.41, 55.59, 55.55, 34.79, 32.21, 30.29, 25.53, 17.88, 17.86. 31 P NMR (162 MHz, benzene-d6) δ-52.45.

[0124] Synthesis of 2-(bis(2,6-dimethoxyphenyl)phosphanyl)-6-(3,6-di-tert-butyl-9H-carbazole-9-yl)phenol

[0125] [ka]

[0126] The glassware was oven-dried. In a nitrogen-atmosphere glove box, 9-(3-(bis(2,6-dimethoxyphenyl)phosphanyl)-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-3,6-di-tert-butyl-9H-carbazole (60.00 g, 78.96 mmol) and diethyl ether (550 mL) were placed in a 2 L multi-necked round-bottom flask equipped with a magnetic stirrer and stirred to produce a slightly cloudy yellow solution. An addition funnel (500 mL) was attached to the center neck of the flask, and the rest was sealed with a rubber septum. HCl in ether (394.78 mL, 789.55 mmol) was added to the addition funnel and also sealed with a rubber septum. The reaction mixture was removed from the glove box, transferred to a fume hood, and placed under a nitrogen pad. Degassed water (170 mL) was added, thereby obtaining two phases of light brown color. A solution of HCl in diethyl ether was added dropwise to the reaction mixture over 55 minutes. A white solid was observed, which precipitated from the solution in the lower phase upon addition of HCl. The reaction was heated overnight at 40°C (heating block temperature). The organic layer was sampled, dried, and then... 1 H and 31 The reaction was analyzed by 1P NMR spectroscopy. After determining that the reaction was complete, the reaction was cooled to room temperature, and water (360 mL) was added to the reaction mixture. Sodium bicarbonate (1.1 equivalents relative to HCl) was carefully added little by little to the reaction mixture. After stirring for a short time, the ether was almost completely removed under reduced pressure. Dichloromethane (650 mL) was added to the residue until the solid dissolved in the solution. The solution was stirred thoroughly, then transferred to a separatory funnel, and the layers were separated. A saturated solution of sodium bicarbonate (1.4 L) was added to the organic phase, and the mixture was shaken vigorously for less than 1 minute. The phases were separated. The organic phase was dried over sodium sulfate, filtered, and concentrated under vacuum to obtain a pale brown solid. NMR analysis showed a product containing some impurities (51.87 g). The solid was pulverized in about 250 mL of warmed methanol (about 40°C), filtered, and washed with further warmed methanol. After drying in a hood under vacuum for several hours, a white solid (37.8 g, 70.8%) was isolated, and the product was analyzed by NMR.

[0127] 1 H NMR (400MHz, benzene-d6) δ8.36(dd,J=2.0,0.6Hz,2H),8.07(ddd,J=11.6,7.6,1.7Hz,1H),7.49-7.37(m,3H),7.25(dt,J=8.0,1 .1Hz,3H),7.01(td,J=8.3,1.1Hz,2H),6.83(td,J=7.7,1.4Hz,1H),6.21(dd,J=8.3,2.9Hz,4H),3.12(s,12H),1.42(s,18H). 13 ¹³C NMR (101MHz, benzene-d6) δ 161.86, 161.78, 155.84, 155.78, 141.76, 140.27, 135.51, 135.15, 129.66, 129.49, 127.91, 127.67, 127.43, 123.97, 123.66, 123.32, 119.19, 119.06, 116.02, 113.00, 112.78, 110.26, 104.09, 55.09, 34.41, 31.88. 31 P NMR (162 MHz, benzene-d6) δ-58.87.

[0128] Synthesis of tetrakis(pyridine)nickel dichloride

[0129] [ka]

[0130] In a nitrogen-atmosphere glove box, NiCl2 (25.318 g, 195.37 mmol) and anhydrous pyridine (253.2 mL, 3143.5 mmol) were placed in a 500 mL round-bottom flask equipped with a stirring bar. The flask was mounted on a Stevens condenser and placed in a fume hood. The reaction mixture was heated under reflux for 3 hours (the boiling point of pyridine is 115 °C). The yellow / orange NiCl2 was poorly soluble in pyridine at room temperature. After a short reflux, a blue-green precipitate was observed. After 3 hours, a bright blue precipitate was observed. The hot plate was turned off and the solution was allowed to cool overnight. The suspension was filtered, washed with hexane, and dried under vacuum to obtain the product as a bright blue powder (83.09 g, 95.8%). This substance was used without purification or characterization.

[0131] Synthesis of bis(pyridine)bis((trimethylsilyl)methyl)nickel

[0132] [ka]

[0133] In a nitrogen-atmosphere glove box, tetrakis(pyridine)nickel dichloride (34.67 g, 77.74 mmol), anhydrous pyridine (19.1 mL, 237.1 mmol), and 630 mL of diethyl ether were placed in a 32-ounce jar equipped with a stirring bar. The jar was cooled in a -30°C freezer for 2 days. A solution of ((trimethylsilyl)methyl)magnesium chloride (1.03 M, 150.94 mL, 155.47 mmol) in diethyl ether was added over 1 hour using an addition funnel. After the addition was complete, the reaction was stirred for 25 minutes. The solution was concentrated under vacuum to obtain a thick slurry. A mixture of pentane (875 mL) and pyridine (21 mL) was prepared. A portion of the pentane / pyridine solution was stirred in the product slurry and then filtered through Celite®. The remaining solution was used to rinse the solid. Additional pentane / pyridine solution and hexane were used for rinsing. Filtration was slow. The filtrate was reduced during vacuum filtration to obtain a solid precipitate. The filtrate was transferred to a 32-ounce jar, and the filter frit was rinsed with hexane / pentane. The jar was covered and placed in a glove box freezer. After several days, the solution was decanted, and the solid was lightly rinsed with cold hexane. The crystalline solid (brown needle-shaped) was vacuum-dried overnight at room temperature (20.72 g was obtained) and then analyzed by NMR. The decanted and rinsed solutions were vacuum-dried, and then sufficient hexane was added to almost dissolve the solid. The solution was transferred to a dry box freezer for recrystallization, and after several days, 4.85 g of solid was obtained. The decanted and rinsed solutions were dried again, and after some time in the freezer with fresh hexane, a third harvest (1.04 g) was obtained. Yield = 87.5%.

[0134] 1 H NMR (400MHz, benzene-d6) δ8.63-8.18(m,4H),6.64(t,J=7.6Hz,2H),6.22(s,4H),0.65-0.25(m,18H),-0.59(s,4H). 13 ¹³C NMR (101 MHz, benzene-d6): δ 150.16, 134.26, 122.99, 3.52, 0.22.

[0135] Synthesis (metallation) of (2-bis((2,6-dimethoxyphenyl)phosphanyl)-6-(3,6-di-tert-butyl-9H-carbazole-9-yl)phenolate)nickel(pyridine)trimethylsilylmethyl

[0136] [ka]

[0137] A solution of 2-(bis(2,6-dimethoxyphenyl)phosphanyl)-6-(3,6-di-tert-butyl-9H-carbazole-9-yl)phenol (75.00 g, 111.0 mmol) in 1.13 L of THF was prepared in a nitrogen-atmosphere glove box. Separately, a solution of bis(pyridine)bis(trimethylsilylmethyl)nickel (43.43 g, 111.0 mmol) in 563 mL of THF containing 1 equivalent of pyridine was prepared in a glove box and added to a 6 L jacketed glass reactor. The ligand solution was added (in batches) to a 500 mL addition funnel, and the ligand was added to the Ni precursor solution over 25-30 minutes to obtain a dark reddish-brown solution, which was stirred at ambient temperature. The aliquots were dried, and the reaction was completed. 31 The reaction was monitored by 1P NMR. After 60 minutes of reaction (t=0, when the ligand solution was completely added to the reactor), 31 The reaction was completed based on the disappearance of the starting material peak in the 1P NMR spectrum. Volatiles were removed under reduced pressure. The residue was ground with 1 L of pentane and collected by filtration to obtain an orange / rust-colored solid, which was then used to make the final product. 1 H, 13 C, and 31 The mixture was analyzed by 1P NMR. To remove residual THF, the solid was returned to a (clean) 6L reactor and approximately 1L of toluene was added. Volatile substances were removed under reduced pressure at 35°C overnight. The resulting dried orange solid was collected and analyzed by NMR, which showed the desired product (77.0g) in quantitative yield.

[0138] 1H NMR(400MHz,ベンゼン-d6)δ8.75-8.59(m,2H),8.39(d,J=1.9Hz,2H),7.91(ddd,J=10.5,7.6 ,1.7Hz,1H),7.65(d,J=8.6Hz,2H),7.50(dd,J=8.6,2.0Hz,2H),7.43(dd,J=7.4,1.7Hz,1 H),7.12(t,J=8.1Hz,3H),6.65(tt,J=7.6,1.6Hz,1H),6.55(td,J=7.5,2.1Hz,1H),6.29( dt,J=7.2,2.7Hz,6H),3.30(s,12H),1.47(s,18H),-0.11(s,9H),-0.66(d,J=9.3Hz,2H). 13 C NMR(101MHz,ベンゼン-d6)δ159.70,149.33,139.00,138.44,133.97,128.58,1 21.51,121.01,113.76,109.97,102.66,102.62,53.26,32.70,30.34,0.22. 31 P NMR (162MHz, ベンゼン-d6) δ-7.17.

[0139] Examples IE1~IE8 and CE1 are overlapping reactors for high voltage reactors. Table 1 shows the polymerization process for producing linear ethylene copolymers. The experiment was conducted in an outdoor miniplant. The procedure for the high-pressure reactor campaign involved supplying purified ethylene mixed with purified tert-butyl acrylate at 7 pph. To prevent autopolymerization, 10–20 ppm by mass of methylhydroquinone was supplied to the tert-butyl acrylate. As part of sample preparation, 100 ppm by mass of 4-hydroxy-TEMPO was added to the tert-butyl acrylate, and the tert-butyl acrylate was then purged with nitrogen to remove residual oxygen. The tert-butyl acrylate was then purified through an AZ-300 absorption bed while being supplied to the process, mainly removing methylhydroquinone, 4-hydroxy-TEMPO, and other impurities. The feeds of ethylene and tert-butyl acrylate were then compressed and pressurized in two stages to 2000 barg to produce a supercritical ethylene flow. The supercritical ethylene flow was then supplied to a 300 mL continuous stirring tank reactor. The reactor temperature was controlled to the target temperature using four electric heating bands on the reactor wall. Separately, mixtures of Ni catalyst 1 diluted in toluene at various concentrations (abbreviated as "conc." in the table) were supplied to the reactor. The supply was controlled to target the set concentration of Ni in the reactor. In some cases, mixtures of MMAO-3A diluted in isopar E at various concentrations were additionally supplied separately. After leaving the reactor, the flow was rapidly depressurized to 1 barg through a valve to separate ethylene from the polymerization material. An oxygen / nitrogen mixture was added to the flow to neutralize the catalyst and freeze the polymer.

[0140] [ka]

[0141] Example CE2 Polymerization process using a low-pressure solution batch reactor to produce linear polar ethylene copolymer The polymerization reaction was carried out in a 2 L Parr batch reactor. The reactor was heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water. The water was pretreated by passing it through an Evoqua water purification system. Both the reactor and the heating / cooling system were controlled and monitored by a Camile TG process computer. A dump valve was installed at the bottom of the reactor to transfer the reactor contents to a lidded dump pot. The dump pot was pre-filled with a catalyst deactivation solution (typically 5 mL of Irgafos / Irganox / toluene mixture). Both the pot and the tank were purged with N2, and the lidded dump pot was aerated to a 15-gallon blowdown tank. All chemicals used for polymerization or catalyst composition were passed through a purification column to remove any impurities that could affect polymerization. Toluene was passed through two columns: a first column containing A2 alumina and a second column containing the Q5 reactant. The tert-butyl acrylate was filtered through activated alumina. Ethylene was passed through two columns: a first column containing A204 alumina and a 4Å molecular sieve, and a second column containing the Q5 reactant. N2, used for transfer, was passed through a single column containing A204 alumina, a 4Å molecular sieve, and the Q5 reactant.

[0142] The reactor was initially filled with shot tanks containing toluene and tert-butyl acrylate. The shot tanks were filled to the set filling level using a differential pressure transducer. After adding the solvent / acrylate, the shot tanks were rinsed twice with toluene, and the rinse liquid was transferred to the reactor (total mass of toluene = 605 g, total mass of tert-butyl acrylate = 9.28 g). The reactor was then heated to the desired polymerization temperature set point (150°C). Once the temperature set point was reached, ethylene was added to the reactor to reach the desired pressure set point (600 psi). The amount of ethylene added to the reactor was monitored using a micro-flow meter (initial ethylene filling amount = 89 g).

[0143] The catalysts, Ni catalyst 1, were handled in an inert atmosphere glove box and introduced into the reactor as a solution in toluene. The catalyst solution was drawn into a syringe and transferred under pressure to a catalyst shot tank (59.2 μmol of catalyst was added). This was followed by three rinses with 5 mL each of toluene. The catalyst was added only after the reactor pressure setpoint had been reached.

[0144] Immediately after catalyst addition, the run timer was started. Then, ethylene was supplied to the reactor (via a Camile controller) to maintain the pressure setpoint. The ethylene / tert-butyl acrylate copolymerization reaction was run for 45 minutes, but the ethylene uptake curve showed that the catalyst was active only for the first 3 minutes of the reaction. After 45 minutes, the stirrer was stopped and the bottom dump valve was opened to discharge the contents of the reactor into a lidded dump pot. The valve on the lidded dump pot was closed, the sealed dump pot was detached from the reactor and placed in a fume hood. Once inside the fume hood, the lid was removed from the dump pot and the contents were poured into trays. The trays were left in the hood for a minimum of 36 hours to evaporate the solvent and tert-butyl acrylate (tBA). The trays containing the remaining polymer were then transferred to a vacuum oven (Note: 4-methoxyphenol was added to the trap to prevent spontaneous polymerization of tert-butyl acrylate), where they were heated to 140°C under vacuum to remove any residual volatile materials. After the trays cooled to ambient temperature, the polymer was weighed for yield / efficiency and subjected to polymer testing. In this experiment, 14.6 g of copolymer was obtained.

[0145] [Table 2]

[0146] [Table 3]

[0147] Experiment 1 (CE1) in Table 1 is a comparative example. The polymerization process did not include polar comonomers.

[0148] [Table 4]

[0149] [Table 5]

[0150] The polymer produced from CE1 has a high melt index and a high melting temperature compared to other inventive examples in Table 3. However, the polymer of CE1 is a linear polymer lacking polar comonomers and is not an exemplary embodiment of the present disclosure.

[0151] In Example CE2, Ni-catalyzed copolymerization of ethylene and tert-butyl acrylate was carried out at low pressure in solution. The molecular weight (MW) of the copolymer in Example CE2 was significantly lower than that achieved in IE1–IE8. When the linear ethylene / tert-butyl acrylate copolymers produced from the polymerization processes of IE1–IE8 were compared with highly branched ethylene / tert-butyl acrylate copolymers (CE3–CE7, Table 5), the polymers of IE1–IE8 had higher melting temperatures (Tm) and higher molecular weights (Mw).

[0152] The process conditions for producing comparative branched polymers (CE3-CE7) are recorded in Table 4.

[0153] Comparative example CE3-CE7 Table 4 shows the polymerization processes for producing comparatively highly branched ethylene copolymers (CE3-CE7). These copolymers were prepared without the addition of a nickel catalyst to the reactor. The procedure for producing branched polyethylene copolymers involved supplying purified ethylene at 7 pph, which was mixed with purified tert-butyl acrylate and isoper E. The ethylene / tert-butyl acrylate mixture was compressed and pressurized to 2000 barg to create a supercritical ethylene flow. The supercritical ethylene flow was then supplied to a 300 mL continuous stirring tank reactor. The reactor temperature was controlled to the target temperature using four electric heating bands on the reactor wall. Separately, a mixture of tert-butyl peroctoate and isoper E was supplied to the reactor to initiate free radical polymerization. The supply was controlled so that the ethylene conversion rate in the reactor remained at 12 + / - 2%, measured based on the total polymer collected. After leaving the reactor, the flow was rapidly depressurized to 1 barg through a valve to separate the ethylene from the polymerization material. Nitrogen was added to the flow to freeze the polymer.

[0154] [Table 6]

[0155] In Table 5, the reactor conditions were very similar to those summarized in Tables 1 and 2. However, the reactor conditions reported in Table 4 did not include a transition metal catalyst. Polymerization was initiated using the radical initiator, tert-butyl peroctoate.

[0156] [Table 7]

[0157] The copolymers recorded in Table 5 are highly branched and have significantly lower melting temperatures compared to the linear copolymers (IE1-IE8) produced under the polymerization conditions recorded in Table 1. Figure 1 graphically illustrates that branched polymers have lower melting temperatures than linear polymers. In general, for the same level (wt%) of acrylate incorporation, linear copolymers (IE1-IE8) have a Tm increase of at least 10°C compared to branched copolymers (CE3-CE7).

[0158] [Table 8]

[0159] The results summarized in Table 6 demonstrate that the catalyst efficiency increases when the ethylene concentration in the reactor increases significantly at a given reaction time, temperature, and C2 / tBA ratio. The reaction process in CE2 was a solution polymerization process at low pressure (41 barg), and the efficiency of Ni catalyst 1 was significantly lower compared to high-pressure experiments IE3 and IE4 (over 2000 barg). For example, CE2 and IE4 were run at the same C2 / tBA ratio, temperature, and reaction time, but the ethylene concentration in the reactor in IE4 was almost seven times higher than in CE2. This resulted in an almost four-fold improvement in catalyst efficiency for IE4, accompanied by an almost three-fold improvement in copolymer MW (while maintaining high t-BA incorporation).

Claims

1. It is a polymerization process, Ethylene, one or more polar comonomers, and optionally one or more (C ３ ~C １２ A polymerization process comprising polymerizing an α-olefin and optionally an aluminum species in the presence of a catalyst system to form an ethylene copolymer in a high-pressure reactor at a pressure exceeding 1000 barg and a temperature exceeding 100°C, wherein the catalyst system includes a transition metal catalyst.

2. The polymerization process according to claim 1, wherein the aluminum species includes aluminoxane or alkylaluminum, or a combination of aluminoxane and alkylaluminum.

3. The polymerization process according to claim 1 or 2, wherein the transition metal catalyst comprises nickel(II) or palladium(II).

4. The transition metal catalyst or transition metal procatalyst comprises nickel(II) or palladium(II) and has a structure according to formula (I), 【Chemistry 1】 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 , -(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 A ligand selected from halogens or hydrogen, and each R Ｃ Independently, substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl, or substituted or unsubstituted (C １ ~C ３０ ) is a heterohydrocarbyl, where 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 arbitrarily linked. P is phosphorus, R １ is independently selected from the group consisting of -H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ -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(=O)(R<00S0093> ) ２、 -P(R Ｃ ) ２－Ｗ (OR Ｃ ) Ｗ -P(O)(R Ｃ ) ２－Ｗ (OR Ｃ ) Ｗ -Ge(R Ｃ ) ３ -P(R Ｐ ) ２ -N(R Ｎ )<OOO0108>-OR<O000109> -SR Ｃ -NO ２ -CN, -CF ３ R Ｃ S(O)-, R Ｃ S(O) ２ -, -N=C(R Ｃ ) ２ R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)-, halogen, a radical having formula (II), a radical having formula (III), and a radical having formula (IV), 【Chemistry 2】 In the formula, R ３１～３５ , R ４１～４８ , and R ５１～５９ Each of these independently is -H, (C １ ~C ４０ ) Hydrocarbyl, (C １ ~C ４０ ) Heterohydrocarbyl, -Si(R Ｃ ) ３ ,-Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C = N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R) Ｎ ) -, (R Ｃ ) ２ Selected from NC(O)- or halogen, R ２ , R ３ , and R ４ This is independently, substitution (C １ ~C ３０ ) Hydrocarbyl, unsubstituted (C １ ~C ３０ ) Hydrocarbyl, substitution (C １ ~C ３０ ) Heterohydrocarbyl, unsubstituted (C １ ~C ３０ ) Heterohydrocarbyl, -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 ) 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(O)R Ｃ , -C(O)N(R Ｃ ) ２ , or selected from halogen, each R Ｃ Independently, substitution or non-substitution (C １ ~C ３０ ) Hydrocarbyl, or substituted or unsubstituted (C １ ~C ３０ ) is a heterohydrocarbyl, where Q is 0, 1, 2, or 3, and W is 0, 1, or 2. R ５ and R ６ This is independently, substitution (C １ ~C ３０ ) Hydrocarbyl, unsubstituted (C １ ~C ３０ ) Hydrocarbyl, substitution (C １ ~C ３０ ) Heterohydrocarbyl, or unsubstituted (C １ ~C ３０ ) Selected from heterohydrocarbils, Optionally, R ５ and R ６ However, they are linked together to form a ring structure, Optionally, R ２ and R ３ However, they are linked together to form a ring structure, or Optionally, R ３ and R ４ The polymerization process according to any one of claims 1 to 3, wherein the molecules are linked together to form a ring structure.

5. R ５ and R ６ However, independently, (C １ ~C ２０ ) alkyl, (C ６ ~C ２０ ) Aryl, or substitution (C ６ ~C ２０ The polymerization process according to claim 4, wherein the polymer is an aryl compound.

6. The polymerization process according to claim 4 or 5, wherein Y is a pyridine, a substituted pyridine, a sulfoxide, a trialkyl, a triarylphosphine, a trialkyl, a triarylphosphine oxide, a substituted heterocycle, an unsubstituted heterocycle, an aliphatic ketone, an aliphatic amine, an alkyl ether, or a cycloalkyl ether.

7. R ２ , R ３ , and R ４ However, (C １ ~C １８ The polymerization process according to any one of claims 4 to 6, wherein the molecule is alkyl or -H.

8. R １ The polymerization process according to any one of claims 4 to 7, wherein the radical is of formula (II), (III), or (IV).

9. X is either substituted or not substituted (C １ ~C ３０ ) Hydrocarbyl, substituted or unsubstituted (C １ ~C ３０ ) The polymerization process according to any one of claims 4 to 8, wherein the result is a heterohydrocarbyl.

10. The polymerization process according to any one of claims 1 to 9, wherein the polar monomer comprises one or more alkyl acrylate monomers.

11. The polymerization process according to any one of claims 1 to 10, wherein the alkyl acrylate is methyl acrylate, ethyl acrylate, n-butyl acrylate, or t-butyl acrylate.

12. The polymerization process according to any one of claims 1 to 11, wherein the temperature is greater than 100°C to 250°C.

13. The polymerization process according to any one of claims 1 to 12, wherein the pressure is greater than 1000 barg to 5000 barg.

14. An ethylene-based polymer produced from a polymerization process according to any one of claims 9 to 12.

15. Procatalysts with any of the structures disclosed herein.

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