Sterically hindered phosphine-amide supported nickel(II) or palladium(II) catalysts for copolymerization of ethylene with polar comonomers

Abstract

A process for polymerizing olefin monomers using a catalyst system and the catalyst system comprises a procatalyst having a structure according to formula (I). [Formula 1] JPEG2023520145000028.jpg25128

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 002,760, filed March 31, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION Embodiments of the present disclosure relate generally to ethylene and polar comonomer polymerization catalyst systems and processes, and more specifically to ethylene and acrylate polymerization catalyst systems comprising sterically hindered phosphine-amide supported nickel(II) catalysts and olefin polymerization processes incorporating the catalyst systems. [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 that of low-density polyethylene (LDPE). Coordination catalysis provides a route to highly linear ethylene / acrylate copolymers with a structure similar to that of 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.

[0004] Common organometallic coordination catalysts suitable for ethylene polymerization are incompatible with systems containing acrylates as comonomers. For example, 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. Because the oxygen atoms of acrylates strongly coordinate with Lewis acidic Group IV metals, during ethylene / acrylate polymerization, the active sites of the metal are blocked by the acrylate, preventing further olefin polymerization.

[0005] Due to the incompatibility of Group IV metal catalysts with acrylates, electron-rich metal catalysts containing Group 10 metals (Pd, Ni) have been explored for the copolymerization reaction of ethylene with acrylate monomers. However, many reported Ni- and Pd-containing metal catalysts suffer from (a) slow polymerization rates and / or (b) poor incorporation of the desired polar monomers. Summary of the Invention

[0006] There is a continuing need to create ligand frameworks for Ni and Pd catalysts that promote both high rates of ethylene copolymerization activity and high incorporation of acrylate comonomers. Using nickel or palladium ligand frameworks, ethylene and polar monomers can be copolymerized via coordination catalysis to form highly linear LLDPE-like copolymers. The highly linear copolymers can exhibit improved creep resistance and dimensional stability at higher temperatures, specifically between 80°C and 150°C, as opposed to temperatures below 80°C.

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

[0008] [ka]

[0009] In formula (I), M is nickel(II) or Pd(II), and X is (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -H, -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, -N(Si(R C )3)2, -NR C Si(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 , -C(O)R C , -C(O)H, -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -NHC(O)H, -C(O)N(R C )2, -C(O)NHR C , —C(O)NH2, or halogen. C are independently: (a) one or more R S optionally substituted with (C1 to C 30 ) hydrocarbyl, or (b) one or more R S optionally substituted with (C1 to C 30 ) heterohydrocarbyl. The subscript Q in the various ligands X is 0, 1, 2, or 3. The subscript W in the various ligands X is 0, 1, or 2. Y is a Lewis base. Optionally, Y and X in formula (I) are covalently bonded.

[0010] In formula (I), R 1is unsubstituted (C6-C 40 ) Aryl, substituted (C6-C 40 ) aryl, unsubstituted (C1-C) with radicals on carbon atoms 40 ) Heteroaryl, substituted with radicals on carbon atoms (C1-C 40 ) heteroaryl or a substituted (C4-C) heteroaryl having at least one tertiary carbon atom and a radical on the tertiary carbon atom 20 ) alkyl.

[0011] In formula (I), R 2 and R 3 is independently selected from radicals having formula (II):

[0012] [ka]

[0013] In formula (II), R 11 , R 12 , R 13 , R 14 , and R 15 are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, -OR N , -NR N 2, -SR N , halogen, or -H, where each R N is (C1~C 30 ) hydrocarbyl, provided that R 11 and R 15 At least one of them is not -H.

[0014] In formula (I), each R S are independently (C1~C 20 ) hydrocarbyl or halogen.

[0015] Embodiments of the present disclosure include 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, wherein the catalyst system comprises a metal-ligand complex according to formula (I) of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0016] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0017] Common abbreviations are listed below. 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, EtOAc: ethyl acetate, C6D6: deuterated benzene or benzene-d6, CDCl3: deuterated chloroform, Na2SO4: sodium sulfate, MgSO4: magnesium sulfate , HCl: hydrogen chloride, n-BuLi: butyl lithium, t-BuLi: tert-butyl lithium, K2CO3: potassium carbonate, N2: 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: molar concentration, min or mins: minute, h or hrs: hour, d: day, R f ; retention factor, TLC; thin layer chromatography, rpm: revolutions per minute.

[0018] The term "independently selected" followed by multiple options is 1 , R 2 , R 3, and R C etc. are used herein to indicate that the individual groups that appear before the term may be the same or different and that there is no dependency on the identity of any other groups that appear before the term.

[0019] 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.

[0020] When used to describe certain carbon atom-containing chemical groups, "(C x ~C y A bracketed expression having the form "(C1-C)" means that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive, including x and y. For example, (C1-C 50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S and R S generally represents any substituent 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", the group may contain more than y carbon atoms. For example, "R S exactly one group R is phenyl (-C6H5) S (C1~C 50 A "(C ) alkyl" can contain from 7 to 56 carbon atoms. Thus, the parenthesized "(C ) alkyl" is generally used. x ~C y )" is a group defined using one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group are both x and y, respectively, and all carbon atom-containing substituents R S The total number of carbon atoms from the olefin is determined by adding the total number of carbon atoms from the olefin.

[0021] The term "substituted" means that at least one heteroatom (-H) bonded to a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ) is replaced by a substituent (e.g., R). The prefix "per" has the conventional meaning of "thoroughly." For example, the term "persubstituted" or "persubstituted" means that all hydrogen atoms (H) bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group have been replaced by a substituent (e.g., R S ) means substituted by a substituent. Thus, a "perfluorinated alkyl" is an alkyl group in which all hydrogen atoms have been replaced by fluorine atoms. The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to carbon or heteroatoms of the corresponding unsubstituted compound or functional group have been replaced by a substituent. 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.

[0022] "(C1~C 50 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical having 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical having from 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is 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 wherein one or more R S is or is not replaced by

[0023] In this disclosure, (C1 to C 50 ) As hydrocarbyl, the following groups are included: (C1-C 50 ) Alkyl, (C3-C 50 ) cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40 ) aryl, or (C6-C20 )Aryl-(C1-C 20 ) alkylene (e.g., benzyl (—CH2—C6H5)).

[0024] "(C1~C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to a group that is unsubstituted or has one or more R S and saturated straight-chain or branched hydrocarbon radicals of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively, substituted by the unsubstituted (C1-C 50 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 2,2-dimethylpropyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C n ] alkyl. n The term "alkyl" refers to a radical containing a substituent containing up to n carbon atoms, where n is an integer from 1 to 45. For example, [C 45 ] alkyl is, for example, one R that is (C1-C5) alkyl. S (C 27 ~C 40 ) alkyl, or, for example, each (C1-C 10 ) two R's that are alkyl S substituted with a group (C 15 ~C 25) alkyl. Examples of (C1-C5) alkyl include methyl, ethyl, 1-propyl, 1-methylethyl, 2,2-dimethylpropyl, and 1,1-dimethylethyl. 1,1-Dimethylethyl is a four-carbon alkyl with the radical on the tertiary carbon. The term "tertiary carbon atom" refers to a carbon atom that is covalently bonded to three other carbon atoms.

[0025] "(C6~C 50 The term "aryl" refers to an aryl group having 6 to 40 carbon atoms, of which at least 6 to 14 carbon atoms are aromatic ring carbon atoms, unsubstituted or (one or more R S "Aromatic hydrocarbon radicals" refers to monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radicals substituted (by) a substituted (by) monocyclic aromatic hydrocarbon radicals, bicyclic aromatic hydrocarbon radicals have two rings, and tricyclic aromatic hydrocarbon radicals have three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring(s) of the aromatic radical may independently be fused or non-fused and aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryl include unsubstituted (C6-C 20 )Aryl, unsubstituted (C6-C 18 )aryl, 2-(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, anthracenyl and phenanthrenyl. 40 Examples of aryl include substituted (C1-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis[(C 20 ) alkyl]-phenyl, 3,5-bis[(C 20 ) alkyl]-phenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0026] "(C3~C 50The term "cycloalkyl" refers to a group that is unsubstituted or has one or more R S means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms substituted with other cycloalkyl groups, such as (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3 to C 40 Examples of cycloalkyl are unsubstituted (C-C 20 ) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0027] (C1~C 50 Examples of hydrocarbylenes include (C6-C 50 ) arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20 Diradicals include, but are not limited to, unsubstituted or substituted forms of groups such as alkylene, alkoxy, methyl ... 20Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH-), and 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (C6-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0028] "(C1~C 50 The term "alkylene" may be unsubstituted or may contain one or more R S means a saturated straight or branched chain diradical of 1 to 50 carbon atoms (i.e., the radical is not on a ring atom) substituted by 50 Examples of alkylene are unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3 and -(CH2)4C * Unsubstituted (C1-C, including (H)(CH3) 20 ) alkylene, wherein "C * " denotes a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 50 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted 1,20-eicosylene). 50 Examples of ) also include 1,2-cyclopentanediylbis(methylene), 1,2-cyclohexanediylbis(methylene), 7,7-dimethyl-bicyclo[2.2.1]heptane-2,3-diylbis(methylene), and bicyclo[2.2.2]octane-2,3-diylbis(methylene).

[0029] "(C3~C 50The term "cycloalkylene" may be unsubstituted or may contain one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms substituted by

[0030] 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(R N )2, -N=C(R C )2, -N=C(NR N 2)(R C ), -Ge(R C )2-, or -Si(R C ) 3, wherein each R C and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or —H, and each R N is unsubstituted (C1 to C 18 ) hydrocarbyl or -H. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more hydrocarbon carbon atoms are replaced with a heteroatom. "(C1-C 50 The term "(C1-C)heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 ) heterohydrocarbyl or (C1-C 50The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The heterohydrocarbyl radical may be present on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be present on a single carbon atom or a single heteroatom. Furthermore, one of the two radicals of the diradical may be present on a carbon atom and the other radical on a different carbon atom; 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 on a different heteroatom. Each (C1-C 50 ) heterohydrocarbyl and (C1-C 50 ) heterohydrocarbylene is unsubstituted or (one or more R S and may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0031] (C1~C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heterohydrocarbyls include (C1-C 50 ) heteroalkyl, (C1-C 50 ) hydrocarbyl-O-, (C1-C 50 ) hydrocarbyl-S-, (C1-C 50 ) hydrocarbyl-S(O)-, (C1-C 50 ) hydrocarbyl-S(O)2-, (C1-C 50 ) Hydrocarbyl-Si(R C )2-, (C l ~C 50 )hydrocarbyl-N(R N )-, (C l ~C 50 ) hydrocarbyl-P(R P )-, (C2~C 50 ) heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20)Cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 50 ) heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene. 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, but are not limited to these.

[0032] "(C4~C 50 The term "heteroaryl" refers to an unsubstituted or substituted heteroaryl group of a total of 2 to 50 carbon atoms and 1 to 10 heteroatoms (one or more R S (by) substituted monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radicals. The heteroaryl radical may be present on a carbon atom or on a heteroatom. A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring(s) of the heteroaromatic radical may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C4-C 12 ) heteroaryl, etc. x ~C y ) heteroaryl (general) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or contains one or more R SThe monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as being substituted with . The monocyclic heteroaromatic hydrocarbon radical is a 5-membered 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 independently be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. A 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and the heteroatoms can be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, pyrazin-2-yl, and 1,3,5-triazin-2-yl. 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. 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.

[0033] "(C1~C 50The term "(C1-C)heteroalkyl" means a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatom of a heteroalkyl or heteroalkylene is 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, S.R. C , S(O), and S(O)2, where each of the heteroalkyl and heteroalkylene groups is unsubstituted or contains one or more R S has been replaced by

[0034] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0035] The term "halogen atom" or "halogen" refers to the radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom (fluoride (F) - ), chloride (Cl - ), bromide (Br- ), or iodide (I - )) means.

[0036] 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 or triple bonds. A saturated chemical group may be formed by one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be substituted by a substituent R S The term "unsaturated" means containing one or more carbon-carbon double or 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), and if present, the substituent R S It does not include any double bonds which may be present in the (hetero)aromatic ring or, if any, in the (hetero)aromatic ring.

[0037] Embodiments of the present disclosure include a catalyst system, which includes a procatalyst having a structure according to formula (I).

[0038] [ka]

[0039] In formula (I), M is nickel(II) or Pd(II), and X is (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -H, -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 (ORC ) Q , -P(R C ) 2-W (OR C ) W , -P(O)(R C ) 2-W (OR C ) W , -N(R C )2, -N(Si(R C )3)2, -NR C Si(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 , -C(O)R C , -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -NHC(O)H, -C(O)N(R C )2, -C(O)NHR C , —C(O)NH2, or a halogen. The subscript Q in the various ligands X is 0, 1, 2, or 3. The subscript W in the various ligands X is 0, 1, or 2. Y is a Lewis base. Optionally, Y and X in formula (I) are covalently bonded.

[0040] In formula (I), R 1 is unsubstituted (C6-C 40 ) Aryl, substituted (C6-C 40 ) aryl, unsubstituted (C1-C) with radicals on carbon atoms 40 ) Heteroaryl, substituted with radicals on carbon atoms (C1-C 40) heteroaryl or a substituted (C4-C) heteroaryl having at least one tertiary carbon atom and a radical on the tertiary carbon atom 20 The term "tertiary carbon atom" refers to a carbon atom that is covalently bonded to three other carbon atoms.

[0041] In formula (I), R 2 and R 3 is independently selected from radicals having formula (II):

[0042] [ka]

[0043] In formula (II), R 11 , R 12 , R 13 , R 14 , and R 15 are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, -OR N , -NR N 2, -SR N , halogen, or -H, provided that at least one or R 11 and R 15 is not -H. Each R N is (C1~C 30 ) hydrocarbyl.

[0044] In formula (I), each R C are independently: (a) one or more R S optionally substituted with (C1 to C 30 ) hydrocarbyl, or (b) one or more R S optionally substituted with (C1 to C 30 ) heterohydrocarbyl. Each R in formula (I) S are independently (C1~C 20 ) hydrocarbyl or halogen.

[0045] In one or more embodiments, in formula (I), R2 and R 3 are identical.

[0046] In various embodiments, in formula (I), R 11 and R 15 are independently -O[(C1~C 10 ) alkyl]. In some embodiments, R 11 and R 15 is methoxy, ethoxy, or isopropoxy, preferably methoxy or ethoxy. 11 and R 15 are independently -N[(C1-C 10 ) alkyl]2.

[0047] In one or more embodiments, R 1 is a radical having formula (III):

[0048] [ka]

[0049] In formula (III), R 31~35 Each of is independently -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R R )3, -Ge(R R )3, -P(R R )2, -P(O)(R R )2, -N(R R )2, -OR R , -SR R , —NO2, —CN, —CF3, or halogen, wherein each R R is (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, halogen, or —H. In some embodiments, R 32 , R 33 , and R 34 are independently (C1~C 40 ) heterohydrocarbyl, -Si[(C1-C10 ) alkyl]3, -N[(C1-C 10 ) alkyl]2, -O[(C1-C 10 In one or more embodiments, R 32 , R 33 , and R 34 is independently selected from methoxy or ethoxy. In some embodiments, R 1 is a 2-frill.

[0050] In some embodiments, in formula (III), R 32 and R 34 is -CF3.

[0051] In the metal-ligand complex according to Formula (I), each Y is bonded to M via a coordinate bond or an ionic bond. In one or more embodiments, Y is a Lewis base. A Lewis base can be a compound or ionic species capable of donating an electron pair to an acceptor moiety. For purposes of this description, the acceptor moiety is M, the metal of the metal-ligand complex of Formula (I). In some embodiments, the Lewis base can be a heterohydrocarbon or 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.

[0052] In one or more embodiments, Y is a neutral Lewis basic aprotic (C-C 40 ) Heterohydrocarbons. 40 ) Heterohydrocarbons are as defined so far (C2-C 40 ) heterohydrocarbons (C2-C 40All hydrogen atoms of the heterohydrocarbon have a pKa greater than 30, where pKa is the negative logarithm of the base-10 of the acid dissociation constant (Ka). In some embodiments, Y is an organic Lewis base. Examples of organic Lewis bases include pyridine or substituted pyridines, sulfoxides, trialkyl or triaryl phosphines, trialkyl or triaryl phosphine oxides, olefins or cyclic olefins, substituted or unsubstituted heterocycles, alkyl esters of aliphatic or aromatic carboxylic acids, aliphatic ketones, aliphatic amines, alkyl or cycloalkyl ethers, or mixtures thereof, wherein each electron donor has 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 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.

[0053] In one or more embodiments, the Lewis base may be a monodentate ligand, which may be a neutral ligand. In some embodiments, the neutral ligand may contain a heteroatom. In certain embodiments, the neutral ligand is R T NR K R L , R K OR L , R K SR L, or R T PR K R L In this case, each R T are independently [(C1~C 10 )hydrocarbyl]3Si(C1-C 10 ) hydrocarbylene, (C1-C 40 ) hydrocarbyl, [(C1-C 10 )hydrocarbyl]Si, or (C1-C 40 ) heterohydrocarbyl, and each R K and R L are independently hydrogen, (C1 to C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl.

[0054] In some embodiments, the Lewis base is (C1-C 20 ) hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene, 1,3-butadiene, or cyclooctene.

[0055] In various embodiments, the Lewis base is (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, Y is tetrahydrofuran, pyrene, dioxane, diethyl ether, or methyl tert-butyl ether (MTBE).

[0056] In various embodiments, the Lewis base is (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is nitrogen. In some embodiments, Y is pyridine, picoline, lutidine, trimethylamine, or triethylamine.

[0057] In various embodiments, the Lewis base is (C1-C 20) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is phosphorus. In some embodiments, Y is trimethylphosphine, triethylphosphine, triphenylphosphine, triethylphosphite, trimethylphosphite, triphenylphosphine oxide.

[0058] In some embodiments, X and Y are covalently linked. Specific examples of organic Lewis bases Y covalently linked together with the X groups include, but are not limited to, 4-cycloocten-1-yl, 2-dimethylaminobenzyl, and 2-dimethylaminomethylphenyl.

[0059] In some embodiments, X and Y are linked and are selected from the group consisting of:

[0060] [ka] In the formula, R C is -H or (C1 to C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, (C1-C 20 ) alkyl, or (C1-C 12 ) alkyl.

[0061] In the metal-ligand complex according to formula (I), X is bonded to M through a covalent or ionic bond. In some embodiments, X can be a monoanionic ligand having a net formal oxidation state of -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) hydrocarbyl carbanions, (C1-C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, bicarbonates, dihydrogen phosphates, hydrogen sulfates, HC(O)O - , HC(O)N(H) - , (C1~C 40 ) Hydrocarbyl C(O)O - , (C1~C 40 ) Hydrocarbyl C(O)N((C1-C 20)hydrocarbyl) - , (C1~C 40 ) Hydrocarbyl C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L Si - where each R K , R L , and R M are independently hydrogen, (C1 to C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R K and R L are combined, (C2~C 40 ) hydrocarbylene or (C1-C 20 ) form a heterohydrocarbylene, and R M is as defined above.

[0062] In some embodiments, X is 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 (C1 to C 20 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 R K R L N- and RK and R L each independently is unsubstituted (C1 to C 10 ) hydrocarbyl.

[0063] 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.

[0064] In one or more embodiments, X is —(CH 2 )SiR X 3, and then each R X are independently (C1~C 30 ) alkyl or (C1-C 30 ) heteroalkyl, and at least one R X is (C1~C 30 ) alkyl. In some embodiments, R X One of them is (C1~C 30 ) heteroalkyl, the heteroatom is a silicon or oxygen atom. In some embodiments, R X is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0065] In one or more embodiments, X is selected from the group consisting of -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(C6H5), -(CH2)Si(CH3)(C6H5), -(CH2)Si(CH3)2(CH2C6H5), -(CH2)Si(CH3)2(CH2CH3), -(CH2)Si(CH3)(CH2CH3), -(CH2)Si(CH2CH3), -(CH2)Si(CH2CH3), -(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, —(CH)Si(CH)(2-ethylhexyl), —(CH)Si(CH)(dodecyl), or —CHSi(CH)CHSi(CH) (referred to herein as —CHSi(CH)(CHTMS)). Optionally, in some embodiments, in a metal-ligand complex according to Formula (I), exactly two R X are covalently bonded or exactly three R X are covalently bonded.

[0066] In some embodiments, X is —CHSi(R C ) 3-Q (OR C ) Q , -Si(R C ) 3-Q (OR C ) Q , -OSi(R C ) 3-Q (OR C ) Q where the subscript Q is 0, 1, 2, or 3, and each R C are independently substituted or unsubstituted (C1 to C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl. In some embodiments, X is —CH 2 Si(CH 3 ) 3 .

[0067] In some embodiments, any or all of the chemical groups of the procatalyst of formula (I) are R 11 or R 15 R may be unsubstituted, except for any of 11 and R 15 In another embodiment, at least one of the chemical groups X and R of the metal-ligand complex of formula (I) is substituted. 1 ~R 4 , R 11~15 , or R 31~35 Zero, any, or all of the may be one or more R S Two or more RS 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 , R 11~15 , or R 31~35 Zero, any, or all of S It can be oversubstituted with R S In chemical groups that are over-substituted with S may all be the same or may be independently selected.

[0068] Some embodiments of the present disclosure include a polymerization process. In some embodiments, the polymerization process includes polymerizing ethylene with 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 includes a metal-ligand complex according to Formula (I) described in this disclosure.

[0069] In some embodiments, a polymerization process comprises polymerizing ethylene, one or more polar monomers, and optionally one or more α-olefin monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene / polar monomer copolymer. The catalyst system comprises a procatalyst according to formula (I) of the present disclosure. In one or more embodiments, a polymerization process comprises polymerizing ethylene, one or more alkyl acrylate monomers, and optionally one or more α-olefin monomers under olefin polymerization conditions in the presence of a catalyst system to form an ethylene / alkyl acrylate copolymer, wherein the catalyst system comprises a procatalyst according to formula (I) of the present disclosure.

[0070] In some embodiments of the polymerization process, the polymerization process comprises the polymerization of ethylene and optionally one or more (C3-C4) olefins in the presence of a catalyst system under olefin polymerization conditions. 10) polymerizing α-olefin monomers or cyclic olefin monomers to form an ethylene-based copolymer, wherein the catalyst system comprises a metal-ligand complex procatalyst having a structure according to formula (I), as described herein.

[0071] In some embodiments of the polymerization process, the polymerization process comprises the polymerization of ethylene, a polar comonomer, and optionally one or more (C3-C6) olefins in the presence of a catalyst system under olefin polymerization conditions. 10 ) polymerizing α-olefin monomers or cyclic olefin monomers to form an ethylene-based copolymer, wherein the catalyst system comprises a metal-ligand complex procatalyst having a structure according to formula (I), as described herein.

[0072] Olefin monomers include propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, styrene, cyclobutene, cyclopentene, norbornene, ethylidene norbornene, alkyl acrylate, glycidyl acrylate, vinyl acetate, CH₂═C(H)C(O)(OR X ), CH2=CHC(O)R X , CH2=CH(OR X ), CH2=CH(CH2)(OR X ), CH2=CHSi(R X ) 3-Y (OR X ) Y , CH2=CH-OSi(R X ) 3-Y (OR X ) Y or CH═CHCl, where R X is -H, substituted or unsubstituted (C1-C 30 ) hydrocarbyl, or substituted or unsubstituted (C1-C 30 ) heterohydrocarbyl, and the subscript Y is 0, 1, 2, or 3.

[0073] In various embodiments of the polymerization process, the polar comonomers include alkyl acrylates CH2=CHC(O)(OR), glycidyl acrylate, 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® 3-T (OR) T or CH2=CHCl. ​​Each R is -H, a substituted (C1-C 30 ) Hydrocarbyl, unsubstituted (C1-C 30 ) Hydrocarbyl, substituted (C1-C 30 ) heterohydrocarbyl, or unsubstituted (C1-C 30 ) heterohydrocarbyl. The subscript T is 0, 1, 2, or 3. The subscript n is 1 to 10. The polar monomer is selected from alkyl acrylate, substituted (C1-C 30 ) Hydrocarbyl acrylate, unsubstituted (C1-C 30 ) Hydrocarbyl acrylate, substituted (C1-C 30 ) heterohydrocarbyl acrylate, or unsubstituted (C1-C 30 ) heterohydrocarbyl acrylate, or unsubstituted (C1-C 30 In embodiments where the acrylate is a heterohydrocarbyl acrylate, the polar ethylene-based copolymer may be deesterified to form an acrylic acid ethylene-based copolymer.

[0074] 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 a combination thereof. In various embodiments, the alkyl acrylate has an alkyl group having 1 to 8 carbons. This is referred to as a C1-C8-alkyl acrylate. In particular embodiments, the alkyl acrylate is t-butyl acrylate or n-butyl acrylate.

[0075] In some embodiments of the polymerization process, the optional α-olefin monomer may 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. In one or more embodiments of the polymerization process, the process comprises the steps of: (C1-C6) 20 ) may further include cyclic olefins such as cyclobutene, cyclopentene, norbornene, and norbornene derivatives substituted with hydrocarbyl groups.

[0076] In an exemplary embodiment, the catalyst system can include a procatalyst according to Formula (I) having the structures of Procatalysts 1-5 listed below.

[0077] [ka] In the formula, TMS is trimethylsilyl, Me is methyl, and Et is ethyl.

[0078] Ethylene / Acrylate Copolymer In various embodiments, the polymerization process of the present disclosure can produce an ethylene-based copolymer, wherein 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 wt% 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.

[0079] In one or more embodiments, the polymerization process of the present disclosure can 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 can be incorporated into the produced polymer in an amount of 0.01 wt.% to 49.9 wt.%, based on the weight of the ethylene-based copolymer.

[0080] In various embodiments, the polymerization process of the present disclosure may produce ethylene-based copolymers having a molecular weight of from 2,000 g / mol to 1,000,000 g / mol. In some embodiments, the produced polymers have a molecular weight of from 25,000 g / mol to 900,000 g / mol, from 30,000 g / mol to 800,000 g / mol, or from 10,000 g / mol to 300,000 g / mol.

[0081] General procedure for PPR screening experiments Polyolefin catalysis screening was performed in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consisted of an array of 48 single-cell (6 × 8 matrix) reactors inside an inert atmosphere glovebox. 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. Unless otherwise indicated, ligands were metallated at a 1:1 ligand:metal (L:M) ratio by premixing the metal precursor solution with the ligand solution. In many cases, the procatalyst complex resulting from the metallation reaction was isolated and purified before being introduced into the PPR reactor. All liquids (i.e., solvent, t-butyl acrylate, and catalyst solutions, as well as optional activator solutions (if used)) were added via robotic syringes. The gas reagent (i.e., ethylene) was added via a gas inlet. Before each run, the reactor was heated to 50°C, purged with ethylene, and evacuated. Tert-butyl acrylate was filtered through a short column of activated alumina before use to remove any polymerization inhibitors (e.g., 4-methoxyphenol).

[0082] 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 pressure. The isolated procatalyst 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. Once the catalyst was added, the PPR software began monitoring the pressure in each cell. The desired pressure (within approximately 2-6 psig) was maintained by opening the valve at 1 psi below the set point, closing the valve when the pressure reached 2 psi above, and adding supplemental ethylene gas. All pressure drops were cumulatively recorded as ethylene "uptake" or "conversion" for the duration of the run or until the desired uptake or conversion value was reached, whichever occurred first. Each reaction was then quenched by adding 1% oxygen in nitrogen at a pressure 40 psi above the reactor pressure for 30 seconds (the elapsed time from the start of the run to the start of the quench is the "quench time"). The shorter the "quench time," the more active the catalyst. To prevent excessive polymer formation in any given cell, the reaction was quenched when a predetermined uptake level of 80 psig was reached. After quenching, all reactors were cooled to approximately 60°C. They were then vented, and the reactor tubes were removed and placed in a centrifugal evaporator. Polymer samples were then dried in the centrifugal evaporator for 12 hours at 60°C and weighed to determine polymer yield and were subjected to IR (t-butyl acrylate incorporation), GPC (molecular weight, polydispersity (PDI)), and DSC (melting point) analyses.

[0083] General procedure for batch reactor experiments NOTE: Because acrylates are sensitizing, contact with tert-butyl acrylate should be minimized, e.g., by using a dump pot with a lid and a well-ventilated fume hood. Care must be taken when transferring the contents of the reactor to the dump pot and emptying the dump pot in the fume hood.

[0084] Polymerization reactions were carried out in a 2 L Parr batch reactor. The reactor was heated with an electric heating mantle and cooled with an internal serpentine cooling coil containing cooling water. 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 attached to the bottom of the reactor, transferring the reactor contents to a covered dump pot. The dump pot was pre-filled with a catalyst deactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). Both the pot and the tank were purged with N2, and the covered dump pot was vented to a 15-gallon blowdown tank. All chemicals used for polymerization or catalyst make-up were passed through purification columns to remove any impurities that could affect the polymerization. Toluene was passed through two columns (the first containing A2 alumina and the second containing Q5 reactant). tert-Butyl acrylate was filtered through activated alumina. Ethylene was passed through two columns, the first containing A204 alumina and 4 Å molecular sieves and the second containing the Q5 reactant. N2 used for transport was passed through a single column containing A204 alumina, 4 Å molecular sieves, and the Q5 reactant.

[0085] The reactor was initially charged from a shot tank containing toluene and tert-butyl acrylate. The shot tank was filled to the load set point using a differential pressure transducer. After the solvent / acrylate addition, the shot tank was rinsed twice with toluene, and the rinse was transferred to the reactor. The reactor was then heated to the desired polymerization temperature set point. Once the temperature set point was reached, ethylene was added to the reactor to reach the desired pressure set point. The rate of ethylene addition to the reactor was monitored by a microflow meter.

[0086] The catalyst was handled in an inert atmosphere glovebox and introduced into the reactor as a solution in toluene. The catalyst solution was drawn into a syringe and pressure transferred to the catalyst shot tank. This was followed by three 5 mL toluene rinses. Catalyst was added only after the reactor pressure set point was reached.

[0087] Immediately after catalyst addition, a run timer was started. Ethylene was then fed to the reactor (via Camile control) to maintain the pressure set point. The ethylene / tert-butyl acrylate copolymerization reaction was carried out for 75 minutes or until 40 g of ethylene uptake occurred, whichever was shorter. The agitator was then stopped, the bottom dump valve was opened, and the reactor contents were emptied into a covered dump pot. The valve on the covered dump pot was closed, and the sealed dump pot was disconnected from the reactor and transferred to a fume hood. In the fume hood, the lid was removed from the dump pot and the contents were poured into a tray. The tray was left in the fume hood for a minimum of 36 hours to allow the solvent and tert-butyl acrylate to evaporate. The tray containing the remaining polymer was then transferred to a vacuum oven and heated to 140°C under vacuum to remove any remaining volatiles. After the tray cooled to ambient temperature, the polymer was weighed for yield / efficiency and, if desired, subjected to polymer testing.

[0088] 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 PL-gel 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 hydroxytoluene (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 with BHT-stabilized TCB. 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 BHT-stabilized TCB 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 BHT-stabilized TCB and stirring at 160°C for 15 minutes. These standards were analyzed to generate a third-order MW calibration curve. A 1-day Q factor, calculated to be approximately 0.4 using the average of five Dowlex 2045 reference samples, was used to convert molecular weight units from polystyrene (PS) units to polyethylene (PE) units.

[0089] FT-IR procedure A 10 mg / mL sample prepared for GPC analysis was also utilized to quantify tert-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 minutes, then deposited 130 μL portions into stainless steel wells formed 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 (CH2: 736-709 cm -1 ) was calculated and fitted to a linear calibration curve to determine total tBA.

[0090] 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 the traces were analyzed individually using TA Universal analysis software or TA Instruments TRIOS software. Equilibrated at 175.00°C Isothermal for 3 minutes Ramp 30.00°C / min to 0.00°C Ramp 10.00°C / min to 175.00°C [Example]

[0091] Examples 1-6 provide synthetic procedures for ligand intermediates and ligands. Examples 7-12 provide synthetic procedures for isolated procatalysts. Examples 13 and 14 list and discuss the results of polymerization reactions of procatalysts 1-5. One or more features of the present disclosure are illustrated in light of the following examples.

[0092] Overview Unless otherwise noted, all reactions were performed in a nitrogen-purged glovebox. All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing them through activated alumina, and in some cases, the Q-5 reactants. The alumina used for solvent purification was activated by passing a stream of nitrogen through the alumina at 300 °C for 8 hours. The Q-5 reactants were activated by heating at 200 °C under a stream of nitrogen for 4 hours, followed by a stream of 5% hydrogen in nitrogen at 200 °C for 3 hours, and finally by flushing with nitrogen gas. Solvents used in experiments performed in a nitrogen-filled glovebox were further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware was dried overnight in an oven before use. HRMS analysis was performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer with electrospray ionization. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. 1 H NMR data are reported as follows: chemical shifts (multiplicities (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integrals, and assignments). Residual protons in deuterated solvents were used as standards. 1 Chemical shifts for H NMR data are reported in ppm downfield from tetramethylsilane (TMS, δ scale). 13 C NMR data, 1 Determined using H decoupling, chemical shifts are reported in ppm relative to tetramethylsilane. 13 The C NMR spectrum was complex due to C-P coupling. 31Chemical shifts for P NMR data are reported in ppm relative to external undiluted H3PO4. Deuterated solvents for NMR analysis were purchased from Cambridge Isotope Laboratories and stored over activated 4 Å molecular sieves in a nitrogen-purged glovebox. Chlorobis(2,6-dimethoxyphenyl)phosphine, chlorobis(2,6-diethoxyphenyl)phosphine, and bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) were prepared according to literature procedures.

[0093] Ligand preparation Example 1 - N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,5-bis(trifluoromethyl)benzamide

[0094] [ka] In a glovebox, 3,5-bis(trifluoromethyl)benzamide (300 mg, 1.17 mmol) and a stir bar were placed in a 20 mL vial, dissolved in 8 mL of THF, and cooled to −35° C. overnight. The mixture was removed from the freezer, and n-butyllithium (2.0 M, 0.64 mL, 1.3 mmol, 1.1 equiv.) was slowly added. The reaction mixture was returned to the freezer. After 20 min, the reaction mixture was removed from the freezer, and a slurry of chlorobis(2,6-dimethoxyphenyl)phosphine (362 mg, 1.19 mmol, 1.02 equiv.) in 3 mL of THF was added. With further stirring, the reaction mixture was allowed to slowly warm to room temperature. All volatiles were removed under vacuum, and 10 mL of dichloromethane was added to the resulting residue. The solution was filtered through a plug of Celite to remove LiCl. The filtrate was clear and light yellow. The filtrate was concentrated to approximately 2 mL and the product was triturated with hexanes and collected by filtration as an off-white powder. 1 H and 31 P NMR confirmed that the isolated off-white powder was the desired product (402 mg, 0.72 mmol, 61% yield).

[0095] 1 H NMR (400MHz, chloroform-d) δ9.51(s,1H), 8.35(s,2H), 8.01(s,1H), 7.26(t,J=8.3Hz,2H), 6.55(dd,J=8.3,2.7Hz,4H), 3.81(s,12H)ppm. 13 C NMR (126 MHz, chloroform-d) δ 161.87 (d, J = 9.7 Hz), 137.91, 131.92 (d, J = 34.1 Hz), 130.95, 127.65, 124.57, 124.18, 122.01, 114.43, 104.58, 56.02 ppm. 31 P NMR (162 MHz, chloroform-d) δ −2.16 ppm. 19 F NMR (376 MHz, chloroform-d) δ -62.91 ppm. HRMS (ESI+) (m / z): [M+H]C 45 H 60 Calculated value of N2O5P: 562.121; Measured value: 562.116.

[0096] Example 2 - N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,4,5-trimethoxybenzamide

[0097] [ka] In a glovebox, 3,4,5-trimethoxybenzamide (300 mg, 1.42 mmol) and a stir bar were placed in a 20 mL vial, dissolved in 10 mL of THF, and cooled to -35 °C overnight. The mixture was removed from the freezer, and n-butyllithium (2.0 M, 0.78 mL, 1.6 mmol, 1.1 equiv.) was slowly added, and the reaction mixture was returned to the freezer. After 20 min, the reaction mixture was removed from the freezer, and a slurry of chlorobis(2,6-dimethoxyphenyl)phosphane (442 mg, 1.45 mmol, 1.02 equiv.) in 4 mL of THF was added. With further stirring, the reaction mixture was allowed to slowly warm to room temperature. A white precipitate formed and was collected by filtration, washed with THF and hexane. The white powder was confirmed as the desired product (495 mg, 0.95 mmol, 67% yield).

[0098] 1 H NMR (400MHz, chloroform-d) δ9.01(s,1H), 7.23(td,J=8.3,0.7Hz,2H), 7.14(s,2H), 6.53(dd,J=8.3,2.6Hz,4H), 4.01-3.86(m,9H), 3.78(s,12H)ppm. 13 C NMR (126 MHz, chloroform-d) δ 161.91 (d, J = 9.5 Hz), 152.93, 140.71, 131.41, 130.56, 115.57 (d, J = 26.9 Hz), 105.00, 104.66, 67.96, 60.89, 56.25, 56.11. 31 P NMR (162MHz, chloroform-d) δ-4.88(d,J=108.0Hz)ppm. HRMS(ESI+)(m / z):[M+H]C 26 H 30 Calculated value of NO8P: 516.178; Measured value: 516.175.

[0099] Example 3 - N-(bis(2,6-diethoxyphenyl)phosphanyl)-3,5-bis(trifluoromethyl)benzamide

[0100] [ka] In a glove box, a glass bottle equipped with a stir bar was charged with 3,5-bis(trifluoromethyl)benzamide (1.0 g, 3.89 mmol) and chilled THF (26.5 mL). The clear solution was placed in a glove box freezer at -35°C for 30 minutes. After 30 minutes, the solution was removed from the freezer, and 2.5 M n-butyllithium in hexane (1.72 mL, 4.30 mmol) was added dropwise with stirring. The resulting red-orange solution was returned to the freezer. After 20 minutes, the reaction mixture was removed from the freezer, and a chilled, cloudy solution of bis(2,6-diethoxyphenyl)chlorophosphine (1.57 g, 3.97 mmol) in THF (10 mL) was added. The reaction mixture was allowed to warm to room temperature with stirring for 1 hour. After 1 hour, an aliquot of the resulting red-brown solution was removed and 31Analysis by 1 P NMR spectroscopy confirmed completion. 31 P NMR spectrum indicated the reaction was complete. The reaction mixture was concentrated to dryness in vacuo, and anhydrous dichloromethane (33 mL) was added. The reaction mixture was filtered through a plug of Celite and concentrated in vacuo to give a dark pink solid (2.62 g). The solid was triturated with hexanes, and dichloromethane (2 mL) was added. The slurry was stirred at room temperature for 5 minutes, and the solid was collected by filtration and washed with hexanes to give 1.79 g (2.92 mmol, 75%) of the desired product as a pink solid.

[0101] 1 H NMR (400MHz, chloroform-d) δ9.16(s,1H), 8.30(s,2H), 7.99(s,1H), 7.20(t,J=8.3Hz,2H ), 6.50(dd,J=8.3,2.7Hz,4H), 3.98(p,J=7.6,6.8Hz,9H), 1.23(t,J=7.0Hz,13H)ppm. 13 C NMR (101 MHz, chloroform-d) δ 165.87 (d, J = 17.2 Hz), 161.05 (d, J = 9.5 Hz), 138.31, 131.85 (q, J = 33.4, 32.6 Hz), 130.47, 127.78, 124.48, 121.73, 115.74 (d, J = 26.4 Hz), 105.32, 64.47, 14.48 ppm. 31 P NMR (162 MHz, chloroform-d) δ -0.30 ppm. 19 F NMR (376 MHz, chloroform-d) δ -63.19 ppm. HRMS (ESI+) (m / z): [M+H]C 29 H 31 Calculated value of F6NO5P: 618.1838; Measured value: 618.1753.

[0102] Example 4 - N-(bis(2,6-dimethoxyphenyl)phosphanyl)furan-2-carboxamide

[0103] [ka] In a glovebox, furan-2-carboxamide (258 mg, 2.32 mmol) and a stir bar were placed in a 20 mL vial, dissolved in 10 mL of THF, and cooled to -35 °C overnight. The mixture was removed from the freezer, and n-butyllithium (2.0 M, 1.28 mL, 2.44 mmol, 1.1 equiv.) was slowly added, and the reaction mixture was returned to the freezer for 15 min. The reaction mixture was removed from the freezer, and a slurry of chlorobis(2,6-dimethoxyphenyl)phosphine (831 mg, 2.44 mmol, 1.05 equiv.) in 5 mL of THF was slowly added. The reaction mixture was allowed to warm to room temperature with stirring for 2 h. All volatiles were then removed from the reaction mixture under vacuum, and the resulting residue was triturated with dichloromethane and filtered through a pad of Celite. The filtrate was concentrated to approximately 2 mL and the product was triturated with hexanes and collected by filtration as a white powder (766 mg isolated, 1.83 mmol, 79% yield).

[0104] 1 H NMR (400MHz, chloroform-d) δ9.25(s,1H), 7.63-7.45(m,1H), 7.21(t,J=8.3Hz,2H), 7.15(d,J=3.5Hz,1H), 6.68-6.42(m,5H), 3.78(d,J=0.9Hz,12H)ppm. 13 C NMR (126 MHz, chloroform-d) δ 161.94 (d, J = 9.6 Hz), 143.64, 130.56, 128.62 (d, J = 102.0 Hz), 115.12 (d, J = 25.9 Hz), 114.13, 112.13, 104.47, 55.98 ppm. 31 P NMR (162 MHz, chloroform-d) δ -7.34 ppm. HRMS (ESI+) (m / z): [M+H]C 21 H 24 Calculated value of NO6P: 416.1257; Measured value: 416.1226.

[0105] Example 5 - Synthesis of N-(bis(2,6-dimethoxyphenyl)phosphanyl)benzamide

[0106] [ka]

[0107] In a glovebox, a 20 mL vial was charged with benzamide (100 mg, 0.83 mmol, 1.0 equiv.), 4-pyrrolidinopyridine (196 mg, 1.32 mmol, 1.6 equiv.), chlorobis(2,6-dimethoxyphenyl)phosphine (281 mg, 0.83 mmol, 1.0 equiv.), 8 mL of THF, and a stir bar. The colorless solution was heated to 65 °C and stirred for 18 h. The next day, the solution was filtered to remove salts, and all volatiles were removed by filtrate under vacuum. Toluene was added to the resulting residue, causing a precipitate to form. The white solid was isolated by filtration, washed with hexane, dried, and identified as clean product (182 mg) by NMR spectroscopy. An equal volume of hexane was added to the filtrate and placed in a freezer at -35 °C overnight. The product precipitated from solution, collected by filtration, and dried (102 mg). The two powders were combined to give 284 mg of product (0.67 mmol, 81% yield).

[0108] 1 H NMR (400MHz, chloroform-d) δ9.10(s,2H), 7.88(d,J=7.4Hz,4H), 7.64-7.38(m,5H), 7.21(t,J=8.3Hz,4H), 6.53(d,J=2.6Hz,4H), 3.76(s,19H)ppm. 13 C NMR (101 MHz, chloroform-d) δ 161.98 (d, J = 9.5 Hz), 131.09, 130.52, 128.31, 127.38, 115.71 (d, J = 27.1 Hz), 104.66, 56.13 ppm. 31 P NMR (162 MHz, chloroform-d) δ -5.29 ppm. HRMS (ESI+) (m / z): [M+H]C 21 H 24 Calculated value of NO6P: 426.1473; Measured value: 426.148.

[0109] Example 6 - N-(diphenylphosphanyl)benzamide

[0110] [ka] In a glovebox, benzamide (250 mg, 1.80 mmol) and a stir bar were added to a 100 mL vial, dissolved / suspended in 20 mL of THF, and cooled to -35 °C overnight. The mixture was removed from the freezer, and n-butyllithium (2.0 M, 0.99 mL, 1.96 mmol, 1.1 equiv.) was slowly added, and the reaction mixture was returned to the freezer for 15 min. The mixture was removed from the freezer, and a slurry of chlorodiphenylphosphine (0.523 mL, 1.89 mmol, 1.05 equiv.) in 5 mL of THF was slowly added with stirring. The solution was allowed to warm to room temperature with stirring for 2 h. All volatiles were then removed from the solution under vacuum, and the resulting residue was triturated with dichloromethane and filtered through a pad of Celite. All volatiles were removed from the filtrate under vacuum, and toluene was added to the resulting residue. Most of the product precipitated as a white solid, which was further triturated with hexanes. The product was collected by filtration as a white powder. The filtrate was concentrated to approximately 2 mL, and the product was triturated with hexane and collected by filtration. The product was isolated as a white powder. Two batches of white powder were combined to give 362 mg (1.19 mmol, 66% yield).

[0111] 1 H NMR (400 MHz, chloroform-d) δ 7.85 (dd, J = 8.4, 1.4 Hz, 2H), 7.59-7.37 (m, 13H), 6.52 (d, J = 5.8 Hz, 1H) ppm. 13 C NMR (101 MHz, chloroform-d) δ 170.03, 138.22 (d, J = 14.8 Hz), 134.06, 132.12, 131.65 (d, J = 21.7 Hz), 129.73, 128.81 (d, J = 6.7 Hz), 128.67, 127.52 ppm. 31 P NMR (162 MHz, chloroform-d) δ 25.39 ppm. HRMS (ESI+) (m / z): [M+H]C 19 H 17 Calculated NOP: 306.1041; Measured: 306.1034.

[0112] Preparation of Ni complexes Example 7 - Synthesis of Procatalyst 2 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,5-bis(trifluoromethyl)benzimidate)((trimethylsilyl)methyl)(pyridine)nickel(II)

[0113] [ka] In a glovebox, a 20 mL vial was charged with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (73 mg, 0.18 mmol, 1.05 equiv.), a stir bar, and 1 mL of toluene. A slurry of N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,5-bis(trifluoromethyl)benzamide (100 mg, 0.18 mmol) in 4 mL of toluene was then slowly added to the orange solution. The resulting solution was a very dark brown / orange in color. After stirring the solution at 45 °C for 30 minutes, the reaction mixture had noticeably lightened to red in color. 31 P NMR spectroscopy indicated that the metallation reaction was complete after 30 min. All volatiles were removed from the solution under vacuum, leaving a dark red sticky residue. The product was triturated with hexane and stirred vigorously. The product was collected by filtration and dried (105 mg, 0.14 mmol, 75% yield).

[0114] 1 H NMR (400MHz, benzene-d6) δ8.94(dd,J=4.8,1.7Hz,2H), 8.91-8.84(m,2H), 7.71(s,1H), 7.22-7.07(m,4H), 6.84(tt,J=7.6 ,1.7Hz,1H), 6.54(t,J=6.7Hz,2H), 6.34(dd,J=8.3,3.7Hz,4H), 3.36(s,12H), -0.16(s,9H), -0.46(d,J=8.8Hz,2H)ppm. 13C NMR (101 MHz, benzene-d6) δ 174.14 (d, J = 3.7 Hz), 161.47 (d, J = 2.1 Hz), 150.64, 139.45 (d, J = 19.2 Hz), 136.36, 130.57, 129.93, 123.56, 113.02 (d, J = 57.3 Hz), 104.64 (d, J = 4.5 Hz), 55.35, 31.59, 22.68, 13.97, 1.97, −16.46 (d, J = 28.6 Hz) ppm. 31 P NMR (162 MHz, benzene-d6) δ 54.98 ppm. 19 F NMR (376 MHz, benzene-d6) δ -62.47 ppm.

[0115] Example 8 - Synthesis of Procatalyst 5 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,4,5-trimethoxybenzimidate)(pyridine)((trimethylsilyl)methyl)nickel(II)

[0116] [ka] In a glovebox, a 20 mL vial was charged with bis((trimethylsilyl)methyl)bis(pyridine)nickel (114 mg, 0.29 mmol, 1.0 equiv.), a stir bar, and 5 mL of toluene, followed by pyridine (23 μL, 0.29 mmol, 1.0 equiv.). Solid N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,4,5-(trimethoxy)benzamide (150 mg, 0.29 mmol) was then slowly added to the orange solution. The resulting solution was a very dark brown / yellow color. The reaction mixture was heated to 55° C. and stirred for 90 minutes. 31 The metallation reaction was complete after 90 min, as indicated by P NMR spectroscopy. The solution was filtered through a Celite plug, and the filtrate was concentrated to approximately 3 mL, at which point an orange precipitate began to form. The product was triturated with hexane (~30 mL), and the resulting solution was placed in the freezer overnight. The mixture was removed from the freezer, and the product was collected by filtration, washed with cold pentane, and dried (182 mg, 0.25 mmol, 85% yield).

[0117] 1 H NMR (400MHz, benzene-d6) δ9.12-8.92(m,2H), 7.79(s,2H), 7.20-7.08(m,2H+C6D6 signal), 6.91(s,1H), 6.59(s,1H) , 6.38(dd,J=8.3,3.6Hz,4H), 3.83(s,3H), 3.41(s,12H), 3.33(s,6H), -0.11(s,9H), -0.49(d,J=8.5Hz,2H)ppm. 13 C NMR (126 MHz, benzene-d6) δ 177.70, 161.51, 152.72, 150.96, 140.78, 136.02, 132.56 (d, J = 18.6 Hz), 130.16, 123.35, 114.12 (d, J = 56.1 Hz), 108.52, 104.68 (d, J = 4.4 Hz), 60.07, 55.48, 55.39, 2.12, −17.08 (d, J = 27.8 Hz) ppm. 31 P NMR (162 MHz, benzene-d6) δ 55.06 ppm.

[0118] Example 9 - Synthesis of Procatalyst 3 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)benzimidate)(pyridine)((trimethylsilyl)methyl)nickel(II)

[0119] [ka] In a glovebox, a 20 mL vial was charged with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (9.2 mg, 0.024 mmol, 1.0 equiv.), N-(bis(2,6-dimethoxyphenyl)phosphanyl)benzamide (10 mg, 0.024 mmol, 1.0 equiv.), a stir bar, and 2 mL of C6D6. The dark red reaction was heated to 60 °C for 1 h and allowed to cool. 1 H NMR spectroscopy results were consistent with that expected for the title structure. All volatiles were removed under vacuum, and hexane was added to the sticky residue to give a dark yellow solid. The mother liquor was removed by pipette, and the product was dried (yield not determined).

[0120] 1 H NMR (500MHz, benzene-d6) δ9.14-8.91(m,2H), 8.52(dd,J=7.9,1.9Hz,2H), 7.21-7.01(m,9H), 6.84(s,1H), 6.67-6.44(m,2H), 6.33(dd,J=8.3,3.6Hz,4H), 3.36(s,12H), -0.15(s,9H), -0.52(d,J=8.5Hz,2H)ppm. 13 C NMR (126MHz, benzene-d6) δ177.78(d,J=2.4Hz), 164.31, 161.54(d,J=1.9Hz), 137.28(d,J=18.5Hz), 135.95, 127 .11, 123.39(d,J=1.9Hz), 114.30(d,J=56.6Hz), 104.84(d,J=4.4Hz), 55.55, 2.11, -16.85(d,J=28.2Hz)ppm. 31 P NMR (162 MHz, benzene-d6) δ 54.79 ppm.

[0121] Example 10 - Synthesis of Procatalyst 1 ((Z)-N-(bis(2,6-diethoxyphenyl)phosphanyl)-3,5-bis(trifluoromethyl)benzimidate)(pyridine)((trimethylsilyl)methyl)nickel(II)

[0122] [ka] In a glovebox, a 110 mL bottle was charged with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (503 mg, 1.28 mmol, 1.0 equiv.), a stir bar, and 10 mL of toluene. A slurry of N-(bis(2,6-diethoxyphenyl)phosphanyl)-3,5-bis(trifluoromethyl)benzamide (750 mg, 1.28 mmol) in 20 mL of toluene was then slowly added to the orange solution. The resulting solution was very dark brown / yellow in color. The reaction mixture was stirred at 45° C. for 20 minutes, after which time the reaction mixture was cooled to room temperature. 31P NMR spectroscopy indicated that the reaction was nearly complete (some of the dialkyl complex and free ligand remained). Pyridine (0.100 mL, 1.28 mmol, 1.0 equiv) was added to the reaction mixture, and the mixture was heated to 45° C. for an additional 20 min. 31 P NMR spectroscopy indicated the reaction was complete. The reaction mixture was cooled to room temperature and filtered through a plug of Celite. All volatiles were then removed from the filtrate under vacuum. Pentane was added and removed under vacuum to dry the crude product. The resulting solid was dissolved in a minimum amount of toluene, and the product was triturated with excess pentane. The orange solid was collected by filtration, washed with pentane, and dried (926 mg, 1.10 mmol, 86% yield).

[0123] 1 H NMR (400MHz, chloroform-d) δ9.16(s,1H), 8.30(s,2H), 7.99(s,1H), 7.20(t,J=8.2Hz ,2H), 6.50(dd,J=8.3,2.7Hz,5H), 4.08-3.91(m,8H), 1.23(t,J=7.0Hz,12H)ppm. 13 C NMR (101 MHz, chloroform-d) δ 166.01 (d, J = 17.4 Hz), 161.18 (d, J = 9.5 Hz), 138.44, 131.99 (q, J = 33.3, 32.4 Hz), 130.60, 127.91, 124.62, 121.87, 115.87 (d, J = 26.6 Hz), 105.45, 64.61, 14.61 ppm. 31 P NMR (162 MHz, chloroform-d) δ -0.30 ppm. 19 F NMR (376 MHz, chloroform-d) δ −63.19 ppm.

[0124] Example 11 - Synthesis of Procatalyst 4 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)furan-2-carbimidate)(pyridine)((trimethylsilyl)methyl)nickel(II)

[0125] [ka] In a glovebox, a 20 mL vial was charged with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (141 mg, 0.36 mmol, 1.0 equiv.), pyridine (0.029 mL, 0.36 mmol), a stir bar, and 4 mL of toluene. A slurry of N-(bis(2,6-dimethoxyphenyl)phosphanyl)furan-2-carboxamide (150 mg, 0.36 mmol) in 3 mL of toluene was then slowly added to the orange solution. The resulting solution was dark red / brown in color. After stirring the solution at 50° C. for 60 minutes, 31 P NMR spectroscopy indicated complete conversion to the desired complex. The reaction mixture was cooled to room temperature and filtered through a plug of Celite. All volatiles were then removed from the filtrate under vacuum, leaving a yellow solid on the vial walls. Pentane was added and the solution was stirred vigorously for 30 minutes. The yellow solid was isolated by filtration and dried under vacuum. (164 mg, 0.26 mmol, 71% yield).

[0126] 1 H NMR (400MHz, benzene-d6) δ9.05(dd,J=4.8,1.7Hz,2H), 7.13(s,1H), 6.86-6.79(m,1H), 6.59-6.52(m,3H), 6.35(dd,J=8.3,3. ppm. 13 C NMR (126MHz, benzene-d6) δ170.17(d,J=4.1Hz), 161.52(d,J=2.0Hz), 152.40(d,J=24.6Hz), 150.92, 142.36, 135.96, 130.18 , 123.40(d,J=1.9Hz), 114.05(d,J=57.6Hz), 112.69, 110.75, 104.79(d,J=4.4Hz), 55.52, 2.07, -17.01(d,J=28.4Hz)ppm. 31 P NMR (162 MHz, benzene-d6) δ 55.22 ppm.

[0127] Example 12: Preparation of Comparative Procatalyst C1 ((Z)-N-(diphenylphosphanyl)benzimidate)(pyridine)((trimethylsilyl)methyl)nickel(II)

[0128] [ka] In a glovebox, a 20 mL vial was charged with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (134 mg, 0.34 mmol, 1.05 equiv.), a stir bar, and 2 mL of toluene. Pyridine (26 μL, 0.33 mmol, 1.0 equiv.) was added to the orange solution, followed by the slow addition of a solution of N-(diphenylphosphanyl)benzamide (100 mg, 0.33 mmol) in 3 mL of toluene. The resulting solution was dark red and clear. After stirring the solution at room temperature for 30 minutes, 31 P NMR spectroscopy indicated the presence of both the desired complex (shown above) and a related nickel complex bearing a neutral ligand and two -CH2SiMe3 substituents. After stirring the solution at 45 °C for 60 min, 31 P NMR spectrum showed complete conversion to the desired complex. The reaction mixture was filtered through a plug of Celite, and all volatiles were removed from the filtrate under vacuum. The resulting crude product was dissolved in a minimum amount of toluene, and the product was triturated with pentane. The product was isolated by filtration as an orange powder, and the structure was confirmed by NMR spectroscopy (106 mg, 0.21 mmol, 61% yield).

[0129] 1 H NMR (500MHz, benzene-d6) δ9.07(td,J=3.3,1.6Hz,2H), 8.99-8.95(m,2H), 8.62-8.52(m,4H), 7.67- 7.47(m,10H), 7.20(t,J=7.7Hz,1H), 6.95-6.83(m,2H), 0.21(s,9H), -0.15(d,J=7.3Hz,2H)ppm. 13C NMR (126 MHz, benzene-d6) δ 180.63, 150.45, 136.55, 136.30, 135.85, 135.78, 135.65, 132.94, 132.86, 130.35, 130.23, 129.81 (d, J = 2.5 Hz), 123.67, 1.97, −10.50 (d, J = 28.8 Hz) ppm. 31 P NMR (162 MHz, benzene-d6) δ 75.96 ppm.

[0130] Example 13 - Ethylene / tert-butyl acrylate copolymerization - parallel pressure reactor testing Catalytic activity (in terms of quench time and polymer yield) and resulting polymer properties were evaluated for procatalysts 1-5 and comparative procatalyst C1 (Comparative C1), which contains the ligand previously described (J. Organomet. Chem. 1983, 249, C38.). Polymerization reactions were carried out in a parallel pressure reactor (PPR) as previously described.

[0131] The results shown in Table 1 were obtained by polymerization reactions in a parallel polymerization reactor (PPR). For each polymerization reaction listed in Table 1, a catalyst stock solution was prepared in toluene (1–2 mM) and immediately transferred to the PPR reactor. Copolymerization experiments were performed using catalyst loadings of 0.25–0.75 μmol and ethylene pressure of 400 psi. Tert-butyl acrylate was purified by filtration through a column of activated alumina, followed by preparation of a solution in toluene. The 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.

[0132] [ka]

[0133] [Table 1]

[0134] The entries in Table 1 are organized primarily by acrylate loading, although temperatures for a particular run may vary. The performance of the catalysts described in this disclosure is compared to Comparative C1.

[0135] As evidenced by the foregoing data, the procatalysts of the present disclosure have higher activity than procatalyst Comparative C1. Furthermore, the polymers produced by procatalysts 1-5 have increased tert-butyl acrylate incorporation and higher molecular weights compared to the polymer produced by Comparative C1. Furthermore, procatalysts 1-5 produce polymers with narrower PDIs than the polymer produced by Comparative C1.

[0136] While not intending to be bound by theory, it is believed that sterically hindered phosphines may be a driving factor for catalytic performance. Sterically hindered phosphines are a common component of procatalysts 1-5 but are absent in Comparative C1. For example, in entry 1, Comparative C1 exhibited very low activity (36 kg / mol h) and a broad PDI (5.85). In that case, the activity of Comparative C1 was too low to obtain sufficient polymer for analyzing acrylate incorporation.

[0137] For example, by including a more sterically hindered phosphine aryl substituent such as 2,6-dimethoxyphenyl, the activity of the catalyst increases by an order of magnitude (entries 2-7) compared to comparative C1. Thus, not all Ni(II) phosphine amide complexes are active ethylene / acrylate copolymerization catalysts, but the structural modifications we have made to the ligand constitute the present invention.

[0138] Example 14 - Ethylene / n-Butyl Acrylate Copolymerization - Parallel Pressure Reactor Testing The results shown in Table 2 were obtained by polymerization reactions in a parallel polymerization reactor (PPR). For each polymerization reaction listed in Table 2, a catalyst stock solution was prepared in toluene (1–2 mM) and immediately transferred to the PPR reactor. Copolymerization experiments were performed using catalyst loadings of 0.25–0.75 μmol and ethylene pressure of 400 psi. n-Butyl acrylate was purified by filtration through a column of activated alumina, followed by preparation of a solution in toluene. The reactor temperature and n-butyl acrylate loading were varied as shown in Table 2. Each entry in Table 2 represents the average of at least two replicate runs.

[0139] [Table 2]

[0140] The entries in Table 2 are organized primarily by acrylate loading, although temperatures for a particular run may vary.

[0141] The relative trends in reactivity for tert-butyl acrylate copolymerization (Table 1) are observed for n-butyl acrylate (Table 2). Catalyst activity and the molecular weight of the resulting copolymer are inversely proportional to the acrylate loading, while incorporation is directly related to the acrylate loading.

[0142] Note that at identical acrylate loadings, higher acrylate incorporation into the copolymer is observed with n-butyl acrylate versus tert-butyl acrylate. For example, procatalyst 1 produces a polymer with 0.9 mol% acrylate incorporation with 250 μmol of n-butyl acrylate (entry 3, Table 2), whereas under the same conditions, but with 250 μmol of tert-butyl acrylate, 0.4 mol% incorporation is observed. This class of catalysts effectively incorporates both sterically hindered and non-sterically hindered polar comonomers.

[0143] Example 15 - Results obtained with a 2 L batch reactor In these experiments, the catalyst was introduced into the reactor as a toluene solution of the isolated metal complex. The copolymerization experiments were carried out at 400 psi ethylene pressure. The reactor temperature and tert-butyl acrylate loading were varied as shown in Table 3. The initial charge of toluene to the reactor was 640 g (740 mL). The ethylene / tert-butyl acrylate copolymerization reaction was carried out for 75 minutes or until 40 g of ethylene uptake had occurred, whichever was shorter.

[0144] [Table 3]

[0145] As can be seen by the results shown in Table 3, the procatalysts of the present disclosure, specifically procatalysts 1 and 2, can catalyze ethylene / tert-butyl acrylate copolymerization reactions in a 2 L batch reactor, resulting in ethylene / tert-butyl acrylate copolymers at multigram scales. Higher catalytic activity was observed in the batch reactor compared to the PPR reactor, accompanied by higher levels of acrylate incorporation. Up to 50 g of polymer was produced per run. In particular, procatalyst 1 performed well (see entry 2), producing a high MW polymer (90,400) with significant acrylate incorporation (1.7 mol%) at high activity (1,500 kg / mol h). The inventions described in the original claims of this application are set forth below. [1] A procatalyst 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, -H, -CH 2 Si(R C ) 3-Q (ORC ) 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 , -N(Si(R C ) 3 ) 2 , -NR C Si(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 , -C(O)R C , -C(O)H, -N(R C )C(O)R C , -N(R C )C(O)H, -NHC(O)R C , -NHC(O)H, -C(O)N(R C ) 2 , -C(O)NHR C , -C(O)NH 2 or halogen, and each R C may independently be one or more R S optionally substituted with (C 1 ~C 30 ) hydrocarbyl, or one or more R S optionally substituted with (C 1 ~C 30 ) heterohydrocarbyl, wherein the subscript Q is 0, 1, 2, or 3, and the subscript W is 0, 1, or 2; Y is a Lewis base, Optionally, Y and X are covalently linked; R 1 is a non-substituted (C 6 ~C 40 ) aryl, substituted (C 6 ~C 40 ) aryl, unsubstituted (C 1 ~C 40 ) heteroaryl, substituted with its radical on a carbon atom (C 1 ~C 40 ) heteroaryl, or at least one tertiary carbon atom, (C 4 ~C 20 ) alkyl with its radical on the tertiary carbon atom (C 4 ~C 20 ) alkyl; R 2 and R 3 are independently selected from radicals having formula (II):

change

change

[10] R 32 、R 33 , and R 34 is independently selected from methoxy or ethoxy.

[11] R 32 and R 34 Ga-CF 3 [8] The procatalyst according to [8], wherein

[12] R 1 The procatalyst according to [1], wherein

[13] X is -CH 2 Si(CH 3 ) 3 The procatalyst according to any one of [1] to

[12] , wherein

[14] A polymerization process comprising the steps of: (a) reacting ethylene with ethylene and optionally one or more (C 3 ~C 10 ) a polymerization process comprising polymerizing an α-olefin monomer or optionally one or more cyclic olefin monomers.

[15] A polymerization process comprising the steps of: polymerizing ethylene, a polar comonomer, and optionally one or more (C 3 ~C 10 ) a polymerization process comprising polymerizing an α-olefin monomer or optionally one or more cyclic olefin monomers.

[16] The polar comonomer is an acrylate (CH 2 =CHC(O)(OR)), glycidyl acrylate, CH 2 =CH(CH 2 ) n C(O)(OR), CH 2 =CHC(O)R, CH 2 =CH(CH 2 ) n C(O)R, CH 2 =CH-OC(O)R, CH 2 =CH(CH 2 ) n -OC(O)R, CH 2 =CH(OR), CH 2 =CH(CH 2 ) n (OR), CH 2 =CHSi(R) 3-T (OR) T , C.H. 2 =CH(CH 2 ) n Si(R) 3-T (OR) T, CH 2 =CH-OSi(R) 3-T (OR) T , C.H. 2 =CH(CH 2 ) n -OSi® 3-T (OR) T or CH 2 ═CHCl, where R is —H, substituted or unsubstituted (C 1 -C 30 ) hydrocarbyl, or substituted or unsubstituted (C 1 ~C 30 ) heterohydrocarbyl, n is an integer of 1 to 10, and T is 0, 1, 2, or 3.

[17] The polymerization process of

[15] , wherein the acrylate comonomer is tert-butyl acrylate.

[18] The polymerization process of

[15] , wherein the acrylate comonomer is n-butyl acrylate.

Claims

1. A procatalyst according to formula (I): 【Chemical 1】 During the ceremony, M is nickel(II) or palladium(II); X is (C １ to C20) hydrocarbyl, (C １ to C20) heterohydrocarbyl, and —CH ２ Si(R Ｃ ) ３－Ｑ (OR Ｃ ) Ｑ and each R Ｃ independently represents one or more R Ｓ (C １ ~C ３０ ) hydrocarbyl, or one or more R Ｓ (C １ ~C ３０ ) heterohydrocarbyl, and the subscript Q is 0, 1, 2, or 3; Y is a Lewis base; Optionally, Y and X are covalently linked; R １ is unsubstituted (C ６ ~C ４０ ) aryl, substituted (C ６ ~C ４０ ) aryl, unsubstituted (C １ ~C ４０ ) heteroaryl, substituted with its radical on a carbon atom (C １ ~C ４０ ) heteroaryl, or at least one tertiary carbon atom, (C ４ ~C ２０ ) alkyl with its radical on a tertiary carbon atom (C ４ ~C ２０ ) alkyl; R ２ and R ３ are independently selected from radicals having formula (II): 【Chemistry 2】 During the ceremony, R 11 and R 15 are independently —O[(C 1 -C 10 )alkyl]; Each R １２ , R １３ and R １４ are independently １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ ) heterohydrocarbyl, —OR Ｎ , -NR Ｎ ２ , -SR Ｎ , halogen, or —H, and R Ｎ is (C １ ~C ３０ ) hydrocarbyl, Each R in formula (I) Ｓ are independently １ ~C ２０ ) a procatalyst which is a hydrocarbyl or halogen.

2. Y is a neutral Lewis basic aprotic (C ２ ~C ４０ 10. The procatalyst of claim 1, wherein the procatalyst is a heterohydrocarbon.

3. R ２ and R ３ 3. The procatalyst of claim 1 or claim 2, wherein:

4. R １１ and R １５ The procatalyst of claim 3 wherein is methoxy.

5. R １１ and R １５ The procatalyst of claim 3 wherein is ethoxy.

6. R １ is a radical having the formula (III) 【Chemistry 3】 In the formula, R ３１～３５ are independently —H, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —Si(R Ｒ ) ３ , -Ge(R Ｒ ) ３ , -P(R Ｒ ) ２ , -P(O)(R Ｒ ) ２ , -N(R Ｒ ) ２ , -OR Ｒ , -SR Ｒ , -NO ２ , -CN, -CF ３ or halogen, and each R Ｒ is (C １ ~C ３０ ) hydrocarbyl, (C １ ~C ３０ 6. The procatalyst of any one of claims 1 to 5, wherein the procatalyst is -H.

7. R ３２ , R ３３ , and R ３４ But independently, (C １ ~C ４０ ) heterohydrocarbyl, —Si[(C １ ~C １０ ) alkyl] ３ , -N[(C １ ~C １０ ) alkyl] ２ , -O[(C １ ~C １０ 7. The procatalyst of claim 6, wherein the procatalyst is selected from the group consisting of: 。

8. R ３２ , R ３３ , and R ３４ 7. The procatalyst of claim 6, wherein is independently selected from methoxy or ethoxy.

9. R ３２ and R ３４ Ga-CF ３ 7. The procatalyst of claim 6, wherein:

10. R １ The procatalyst of claim 1 wherein is 2-furyl.

11. X is -CH ２ Si(CH ３ ) ３ The procatalyst of any one of claims 1 to 10, wherein 12. The procatalyst of claim 1, wherein X is a trimethylsilylmethyl group, and R 11 and R 15 are each independently a methoxy group or an ethoxy group.

13. A polymerization process comprising the step of polymerizing ethylene and optionally one or more (C ３ ~C １０ 2.) A polymerization process comprising polymerizing an α-olefin monomer or optionally one or more cyclic olefin monomers.

14. A polymerization process comprising the steps of: polymerizing ethylene, a polar comonomer, and optionally one or more (C ３ ~C １０ 2.) A polymerization process comprising polymerizing an α-olefin monomer or optionally one or more cyclic olefin monomers.

15. The polar comonomer is an acrylate (CH ２ = CHC(O)(OR)), glycidyl acrylate, CH ２ =CH(CH ２ ) ｎ C(O)(OR), CH ２ =CHC(O)R,CH ２ =CH(CH ２ ) ｎ C(O)R, CH ２ =CH-OC(O)R, CH ２ =CH(CH ２ ) ｎ -OC(O)R,CH ２ =CH (OR), CH ２ =CH(CH ２ ) ｎ (OR), CH ２ =CHSi(R) ３－Ｔ (OR) Ｔ , C.H. ２ =CH(CH ２ ) ｎ Si(R) ３－Ｔ (OR) Ｔ， CH ２ =CH-OSi(R) ３－Ｔ (OR) Ｔ , C.H. ２ =CH(CH ２ ) ｎ -OSi(R) ３－Ｔ (OR) Ｔ or CH ２ =CHCl, where R is —H, substituted or unsubstituted (C １ -C ３０ ) hydrocarbyl, or substituted or unsubstituted (C １ ~C ３０ 15. The polymerization process of claim 14, wherein n is an integer from 1 to 10, and T is 0, 1, 2, or 3.

16. 15. The polymerization process of claim 14, wherein the polar comonomer is tert-butyl acrylate.

17. 15. The polymerization process of claim 14, wherein the polar comonomer is n-butyl acrylate.

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