Pro-catalyst and polymerization process

Abstract

PRO-CATALYST, CATALYST SYSTEM, AND POLYMERIZATION PROCESS. This refers to polymerization processes of olefin monomers using catalyst systems and catalyst systems that include a pro-catalyst having a structure according to the formula.

Description

[001] The embodiments of the present disclosure generally relate to ethylene and polar comonomer polymerization catalyst systems and processes and, more specifically, to ethylene and acrylate polymerization catalyst systems that include nickel (II) catalysts supported by sterically hindered phosphine-amide, and to olefin polymerization processes that incorporate catalyst systems. BACKGROUND

[002] Commercially, ethylene / acrylate copolymers are formed by 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 routes to highly linear ethylene / acrylate copolymers with structures similar to linear low-density polyethylene (LLDPE). Linear ethylene / acrylate copolymers formed by coordination catalysis exhibit higher crystallinity and greater thermal resistance than copolymers formed through radical processes.

[003] Common organometallic coordination catalysts suitable for ethylene polymerization are not compatible with systems that include acrylates as comonomers. For example, Group IV metal catalysts (TiZr, Hf) used in the industrial manufacture of LLDPE (ethylene / α-olefin copolymers) are not compatible with polar olefinic monomers, including acrylates. Because the oxygen atoms of acrylates coordinate strongly to Lewis Group IV metals, during ethylene / acrylate polymerization, the metal active site becomes blocked by the acrylate and further olefin polymerization is prevented.

[004] Due to the incompatibility of Group IV metal catalysts with acrylates, electron-rich metal catalysts containing Group 10 metals (Pd, Ni) have been explored in the copolymerization reactions of ethylene with acrylate monomers. However, many reported Ni and Pd-containing metal catalysts have (a) low polymerization rates and / or (b) low incorporation of the polar monomers of interest. Petition 870250003175, dated 15 / 01 / 2025, page 14 / 106 2 / 41 SUMMARY

[005] There is an ongoing need to create a linker structure for Ni and Pd catalysts that promotes high ethylene copolymerization activity rates and high incorporation of the acrylate comonomer. With a linker structure for Ni, or palladium, ethylene and polar monomers can be copolymerized via coordination catalysis to form a highly linear LLDPE-like copolymer. Highly linear copolymers can exhibit improved creep resistance and dimensional stability at higher temperatures, specifically from 80°C to 150°C, in contrast to temperatures below 80°C.

[006] The embodiments of this disclosure include catalyst systems. The catalyst systems include a pro-catalyst with a structure according to formula (I): (I)

[007] In formula (I), M is nickel(II) or Pd(II); X is a ligand chosen from (Ci-C40)hydrocarbyl, (Ci-C40)heterohydrocarbyl, -H, -CH2Si(Rc)3-q(ORc)q, -SÍ(Rc)3_q(ORc)q, -OSí(Rc)3_q(ORc)q, -Ge(RC)3_Q(ORC)Q, -P(Rc)2-w(ORc)w, -P(O)(Rc)2-w(ORc)w, -N(RC)2, -N(SÍ(Rc)3)2, -NRcSÍ(Rc)3, -ORc, -SRc, -NO2, -CN, -CF3, -OCF3, -S(O)Rc, -S(O)2Rc, -OS(O)2Rc, -N=C(Rc)2, -N=CH(RC), -N=CH2. -N=P(Rc)3, -OC(O)RC, -C(O)ORC, -C(O)RC, -C(O)H, -N(RC)C(O)RC, -N(Rc)C(O)H, -NHC(O)RC, -NHC(O)H, -C(O)N(Rc)2, -C(O)NHRC, -C(O)NH2, or a halogen. Each RC in formula (I) is independently (a) a (C1-C30) hydrocarbyl optionally substituted with one or more RS; or (b) a (C1-C30) heterohydrocarbyl optionally substituted with one or more RS. The Q subscript on the various X ligands is 0, 1, 2, or 3. The W subscript on the various X ligands is 0, 1, or 2. Y is a Lewis base. Optionally, Y and X in formula (I) are covalently connected.

[008] In formula (I), R1 is chosen from unsubstituted (C6-C40)aryl, substituted (C6-C40)aryl, unsubstituted (C1-C40)heteroaryl having its radical on a carbon atom, or substituted (C1-C40)heteroaryl having its radical on a carbon atom, Petition 870250003175, dated 15 / 01 / 2025, p. 15 / 106 3 / 41 or (C4-C2o)substituted alkyl having at least one tertiary carbon atom and having its radical on the tertiary carbon atom.

[009] In formula (I), R2 and R3 are selected independently from radicals that have formula (II): (II)

[0010] In formula (II), R11, R12, R13, R14, and R15 are independently (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, -ORN, -NRn2, -SRn, halogen, or -H, where each RN is (C1-C30)hydrocarbyl, provided that at least one of R11 and R15 is not -H.

[0011] In formula (I), each Rs in formula (I) is independently (C1-C20) hydrocarbyl or halogen.

[0012] The embodiments of this disclosure include a polymerization process. The polymerization process of this disclosure includes polymerizing ethylene and one or more polar monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based copolymer. The catalyst system includes a metal-ligand complex according to formula (I) of this disclosure. detailed description

[0013] Specific embodiments of catalyst systems will now be described. It should be understood that the catalyst systems of this disclosure may be represented as embodiments in different forms and should not be interpreted as limited to the specific embodiments presented in this disclosure. Instead, the embodiments are provided so that this disclosure is detailed and complete and fully conveys the scope of the subject to those skilled in the art.

[0014] Common abbreviations are shown below:

[0015] Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; i-Pr: iso-propyl; 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: benzene or benzene Petition 870250003175, dated 15 / 01 / 2025, page 16 / 106 4 / 41 d6 deuterated: CDCl3: deuterated chloroform; Na2SÜ4: sodium sulfate; MgSÜ4: magnesium sulfate; HCl: hydrogen chloride; n-BuLi: butyllithium; t-BuLi: tert-butyllithium; K2CÜ3: potassium carbonate; N2: nitrogen gas; PhMe: toluene; PPR: parallel pressure reactor; MAÜ: methylaluminoxane; MMAÜ: modified methylaluminoxane; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimoles; mL: milliliters; M: molar; min or mins: minute; h or hrs: hours; d: day; Rf: retention factor; TLC: thin-layer chromatography; rpm: revolutions per minute.

[0016] The independently selected term followed by multiple options is used in this document to indicate that individual groups appearing before the term, such as R1, R2, R3, and RC, may be identical or different, without depending on the identity of any other group that also appears before the term.

[0017] The term pro-catalyst refers to a compound that has catalytic activity after activation, for example, after removal of the Lewis base coordinated with the Ni or Pd metal center.

[0018] When used to describe certain chemical groups containing carbon atoms, a parenthetical expression having the form (Cx-Cy) means that the unsubstituted form of the chemical group has from x to y carbon atoms, including x and y. For example, a (C1-C50)alkyl is an alkyl group having from 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted by one or more substituents, such as RS, where RS generically represents any substituent defined in this application. An RS-substituted version of a chemical group defined by the use of the parenthetical expression (Cx-Cy) may contain more than y carbon atoms depending on the identity of any RS groups. For example, a (C1-C50)alkyl substituted with exactly one RS group, where RS is phenyl (-C6H5), may contain from 7 to 56 carbon atoms.Thus, in general, when a chemical group defined using (Cx-Cy) in parentheses is replaced by one or more substituents containing carbon atoms, the minimum and maximum total number of carbon atoms in the chemical group will be determined by adding ax and y, respectively, to the combined sum of the number of carbon atoms of all the substituents. Petition 870250003175, dated 15 / 01 / 2025, p. 17 / 106 5 / 41 RS substituents that contain carbon atoms.

[0019] The term substitution means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding functional group or unsubstituted compound is replaced by a substituent (e.g., RS). The prefix per has its usual meaning of completely. The term persubstitution means that each hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding functional group or unsubstituted compound is replaced by a substituent (e.g., RS). Thus, a perfluorinated alkyl is an alkyl group in which each hydrogen atom is replaced by a fluorine atom. The term polysubstitution means that at least two, but less than all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding functional group or unsubstituted compound are replaced by a substituent.The term -H means a hydrogen or hydrogen radical that is covalently bonded to another atom. Hydrogen and -H are interchangeable and, unless clearly specified, have identical meanings.

[0020] The term (C1-C50)hydrocarbyl means a hydrocarbon radical of 1 to 50 carbon atoms and the term (C1-C50)hydrocarbylene means a hydrocarbon diradical of 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, linear or branched chain, cyclic (having three or more carbons, and including mono- and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic and substituted by one or more RS or unsubstituted.

[0021] In this disclosure, a (C1-C50)hydrocarbyl includes, without limitation, unsubstituted or substituted forms of the following groups: (C1-C50)alkyl, (C3-C50)cycloalkyl, (C3-C20)cycloalkyl-(C1-C20)alkylene, (C6-C40)aryl, or (C6-C20)aryl-(C1-C20)alkylene (as benzyl (-CH2-C6H5)).

[0022] The terms (C1-C50)alkyl and (C1-C18)alkyl mean a saturated straight or branched hydrocarbon radical of 1 to 50 carbon atoms and a saturated straight or branched hydrocarbon radical of 1 to 18 carbon atoms, respectively, that is substituted or unsubstituted by one or more RS. The radical may be on any carbon atom of the alkyl. Examples of non-substituted (C1-C50)alkyl Petition 870250003175, dated 15 / 01 / 2025, p. 18 / 106 Examples of substituted 6 / 41 alkyl groups include unsubstituted (C1-C2o)alkyl; unsubstituted (C1-C1o)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. Examples of substituted (C1-C4o)alkyl groups include substituted (C1-C2o)alkyl, substituted (C1-C1o)alkyl, trifluoromethyl, and [Cn]alkyl. The term alkyl [Cn] means the radical, including substituents, contains up to a maximum of n carbon atoms, where n is an integer from 1 to 45. For example, a [C45]alkyl is, for instance, a (C27-C40)alkyl substituted by an RS group, which is a (C1-C5)alkyl, or is, for instance, a (C15-C25)alkyl substituted by two RS groups, which are each a (C1-C10)alkyl. Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 2,2-dimethylpropyl; 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 that is covalently bonded to three other carbon atoms.

[0023] The term (C6-C50)aryl means an unsubstituted or substituted (by one or more RS) monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical of 6 to 40 carbon atoms, of which at least 6 to 14 of the carbon atoms are carbon atoms of the aromatic ring. A monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or unfused and aromatic or non-aromatic.Examples of unsubstituted (C6-C50)aryl compounds include unsubstituted (C6-C20)aryl compounds, unsubstituted (C6-C18)aryl compounds; 2-(C1-C5)alkylphenyl compounds; phenyl compounds; fluorenyl compounds; tetrahydrofluorenyl compounds; indacenyl compounds; hexaindacenyl compounds; indenyl compounds; dihydroindenyl compounds; naphthyl compounds; tetrahydronaphthyl compounds; anthracenyl compounds; and phenanthrenyl compounds. Examples of substituted (C6-C40)aryl compounds include: substituted (C1-C20)aryl compounds; substituted (C6-C18)aryl compounds; 2,4-bis[(C20)alkyl]phenyl compounds; 3,5-bis[(C20)alkyl]phenyl compounds; pentafluorophenyl compounds; and fluoren-9-one-1-yl compounds.

[0024] The term (C3-C50)cycloalkyl means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms that is unsubstituted or substituted with a Petition 870250003175, dated 15 / 01 / 2025, p. 19 / 106 7 / 41 or more RS. Other cycloalkyl groups (e.g., (Cx-Cy)cycloalkyl) are defined in an analogous manner as having x and y carbon atoms and being either unsubstituted or substituted with one or more RS. Examples of unsubstituted (C3-C40)cycloalkyl are unsubstituted (C3-C20)cycloalkyl, unsubstituted (C3-C10)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C40)cycloalkyl are substituted (C3-C20)cycloalkyl, substituted (C3-C10)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0025] Examples of (C1-C50)hydrocarbylene include, without limitation, unsubstituted or substituted forms of groups such as (C6-C50)arylene, (C3-C50)cycloalkylene, and (C1-C50)alkylene (e.g., (C1-C20)alkylene). Diradicals may be on the same carbon atom (e.g., ±CH2±) or on adjacent carbon atoms (i.e., 1,2-diradicals), or they may be separated from each other by one, two, or more than two intermediate carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4- or an α,ω-diradical, and others, a 1,2-diradical. The α,ω-diradical is a diradical that has maximum backbone carbon spacing between the carbons of the radical. Some examples of α,ω-diradicals (C2-C20)alkylene include ethan-1,2-di-yl (i.e. -CH2CH2-), propan-1,3-di-yl (i.e. -CH2CH2CH2-), 2-methylpropan-1,3-di-yl (i.e. -CH2CH(CH3)CH2-).Some examples of α,ω-diradicals (C6-C50)arylene include phenyl-1,4-diyl, naphthalen-2,6-diyl, or naphthalen-3,7-diyl.

[0026] The term (C1-C50)alkylene means a saturated linear or branched chain diradical (i.e., the radicals are not on the ring atoms) of 1 to 50 carbon atoms that is unsubstituted or substituted with one or more RS. Examples of unsubstituted (C1-C50)alkylene are unsubstituted (C1-C20)alkylene, including ±CH2CH2±, ±(CH2)3±, ±(CH2)4±, ±(CH2)5±, ±(CH2>6±), ±(^2)7+, ±(CH2>8±), ±CH2C*HCH3, and ±(CH2)4C*(H)(CH3) unsubstituted, where C* denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1-C50)alkylene are substituted (C1-C20)alkylene, ±CF2±, ±C(O)±, and ±(CH2)14C(CH3)2(CH2)5± (i.e., a 1,20-eicosylene). 6,6-dimethyl-substituted). (C1-C50)substituted alkylene Petition 870250003175, dated 15 / 01 / 2025, p. 20 / 106 8 / 41 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).

[0027] The term (C3-C5o)cycloalkylene means a cyclic radical (i.e., the radicals are on ring atoms) of 3 to 50 carbon atoms that is unsubstituted or substituted with one or more RS.

[0028] The term heteroatom refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include -O-, -S-, -S(O)-, -S(O)2-, -Si(RC)2-, -P(RP)-, -P(Rp)2, -P(O)(RP)2, -N(Rn)-, -N(Rn)2, -N=C(Rc)2, -N=C(NRN2)(Rc), -Ge(RC)2-, or -Si(RC)3, where each RC and each RP is an unsubstituted (C1-C18) hydrocarbyl or -H, and where each RN is an unsubstituted (C1-C18) hydrocarbyl or -H. The term heterohydrocarbon refers to a molecule or molecular structure in which one or more carbon atoms of a hydrocarbon are substituted with a heteroatom. The term (C1-C50)heterohydrocarbyl means a heterohydrocarbon radical with 1 to 50 carbon atoms, and the term (C1-C50)heterohydrocarbylene means a heterohydrocarbon diradical with 1 to 50 carbon atoms. The heterohydrocarbon (C1-C50)heterohydrocarbyl or (C1-C50)heterohydrocarbylene has one or more heteroatoms.The heterohydrocarbyl radical can be on a carbon atom or a heteroatom. The two heterohydrocarbylene radicals can be on a single carbon atom or a single heteroatom. Additionally, one of the two diradical radicals can be on a carbon atom and the other radical can be on a different carbon atom; one of the two radicals can be on a carbon atom and the other on a heteroatom; or one of the two radicals can be on a heteroatom and the other radical on a different heteroatom. Each (C1-C50)heterohydrocarbyl and (C1-C50)heterohydrocarbylene can be unsubstituted or substituted (with one or more RS), aromatic or non-aromatic, saturated or unsaturated, linear or branched chain, cyclic (including mono- and polycyclic, fused and non-fused polycyclic), or acyclic.

[0029] The (C1-C50)heterohydrocarbyl may be substituted or unsubstituted. Non-limiting examples of (C1-C50)heterohydrocarbyl include (C1-C50)heteroalkyl, Petition 870250003175, dated 15 / 01 / 2025, p. 21 / 106 9 / 41 (Ci-C5o)hydrocarbyl-O-, (Ci-C5o)hydrocarbyl-S-, (Ci-C5o)hydrocarbyl-S(0)±, (Ci-C5o)hydrocarbyl-S(0)2±, (Ci-C5o)hydrocarbyl-Si(RC)2±, (Ci-C5o)hydrocarbyl-N(RN)±, (C1-C5o)hydrocarbyl-P(RP)±, (C2-C5o)heterocycloalkyl, (C2-C19)heterocycloalkyl(C1-C20)alkylene, (C3-C20)cycloalkyl-(C1-C19)heteroalkylene, (C2-C19)heterocycloalkyl-(C1-C2o)heteroalkylene, (C1-C5o)heteroaryl, (C1-C19)heteroaryl-(C1-C20)alkylene, (C6-C20)aryl-(C1-C19)heteroalkylene, or (C1-C19)heteroaryl-(C1-C2o)heteroalkylene. Additional examples include, but are not limited to, -Si(Rc)3-q(ORc)q, -Osi(Rc)3-q(ORc)q, -Ge(RC)3-Q(ORC)Q, -P(RC)2W(ORC)W, -P(O)(RC)2-W(ORC)W, -N(RC)2, -NH(RC)2, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=P(RC)3, -OC(O)RC, C(O)RC, -C(O)ORC, -N(RC)C(O)RC, and -C(O)N(RC)2.

[0030] The term (C4-C50)heteroaryl means an unsubstituted or substituted monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical (by one or more RS) with a total of 2 to 50 carbon atoms and 1 to 10 heteroatoms. The heteroaryl radical may be on a carbon atom or a heteroatom. A monocyclic heteroaromatic hydrocarbon radical includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may be independently fused or unfused and aromatic or non-aromatic.Other heteroaryl groups (e.g., (Cx-Cy)heteroaryl, usually as (C4-C12)heteroaryl) are defined in an analogous manner as having x and a carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted with one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3, or 4; and each heteroatom can be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals are pyrrole-1-yl; pyrrole-2-yl; furan-3-yl; thiophen-2-yl; pyrazole-1-yl; isoxazole-2-yl; isothiazole-5-yl; imidazole-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl;. Petition 870250003175, dated 15 / 01 / 2025, p. 22 / 106 10 / 41 tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and the heteroatoms can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl; 1,3,5-thiadiazole-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a 5,6- or fused -6,6-ring system. Examples of the fused -5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indole-1-yl; and benzimidazole-1-yl. Examples of the fused -6,6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-1-yl. The bicyclic heteroaromatic hydrocarbon radical can be a 5,6,5; -5,6,6; 6,5,6; or -6,6,6 fused ring system. An example of the 5,6,5 ring system is 1,7-hydropyrrolo[3,2f]indol-1-yl. An example of the 5,6,6 fused ring system is 1H-benzo[f]indol-1-yl.An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0031] The term (C1-C50)heteroalkyl means a saturated linear or branched chain diradical containing from 1 to 50 carbon atoms and one or more heteroatoms. The term (C1-C50)heteroalkylene means a saturated linear or branched chain diradical containing from 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of heteroalkyls or heteroalkylenes may include, but are not limited to, Si(RC)3, Ge(RC)3, Si(RC)2, Ge(RC)2, P(RP)2, P(RP), P(O)(RP)2, N(RN)2, N(RN), N, O, ORC, S, SRC, S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or is substituted by one or more RS.

[0032] Examples of unsubstituted (C2-C40)heterocycloalkyl include unsubstituted (C2-C20)heterocycloalkyl, unsubstituted (C2-C10)heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophen-S,Sdioxido-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0033] The term halogen atom or halogen means the radical of a fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) atom. The term halide means the anionic form of the halogen atom: fluoride (F-), chloride (Cl-), Petition 870250003175, dated 15 / 01 / 2025, p. 23 / 106 11 / 41 bromide (Br-) or iodide (I-).

[0034] The term saturated means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen, carbon-phosphorus, nitrogen-nitrogen, nitrogen-phosphorus, and carbon-silicon double or triple bonds. When a saturated chemical group is substituted by one or more RS substituents, one or more double and / or triple bonds may or may not be present in the RS substituents. The term unsaturated means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in groups containing heteroatoms) one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds, not including double or triple bonds that may be present in the RS substituents, if any, or in (hetero)aromatic rings, if any.

[0035] The embodiments of this disclosure include catalyst systems. The catalyst system includes a pro-catalyst having a structure according to formula (I): (I)

[0036] In formula (I), M is nickel(II) or Pd(II); X is a ligand chosen from (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, -H, -CH2Si(Rc)3-q(ORc)q, -SÍ(Rc)3-q(ORc)q, -OSÍ(Rc)3-q(ORc)q, -Ge(RC)3-Q(ORC)Q, -P(Rc)2-w(ORc)w, -P(O)(RC)2-W(ORC)W, -N(RC)2, -N(Si(RC)3)2, -NRCSi(RC)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(RC), -N=CH2 -N=P(RC)3, -OC(O)RC, -C(O)ORC, -C(O)RC, -N(RC)C(O)RC, -N(RC)C(O)H, -NHC(O)RC, -NHC(O)H, -C(O)N(RC)2, -C(O)NHRC, -C(O)NH2, or a halogen. Q subscript on the various X ligands is 0, 1, 2, or 3. OW subscript on the various X ligands is 0, 1, or 2. Y is a Lewis base. Optionally, Y and X in formula (I) are covalently connected.

[0037] In formula (I), R1 is chosen from unsubstituted (C6-C4o)aryl, substituted (C6-C4o)aryl, unsubstituted (C1-C4o)heteroaryl having its radical on a carbon atom, or substituted (C1-C4o)heteroaryl having its radical on an atom Petition 870250003175, dated 15 / 01 / 2025, p. 24 / 106 12 / 41 carbon, or (C4-C2o)substituted alkyl having at least one tertiary carbon atom and having its radical on the tertiary carbon atom. The term tertiary carbon atom refers to a carbon atom that is covalently bonded to three other carbon atoms.

[0038] In formula (I), R2 and R3 are selected independently of radicals that have formula (II): R13 RlVxL^R12Y Y (II) R15^^R11

[0039] In formula (II), R11, R12, R13, R14, and R15 are independently (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, -ORN, -NRn2, -SRn, halogen, or -H; provided that at least one or R11 and R15 is not -H. Each RN is (C1-C30)hydrocarbyl.

[0040] In formula (I), each RC in formula (I) is independently (a) a (C1-C30) hydrocarbyl, optionally substituted with one or more RS; or (b) a (C1-C30) heterohydrocarbyl optionally substituted with one or more RS. Each RS in formula (I) is independently a (C1-C20) hydrocarbyl or halogen. in one or more forms, in formula (I), R2 and R3 are identical. In several embodiments, in formula (I), R11 and R15 are independently -O[(C1-C10)alkyl]. In some embodiments, R11 and R15 are methoxyl, ethoxyl or isopropoxyl, preferably methoxyl or ethoxyl. In one or more embodiments, R11 and R15 are independently -N[(C1-C10)alkyl]2. one or more forms, R1 is a radical that has the formula (III): R33 R35 R R32 R31(III)

[0041] In formula (III), each of R31 35 is independently chosen from -H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, -Si(RR)3, -Ge(RR)3, -P(Rr)2, P(O)(Rr)2, -N(Rr)2, -ORr, -SRr, -NO2, -CN, -CF3, or halogen, where each RR is (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, halogen, or -H. In other embodiments, R32, R33, and R34 are independently chosen from (C1-C40)heterohydrocarbyl Petition 870250003175, dated 15 / 01 / 2025, p. 25 / 106 13 / 41 hydrocarbyl, -Si[(Ci-Cio)alkyl]3, -N[(Ci—Cio)alkyl]2, -O[(Ci—Cio)alkyl]. In one or more embodiments, R32, R33, and R34 are independently selected from methoxyl or ethoxyl. In some embodiments, R1 is 2-furyl. In some forms, in formula (III), R32 and R34 are -CF3.

[0042] In the metal-ligand complex according to formula (I), each X is linked to M through a covalent bond or an ionic bond. In one or more embodiments, Y is a Lewis base. The Lewis base can be a compound or an ionic species, which can donate an electron pair to an acceptor moiety. For the 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 a hydrocarbon. Examples of 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. In one or more embodiments, Y is a Lewis aprotic (C2-C40)heterohydrocarbon. Aprotic (C2-C40)heterohydrocarbons are (C2-C40)heterohydrocarbons, as previously defined, for which each hydrogen atom of the (C2-C40)heterohydrocarbon has a pKa greater than 30, where pKa is the negative base-10 logarithm of the acid dissociation constant (Ka). In some embodiments, Y is a Lewis organic base. Examples of organic Lewis bases include pyridine, or a substituted pyridine, a sulfoxide, a triaryl or triarylphosphine, a triaryl or triarylphosphine oxide, an olefin or cyclic olefin, a substituted or unsubstituted heterocycle, an alkyl ester of an aliphatic or aromatic carboxylic acid, an aliphatic ketone, an aliphatic amine, an alkyl or cycloalkyl ether, or mixtures thereof, wherein 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; and dialkyl, diaryl, and alkylaryl ketones having 3 to 20 carbon atoms; and alkyl esters having 2 to 20 carbon atoms. Specific examples of an organic Lewis base include, but are not limited to: methyl formate, ethyl acetate, butyl acetate, ethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethyl formate, dimethylformamide. Petition 870250003175, dated 15 / 01 / 2025, page 26 / 106 14 / 41 methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, tetrahydrofuran, ethyl propionate, lutidine, picolin, pyridine dimethyl sulfoxide, trimethylphosphine, triphenylphosphine, cyclooctadiene, cyclopentene, ethylene, propylene, tert-butylethylene, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, 1-methylimidazole, or 1-methylpyrazole. In one or more embodiments, the Lewis base can 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 a neutral Lewis base group, such as RTNRKRL, RKORL, RKSRL, or RTPRKRL, wherein each RT independently is [(C1-C10)hydrocarbyl]3Si(C1-C10)hydrocarbylene, (C1-C40)hydrocarbyl, [(C1-C10)hydrocarbylhSi, or (C1-C40)heterohydrocarbyl and each RK and R independently is hydrogen, (C1-C40)hydrocarbyl, or (C1-C40)heterohydrocarbyl. In some embodiments, the Lewis base is a (C1-C20) hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene, 1,3-butadiene, or cyclooctene. In several embodiments, the Lewis base is a (C1-C20)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). In several embodiments, the Lewis base is a (C1-C20)heterohydrocarbon, and the heteroatom of the heterohydrocarbon is nitrogen. In some embodiments, Y is pyridine, picoline, lutidine, trimethylamine, or triethylamine. In several embodiments, the Lewis base is a (C1-C20)heterohydrocarbon, and the heteroatom of the heterohydrocarbon is phosphorus. In some embodiments, Y is trimethylphosphine, triethylphosphine, triphenylphosphine, triethylphosphite, trimethylphosphite, triphenylphosphite, or triphenylphosphine oxide. In some embodiments, X and Y are covalently linked. Specific examples of an organic Lewis base Y covalently linked to an X group include, but are not limited to: 4-cycloocten-1-yl, 2-dimethylaminobenzyl, and 2-dimethylaminomethylphenyl. In some modalities, X and Y are connected and selected from the group consisting of: Petition 870250003175, dated 15 / 01 / 2025, p. 27 / 106 15 / 41 which RC is -H or (C1-C3o)hydrocarbyl, (C1-C3o)heterohydrocarbyl, (C1-C20)alkyl, or (Ci—Ci2)alkyl.

[0043] In the metal-ligand complex according to Formula (I), X is linked to M through a covalent bond or an ionic bond. In some embodiments, X may be a monoanionic ligand having a net formal oxidation state of -1. Each monoanionic ligand may independently be a hybrid, (C1-C40)hydrocarbyl carbanion, (C1-C40)heterohydrocarbyl carbanion, halide, nitrate, hydrogen carbonate, dihydrogen phosphate carbonate, hydrogen sulfate, HC(O)O-, HC(O)N(H)-, (C1-C40)hydrocarbylC(O)O-, (C1-C40)hydrocarbylC(O)N((C1-C20)hydrocarbyl)-, (C1-C40)hydrocarbylC(O)N(H)-, RKRLB--, RKRLN-, RKO-, RKS-, RKRLP-, or RMRKRLSi-, wherein each RK, RL, and RM independently is hydrogen, (C1-C40)hydrocarbyl, or (C1-C40)heterohydrocarbyl, or RK and RL are considered together to form a (C2-C40)hydrocarbylene or (C1-C20)heterohydrocarbylene and RM is as defined above. In some embodiments, X is a halogen, (C1-C20)hydrocarbyl, (C1-C20)heterohydrocarbyl, (C1-C20)hydrocarbylC(O)O-, or RKRLN-, wherein each of RK and RL is independently a (C1-C20)hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C10)hydrocarbyl (e.g., (C1-C10)alkyl or benzyl), unsubstituted (C1-C10)hydrocarbylC(O)O-, or RKRLN-, wherein each RK and RL is independently an unsubstituted (C1-C10)hydrocarbyl. In other embodiments, X is selected from methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-methylpropyl; trimethylsilylmethyl; dimethylphenylsilylmethyl; methyldiphenylsilylmethyl; triphenylsilylmethyl; benzyldimethylsilylmethyl; trimethylsilylmethyldimethylsilylmethyl; phenyl; benzyl; or chlorine. Petition 870250003175, dated 15 / 01 / 2025, p. 28 / 106 16 / 41 In one or more embodiments, X is-(CH2)SiRX3, wherein each RX is independently a (C1-C30)alkyl or a (C1-C30)heteroalkyl and at least one RX is a (C1-C30)alkyl. In some embodiments, when one of the RX is a (C1-C30)heteroalkyl, the heteroatom is a silica or oxygen atom. In some embodiments, RX is methyl, ethyl, propyl, 2-propyl, butyl, 1,1-dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl. One or more forms of X are -(CH2)Si(CH3)3, -(CH2)Si(CH3)2(C6H5), -(CH2)Si(CH3)(C6H5)2, -(CH2)Si(C6H5)3, -(CH2)Si(CH3HCH2C6H5), -(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)RX, -(CH2)Si(CH3)2RX, -(CH2)Si(n-oct)RX2, -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), or -CH2Si(CH3)2CH2Si(CH3)3(in the present invention called -CH2Si(CH3)2(CH2TMS). Optionally, in some embodiments, the metal-ligand complex according to formula (I), exactly two RXs are covalently linked or exactly three RXs are covalently linked. In some embodiments, X is -CH2Si(Rc)3-q(ORc)q, -Si(Rc)3-q(ORc)q, -OSi(RC)3q(ORc)q, where the subscript Q is 0, 1, 2 or 3 and each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl. In some embodiments, X is -CH2Si(CH3)3. In some embodiments, any or all of the chemical groups of the procatalysts of formula (I) may be unsubstituted, except for R11 or R15. At least one of R11 and R15 is substituted. In other embodiments, none, any, or all of the chemical groups X and R1-R4, R11-15, or R31-35 of the metal-ligand complex of formula (I) may be substituted by one or more RS. When two or more RS are attached to the same chemical group of the procatalysts of formula (I), the individual RS of the chemical group may be attached to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, none, any, or all of the chemical groups X and R1-R4, R11-15, or R31-35 may be persubstituted with RS. In chemical groups that are persubstituted with RS, the individual RS can be the same or can be chosen independently. Petition 870250003175, dated 15 / 01 / 2025, p. 29 / 106 17 / 41

[0044] The embodiments of this disclosure include polymerization processes. In some embodiments, the polymerization process includes polymerizing ethylene with one or more olefinic monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based polymer. The catalyst system includes a metal-ligand complex according to formula (I) of this disclosure. In some embodiments, the polymerization processes include polymerizing ethylene, one or more polar monomers, and optionally one or more α-olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene / polar monomer copolymer. The catalyst system includes a pro-catalyst according to formula (I) of this disclosure. In one or more embodiments, the polymerization processes include polymerizing ethylene, one or more alkyl acrylate monomers, and optionally one or more α-olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene / alkyl acrylate copolymer, wherein the catalyst system comprises a pro-catalyst according to formula (I) of this disclosure. In some embodiments of the polymerization process, the polymerization process comprises polymerizing ethylene and optionally one or more α-olefin (C3-C10) monomers or cyclic olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based copolymer, wherein the catalyst system comprises a metal-ligand complex having the structure according to formula (I) as described in this disclosure. In some embodiments of the polymerization process, the polymerization process comprises polymerizing ethylene, a polar comonomer, and optionally one or more (C3-C10)α-olefin monomers or cyclic olefin monomers in the presence of a catalyst system under olefin polymerization conditions to form an ethylene-based copolymer, wherein the catalyst system comprises a metal-ligand complex according to formula (I) as described in this disclosure.

[0045] Olefinic monomers may include, but are not limited to, propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, Petition 870250003175, dated 15 / 01 / 2025, page 30 / 106 18 / 41 1-hexene, 1-octene, 1-dodecene, 4-methyl-1-pentene, styrene, cyclobutene, cyclopentene, norbornene, ethylidene norbornene, alkyl acrylate, glycidyl acrylate, vinyl acetate, CH2=C(H)C(O)(ORx), CH2=CHC(O)Rx, CH2=CH(ORx), CH2=CH(CH2)(ORx), CH2=CHSi(Rx)3-y(ORx)y, CH2=CH-OSi(Rx)3-y(ORx)y, or CH=CHCl, wherein RX is chosen from -H, a substituted or unsubstituted (C1-C3o)hydrocarbyl, or a substituted or unsubstituted (C1-C3o)heterohydrocarbyl, and the subscript Y is 0, 1, 2, or 3. various embodiments of the processes of In polymerization, the polar comonomer includes alkyl acrylates CH2=CHC(O)(OR), glycidyl acrylate, CH2=CH(CH2)nC(O)(OR), CH2=CHC(O)R, CH2=CH(CH2)nC(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)nSi(R)3-T(OR)T, CH2=CH-OSí(R)3-t(OR)t, CH2=CH(CH2)nOSí(R)3-t(OR)t or CH2=CHCl. ​​Each R is chosen from -H, substituted (C1-C3o)hydrocarbyl, unsubstituted (C1-C3o)hydrocarbyl, substituted (C1-C3o)heterohydrocarbyl or unsubstituted (C1-C3o)heterohydrocarbyl. The subscript T is o, 1, 2 or 3. The subscript n is from 1 to 1o. In embodiments where the polar monomer is an alkyl acrylate, substituted (C1-C3o)hydrocarbyl acrylate, unsubstituted (C1-C3o)hydrocarbyl acrylate, substituted (C1-C3o)hydrocarbyl acrylate, or unsubstituted (C1-C3o)heterohydrocarbyl acrylate, or unsubstituted (C1-C3o)heterohydrocarbyl acrylate, the ethylene-based polar copolymer can be de-esterified to form an ethylene-based acrylic acid copolymer. In some embodiments of the polymerization process, the alkyl acrylate monomer may be, by way of example and not limitation, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, or combinations thereof. In several embodiments, the alkyl acrylate has an alkyl group with 1 to 8 carbons. This is designated a C1-C8 alkyl acrylate. In some embodiments, the alkyl acrylate is t-butyl acrylate or n-butyl acrylate. In some embodiments of the polymerization process, the optional α-olefin monomer may be, by way of example and not limitation, propene, 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 may also include a cyclic olefin, such as cyclobutene, Petition 870250003175, dated 15 / 01 / 2025, p. 31 / 106 19 / 41 cyclopentene, norbornene and norbornene derivatives that are substituted at positions 5 and 6 with (C1-C20)hydrocarbyl groups. Illustrative embodiments, catalyst systems may include a pro-catalyst according to formula (I) which has the structure of the pro-catalyst 1-5 mentioned below: Pro-catalyst 1 Pro-catalyst 2 Pro-catalyst 3 Pro-catalyst 4 Pro-catalyst 5, where TMS stands for trimethylsilyl, Me is methyl, and Et is ethyl. Ethylene / acrylate copolymer in various embodiments; the polymerization process of this development can produce ethylene-based copolymers, in which the polar ethylene-based copolymers contain at least 50 percent by weight (% by weight) of ethylene based on the weight of the polar ethylene-based copolymer. In some embodiments, the polar ethylene-based copolymer Petition 870250003175, dated 15 / 01 / 2025, page 32 / 106 20 / 41 of ethylene is the reaction product of 70% by weight to 99.9% by weight of ethylene units and 0.1% by weight to 30% by weight of polar comonomer units based on the sum of ethylene units and polar comonomer units. In one or more embodiments, the polymerization process of this disclosure may include ethylene monomers, alkyl acrylate monomers, and optionally, one or more α-olefins. In some embodiments of the polymerization process that includes α-olefins, the α-olefins may be incorporated into the polymers produced in amounts from 0.01% by weight to 49.9% by weight based on the weight of the ethylene-based copolymer. In various embodiments, the polymerization process of this development can produce ethylene-based copolymer with a molecular weight of 2,000 g / mol to 1,000,000 g / mol. In some embodiments, the polymer produced has a molecular weight of 25,000 g / mol to 900,000 g / mol, 30,000 g / mol to 800,000 g / mol, or 10,000 g / mol to 300,000 g / mol. General procedure for PPR screening experiments

[0046] 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 reactors (6 x 8 array) in an inert atmosphere glove box. Each cell was fitted with a glass insert (reactor tube) with an internal working liquid volume of approximately 5 ml. Each cell had independent pressure controls and was continuously stirred at 500 rpm. Catalyst, ligand, and metal precursor solutions, and optional activator solutions (if used), unless otherwise specified, were prepared in toluene. Unless otherwise specified, ligands were metallated at a 1:1 ligand:metal (L:M) ratio by premixing a metal precursor solution with a ligand solution. In many cases, the pro-catalyst complex resulting from the metallation reactions was isolated and purified before introduction into the PPR reactor.All liquids (i.e., solvent, tert-butyl acrylate, and optional catalyst and activator solutions (if used)) were added via robotic syringes. Gaseous reagents (i.e., ethylene) were added via a gas injection port. Before each run, the reactors were heated to 50°C, purged with ethylene, and discharged. The tert-butyl acrylate was filtered through a short activated alumina column. Petition 870250003175, dated 15 / 01 / 2025, page 33 / 106 21 / 41 before use to remove any polymerization inhibitors (e.g., 4-methoxyphenol).

[0047] All desired cells were injected with tert-butyl acrylate followed by a portion of toluene. The reactors were heated to the running temperature and then pressurized to the appropriate pressure with ethylene. Isolated procatalyst complexes or in situ metallized ligands and optional activator solutions (if used) were then added to the cells. Each catalyst addition was followed with a small amount of toluene so that after the final addition, a total reaction volume of 5 ml was achieved. After the catalyst addition, the PPR software began monitoring the pressure of each cell. The desired pressure (within approximately 2 to 6 psig) was maintained by the supplementary addition of ethylene gas by opening the valve at the minus 1 psi setpoint and closing it when the pressure reached 2 psi higher.All pressure drops were cumulatively recorded as ethylene absorption or conversion during the run or until the desired absorption or conversion value was reached, whichever came first. Each reaction was then flash-cooled by adding 1% oxygen to nitrogen for 30 seconds at 40 psi higher than the reactor pressure (the time elapsed from the start of the run until the point where flash cooling begins is the flash cooling time). The shorter the flash cooling time, the more active the catalyst. In order to avoid the formation of excess polymer in any given cell, the reaction was flash-cooled after reaching a predetermined absorption level of 80 psig. After flash cooling of all reactors, they were allowed to cool to approximately 60°C. They were then vented and the reactor tubes were removed and placed in a centrifugal evaporator.The polymer samples were then dried in a centrifugal evaporator at 60°C for 12 hours, weighed to determine the polymer yield, and subjected to IR (t-butyl acrylate incorporation), GPC (molecular weight, polydispersity (PDI)), and DSC (melting point) analyses. General procedure for batch reactor experiments

[0048] Note: Contact with tert-butyl acrylate should be minimized because acrylates are sensitizers, for example, by using a sealed waste container and a well-ventilated fume hood. Care should be taken Petition 870250003175, dated 15 / 01 / 2025, page 34 / 106 22 / 41 Caution when transferring the contents of the reactor to the discharge pot and while emptying the discharge pot in a fume hood.

[0049] Polymerization reactions were carried out in a 2 L Parr batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water. The water was pre-treated by passing it through an Evoqua water purification system. Both the reactor and the heating / cooling system were controlled and monitored by a Camille TG process computer. The bottom of the reactor was fitted with a discharge valve, which emptied the reactor contents into a lidded discharge pot. The discharge pot was pre-loaded with a catalyst inactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The lidded discharge pot was discharged into a 15-gallon purge tank, with the pot and tank purged with N2.All chemicals used for polymerization or catalyst composition were passed through purification columns to remove any impurities that could affect polymerization. Toluene was passed through two columns, the first containing alumina A2 and the second containing reagent Q5. tert-Butyl acrylate was filtered through activated alumina. Ethylene was passed through two columns, the first containing alumina A204 and 4 Å molecular sieves, the second containing reagent Q5. N2, used for transfers, was passed through a single column containing alumina A204, 4 Å sieves, and reagent Q5.

[0050] The reactor was first charged from an injection tank containing toluene and tert-butyl acrylate. The injection tank was filled to the charge setpoints using a differential pressure transducer. After the addition of the solvent / acrylate, the injection tank was washed twice with toluene, and the washes were transferred to the reactor. The reactor was then heated to the desired polymerization temperature setpoint. After reaching the temperature setpoint, ethylene was added to the reactor to achieve the desired pressure setpoint. The amount of ethylene added to the reactor was monitored by a micromovement flowmeter.

[0051] The catalysts were handled in an inert atmosphere glove box and Petition 870250003175, dated 15 / 01 / 2025, page 35 / 106 23 / 41 introduced into the reactor as solutions in toluene. The catalyst solution was withdrawn into a syringe and transferred under pressure to the catalyst injection tank. This was followed by 3 toluene rinses, 5 mL each. The catalyst was added only after the reactor pressure setpoint was reached.

[0052] Immediately after the addition of the catalyst, the run timer was started. Ethylene was then fed (from a Camille control) into the reactor in order to maintain the pressure setpoint. The ethylene / tert-butyl acrylate copolymerization reactions were run for 75 minutes or until 40 g of ethylene absorption occurred, whichever was shorter. The stirrer was then stopped and the bottom discharge valve was opened to empty the reactor contents into the capped discharge pot. The valves on the capped discharge pot were closed and the sealed discharge pot was disconnected from the reactor and taken to a fume hood. In the fume hood, the lid was removed from the discharge pot and the contents were poured into trays. The trays were left in the fume hood for a minimum of 36 hours to allow evaporation of the solvent and tert-butyl acrylate.The trays containing the remaining polymer were then transferred to a vacuum oven, where they were heated to 140°C under vacuum to remove any residual volatile material. After the trays cooled to room temperature, the polymers were weighed for yield / efficiency and subjected to polymer testing, if desired. GPC Procedure

[0053] High-temperature GPC analysis was performed using a Dow Robot-Assisted Delivery (RAD) system equipped with a PolymerChar (IR5) infrared detector and Agilent PLgel Mixed A columns. Decane (10 pl) was added to each sample for use as an internal flow marker. Samples were first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxytoluene (BHT) to a concentration of 10 mg / ml and dissolved by stirring at 160°C for 120 minutes. Before injection, samples were further diluted with BHT-stabilized TCB to a concentration of 3 mg / ml. The samples (250 pL) were eluted through a PL-gel 20 pm (50 x 7.5 mm) guard column followed by two Mixed-A PL-gel 20 pm (300 x 7.5 mm) columns maintained at 160°C with TCB. Petition 870250003175, dated 15 / 01 / 2025, page 36 / 106 24 / 41 stabilized with BHT at a flow rate of 1.0 ml / min. The total run time was 24 minutes. To calibrate for molecular weight (MW), Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 ml of BHT-stabilized TCB and dissolved by stirring at 160°C for 15 minutes. These standards are analyzed to create a 3rd-order MW calibration curve. Molecular weight units are converted from polystyrene (PS) units to polyethylene (PE) units using a daily Q factor calculated around 0.4 using the average of 5 Dowlex 2045 reference samples. FT-IR procedure

[0054] The 10 mg / mL samples prepared for GPC analysis are also used to quantify tert-butyl acrylate (tBA) incorporation by Fourier transform infrared spectroscopy (FTIR). A Dow robotic preparation station heated and stirred the samples at 160°C for 60 minutes, then deposited 130 pL portions into stainless steel wells promoted on a silicon wafer. TCB was evaporated at 160°C under nitrogen purge. IR spectra were collected using a Nexus 6700 FT-IR equipped with a 4000-400 cm-1 KBr DTGS detector using 128 scans with a resolution of 4 cm-1. The ratio between the peak area of ​​tBA (C=O: 1762-1704 cm-1) and the peak area of ​​ethylene (CH2: 736-709 cm-1) was calculated and fitted to a linear calibration curve to determine the total tBA. DSC procedure

[0055] The melting temperature (Tm), glass transition temperature (Tg), crystallization temperature (Tc), and heat of fusion are 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 are subjected to the temperature profile below and the traces were analyzed individually using TA Universal Analysis software or TA Instruments TRIOS software.

[0056] Equilibrate at 175.00°C

[0057] Isothermal for 3 minutes

[0058] Ramp from 30.00°C / min to 0.00°C

[0059] Ramp from 10.00°C / min to 175.00°C Petition 870250003175, dated 15 / 01 / 2025, page 37 / 106 25 / 41 Examples

[0060] Examples 1 to 6 are synthetic procedures for ligand intermediates and ligands. Examples 7 to 12 are synthetic procedures for isolated procatalysts. In Examples 13 and 14, the results of the polymerization reactions of procatalysts 1 to 5 are tabulated and discussed. One or more features of the present disclosure are illustrated in view of the examples according to the following: General considerations

[0061] All reactions were carried out in a nitrogen-purged glove box unless otherwise indicated. All solvents and reagents were obtained from commercial sources and used as received unless otherwise indicated. Anhydrous toluene, hexanes, tetrahydrofuran, and diethyl ether were purified by passing through activated alumina and, in some cases, reagent Q-5. Alumina for solvent purification was activated by passing a stream of nitrogen through the alumina for 8 hours at 300°C. Reagent Q-5 was 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 washing with nitrogen gas. Solvents used for experiments carried out in a nitrogen-charged glove box were additionally dried by storage on activated 4 Å molecular sieves.The glassware for moisture-sensitive reactions was dried in an oven overnight before use. HRMS analyses were performed using an Agilent 1290 Infinity LC with a 2.1 x 50 mm Zorbax Eclipse Plus C18 1.8 pm column coupled to an Agilent 6230 TOF mass spectrometer with electrovaporization ionization. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. 1H NMR data are presented as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet, em = multiplet), integration and assignment). Chemical shifts for 1H NMR data are reported in ppm downstream of tetramethylsilane (TMS, δ scale) using residual protons from the deuterated solvent as references. 13C NMR data were determined with 1H decoupling, and chemical shifts are reported in ppm as a function of tetramethylsilane.The 13C NMR spectra of... Petition 870250003175, dated 15 / 01 / 2025, p. 38 / 106 26 / 41 phosphines were complexed due to CP coupling. Chemical shifts for the 31P NMR data are reported in ppm relative to external pure H3PO4. Deuterated solvents for NMR analyses were purchased from Cambridge Isotope Laboratories and stored on activated 4 Å molecular sieves in a nitrogen-purged glove box. Chlorobis(2,6-dimethoxyphenyl)phosphine, chlorobis(2,6-diethoxyphenyl)phosphine, and bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) were prepared according to literature procedures. Binder preparation Example 1 - N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,5-bis(trifluoromethyl) benzamide MeO' O OMe In a box of gloves, 3,5-bis(trifluoromethyl)benzamide (300 mg, 1.17 mmol) was added to a 20 mL flask fitted with a stirring bar, which was 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 eq) was added slowly, and the reaction mixture was placed back in the freezer. After 20 minutes, the reaction mixture was removed from the freezer and a fluid paste of chlorobis(2,6-dimethoxyphenyl)phosphine (362 mg, 1.19 mmol, 1.02 equiv) in 3 mL of THF was added. The reaction mixture was allowed to warm to room temperature and stirred for another hour. All volatiles were removed under vacuum and 10 mL of dichloromethane were added to the resulting residue. The solution was filtered through Celite buffer to remove LiCl. The filtrate was clear and light yellow.The filtrate was concentrated to approximately 2 mL, the product was triturated with hexane and collected by filtration as a whitish powder. 1H e31P NMR confirmed that the whitish powder that was isolated was the desired product (402 mg, 0.72 mmol, 61% yield).

[0062] 1H NMR (400 MHz, Chloroform-d) δ 9.51 (s, 1H), 8.35 (s, 2H), 8.01 (s, 1H), 7.26 (t, J = 8.3 Hz, 2H), 6.55 (dd, J = 8.3, 2.7 Hz, 4H), 3.81 (s, 12H) ppm. NMR13C Petition 870250003175, dated 15 / 01 / 2025, page 39 / 106 27 / 41 (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. RMN31P (162 MHz, Chloroform-d) δ -2.16 ppm. RMN19F (376 MHz, Chloroform-d) δ -62.91 ppm. HRMS (ESI) (m / z of m / z): [M+H] calculated for C45H60N2O5P: 562.121; Found: 562,116. Example 2 - N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,4,5-trimethoxybenzamide In a glove box, 3,4,5-trimethoxybenzamide (300 mg, 1.42 mmol) was added to a 20 mL flask fitted with a stirring bar, which was dissolved in 10 mL of THF and cooled to -35°C overnight. The mixture was removed from the freezer, n-butyllithium (2.0 M, 0.78 mL, 1.6 mmol, 1.1 eq) was added slowly, and the reaction mixture was placed back in the freezer. After 20 minutes, the reaction mixture was removed from the freezer and a fluid paste of chlorobis(2,6-dimethoxyphenyl)phosphine (442 mg, 1.45 mmol, 1.02 equiv) in 4 mL of THF was added. The reaction mixture was allowed to warm slowly to room temperature and stirred for another hour. A white precipitate formed and was collected by filtration and washed with THF and hexane. The white powder was confirmed as the desired product (495 mg, 0.95 mmol, 67% yield).

[0063] 1H NMR (400 MHz, Chloroform-d) δ 9.01 (s, 1H), 7.23 (td, J = 8.3, 0.7 Hz, 2H), 7.14 (s, 2H), 6.53 (dd, J = 8.3, 2.6 Hz, 4H), 4.01 - 3.86 (m, 9H), 3.78 (s, 12H) ppm. RMN13C (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. RMN31P (162 MHz, Chloroform-d) δ -4.88 (d, J = 108.0 Hz) ppm. HRMS (ESI) (m / z of m / z): [M+H] calculated for C26H30NO8P: 516.178; found: 516,175. Example 3 - N-(bis(2,6-diethoxyphenyl)phosphanyl)-3,5-bis(trifluoromethyl) benzamide Petition 870250003175, dated 15 / 01 / 2025, p. 40 / 106 28 / 41 In a glove box, a glass vial fitted with a stirring bar was loaded with 3,5-bis(trifluoromethyl)benzamide (1.0 g, 3.89 mmol) and cooled THF (26.5 mL). The clear solution was placed in the 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 hexanes (1.72 mL, 4.30 mmol) was added dropwise with stirring. The resulting reddish-orange solution was returned to the freezer. After 20 minutes, the reaction mixture was removed from the freezer and a cooled dark solution of bis(2,6-diethoxyphenyl)chlorophosphine (1.57 g, 3.97 mmol) in THF (10 mL) was added. The solution was allowed to warm to room temperature and stirred for 1 hour. After 1 hour, an aliquot of the resulting reddish-brown solution was removed and analyzed by 31P NMR spectroscopy to verify completion. The 31P NMR spectrum showed that the reaction was complete.The reaction mixture was concentrated under vacuum to dryness and anhydrous dichloromethane (33 mL) was added. The reaction mixture was filtered through Celite buffer and concentrated under vacuum to produce a dark peach-colored solid (2.62 g). The solid was ground with hexanes and dichloromethane (2 mL) was added. The fluid paste was stirred for 5 minutes at room temperature and the solid was collected by filtration and washed with hexanes to produce 1.79 g (2.92 mmol, 75%) of the desired product as a peach-colored solid.

[0064] 1H NMR (400 MHz, Chloroformio-d) δ 9.16 (s, 1H), 8.30 (s, 2H), 7.99 (s, 1H), 7.20 (t, J = 8.3 Hz, 2H), 6.50 (dd, J = 8.3 Hz, 27 Hz), 3.98 (p, J = 7.6, 6.8 Hz, 9H), 1.23 (t, J = 7.0 Hz, 13H) ppm. NMR13C (101 MHz, Chloroformio-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), 124.48, 121.73, 115.74 (d, J = 26.4 Hz), 105.32, 64.47, 14.48 ppm. NMR31P (162 MHz, Chloroformio-d) δ -0.30 ppm. NMR19F (376 MHz, Chloroformio-d) δ -63.19 ppm. HRMS (ESI) (m / z of m / z): [M+H] calculated for C29H31F6NO5P: 618.1838; found: 618.1753. Petition 870250003175, of 15 / 01 / 2025, p. 41 / 106 29 / 41 Example 4 - N-(bis(2,6-dimethoxyphenyl)phosphanyl)furan-2-carboxamide In a glove box, furan-2-carboxamide (258 mg, 2.32 mmol) was added to a 20 mL flask fitted with a stirring bar, which was dissolved in 10 mL of THF and cooled to -35°C overnight. The mixture was removed from the freezer, n-butyllithium (2.0 M, 1.28 mL, 2.44 mmol, 1.1 eq) was added slowly, and the reaction mixture was placed back in the freezer for 15 min. The reaction mixture was removed from the freezer and a fluid paste of chlorobis(2,6-dimethoxyphenyl)phosphine (831 mg, 2.44 mmol, 1.05 eq) in 5 mL of THF was added slowly. The reaction mixture was allowed to warm to room temperature under stirring for 2 h. All volatiles were then removed from the reaction mixture under vacuum, and the resulting residue was ground with dichloromethane and filtered through a Celite pad.The filtrate was concentrated to about 2 mL, the product was triturated with hexane and collected by filtration as a white powder (766 mg alone, 1.83 mmol, 79% yield).

[0065] 1H NMR (400 MHz, Chloroform-d) δ 9.25 (s, 1H), 7.63 - 7.45 (m, 1H), 7.21 (t, J = 8.3 Hz, 2H), 7.15 (d, J = 3.5 Hz, 1H), 6.68 - 6.42 (m, 5H), 3.78 (d, J = 0.9 Hz, 12H) ppm. RMN13C (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. RMN31P (162 MHz, Chloroform-d) δ -7.34 ppm. HRMS (ESI) (m / z of m / z): [M+H] calculated for C21H24NO6P: 416.1257; found: 416.1226. Example 5 - Synthesis of N-(bis(2,6-dimethoxyphenyl)phosphanyl)benzamide a box of gloves, a 20 mL vial was loaded with benzamide (100 mg, 0.83 Petition 870250003175, dated 15 / 01 / 2025, p. 42 / 106 30 / 41 mmol, 1.0 eq), 4-pyrrolidinopyridine (196 mg, 1.32 mmol, 1.6 eq), chlorobis(2,6-dimethoxyphenyl)phosphine (281 mg, 0.83 mmol, 1.0 eq), 8 mL of THF and a stirring bar. The colorless solution was heated to 65°C and stirred for 18 h. The following day, the solution was filtered to remove the salts, and all volatiles were removed from the filtrate under vacuum. After the addition of toluene to the resulting residue, a precipitate formed. The white solid was isolated by filtration, washed with hexane, dried, and identified by NMR spectroscopy as the clean product (182 mg). An equal portion of hexane was added to the filtrate and placed in a freezer at 35°C overnight. The product precipitated from the solution and was collected by filtration and dried (102 mg). The two powders were combined to provide 284 mg of product (0.67 mmol, 81% yield).

[0066] 1H NMR (400 MHz, Chloroformio-d) δ 9.10 (s, 2H), 7.88 (d, J = 7.4 Hz, 4H), 7.64 - 7.38 (m, 5H), 7.21 (t, J = 8.3 Hz, 43 Hz), J 2.6 Hz, 4H), 3.76 (s, 19H) ppm. NMR13C (101 MHz, Chloroformio-d) δ 161.98 (d, J = 9.5 Hz), 131.09, 130.52, 128.31, 127.38, 115.71 (d, J = 27.1 Hz), 6.6, 6.6 ppm. NMR31P (162 MHz, Chloroformio-d) δ -5.29 ppm. HRMS (ESI) (m / z of m / z): [M+H] calculated for C21H24NO6P: 426.1473; found: 426,148. Example 6 - N-(diphenylphosphanyl)benzamide In a glove box, benzamide (250 mg, 1.80 mmol) was added to a 100 mL flask equipped with a stirring bar, which was dissolved in 20 mL of THF and cooled to -35°C overnight. The mixture was removed from the freezer, n-butyllithium (2.0 M, 0.99 mL, 1.96 mmol, 1.1 eq) was added slowly, and the reaction mixture was placed back in the freezer for 15 min. The mixture was removed from the freezer and a fluid paste of chlorodiphenylphosphine (0.523 mL, 1.89 mmol, 1.05 eq) in 5 mL of THF was added slowly 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 ground with Petition 870250003175, dated 15 / 01 / 2025, p. 43 / 106 31 / 41 dichloromethane was filtered through a Celite pad. All volatiles were removed from the filtrate under vacuum and toluene was added to the resulting residue. The product precipitated almost completely as a white solid and was further triturated with hexane. The product was collected by filtration as a white powder. The filtrate was concentrated to about 2 mL and the product was triturated with hexane and collected by filtration. The product was isolated as a white solid. The two batches of white powder were combined to give 362 mg (1.19 mmol, 66% yield).

[0067] 1H 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. RMN13C (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. RMN31P (162 MHz, Chloroform-d) δ 25.39 ppm. HRMS (ESI) (m / z of m / z): [M+H] calculated for C19H17NOP: 306.1041; found: 306.1034. Preparation of Ni complexes Example 7 - Synthesis of pro-catalyst 2 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosfanyl)-3,5-bis(trifluoromethyl)benzimidate) ((trimethylsilyl)methyl)(pyridine)nickel (II)

[0068] A box of gloves, a 20 mL flask was loaded with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (73 mg, 0.18 mmol, 1.05 eq), a stirring bar, and 1 mL of toluene. A fluid paste of N-(bis(2,6-dimethoxyphenyl)phosfanyl)-3,5bis(trifluoromethyl)benzamide (100 mg, 0.18 mmol) in 4 mL of toluene was then slowly added to the orange solution. The resulting solution had a very dark brown / orange color. After stirring the solution for 30 min at 45°C, the color of the reaction mixture lightened significantly and became red. Spectroscopy of Petition 870250003175, dated 15 / 01 / 2025, page 44 / 106 32 / 41 31P NMR showed that the metallation reaction was complete after 30 minutes. All volatiles were removed from the solution under vacuum, leaving a dark sticky residue. The product was ground with hexane and stirred vigorously. The product was collected by filtration and dried (105 mg, 0.14 mmol, 75% yield).

[0069] 1H NMR (400 MHz, Benzeno-d6) δ 8.94 (dd, J = 4.8, 1.7 Hz, 2H), 8.91 - 8.84 (m, 2H), 7.71 (s, 1H), 7.22 - 7.07 (m, J = 6.84), J 7.6, 1.7 Hz, 1H), 6.54 (t, J = 6.7 Hz, 2H), 6.34 (dd, J = 8.3, 3.7 Hz, 4H), 3.36 (s, 12H), -0.16 (s, 9H), -0.46 (d, J = 8.8 Hz, 2H) ppm. NMR13C (101 MHz, Benzeno-dβ) 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, 139.45 (d, J = 19.2 Hz), 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. NMR31P (162 MHz, Benzeno-d6) δ 54.98 ppm. NMR19F (376 MHz, Benzeno-d6) δ -62.47 ppm. Example 8 - Synthesis of pro-catalyst 5 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosphanyl)-3,4,5-trimethoxybenzimidate)(pyridine) ((trimethylsilyl) methyl)nickel(II) MeO In a glove box, a 20 mL flask was loaded with bis((trimethylsilyl)methyl)bis(pyridine)nickel (114 mg, 0.29 mmol, 1.0 eq), a stirring rod, and 5 mL of toluene followed by pyridine (23 µL, 0.29 mmol, 1.0 eq). N-(bis(2,6-dimethoxyphenyl)phosfanyl)-3,4,5-(trimethoxy)benzamide (150 mg, 0.29 mmol) was then slowly added to the orange solution. The resulting solution had a very dark orange-brown color. The mixture was heated to 55°C and stirred for 90 hours. The metalation reaction was complete after 90 minutes, as indicated by 31P NMR spectroscopy. The solution was filtered through Celite buffer, and the filtrate was concentrated to about 3 mL, at which point the orange precipitate began to form. The product was crushed with hexane (~30 mL) and the solution Petition 870250003175, dated 15 / 01 / 2025, p. 45 / 106 33 / 41 resulting 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).

[0070] 1H NMR (400 MHz, Benzene-dβ) δ 9.12 - 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, 3.6 Hz, 4H), 3.83 (s, 3H), 3.41 (s, 12H), 3.33 (s, 6H), -0.11 (s, 9H), -0.49 (d, J = 8.5 Hz, 2H) ppm. RMN13C (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. RMN31P (162 MHz, Benzene-d6) δ 55.06 ppm. Example 9 - Synthesis of pro-catalyst 3; ((Z)-N-(bis(2,6-dimethoxyphenyl)phosfanyl)benzimidate)(pyridine)((trimethylsilyl)methyl)nickel(II) A box of gloves, a 20 mL flask was loaded with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II), (9.2 mg, 0.024 mmol, 1.0 eq), N-(bis(2,6-dimethoxyphenyl)phosphanyl)benzamide (10 mg, 0.024 mmol, 1.0 eq), and a stirring rod and 2 mL of C6D6. The dark red reaction was heated to 60°C for 1 hour and cooled. 1H NMR spectroscopy was consistent with that expected for the title structure. All volatiles were removed under vacuum and hexane was added to the sticky residue, resulting in a dark yellow solid. The mother liquor was removed with a pipette and the product was dried (no yield was determined).

[0071] 1H NMR (500 MHz, Benzeno-d6) δ 9.14 - 8.91 (m, 2H), 8.52 (dd, J = 7.9, 1.9 Hz, 2H), 7.21 - 7.01 (m, 9H), 6.84 (s), 6.67 H (m, 2H), 6.33 (dd, J = 8.3, 3.6 Hz, 4H), 3.36 (s, 12H), -0.15 (s, 9H), -0.52 (d, J = 8.5 Hz, 2H) ppm. NMR13C (126 MHz, Benzeno-d6) δ 177.78 (d, J = 2.4 Hz), 164.31, 161.54 (d, J = 1.9 Hz), 135.95, 137.28 (d, J = 18.5 Hz), = 1.9 Hz), 114.30 (d, J = 56.6 Hz), 104.84 (d, J Petition 870250003175, of 15 / 01 / 2025, p. 46 / 106 34 / 41 = 4.4 Hz), 55.55, 2.11, -16.85 (d, J = 28.2 Hz) ppm. NMR31P (162 MHz, Benzeno-d6) δ 54.79 ppm. Example 10 - Synthesis of pro-catalyst 1 ((Z)-N-(bis(2,6-diethoxyphenyl)phosphanyl)-3,5-bis(trifluoromethyl)benzimidate) (pyridine)((trimethylsilyl) methyl)nickel (II) A glove box, a 110 mL flask was loaded with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (503 mg, 1.28 mmol, 1.0 eq), a stirring bar, and 10 mL of toluene. A fluid paste of N-(bis(2,6-diethoxyphenyl)phosfanyl)-3,5bis(trifluoromethyl)benzamide (750 mg, 1.28 mmol) in 20 mL of toluene was then slowly added to the orange solution. The resulting solution had a very dark orange-brown color. The reaction mixture was stirred for 20 min at 45°C; after this time, 31P NMR spectroscopy showed that the reaction was almost complete (part of the dialkyl complex and free ligand remained). Pyridine (0.100 mL, 1.28 mmol, 1.0 eq) was added to the reaction mixture, and the mixture was heated to 45°C for a further 20 min. 31P NMR spectroscopy showed that the reaction was complete. The reaction mixture was cooled to room temperature and filtered through Celite buffer. 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 minimal amount of toluene, and the product was ground with excess pentane. The orange solid was collected by filtration, washed with pentane, and dried (926 mg, 1.10 mmol yield, 86%).

[0072] 1H NMR (400 MHz, Chloroform-d) δ 9.16 (s, 1H), 8.30 (s, 2H), 7.99 (s, 1H), 7.20 (t, J = 8.2 Hz, 2H), 6.50 (dd, J = 8.3, 2.7 Hz, 5H), 4.08 - 3.91 (m, 8H), 1.23 (t, J = 7.0 Hz, 12H) ppm. RMN13C (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, Petition 870250003175, dated 15 / 01 / 2025, page 47 / 106 35 / 41 121.87, 115.87 (d, J = 26.6 Hz), 105.45, 64.61, 14.61 ppm. RMN31P (162 MHz, Chloroform-d) δ -0.30 ppm. RMN19F (376 MHz, Chloroform-d) δ -63.19 ppm. Example 11 - Synthesis of pro-catalyst 4 ((Z)-N-(bis(2,6-dimethoxyphenyl)phosfanyl)furan-2-carbimidate)(pyridine) ((trimethylsilyl)methyl)nickel (II) MeO In a glove box, a 20 mL flask was loaded with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (141 mg, 0.36 mmol, 1.0 eq), pyridine (0.029 mL, 0.36 mmol), a stirring bar, and 4 mL of toluene. A fluid paste of N-(bis(2,6-dimethoxyphenyl)phosfanyl)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. The solution was stirred for 60 min at 50°C, after which 31P NMR spectroscopy showed complete conversion to the desired complex. The reaction mixture was cooled to room temperature and filtered through Celite buffer. All volatiles were then removed from the filtrate under vacuum, leaving a yellow solid on the walls of the flask. Pentane was added and the solution was shaken vigorously for 30 min. The yellow solid was isolated by filtration and dried under vacuum. (164 mg, 0.26 mmol, 71% yield).

[0073] 1H NMR (400 MHz, Benzeno-d6) δ 9.05 (dd, J = 4.8, 1.7 Hz, 2H), 7.13 (s, 1H), 6.86 - 6.79 (m, 1H), 6.59 - 6.52 (m, J = 35), J 8.3, 3.7 Hz, 6H), 6.16 (dd, J = 8.3, 3.2 Hz, 1H), 5.99 (dd, J = 3.3, 1.7 Hz, 1H), 3.39 (s, 15H), -0.12 (s, 10H), -0.49 (d, Jpm, 2.8 Hz). NMR13C (126 MHz, Benzeno-d6) δ 170.17 (d, J = 4.1 Hz), 161.52 (d, J = 2.0 Hz), 152.40 (d, J = 24.6 Hz), 123.40 (d, J = 1.9 Hz), 114.05 (d, J = 57.6 Hz), 112.69, 110.75, 104.79 (d, J = 4.4 Hz), 55.52, 2.07, 17.01 (d, J = 28 Hz) ppm. NMR31P (162 MHz, Benzeno-dβ) δ 55.22 ppm. Example 12 — Comparative Pro-Catalyst Synthesis C1 Petition 870250003175, of 15 / 01 / 2025, p. 48 / 106 36 / 41 ((Z)-N-(diphenylphosphanyl)benzimidate)(pyridine)((trimethylsilyl)methyl)nickel(II) A glove box, a 20 mL flask was loaded with bis((trimethylsilyl)methyl)bis(pyridine)nickel(II) (134 mg, 0.34 mmol, 1.05 eq), a stirring bar, and 2 mL of toluene. Pyridine (26 pL, 0.33 mmol, 1.0 eq) 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. The solution was stirred at room temperature for 30 min, after which 31P NMR spectroscopy showed the presence of both the desired complex (shown above) and a related nickel complex containing a neutral ligand and two -CH2SiMe3 substituents. The solution was stirred at 45°C for 60 min, after which the 31P NMR spectrum showed complete conversion to the desired complex. The reaction mixture was filtered through Celite buffer and all volatiles were removed from the filtrate under vacuum.The resulting crude product was dissolved in a minimal 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).

[0074] 1H NMR (500 MHz, Benzene-d6) δ 9.07 (td, J = 3.3, 1.6 Hz, 2H), 8.99 - 8.95 (m, 2H), 8.62 - 8.52 (m, 4H), 7.67 - 7.47 (m, 10H), 7.20 (t, J = 7.7 Hz, 1H), 6.95 - 6.83 (m, 2H), 0.21 (s, 9H), -0.15 (d, J = 7.3 Hz, 2H) ppm. RMN13C (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. RMN31P (162 MHz, Benzene-d6) δ 75.96 ppm. Example 13 - Copolymerization of ethylene / tert-butyl acrylate - Studies carried out in a parallel pressure reactor

[0075] Catalyst activity (in terms of flash cooling time and Petition 870250003175, dated 15 / 01 / 2025, page 49 / 106 37 / 41 polymer yield) and the resulting polymer characteristics were evaluated for pro-catalysts 1 to 5 and the comparative pro-catalyst C1 (Comp. C1). Comp. C1 contains a previously described ligand. (See J. Organomet. Chem. 1983, 249, C38.). The polymerization reactions were carried out in a parallel pressure reactor (PPR), as previously described.

[0076] The results tabulated in Table 1 were obtained through a polymerization reaction in a parallel polymerization reactor (PPR). For each polymerization reaction shown in Table 2, a catalyst stock solution was prepared (1 to 2 mM) in toluene and immediately fed to the PPR reactor. Copolymerization experiments were performed at 400 psi ethylene pressure with a catalyst loading of 0.25 to 0.75 pmol. tert-Butyl acrylate was purified by filtration through an activated alumina column, and a solution was subsequently prepared in toluene. The reactor temperature and tert-Butyl acrylate loadings varied as shown in Table 1. Each entry in Table 1 represents the average of at least 2 replicated runs. Comparative Pro-catalyst C1 Comparison of the performance of phosphine-amide catalysts (new invention) with the comparative pro-catalyst C1 (Comp. C1) Catalyst Input (pmol) Acrylate Charge (pmol) Reactor Temp. (°C) Activity (kg / mol-h) Mw PDI Tm (°C) % mol t-BA % wt t-BA 1* Comp. C1 (0.75) 250 90 37 4,700 5.85 117 N / AN / A 2 Pro-cat. 2 (0.25) 250 90 620 21,500 2.37 121 1.1 5.0 3 Pro-cat. 1 (0.25) 250 90 1400 124,000 2.29 124 0.4 1.7 5 Pro-cat. 4 (0.25) 250 90 110 23,800 2.29 117 1.5 6.5 6 Pro-cat. 5 (0.25) 250 90 120 23,100 2.48 118 1.3 5.8 Petition 870250003175, dated 15 / 01 / 2025, page 50 / 106 38 / 41 7 Pro-cat. 3 (0.25) 250 90 200 21,700 2.42 117 1.3 5.7 8* Comp. C1 (0.75) 750 100 17 N / AN / AN / AN / AN / A 9 Pro-cat. 1 (0.25) 750 100 210 49 700 2.15 116 1.4 6.2 10 Pro-cat. 4 (0.75) 750 90 73 10,700 2.17 97 4.9 19 11 Pro-cat. 5 (0.75) 750 90 73 9 500 2.20 103 4.4 16 12 Pro-cat. 3 (0.75) 750 100 82 8,700 2.22 85 3.7 15 13* Comparative C1 (0.75) 1000 100 14 N / AN / AN / AN / AN / A 14 Pro-cat. 1 (0.25) 1000 100 130 40,700 2.24 112 2.2 9.4 15 Pro-cat. 2 (0.75) 1000 90 91 9,000 2.15 100 4.5 18 16 Pro-cat. 4 (0.75) 1000 90 58 8,590 1.93 90 6.1 23 17 Pro-cat. 5 (0.75) 1000 90 54 7,230 2.35 99 5.7 21 18 Pro-cat. 3 (0.75) 1000 100 73 6,760 2.29 87 5.2 20 *Did not produce enough polymer to be characterized in these categories. Acrylate = tert-butyl acrylate.

[0077] The entries in Table 1 are organized primarily by acrylate charge, although the temperature for certain runs may vary. The performance of the catalysts described in this disclosure is compared with Comp. C1.

[0078] As evidenced by the previous data, the pro-catalysts of this discovery have higher activity than the pro-catalyst Comp. C1. Furthermore, the polymers produced by pro-catalysts 1 to 5 have an increased incorporation of butyl acrylate and higher molecular weight compared to the polymers produced by Comp. C1. Additionally, pro-catalysts 1 to 5 produce a polymer with a narrower PDI than the polymer produced by Comp. C1.

[0079] Without intending to delve into theory, it is believed that sterically hindered phosphine may be a determining factor for catalyst performance. Sterically hindered phosphine is a common component of pro-catalysts 1 to 5 that is not present in Comp. C1. For example, in entry 1, Comp. C1 exhibited Petition 870250003175, dated 15 / 01 / 2025, page 51 / 106 39 / 41 very low activity (36 kg / mol h) and a wide PDI (5.85). In this case, the activity of Comp. C1 was too low to obtain sufficient polymer for acrylate incorporation analysis.

[0080] The inclusion of more sterically hindered phosphine aryl substituents, such as 2,6-dimethoxyphenyl, for example, enhances the catalyst activity by an order of magnitude (entries 2 to 7) compared to Comp. C1 (entry 1). Therefore, not all Ni(II) phosphine-amide complexes are active ethylene / acrylate copolymerization catalysts, and the structural modifications we made to the ligand constitute an invention. Example 14 - Copolymerization of ethylene / n-butyl acrylate - Studies carried out in a parallel pressure reactor

[0081] The results organized in Table 2 were obtained through a polymerization reaction in a parallel polymerization reactor (PPR). For each polymerization reaction shown in Table 2, a catalyst stock solution was prepared (1 to 2 mM) in toluene and immediately fed to the PPR reactor. Copolymerization experiments were performed at 400 psi ethylene pressure with a catalyst loading of 0.25 to 0.75 pmol. n-Butyl acrylate was purified by filtration through an activated alumina column and a solution was subsequently prepared in toluene. The reactor temperature and tert-butyl acrylate loadings varied as shown in Table 2. Each entry in Table 2 represents the average of at least 2 replicated runs. Table 2: Copolymerization of ethylene / n-butyl acrylate with pro-catalysts 1 and 2 (new invention). Catalyst Input (pmol) Acrylate Charge (pmol) Reactor Temp. (°C) Activity (kg / mol·h) Mw PDI Tm (°C) % by mol t-BA % by weight tBA 1 Pro-cat. 1 (0.25) 125 90 3,110 107,000 2.16 126 0.6 2.6 2 Pro-cat. 1 (0.25) 187 90 1,600 90,700 2.22 122 0.7 3.2 3 Pro-cat. 1 (0.25) 250 90 700 81,600 2.14 120 0.9 4.0 5 Pro-cat. 1 (0.25) 500 90 160 51,500 2.28 113 1.9 8.0 Petition 870250003175, dated 15 / 01 / 2025, page 52 / 106 40 / 41 6 Pro-cat. 2 (0.25) 125 90 280 22,400 2.29 121 0.9 4.1 7 Pro-cat. 2 (0.25) 187 90 170 18,600 2.42 117 1.4 6.1 8 Pro-cat 2 (0.25) 250 110 100 10,100 2.27 111 1.7 7.5 Acrylate = n-butyl acrylate.

[0082] The entries in Table 2 are organized primarily by acrylate charge, although the temperature for certain runs may vary.

[0083] The relative trends in reactivity for the copolymerization of tert-butyl acrylate (Table 1) are observed for n-butyl acrylate (Table 2). The catalyst activity and the molecular weight of the resulting copolymer are inversely related to the acrylate charge, while the incorporation is directly related to the acrylate charge.

[0084] It should be noted that, under identical acrylate loadings, higher acrylate incorporation into the copolymer is observed for n-butyl acrylate compared to tert-butyl acrylate. For example, pro-cat. 1 with 250 pmol n-butyl acrylate produces a polymer with 0.9 mol% acrylate incorporation (entry 3, Table 2), while under the same conditions but with 250 pmol tert-butyl acrylate, 0.4 mol% incorporation is observed. This class of catalyst effectively incorporates sterically hindered and non-sterically hindered polar comonomers. Example 15 - Results obtained from the 2 L batch reactor

[0085] In these experiments, the catalysts were introduced into the reactor as toluene solutions of the isolated metal complexes. The copolymerization experiments were performed at an ethylene pressure of 400 psi. The reactor temperature and tert-butyl acrylate charge varied as shown in Table 2. The initial toluene charge to the reactor was 640 g (740 mL). The ethylene / tert-butyl acrylate copolymerization reactions were carried out for 75 minutes or until 40 g of ethylene absorption occurred, whichever was shorter. Performance of pro-catalyst 1 and pro-catalyst 2 catalysts in a 2 L batch reactor at 400 psi of ethylene. Petition 870250003175, dated 15 / 01 / 2025, page 53 / 106 41 / 41 Catalyst Input Cat. (pmol) Acrylate (mmol) Reactor Temp. (°C) Activity (kg / mol-h) Mw PDI Tm (°C) % mol of t-BA Yield (g) 1 Pro-cat. 1 60 74 110 2,100 53,500 2.22 120 1.0 45.8 2 Pro-cat. 1 60 74 90 1,500 90,400 2.16 1 19 1.7 43.0 3 Pro-cat. 1 60 222 90 440 47,100 2.35 1 10 2.6 32.4 4 Pro-cat. 1 178 222 110 920 26,700 2.15 111 2.9 51.4 5 Pro-cat. 2 178 74 90 660 17,800 2.30 117 1.4 47.0 6 Pro-cat. 2 178 74 1 10 170 1 1,300 2.51 114 2.2 36.6 7 Pro-cat. 2 178 222 110 59 4,700 2.27 88 4.1 13.2 8 Pro-cat. 2 178 222 90 140 7,500 2.52 97 5.1 30.5

[0086] As shown by the results tabulated in Table 2, the pro-catalysts of this discovery, specifically pro-catalysts 1 and 2, are capable of catalyzing ethylene / n-butyl acrylate copolymerization reactions in a 2 L batch reactor to produce ethylene / tert-butyl and butyl acrylate copolymer on a multigram scale. Higher activities for the catalysts were observed in the batch reactor compared to the PPR reactors, accompanied by higher levels of acrylate incorporation. Up to 50 g of polymer were produced per pass. In particular, pro-catalyst 1 performed well (see entry 2), producing high MW polymer (90,400) with significant acrylate incorporation (1.7 mol%) at high activity (1,500 kg / mol h).

Claims

1. Pro-catalyst, characterized by being in accordance with formula (I): I / P\-R2 R1^N R3 where: M is nickel(II) or palladium(II); X is a ligand chosen from (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, -H, -CH2Si(Rc)3-q(ORc)q, -Si(Rc)3-q(ORc)q, -OSi(Rc)3-q(ORc)q, -Ge(RC)3-Q(ORC)Q, -P(Rc)2-w(ORc)w, -P(O)(Rc)2-w(ORc)w, -N(Rc)2, -N(Si(RCh)2, -NRCSi(RC)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(RC), -N=CH2, -N=P(RC)3, -OC(O)RC, -C(O)ORC, -C(O)RC, -C(O)H, -N(RC)C(O)RC, -N(RC)C(O)H, -NHC(O)RC, -NHC(O)H, -C(O)N(RC)2, -C(O)NHRC, -C(O)NH2, or a halogen, wherein each RC is independently an unsubstituted (C1-C30)hydrocarbyl, a (C1-C30)hydrocarbyl substituted with one or more RS, an unsubstituted (C1-C30)heterohydrocarbyl, or a (C1-C30)heterohydrocarbyl substituted with one or more RS, wherein Q subscript 0, 1, 2, or 3, and wherein W subscript 0, 1, or 2; Y is a Lewis base;R1 is chosen from unsubstituted (C6-C40)aryl, substituted (C6-C40)aryl, unsubstituted (C1-C40)heteroaryl having its radical on a carbon atom, or substituted (C1-C40)heteroaryl having its radical on a carbon atom, or substituted (C4-C20)alkyl having at least one tertiary carbon atom and its radical on the tertiary carbon atom of the (C4-C20)alkyl, provided that: R2 and R3 are independently selected from radicals having the formula (II): R13 R1* R12 R11 (II) R15 where: each R11, R12, R13, R14, and R15 are independently (C1-C30)hydrocarbyl, Petition 870250003175, dated 15 / 01 / 2025, p. 55 / 106 2 / 4 (C1-C30)heterohydrocarbyl, -ORN, -NRN2, -SRn, halogen, or -H, where RN is (C1-C30)hydrocarbyl; provided that at least one of R11 and R15 is not -H; and each Rs in formula (I) is independently (C1-C20)hydrocarbyl or halogen.; 2. Pro-catalyst, according to claim 1, characterized in that Y is a neutral Lewis basic aprotic (C2-C4o)heterohydrocarbon.

3. Pro-catalyst, according to either claim 1 or 2, characterized in that R2 and R3 are identical.

4. Pro-catalyst, according to claim 3, characterized in that R11 and R15 are independently -O[(C1-C1o)alkyl].

5. Pro-catalyst, according to claim 3, characterized in that R11 and R15 are methoxyl.

6. Pro-catalyst, according to claim 3, characterized in that R11 and R15 are ethoxyl.

7. Pro-catalyst, according to claim 3, characterized in that R11 and R15 are independently -N[(C1-C1o)alkyl]2.

8. Pro-catalyst, according to any one of claims 1 to 7, characterized in that R1 is a radical having the formula (III): r33 r3?zX / r32 T JL (ui) r35 wherein R31-35 is independently chosen from -H, (C1-C4o)hydrocarbyl, (C1-C4o)heterohydrocarbyl, -Si(RR)3, -Ge(RR)3, -P(Rr)2, -P(O)(Rr)2, -N(Rr)2, -ORr, -SRr, -NO2, -CN, -CF3, or halogen, wherein each Rr is (C1-C3o)hydrocarbyl, (C1-C3o)heterohydrocarbyl, or -H.

9. Pro-catalyst according to claim 8, characterized in that R32, R33, and R34 are independently selected from (C1-C4o)heterohydrocarbyl, -Si[(C1-C1o)alkyl]3, -N[(C1-C1o)alkyl]2, -O[(C1-C1o)alkyl].

1. Pro-catalyst according to claim 8, characterized in that R32, R33, and R34 are independently selected from methoxyl or ethoxyl. Petition 870250003175, dated 15 / 01 / 2025, p. 56 / 106 3 / 4 11. Pro-catalyst, according to claim 8, characterized in that R32 and R34 are -CF3.

12. Pro-catalyst, according to claim 1, characterized in that R1 is 2-furyl.

13. Pro-catalyst, according to any one of claims 1 to 12, characterized in that X is -CH2Si(CH3)3.

14. Pro-catalyst, according to any one of claims 1 to 13, characterized in that Y and X are covalently connected.

15. Polymerization process, characterized in that it comprises polymerizing ethylene, or ethylene and one or more α-olefin (C3-C10) monomers, or ethylene and one or more cyclic olefin monomers in the presence of a catalyst system comprising a metal-ligand complex pro-catalyst, as defined in any one of claims 1 to 14.

16. Polymerization process, characterized in that it comprises polymerizing ethylene and a polar comonomer; or ethylene, a polar comonomer and one or more α-olefin (C3-C10) monomers, or ethylene, a polar comonomer and one or more cyclic olefin monomers in the presence of a catalyst system comprising a metal-ligand complex pro-catalyst, as defined in any one of claims 1 to 14.

17. Polymerization process according to claim 16, characterized in that the polar comonomer is chosen from acrylate (CH2=CHC(O)(OR)), glycidyl acrylate, CH2=CH(CH2)nC(O)(OR), CH2=CHC(O)R, CH2=CH(CH2)nC(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)nSi(R)3-T(OR)T, CH2=CH-OSi(R)3-t(OR)t, CH2=CH(CH2)n-OSi(R)3-T(OR)T or CH2=CHCl, wherein R is chosen from -H, a (C1-C30)substituted or unsubstituted hydrocarbyl, or a (C1-C30) substituted or unsubstituted heterohydrocarbyl, n is an integer from 1 to 10, and where T is 0, 1, 2, or 3.

18. Polymerization process according to claim 16, characterized in that the acrylate comonomer is terebutyl acrylate.

19. Polymerization process, according to claim 16, characterized by the fact that the acrylate comonomer is n-butyl acrylate.