Olefin Polymerization Process, Olefin Pre-Polymerization Catalyst, and Olefin Polymerization Catalyst System

Abstract

POLYMERIZATION CATALYST HAVING A TETRADENTATE LIGAND. The present invention relates to a novel olefin polymerization catalyst that is linked to a tetradentate ligand having a phenoxy / amino / ether / phenoxy (O / N / O / O) atom donor set. The novel zirconium- or hafnium-based polymerization catalyst produces a high molecular weight ethylene copolymer with high levels of comonomer incorporation.

Description

"OLEFIN POLYMERIZATION PROCESS, OLEFIN PRE-POLYMERIZATION CATALYST AND OLEFIN POLYMERIZATION CATALYST SYSTEM" FIELD OF THE INVENTION

[001] A novel polymerization catalyst having a tetradentate ligand is used to copolymerize ethylene with an alpha olefin. The novel polymerization catalyst, which is zirconium or hafnium based, is linked to a ligand having a phenoxy / amino / ether / phenoxy (O / N / O / O) atom donor cluster. FUNDAMENTALS OF THE INVENTION

[002] Since their discovery, the use of “post-metallocene” olefin polymerization catalysts containing polyvalent aryloxyether ligands has become a well-developed field of the art, and numerous catalyst variants are available in the patent literature. These catalysts are particularly noteworthy for their ability to function well in a high-temperature solution polymerization process. SUMMARY OF THE INVENTION

[003] In an effort to build the scope of these “post-metallocene” catalysts and their use in a solution-phase polymerization process, a novel olefin polymerization catalyst linked to a tetradentate ligand having a phenoxy / amino / ether / phenoxy (O / N / O / O) atom donor set was discovered.

[004] One embodiment of the description is a polymerization process comprising polymerizing ethylene with one or more C3-12 alpha olefins in the presence of a polymerization catalyst system comprising: i) a catalyst composition having the formula: Petition 870240079715, dated 09 / 18 / 2024, page 11 / 60 2 / 44 where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each R2 is independently an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; L is an optionally substituted divalent hydrocarbyl group, or an optionally substituted divalent heteroatom-containing hydrocarbyl group; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group; and ii) a catalyst activator.

[005] One embodiment of the description is a prepolymerization catalyst for olefins having the formula: Petition 870240079715, dated 09 / 18 / 2024, page 12 / 60 3 / 44 THE where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; each R2 is independently an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; L is an optionally substituted divalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted divalent heteroatom; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group.

[006] One embodiment of the description is an olefin polymerization catalyst system comprising: i) a catalyst composition having the formula: Petition 870240079715, dated 09 / 18 / 2024, page 13 / 60 4 / 44 where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each R2 is independently an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; L is an optionally substituted divalent hydrocarbyl group, or an optionally substituted divalent heteroatom-containing hydrocarbyl group; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group; and ii) a catalyst activator. DETAILED DESCRIPTION

[007] The olefin polymerization catalysts described here generally require activation by one or more cocatalytic or activating species in order to provide polymer from olefins. Therefore, a non-activated olefin polymerization catalyst can be described as an “olefin prepolymerization catalyst”.

[008] The olefin polymerization catalyst employed in the present Petition 870240079715, dated 09 / 18 / 2024, page 14 / 60 5 / 44 description is one that has a tetradentate type ligand, one that has a phenoxy / amino / ether / phenoxy (O / N / O / O) atom donor set.

[009] The olefin polymerization catalyst can be used in combination with other catalyst components, such as, but not limited to, one or more of a support, one or more of a catalyst activator and one or more of a catalyst modifier.

[010] The olefin prepolymerization catalyst used in one embodiment of the description is defined by the following formula: where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; each R2 is independently an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; L is an optionally substituted divalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted divalent heteroatom; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group. Petition 870240079715, dated 09 / 18 / 2024, page 15 / 60 6 / 44

[011] As used in this document, the terms “hydrocarbyl”, “hydrocarbyl radical” or “hydrocarbyl group” refer to acyclic, cyclic, linear or branched, aliphatic, olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogen and carbon that are deficient for a hydrogen.

[012] The term “cyclic” denotes hydrocarbyl groups or heteroatom-containing hydrocarbyl groups comprising cyclic moieties and which may have one or more cyclic aromatic rings and / or one or more non-aromatic rings. The term “acyclic” denotes hydrocarbyl groups or heteroatom-containing hydrocarbyl groups that do not have cyclic moieties, such as aromatic or non-aromatic ring structures present within them.

[013] As used in this document, the phrase “heteroatom” includes any atom other than carbon and hydrogen that can be bonded to carbon. The term “heteroatom-containing” or “heteroatom-containing hydrocarbyl group” means that one or more non-carbon atoms will be present in the group being referred to (e.g., the hydrocarbyl group). Some non-limiting examples of non-carbon atoms that may be present in a heteroatom-containing hydrocarbyl group are N, O, S, P, B, and Si, as well as halides such as, for example, Br and metals such as Sn. Some non-limiting examples of heteroatom-containing hydrocarbyl groups include, for example, imines, amine moieties, oxide moieties, phosphine moieties, ethers, ketones, heterocycles, oxazolines, thioethers, and the like.

[014] As used in this document, the term “substituted” means that the group referred to by this term has one or more moieties that have substituted one or more hydrogen radicals at any position within the group; non-limiting examples of moieties include halogen radicals (F, Cl, Br), an alkyl group, an alkylaryl group, an arylalkyl group, an alkoxy group, an aryl group, an aryloxy group, an amido group, a silyl group or a germanyl group, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, phenyl groups, Petition 870240079715, dated 09 / 18 / 2024, p. 16 / 60 7 / 44 naphthyl groups, C1 to C10 alkyl groups, C2 to C10 alkenyl groups and combinations thereof.

[015] By using the term “optional” or “optionally”, it is understood that the circumstance described subsequently may or may not occur or be present and that the description includes cases in which the circumstance occurs and cases in which it does not occur. For example, the phrase “optionally substituted hydrocarbyl group” means that a hydrocarbyl group may or may not be substituted and that the description includes both a substituted hydrocarbyl group and a hydrocarbyl group that is not additionally substituted.

[016] A “bivalent hydrocarbyl group” is a hydrocarbyl group that joins two molecular moieties. Such “bivalent hydrocarbyl groups” include “alkylene”, “alkenylene” and “alkynylene” groups which may optionally be further substituted. Such “bivalent hydrocarbyl groups” also include aryl moieties that are linked at two points to atoms, molecules or moieties with the two points of attachment being covalent bonds.

[017] A “divalent heteroatom-containing hydrocarbyl group” means that one or more non-carbon atoms will be present within the hydrocarbyl group. Some non-limiting examples of non-carbon atoms that may be present within a divalent heteroatom-containing hydrocarbyl group are N, O, S, P and Si, as well as halides such as, for example, Br and metals such as Sn.

[018] As used in this document, an “alkyl radical” or “alkyl group” includes linear, branched, and cyclic paraffin radicals that are deficient in a hydrogen radical; non-limiting examples include methyl (-CH3) and ethyl (CH2CH3) radicals.

[019] In one embodiment of the description, an alkyl group has from 1 to about 50 carbon atoms.

[020] In descriptive embodiments, an alkyl is methyl, ethyl, n-propyl, Petition 870240079715, dated 09 / 18 / 2024, p. 17 / 60 8 / 44 isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl and similar groups, as well as cycloalkyl groups, such as cyclopentyl, cyclohexyl and similar groups.

[021] In one embodiment of the description, an alkyl group contains from 1 to 12 carbon atoms.

[022] A “substituted alkyl” refers to an alkyl substituted by one or more substituent groups (e.g., benzyl or chloromethyl), and the terms “heteroatom-containing alkyl”, “heteroatom-containing alkyl group” and “heteroalkyl” refer to an alkyl group in which at least one carbon atom is substituted by a heteroatom (e.g., -CH2OCH3 is an example of a heteroalkyl).

[023] The term “alkenyl radical” or “alkenyl group” refers to linear, branched, and cyclic hydrocarbons containing at least one carbon-carbon double bond that is deficient by a hydrogen radical. In one embodiment of the description, an “alkenyl” group is a branched or unbranched hydrocarbon group having from 2 to 50 carbon atoms and at least one double bond. Some non-limiting examples of an alkenyl group include ethenyl, n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, and the like.

[024] In one embodiment of the description, an alkenyl group contains from 2 to about 12 carbon atoms.

[025] A “substituted alkenyl” refers to an alkenyl group substituted by one or more substituent groups, and the terms “heteroatom-containing alkenyl”, “heteroatom-containing alkenyl group” and “heteroalkenyl” refer to an alkenyl group in which at least one carbon atom is substituted by a heteroatom.

[026] The term “alkynyl radical” or “alkynyl group” refers to linear, branched, and cyclic hydrocarbons containing at least one carbon-carbon triple bond that is deficient in a hydrogen radical. In one embodiment of the description, an “alkynyl” group is a branched or unbranched hydrocarbon group containing from 2 to 50 carbon atoms and at least one bond Petition 870240079715, dated 09 / 18 / 2024, p. 18 / 60 9 / 44 triple. Some non-limiting examples of an alkynyl group include ethinyl, n-propynyl, isopropynyl, n-butynyl, isobutynyl, octinyl, decinyl, and the like.

[027] In one embodiment of the description, an alkynyl group has from 2 to 12 carbon atoms.

[028] A “substituted alkynyl” refers to an alkynyl group substituted by one or more substituent groups, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer to an alkynyl group in which at least one carbon atom is substituted by a heteroatom.

[029] As used in this document, the term “aryl” group includes phenyl, naphthyl, pyridyl, and other radicals whose molecules have an aromatic ring structure; non-limiting examples include naphthylene, phenanthrene, and anthracene. An “alkylaryl” group is an alkyl group having an aryl group pendant from it; non-limiting examples include benzyl, phenethyl, and tolylmethyl. An “arylalkyl” is an aryl group having one or more pendant alkyl groups; non-limiting examples include tolyl, xylyl, mesityl, and cumyl.

[030] “Substituted aryl” refers to an aryl moiety substituted with one or more substituent groups (e.g., tolyl, mesityl, and perfluorophenyl) and the terms “heteroatom-containing aryl” and “heteroaryl” refer to aryl in which at least one carbon atom is substituted by a heteroatom (e.g., rings such as thiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, etc., or benzo-fused analogs of these rings are included in the term “heteroaryl”).

[031] In some embodiments of this document, multi-ring portions are substituents and, in such embodiments, the multi-ring portion may be attached to an appropriate atom. For example, “naphthyl” may be 1-naphthyl or 2-naphthyl; “anthracenyl” may be 1-anthracenyl, 2-anthracenyl or 9-anthracenyl; and “phenanthrenyl” may be 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl or 9-phenanthrenyl. Petition 870240079715, dated 09 / 18 / 2024, p. 19 / 60 10 / 44

[032] The terms “halide” and “halogen” are used in the conventional sense to refer to a chlorine, bromine, fluorine, or iodine substituent. The terms “haloalkyl”, “haloalkenyl”, or “haloalkynyl” (or “halogenated alkyl”, “halogenated alkenyl”, or “halogenated alkynyl”) refer to an alkyl, alkenyl, or alkynyl group, respectively, in which at least one of the hydrogen atoms in the group has been replaced by a halogen atom.

[033] In one embodiment of the description, a heteroatom-containing hydrocarbyl group is a hydrocarbyl group containing 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur.

[034] The terms “cyclic heteroatom-containing hydrocarbyl” or “heterocyclic” refer to ring systems having a carbon backbone that further comprises at least one heteroatom selected from the group consisting of, for example, boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur.

[035] An “alkoxy” group is an oxy group having an alkyl group hanging from it; and includes, for example, a methoxy group, an ethoxy group, an isopropoxy group and the like.

[036] An “aryloxy” group is an oxy group having an aryl group hanging from it; and includes, for example, a phenoxy group and the like.

[037] In one embodiment of the description, an olefin prepolymerization catalyst is defined by the following formula: Petition 870240079715, dated 09 / 18 / 2024, page 20 / 60 11 / 44 where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; each R2 is independently an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; L is an optionally substituted divalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted divalent heteroatom; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group.

[038] In one embodiment of the description, an olefin polymerization catalyst system comprises: i) a catalyst composition having the formula: Petition 870240079715, dated 09 / 18 / 2024, page 21 / 60 12 / 44 where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each R2 is independently an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; L is an optionally substituted divalent hydrocarbyl group, or an optionally substituted divalent heteroatom-containing hydrocarbyl group; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group; and ii) a catalyst activator.

[039] In one embodiment of the description, each R2 is independently an optionally substituted aryl group or an optionally substituted heteroatom-containing aryl group.

[040] In one embodiment of the description, each R2 is independently an aryl group containing an optionally substituted heteroatom.

[041] In one embodiment of the description, each R2 is independently an aryl group containing a substituted heteroatom.

[042] In one embodiment of the description, each R2 is an aryl group containing Petition 870240079715, dated 09 / 18 / 2024, p. 22 / 60 13 / 44 substituted heteroatom.

[043] In one embodiment of the description, each R2 has the formula: x / wwv\

[044] In one embodiment of the description, L is an optionally substituted divalent hydrocarbyl group.

[045] In one embodiment of the description, L is a divalent hydrocarbon group.

[046] In one embodiment of the description, L is a divalent alkylene group.

[047] In one embodiment of the description, L is a divalent cycloalkylene group.

[048] In one embodiment of the description, L is a divalent aryl group.

[049] In one embodiment of the description, L is a divalent alkylene group having 2 to 8 carbon atoms.

[050] In one embodiment of the description, L is a divalent n-propyl group having the formula: -CH2CH2CH2-.

[051] In one embodiment of the description, A2e A8 are independently an optionally substituted hydrocarbon group or a hydrocarbon group containing an optionally substituted heteroatom.

[052] In one embodiment of the description, A2e A8 are independently an optionally substituted hydrocarbon group.

[053] In one embodiment of the description, A2e A8are independently a hydrocarbon group.

[054] In one embodiment of the description, A2 and A8 are independently a Petition 870240079715, dated 09 / 18 / 2024, p. 23 / 60 14 / 44 alkyl group optionally replaced.

[055] In one embodiment of the description, A2e A8are independently an alkyl group.

[056] In one embodiment of the description, A2e A8são, each one, is an alkyl group having from 1 to 20 carbon atoms.

[057] In one embodiment of the description, A2e A8são, each one, is an alkyl group having from 1 to 8 carbon atoms.

[058] In one embodiment of the description, A2e A8são, each one, is a methyl group.

[059] In one embodiment of the description, A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each either a hydrogen or a halide.

[060] In one embodiment of the description, A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each hydrogen.

[061] In one embodiment of the description, A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each either a hydrogen or a fluoride.

[062] In one embodiment of the description, A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each a halide.

[063] In one embodiment of the description, A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each fluoride.

[064] In one embodiment of the description, R1 is an optionally substituted hydrocarbyl group or a hydrocarbyl group containing an optionally substituted heteroatom.

[065] In one embodiment of the description R1 is a hydrogen.

[066] In one embodiment of the description, R1 is an optionally substituted hydrocarbyl group.

[067] In one embodiment of the description R1 is a substituted hydrocarbyl group.

[068] In one embodiment of the description R1 is a hydrocarbyl group. Petition 870240079715, dated 09 / 18 / 2024, p. 24 / 60 15 / 44

[069] In one embodiment of the description R1 is an optionally substituted alkyl group.

[070] In one embodiment of the description R1 is a substituted alkyl group.

[071] In one embodiment of the description, R1 is a substituted alkyl group having one or more halide atoms.

[072] In one embodiment of the description, R1 is a substituted alkyl group having one or more fluoride atoms.

[073] In one embodiment of the description, R1 is an alkyl group.

[074] In one embodiment of the description, R1 is an alkyl group having from 1 to 20 carbon atoms.

[075] In one embodiment of the description, R1 is an alkyl group having 1 to 8 carbon atoms.

[076] In one embodiment of the description R1 is a methyl group.

[077] In the current description, the term “activatable” means that the ligand X can be cleaved from the metal center M by means of a protolysis reaction or abstracted from the metal center M by suitable acid or electrophilic catalyst activating compounds (also known as “cocatalyst compounds”) respectively, examples of which are described below. The activatable ligand X can also be transformed into another ligand that is cleaved or abstracted from the metal center M (for example, a halide can be converted into an alkyl group). Without wanting to limit ourselves to a single theory, protolysis or abstraction reactions generate an active “cationic” metal center that can polymerize olefins.

[078] In embodiments of the present description, the activatable ligand, X, is independently selected from the group consisting of a hydrogen atom; a halogen atom, a C1-10 hydrocarbyl radical; a C1-10 alkoxy radical; and a C6-10 aryl or aryloxy radical, wherein each of the hydrocarbyl, alkoxy, aryl or aryloxy radicals may be unsubstituted or additionally substituted by a Petition 870240079715, dated 09 / 18 / 2024, p. 25 / 60 16 / 44 or more halogens or other group; a C1-8 alkyl; a C1-8 alkoxy, a C1-10 aryl or aryloxy; an amido or phosphide radical, but where X is not a cyclopentadienyl. Two X ligands may also be joined to each other and form, for example, a substituted or unsubstituted diene ligand (i.e., 1,3-butadiene); or a group containing a delocalized heteroatom such as an acetate or acetamidinate group. In a convenient embodiment of the description, each X is independently selected from the group consisting of a halide atom, a C1-4 alkyl radical and a benzyl radical.

[079] In one embodiment, particularly suitable activatable ligands are monoanionic, such as a halide (e.g., chloride) or a hydrocarbyl (e.g., methyl, benzyl).

[080] The catalyst activator (or simply the “activator” for short) used to activate the olefin polymerization catalyst may be any suitable activator including one or more activators selected from the group consisting of alkylaluminoxanes and ionic activators, optionally in conjunction with an alkylating agent.

[081] Without wanting to be limited to theory, alkylaluminoxanes are believed to be aluminum complex compounds of the formula: R32Al1O(R3Al1O)mAl1R32, where each R3 is independently selected from the group consisting of C1-20 hydrocarbyl radicals in the range of 3 to 50. Optionally, a hindered phenol can be added to the alkylaluminoxane to provide an Al1:hindered phenol molar ratio of 2:1 to 5:1 when the hindered phenol is present.

[082] In one embodiment of the description, R3do alkylaluminoxane is a methyl radical in e is from 10 to 40.

[083] Alkylaluminoxanes are typically used in substantial molar excess compared to the amount of olefin polymerization catalyst. The metal molar ratios of the Al1:olefin polymerization catalyst Petition 870240079715, dated 09 / 18 / 2024, page 26 / 60 17 / 44 ratios can range from approximately 10:1 to approximately 10,000:1, preferably from approximately 30:1 to approximately 500:1.

[084] In one embodiment of the description, the catalyst activator comprises methylaluminoxane (MAO).

[085] In one embodiment of the description, the catalyst activator comprises modified methylaluminoxane (MMAO).

[086] It is well known in the art that alkylaluminoxane can play dual roles as an alkylator and an activator. Thus, an alkylaluminoxane activator is often used in combination with activatable ligands, such as halogens.

[087] Alternatively, the catalyst activator of the present description may be a combination of an alkylating agent (which may also serve as a sequestrant) with an activator capable of ionizing the group 4 metal of the olefin polymerization catalyst, or pre-catalyst (i.e., an ionic activator). In this context, the activator may be chosen from one or more alkylaluminoxanes and / or an ionic activator, since an alkylaluminoxane may serve as both an activator and an alkylating agent.

[088] When present, the alkylating agent may be selected from the group consisting of (R4)p MgX22-p where X2 is a halide and each R4 is independently selected from the group consisting of C1-10 alkyl radicals eq is 1 or 2; R4Li where R4 is as defined above, (R4)qZnX22-q where R4 is as defined above, X2 is a halogen eq is 1 or 2; and

[089] (R4)s Al2X23-s where R4 is as defined above, X2 is a halogen and s is an integer from 1 to 3. In embodiments of the description, in the compounds above, R4 is a C1-4 alkyl radical, and X2 is chlorine. Commercially available compounds include triethyl aluminum (TEAL), trimethyl aluminum, triisobutyl aluminum, tributyl aluminum, diethyl aluminum chloride (DEAC), dibutyl magnesium ((Bu)2Mg) and butyl ethyl magnesium. Petition 870240079715, dated 09 / 18 / 2024, p. 27 / 60 18 / 44 (BuEtMg or BuMgEt). Alkylaluminoxanes can also be used as alkylating agents.

[090] The ionic activator may be selected from the group consisting of: (i) compounds of the formula [R5]+ [B(R6)4]- wherein B is a boron atom, R5 is a cyclic aromatic C5-7 cation or a triphenyl methyl cation and each R6 is independently selected from the group consisting of phenyl radicals that are unsubstituted or are substituted by 3 to 5 substituents selected from the group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical that is unsubstituted or is substituted by a fluorine atom; and a silyl radical of formula --Si-(R7)3; wherein each R7 is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical;and (ii) compounds of formula [(R8)t ZH]+ [B(R6)4]- wherein B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or a phosphorus atom, t is 2 or 3 and R8 is selected from the group consisting of C1-8 alkyl radicals, a phenyl radical that is unsubstituted or is substituted by up to three C1-4 alkyl radicals, or an R8 taken together with the nitrogen atom may form an aniline radical and R6 is as defined above; and (iii) compounds of formula B(R6)3 where R6 is as defined above.

[091] In embodiments of the description, in the compounds above, R6 is a pentafluorophenyl radical, and R5 is a triphenyl methyl cation, Z is a nitrogen atom and R8 is a C1-4 alkyl radical or R8 taken together with the nitrogen atom forms an aniline radical that is substituted by two C1-4 alkyl radicals.

[092] Examples of compounds capable of ionizing the phosphinimide catalyst include the following compounds: triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, Petition 870240079715, dated 09 / 18 / 2024, page 28 / 60 19 / 44 tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethylaniline tetra(phenyl)boron, di-(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropylium tetraquispentafluorophenyl borate, triphenylmethyl tetraquispentafluorophenyl borate, benzene (diazonium) tetraquispentafluorophenyl borate, tropylium phenyltris-pentafluorophenyl borate, triphenylmethyl phenyltrispentafluorophenyl borate, benzene (diazonium) phenyltrispentafluorophenyl borate, tropylium tetrakis(2,3,5,6-tetrafluorophenyl) borate, triphenylmethyl tetrakis(2,3,5,6-tetrafluorophenyl) borate, benzene (diazonium) tetrakis(3,4,5-trifluorophenyl) borate, tropylium tetrakis(3,4,5-trifluorophenyl) borate, benzene (diazonium) tetrakis(3,4,5-trifluorophenyl) borate,tropylium tetrakis(1,2,2-trifluoroethenyl) borate, trophenylmethyl tetrakis(1,2,2-trifluoroethenyl) borate, benzene(diazonium) tetrakis(1,2,2-trifluoroethenyl) borate, tropylium tetrakis(2,3,4,5-tetrafluorophenyl) borate, triphenylmethyl tetrakis(2,3,4,5-tetrafluorophenyl) borate, and benzene(diazonium) tetrakis(2,3,4,5-tetrafluorophenyl) borate.

[093] Commercially available activators that are capable of ionizing the phosphinimide catalyst include: N,N-dimethylaniline tetrakispentafluorophenyl borate (“[Me2NHPh][B(C6F5)4]”); triphenylmethyl tetrakispentafluorophenyl borate (“[PhaC][B(CsF5)4]”); and trispentafluorophenyl boron.

[094] In one embodiment of the description, ionic activating compounds can be used in amounts that provide a molar ratio of group 4 transition metal to boron that will be from 1:1 to 1:6.

[095] Optionally, mixtures of alkylaluminoxanes and ionic activators can be used as activators for the olefin polymerization catalyst.

[096] The olefin prepolymerization catalysts of the present description can be used in any conventional olefin polymerization process, Petition 870240079715, dated 09 / 18 / 2024, page 29 / 60 20 / 44 such as gas-phase polymerization, paste-phase polymerization or solution-phase polymerization. The use of a “heterogeneous” catalyst system is preferred for use in gas-phase and paste-phase polymerization, while a homogeneous catalyst is preferred in solution-phase polymerization. A heterogeneous catalyst system can be formed by supporting a pre-polymerization catalyst, optionally together with an activator on a support, such as, for example, a silica support, as is well known to those skilled in the art.

[097] Solution polymerization processes for the polymerization or copolymerization of ethylene are well known in the art (see, for example, US Patents Nos. 6,372,864 and 6,777,509). These processes are conducted in the presence of an inert hydrocarbon solvent, typically a C5-12 hydrocarbon that may be unsubstituted or may be substituted with a C14 alkyl group such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, and hydrogenated naphtha. An example of a suitable solvent that is commercially available is “Isopar E” (C8-12 aliphatic solvent, Exxon Chemical Co.).

[098] The polymerization temperature in a conventional solution process is from about 80°C to about 300°C. In one embodiment of the description, the polymerization temperature in a solution process is from about 120°C to about 250°C. The polymerization pressure in a solution process can be a “medium pressure process,” meaning that the pressure in the reactor is less than about 6,000 psi (about 42,000 kiloPascals or kPa). In one embodiment of the description, the polymerization pressure in a solution process can be from about 10,000 to about 40,000 kPa or from about 14,000 to about 22,000 kPa (i.e., from about 2,000 psi to about 3,000 psi).

[099] Suitable monomers for copolymerization with ethylene include C3 Petition 870240079715, dated 09 / 18 / 2024, p. 30 / 60 21 / 44 monoolefins and diolefins. Comonomers include C3-12 alpha olefins that are unsubstituted or substituted by up to two C1-6 alkyl radicals, C8-12 vinyl aromatic monomers that are unsubstituted or substituted by up to two substituents selected from the group consisting of C1-4 alkyl radicals, C4-12 linear or cyclic chain diolefins that are unsubstituted or substituted by a C1-4 alkyl radical. Illustrative but not limiting examples of such alpha olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, styrene, alpha methyl styrene, and ring-restricted cyclic olefins such as cyclobutene, cyclopentene, dicyclopentadiene norbornene, alkyl-substituted norbornenes, alkenyl-substituted norbornenes and the like (for example, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, bicyclo-(2,2,1)-hepta-2,5-diene).

[0100] In embodiments, the polyethylene polymers that can be prepared according to the present description are LLDPEs and may comprise not less than 60 or not less than 75% by weight of ethylene with the balance being one or more C4-10 alpha olefins, such as alpha olefins selected from the group consisting of 1-butene, 1-hexene and 1-octene.

[0101] In embodiments of the description, the alpha olefin present in a polyethylene polymer may be present in an amount of about 3 to 30% by weight, or about 4 to 25% by weight.

[0102] The polyethylene prepared according to the present description can be LLDPE with a density of about 0.910 to 0.935 g / cm3 or high-density (linear) polyethylene with a density above 0.935 g / cm3. The present description can also be useful for preparing polyethylene with a density below 0.910 g / cm3 - the so-called very low and ultra-low density polyethylenes.

[0103] The present description can also be used to prepare copolymers and terpolymers of ethylene, propylene and, optionally, one or more diene monomers. Generally, these polymers will contain about 50 to about Petition 870240079715, dated 09 / 18 / 2024, page 31 / 60 22 / 44 75% by weight of ethylene, or about 50 to 60% by weight of ethylene and correspondingly 50 to 25% by weight of propylene. A portion of the monomers, typically the propylene monomer, may be replaced by a conjugated diolefin. The diolefin may be present in amounts up to 10% by weight of the polymer, although it is typically present in amounts of about 3 to 5% by weight. The resulting polymer may have a composition comprising 40 to 75% by weight of ethylene, 50 to 15% by weight of propylene, and up to 10% by weight of a diene monomer to provide 100% by weight of the polymer. Non-limiting examples of dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene, especially 5-ethylidene-2norbornene and 1,4-hexadiene.

[0104] In solution polymerization, monomers are dissolved / dispersed in the solvent before being fed into the reactor (or for gaseous monomers, the monomer can be fed into the reactor so that it dissolves in the reaction mixture). Before mixing, the solvent and monomers are usually purified to remove potential catalyst poisons such as water, oxygen, or metallic impurities. Purification of the raw material follows standard practices in the art, for example, molecular sieves, alumina beds, and oxygen removal catalysts are used for monomer purification. The solvent itself (e.g., methyl pentane, cyclohexane, hexane, or toluene) can also be treated similarly.

[0105] The raw material can be heated or cooled before feeding into the reactor.

[0106] Generally, the catalyst components (the olefin prepolymerization catalyst, an ionic activator, and optionally an alkylaluminoxane) can be premixed in the solvent for the reaction or fed as separate streams into the reactor. In some cases, premixing may be desirable for Petition 870240079715, dated 09 / 18 / 2024, page 32 / 60 23 / 44 provide a reaction time for the catalyst components before entering the reaction. Such an “in-line mixing” technique is described in several patents in the name of DuPont Canada Inc. (e.g., U.S. Patent No. 5,589,555 issued December 31, 1996).

[0107] One embodiment of the description is a polymerization process comprising polymerizing ethylene optionally with one or more C3-12 alpha olefins in the presence of a polymerization catalyst system comprising: i) a catalyst composition having the formula: where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each R2 is independently an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; L is an optionally substituted divalent hydrocarbyl group, or an optionally substituted divalent heteroatom-containing hydrocarbyl group; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group; and ii) a catalyst activator. Petition 870240079715, dated 09 / 18 / 2024, page 33 / 60 24 / 44

[0108] In one embodiment of the description, the polymerization process is a solution-phase polymerization process carried out in a solvent.

[0109] In one embodiment of the description, the polymerization process comprises polymerizing ethylene with one or more C3-12 alpha olefins.

[0110] In one embodiment of the description, the polymerization process comprises polymerizing ethylene with 1-octene.

[0111] Other non-limiting details of the description are provided in the following examples. The examples are presented for the purpose of illustrating selected embodiments of this description, it being understood that the examples presented do not limit the claims made. EXAMPLES General Experimental Methods

[0112] All reactions were conducted under nitrogen using standard Schlenk techniques or in an inert atmosphere glove box. Reaction solvents were purified using the system described by Grubbs et al. (see: Pangborn, AB; Giardello, MA; Grubbs, RH; Rosen RK; Timmers, FJ Organometallics 1996, 15, 1518-1520) and then stored on activated molecular sieves in an inert atmosphere glove box. 13X molecular sieves were purchased from Grace and activated at 260°C overnight. 2,6-di-tert-butyl-4-ethylphenol (BHEB) was purchased from Aldrich and used as received. MMAO-7 (7% wt solution in ISOPAR-E) was purchased from Akzo Nobel and used as received. Triphenylcarbenium tetrakis(pentafluorophenyl)borate was purchased from Albemarle Corp. and used as received.Deuterated NMR solvents, ds-toluene and d2-dichloromethane, were acquired from Aldrich and stored in 13X molecular sieves prior to use. NMR spectra were recorded on a Bruker 400 MHz spectrometer (1H: 400.1 MHz).

[0113] Molecular weight information (Mw, Mn and Mz in g / mol) and Petition 870240079715, dated 09 / 18 / 2024, page 34 / 60 25 / 44 Molecular weight distribution (Mw / Mn) and z-average molecular weight distribution (Mz / Mw) were analyzed by gel permeation chromatography (GPC) using an instrument sold under the commercial name “Waters 150c”, with 1,2,4-trichlorobenzene as the mobile phase at 140°C. Samples were prepared by dissolving the polymer in this solvent and were processed without filtration. Molecular weights are expressed as polyethylene equivalents with a relative standard deviation of 2.9% for the number-average molecular weight (“Mn”) and 5.0% for the weight-average molecular weight (“Mw”). Polymer sample solutions (1 to 2 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating it on a wheel for 4 hours at 150°C in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in order to stabilize the polymer against oxidative degradation. The concentration of BHT was 250 ppm.Sample solutions were chromatographed at 140°C in a PL 220 high-temperature chromatography unit equipped with four SHODEX columns (HT803, HT804, HT805, and HT806) using TCB as the mobile phase at a flow rate of 1.0 mL / minute, with differential refractive index (DRI) as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect the columns from oxidative degradation. The sample injection volume was 200 mL. Raw data were processed using CIRRUS® GPC software. The columns were calibrated with narrow-distribution polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in ASTM standard test method D6474.

[0114] The branching frequency of copolymer samples (i.e., short-chain branching, SCB per 1000 carbon atoms of the main chain) and the Cs comonomer content (% by weight) were determined by Fourier Transform Infrared Spectroscopy (FTIR) according to ASTM method D6645-01. A Thermo-Nicolet 750 Magna-IR spectrophotometer equipped with the Petition 870240079715, dated 09 / 18 / 2024, page 35 / 60 26 / 44 software OMNIC® version 7.2a was used for the measurements.

[0115] The determination of branching frequency as a function of molecular weight (and therefore comonomer distribution) was performed using high-temperature Gel Permeation Chromatography (GPC) and FT-IR of the eluent. Polyethylene standards with a known branching content, polystyrene, and hydrocarbons with a known molecular weight were used for calibration. Catalyst Synthesis

[0116] The general synthetic steps and methods employed to make the ligand, L, and the precatalysts of Examples 1 and 2, are given below. Compound A: H A^ / NH2 i) NaH, 0°C I ii) MeI, 0oC a rt THE

[0117] To a 200 mL Schlenk flask charged with 45.7 mmol (10 g) of 2-iodoaniline in 90 mL of dry THF, NaH (2.009 g, 1.1 equiv., 60% in distribution oil) was slowly added at 0°C. After the resulting pale gray suspension had been stirred at 0°C for one hour, it was slowly warmed to room temperature, followed by the dropwise addition of MeI (3.2 mL, 1.1 equiv.) at 0°C. After the reaction had been stirred at room temperature overnight, it was concentrated under vacuum and diluted in dichloromethane, DCM. The organic layer was washed with water and a brine solution, then dried with Na2SO4, filtered, and concentrated under vacuum to give a dark red oil (10.24 g, 94%). 1H NMR indicates about 15% superalkylation product. The crude product was subjected to the next reaction without further purification. 1H NMR (400 MHz, CD2CU δ): 7.64 (dd, 1H), 7.23 (td, 1H), 6.56 (dm, 1H), 6.43 (tm, 1H), 4.22 (br.s, 1H), 2.87 (d, 3H, J = 5 Hz). Compound B: Petition 870240079715, dated 09 / 18 / 2024, p. 36 / 60 27 / 44 EtOH, 75C ---------* KI

[0118] 2-iodophenol (11.0 g, 50 mmol) in a solution of EtOH (30 mL) was added to a stirred solution of NaOH (2 g, 50 mmol) and KI (0.83 g, 5 mmol) in EtOH (40 mL). The mixture was stirred for 3 hours at room temperature. This solution was slowly added to a solution of 1,2-dibromopropane (50 g, 248 mmol) in EtOH (50 mL) over 1.5 hours. The mixture was stirred at 75°C for a weekend and pumped dry. An aqueous solution of NaOH (100 mL, 2M) and diethyl ether (150 mL) was used to process the reaction. The organic layer was dried with MgSO4 and pumped dry. 9.8 g of crystalline solid were obtained by vacuum distillation (140°C).1H NMR (400 MHz, CD2Cl2, δ): 7.77 (d, 1H), 7.32 (dd, 1H), 6.86 (d, 1H), 6.73 (dd, 1H), 4.15 (t, 2H, J = 6Hz), 3.72 (t, 2H, J = 6Hz), 2.36 (p, 2H, J = 6Hz). Compound C: Petition 870240079715, dated 09 / 18 / 2024, p. 37 / 60 28 / 44

[0119] A 200 mL round-bottom, double-necked flask containing 43 mmol (8.71 g) of crude compound A in 65 mL of DMF was added to compound B (13 g, 1.2 equiv.) and diisopropylethylamine (DIPEA, 14 mL, 2.5 equiv.). After the resulting light orange solution was heated to 120°C for 4 days, it was concentrated under vacuum and diluted in Et2O (150 mL). The organic layer was washed with H2O (200 mL x 5), then brine solution, then dried with Na2SO4, filtered, and concentrated under vacuum to yield a crude oil. The crude oil was dissolved in 100 mL of Et2O, filtered to remove some solids. 4.2 mL of HCl (12 M) were added to the diethyl ether solution to produce a paste. The paste was vigorously stirred for one hour and filtered. The solid was washed with Et2O and dissolved in CH2Cl2 (100 mL). The solution was washed with 1M NaOH and brine. The organic phase was dried with Na2SO4, filtered, and concentrated under vacuum to yield a dark red oil.The final product was purified by distillation (125°C under total vacuum) to obtain a pure product as a light orange oil (2.3 g). 1H NMR (400 MHz, CD2Cl2) δ ppm 7.85 (dd, J = 7.9, 1.4 Hz, 1 H), 7.74 (dd, J = 7.8, 1.6 Hz, 1 H), 7.31 7.37 (m, 1 H), 7.25 - 7.31 (m, 1H), 7.19 (dd, J = 8.0, 1.5 Hz, 1 H), 6.84 (dd, J = 8.1, 1.3 Hz, 1 H), 6.81 (ddd, J = 7.7, 7.3, 1.5 Hz, 1 H), 6.69 (ddd, J = 7.9, 7.6, 1.4 Hz, 1 H), 4.12 (t, J = 6.2Hz, 2H), 3.22 (t, J = 6.9 Hz, 2 H), 2.71 (s, 3H), 2.02 (tt, J=6.9, 6.2 Hz, 2H). Petition 870240079715, dated 09 / 18 / 2024, pp. 38 / 60 29 / 44 Compound D:

[0120] 2-iodo-4-methylphenol (13.0 g, 55.55 mmol) and 3,4-dihydropyran (4.90 g, 58.25 mmol) were weighed into a 250 mL round-bottom flask. Dichloromethane (15 mL) was added to the flask. While the mixture was being stirred, CF3COOH (1.27 g, 20 mol%) in a 10 mL hypoflask was added dropwise. The flask was washed with 5 mL of dichloromethane, and the washing solution was added back to the flask. The mixture was stirred for 3.5 hours (note: a reaction time of more than 3.5 hours leads to byproducts) and cooled by slowly adding 30 mL of a saturated aqueous solution of sodium carbonate. Dichloromethane was removed by vacuum pumping, and a solution of NaOH (1 M, 150 mL) and diethyl ether (250 mL) was added to the flask. The contents were transferred to a separatory funnel and shaken vigorously. The organic phase was thoroughly washed with a solution of NaOH (3 x 150 mL) to completely remove any trace amount of 2-iodo-4-methylphenol.The diethyl ether solution was dried with anhydrous MgSO4. A solution in pentane / ethyl acetate (volume ratio 19:1,400 mL) was filtered through a silica gel buffer (1” diameter, 3” height) and GC-MS showed the product to be pure (M+ = 318). The solvents were removed under vacuum to give the product as a nearly colorless oil (17.5 g). Compound E: Petition 870240079715, dated 09 / 18 / 2024, pp. 39 / 60 30 / 44 Cui CH3NHCH2CH2NHCH3 K3PO4

[0121] 3,6-di-tert-butyl-9H-carbazole (11.35 g, 40.60 mmol), tetrahydro-2-(2-iodine 4-methylphenoxy)-2H-pyran (12.92 g, 40.60 mmol; compound D), anhydrous K3PO4 (25.8 g, 121.80 mol), CuI (1.65 g, 8.65 mmol) and CH3NHCH2CH2NHCH3 (1.14 g, 13 mmol) were weighed into a 250 mL Schlenk flask. The mixture was refluxed (at a bath temperature of 130°C) for 48 hours. The contents were filtered through a 1” and 8” diameter silica gel buffer, and the buffer was rinsed with 300 mL of toluene. The light yellow filtrate was roto-vaporized to dryness (an oil), and 60 mL of acetonitrile were added. The solution was left to stand, and crystals began to form after about 10 minutes. After 48 hours, the solid product was filtered and washed with cold acetonitrile (2 x 30 mL, -20°C). 13.0 g of product were obtained after vacuum drying. 1H NMR (400 MHz, CD2Cl2) δ ppm 8.15 (d, J = Hz, 2H), 7.44 (td, J = 2Hz, J = 9Hz, 2H), 7.30 (d, J = 2Hz, 1H), 7.29 (s, 1H), 7.24 (dd, J = 2Hz, J = 9Hz, 1H), 7.16 (d, J = 9Hz, 1H), 7.09 (d, J = 9Hz, 1H), 5.19 (t, J = 3 Hz, 1H), 3.68 (td, J = 3 Hz, J = 11 Hz, 1H), 3.44 (dt, J = 4 Hz, J = 11 Hz, 1H), 2.38 (s, 3H), 1.46 (s, 18H), 1.44 - 1.34 (m, 2H), 1.33 - 1.23 (m, 1H), 1.22 - 1.03 (m, 3H). Compound F: Petition 870240079715, dated 09 / 18 / 2024, pp. 40 / 60 31 / 44 3. H2O / HCl

[0122] To a 1 L round-bottom, three-necked flask containing compound E (10.0 g, 21.3 mmol) in 400 mL of dry THF, a 1.6 M nBuLi solution (16 mL, 25.55 mmol, 1.2 equiv.) at 0°C was slowly added. After the resulting mixture was heated to room temperature and stirred for 3 hours, B(OiPra) (5.2 g, 27.68 mmol) was added to the reaction mixture dropwise at 0°C. The resulting mixture was then left under stirring at room temperature overnight. The reaction was concentrated under vacuum and cooled with H2O (300 mL). The mixture was then stirred for 30 minutes and the white suspension was extracted with Et2O (3 x 200 mL). The combined organic layers were washed with H2O, then with brine solution, then dried with Na2SO4 and filtered to provide the final product (10.1 g, 93%).1H NMR (400 MHz, CD2Cl2) δ ppm 8.17 (d, J = 1.8 Hz, 1 H), 8.13 (d, J = 1.8 Hz, 1 H), 7.69 (d, J = 1.8 Hz, 1 H), 7.49 (dd, J = 1.8 Hz, 1 Hz), 1 H 7.44 (dd, J = 8.7, 1.9 Hz, 1 H), 7.36 (d, J = 1.9 Hz, 1 H), 7.23 (d, J = 8.6 Hz , 1 H), 7.00 (d, J = 8.7 Hz, 1 H), 6.34 (s, 2, 0, 09 Hz), J 2.3 Hz, 1 H), 3.83 (ddd, J = 11.4, 2.2 , 1.5 Hz, 1 H), 3.04 (td, J = 11.5, 2.6 Hz, 1 H), 2.40 (s,3 H), 1.47 (s, 9 H), = 8.3, 6.2 Hz, 3 H), 1.13 - 1.20 (m, 1 H), 0.96 (tdd, J = 12.8, 12.8, 9.0, 4.1 Hz, 1 H), 0.46 - 0.68 (m, 1 H) 1H). Ligand L: Petition 870240079715, of 18 / 09 / 2024, p. 41 / 60 32 / 44

[0123] A 500 mL round-bottom, three-necked flask was loaded with compound C (2.3 g, 4.67 mmol), compound F (6 g, 11.68 mmol, 2.5 equiv.) and Pd(PPh3)4 (270 mg, 0.23 mmol, 0.05 equiv.) in 50 mL of dry THF, a 0.65 M NaOH solution (degassed solution, 1.3 g in 50 mL of water, 7.0 equiv.) and 100 mL of degassed dimethoxyethane. After the resulting mixture was refluxed for 3 days, it was concentrated under vacuum and extracted with DCM (~80 mL), the organic layer was washed with H2O, then brine solution, then dried with Na2SO4, filtered and concentrated under vacuum to obtain a brown solid. The crude product was added to a 500 mL round-bottom flask, followed by 200 mL of MeOH and 2 mL of HCl (12M).After the cloudy orange solution was refluxed overnight, it was concentrated under vacuum and diluted with Et2O. The organic layer was washed with H2O, then brine solution, then dried with Na2SO4, filtered, and concentrated under vacuum to yield a yellow solid. Petition 870240079715, dated 09 / 18 / 2024, p. 42 / 60 33 / 44 pale. The final product was purified by filtration through silica buffer, followed by recrystallization in acetonitrile (3.25 g, 70% in two steps). 1H NMR (400 MHz, CD2Cl2) δ ppm 10.70 (s, 1 H), 8.14 (s, 4 H), 7.49 (dd, J = 7.3, 2.0 Hz, 1 H), 7.38 (dd, J = 8.6, 7.3 Hz, 1 H), 7.38 (d, J = 1.9 Hz, 1 H), 7.37 (dd, J = 8.6, 7.3 Hz, 1 H), 7.38 (dd, J = 8.5, 7.9 Hz, 1 H), 7.37 (dd, J = 8.7, 2.0 Hz, 5 H), 7.30 (d, J = 1.9 Hz, 1 H), 7.22 7.26 (m, 2 H), 7.18 - 7.21 (m, 3 H), 7.16 (d, J = 1.9 Hz, 1 H), 7.07 (d, J = 8.8 Hz, 3 H), 7.03 (d, J = 8.6 Hz, 2 H), 6.81 (d, J = 7.3 Hz, 1 H), 6.69 (d, J = 7.9 Hz, 1 H), 5.80 (s, 1 H), 3.83 (t, J = 5.9 Hz, 2 H), 2.86 (dd, J = 7.6, 7.4 Hz, 2 H), 2.38 (d, J = 4.0Hz, 6H), 2.33 (s, 3 H), 1.78 (ddt, J = 7.6, 7.4, 5.9, 5.9 Hz, 2 H), 1.78 (ddt, J = 7.6, 7.4, 5.9, 5.9 Hz, 2 H), 1.43 (s, 18 H), 1.42 (s, 19 H). Pre-catalyst, Example 1:

[0124] A 200 mL Schlenk flask filled with HfCl4 (222 mg, 0.69 mmol) in 30 mL of dry toluene was filled with a 3M MeMgBr solution (1.04 mL, 4.5 equiv., the flask was washed with 5 mL of dry Et2O) at -30°C. After the resulting clear solution was stirred at -30°C for 15 minutes, a solution of L ligand (700 mg, 0.69 mmol) in 20 mL of dry toluene was slowly added. Petition 870240079715, dated 09 / 18 / 2024, pp. 43 / 60 34 / 44 and rinsed with dry toluene (2 x 20 mL). The resulting cloudy whitish mixture was stirred at -30°C for one hour, then warmed to room temperature overnight. The reaction was concentrated, and then extracted with heptane (3 x 50 mL). The heptane layers were combined and concentrated to provide the final precatalyst as a whitish solid (0.705 g, 83%). 1H NMR (400 MHz, toluene-d8) δ ppm 8.59 (d, J = 1.4 Hz, 1 H), 8.53 (d, J = 1.4 Hz, 1 H), 8.31 (d, J = 1.1 Hz, 1 H) , 8,24 (d, J = 1,1 Hz, 1 H), 7,58 (dd, J = 8,6, 1,8 Hz, 1 H), 7,55 (dd, J = 8,6, 1,8 Hz, 1 H), 7,48 (d, J = 8,5 Hz, 1 H), 7,34 - 7,46 (m, 3 H), 7,21 - 7,34 (m, 4 H), 7,16 (d, J = 1,8 Hz, 1 H), 7,04 - 7,09 (m, 2 H), 7,00 (d, J = 2,7 Hz, 1 H), 6,80 - 6,91 (m, 1 H), 6,70 - 6,80 (m, 3 H), 5,80 (d, J = 8,5 Hz, 1 H), 5,05 (ddd, J = 7,5, 2,0, 1,0 Hz, 1 H), 4,22 (br ddd, J = 11,1, 1,0 Hz, 1 H), 3,57 (br ddd, J = 12,1, 1,0 Hz, 1 H), 2,94 (br ddd, J = 10,4, 1,0 Hz, 1 H), 2,28 (s, 2 H), 2,29 (dddd, J = 12,1, 11,1, 10,4, 7,5 Hz, 1 H), 2,21 (s, 3 H), 1,86 - 1,96 ( m, 3 H), 1,62 (m, 1 H), 1,61 (s, 9 H), 1,57 (s, 9 H), 1,30 (s, 9 H), 1,26 (s, 9 H), 0,42 (br d , J=14,9 Hz, 1H), -1,21 (s, 3H), -1,52 (s, 3H). Pré-catalisador, Exemplo 2: L ZrCl4, MeMgBr -30° C a r.t. tolueno

[0125] A 300 mL Schlenk vial loaded with ZrCl4 (463 mg, 1.98 Petition 870240079715, dated 09 / 18 / 2024, pp. 44 / 60 A solution of 3M MeMgBr (35 / 44 mmol) in 100 mL of dry toluene was added to a 3M MeMgBr solution (3 mL, 4.5 equiv.) at -30°C. After the resulting clear solution was stirred at -30°C for 15 minutes, a solution of L ligand (2.0 g, 1.98 mmol) in 20 mL of dry toluene was added very slowly at -30°C (the flask was rinsed with toluene, 3 x 10 mL). The resulting cloudy brown mixture was stirred at -30°C for one hour, then warmed to room temperature overnight in a cold bath. The reaction was dried under vacuum and then extracted with heptane (3 x 100 mL). The heptane layers were combined and concentrated to provide the final precatalyst as a whitish solid (1.33 g, 59%).1H (400 MHz, tolueno-d8) δ ppm 8,58 (d, J = 1,4 Hz, 1 H), 8,53 (d, J = 1,4 Hz, 1H), 8,30 (d, J = 1,3 Hz, 1 H), 8,24 (d, J = 1,2 Hz, 1 H), 7,55 (dd, J = 8,7, 2,0 Hz, 1 H), 7,58 (dd, J = 8,7, 2,0 Hz, 1 H), 7,44 (d, J = 8,7 Hz , 1H), 7,43 (d, J = 8,7 Hz, 1H), 7,49 (d, J = 8,7Hz, 1H), 7,46 (d, J = 8,7 Hz, 1H), 7,30 (dd, J = 8,6, 2,0 Hz, 2 H), 7,26 (dd, J = 8,7, 2,0 Hz, 1 H), 7,25 (ddd, J = 8,1,3,7, 1,8 Hz, 1 H), 7,15 (d, J = 4309,8 Hz, 1 H), 7,09 (d, J = 2,2 Hz, 1 H), 7,05 (d, J = 2,1 Hz, 1 H), 6,84 (t, J = 8,0 Hz, 1 H), 6,77 (d, J = 7,6 Hz, 1 H), 6,69 - 6,75 (m, 2 H), 5,77 (d, J = 8,3 Hz, 1 H), 5,05 (dd, J = 6,1, 3,4 Hz, 1 H), 4,17 (br t, J =10,8Hz, 1H), 3,53 (br t, J=12,0 Hz, 1H), 2,93 (br d, J=9,5 Hz, 1H), 2,28 (s, 3H), 2,21 (s, 3H) , 1,88 (s, 3 H), 1,61 (s, 9 H), 1,57 (s, 9 H), 1,49 (br d, J = 14,0 Hz, 1 H), 1,30 (s, 9 H), 1,26 (s , 9H), 0,42 (br d, J=14,0 Hz, 1H), -0,99 (s, 3H), -1,27 (s, 3H). Polimerização em Solução

[0126] Continuous solution polymerizations were conducted in a continuous polymerization unit (CPU) using cyclohexane as the solvent. The CPU contained a 71.5 mL stirred reactor and was operated at a temperature of 140°C or 160°C for the polymerization experiments. An upstream mixing reactor with a volume of 20 mL was operated at 5°C lower than the polymerization reactor. The mixing reactor was used to preheat the ethylene, 1-octene, and some of the solvent streams. Catalyst feeds (xylene solutions) Petition 870240079715, dated 09 / 18 / 2024, pp. 45 / 60 36 / 44 or cyclohexane from the pre-catalyst complex and (Ph3C)[B(C6F5)4] as a catalyst activator) and additional solvent were added directly to the polymerization reactor in a continuous process. Additional feeds of MMAO-7 and 2,6-di-tert-butyl-4-ethylphenol (BHEB) and solvent are premixed to passivate the trimethylaluminum (TMA) before entering the polymerization unit. A continuous total flow rate of 27 mL / min was maintained in the polymerization reactor.

[0127] The copolymers were prepared at a 1-octene / ethylene weight ratio of 0.1 to 0.5. Ethylene was fed at a concentration of 10% by weight of ethylene into the polymerization reactor. The CPU system operated at a pressure of 10.5 MPa. The solvent, monomer, and comonomer streams were all purified by the CPU systems before entering the reactor. The polymerization activity, kp (expressed in mM-1· min-1), is defined as: kp = (1õo^õ) ([M]) (hüt) where Q is the ethylene conversion (%) (measured using an in-line gas chromatograph (GC)), [M] is the catalyst concentration in the reactor (mM), and HUT is the holding time in the reactor (2.6 min).

[0128] The copolymer samples were generally collected at 90±1% ethylene conversion (Q), vacuum oven dried, milled, and then analyzed using FTIR (for short chain branching frequency) and GPC-RI (for molecular weight and distribution). The polymerization conditions are listed in Table 1 and the copolymer properties are listed in Table 2.

[0129] The ethylene copolymerizations of the invention with 1-octene using the precatalyst of Example No. 1 (the hafnium-based catalyst) were carried out as polymerization runs Nos. 1 to 4.

[0130] The ethylene copolymerizations of the invention with 1-octene using the precatalyst of Example No. 2 (the zirconium-based catalyst) were carried out as polymerization runs Nos. 5 to 9. Petition 870240079715, dated 09 / 18 / 2024, pp. 46 / 60 37 / 44

[0131] Comparative copolymerizations of ethylene with 1-octene using the catalyst (cyclopentadienyl)((t-Bu)3PN)TiCl2, as a comparator, were carried out in polymerization runs Nos. 10 and 11. Feeds of catalysts (xylene solutions of (cyclopentadienyl)((t-Bu)3PN)TiCl2, (Ph3C)[B(C6F5)4] and MMAO-7 / BHEB) and additional solvent were added directly to the polymerization reactor in a continuous process. The MMAO-7 and BHEB solution streams were combined before the reactor to ensure that all phenolic OH had been passivated through reaction with MMAO-7 before reaching the reactor. TABLE 1 Ethylene / 1-octene copolymerization conditions Polymerization Run No. Catalyst Example No. [Target I] (μΜ) B (from borate) / M Al (from MM AO -7) / M BH EB / Al Tem Ρdo Rea tor (° C) Flux o C2 (g / min) 08 / C2 Conversions from C2, Q (%) kP (mM -1 • min-1) 1 1 Hf, 21.48 1.2 0.93 0.3 160 2.7 0.3 86.15 111 2 1 Hf, 13.33 1.2 0.89 0.3 140 2.1 0.3 89.16 237 3 1 Hf, 13.33 1.2 0.93 0.3 140 2.1 0.5 90.28 268 4 1 Hf, 12.59 1.2 0.94 0.3 140 2.1 0.1 5 89.81 269 5 2 Zr, 25.93 1.2 0.77 0 190 3.5 0.1 75.91 47 6 2 Zr, 7.41 1.2 2.7 0 140 2.1 0.1 5 89.89 462 7 2 Zr, 8.89 1.2 2.25 0 140 2.1 0.3 90.49 412 8 2 Zr, 8.89 1.2 2.25 0 140 2.1 0.5 89.76 379 9 2 Zr, 25.93 1.2 0.77 0 160 2.7 0 88.57 115 10 Comp Ti, 0.18 0.21 14.07 4.2 2 140 2.1 0.1 5 89.52 186 75 11 Comp. Ti, 0.24 0.24 16.30 4.8 9 140 2.1 0.3 0 89.85 167 14 Note: C2 = ethylene; C8 = 1-octene Petition 870240079715, dated 09 / 18 / 2024, pp. 47 / 60 38 / 44 TABLE 2 Copolymer Properties Polymerization Run No. Catalyst Example No. FTIR Content of 1 octene (percentage by weight, wt%) Short chain branching FTIR per 1000 carbon atoms (SCB / 1000 C) Mw Mn Mw / Mn 1 1 6.4 8.4 2442 58 1121 77 2.18 2 1 6.8 9.0 3367 56 1451 74 2.32 3 1 11.4 15.5 3003 83 1047 76 2.87 4 1 3.7 4.8 4424 08 1519 15 2.91 5 2 1.3 1.6 1867 33 9726 9 1.92 6 2 2.8 3.6 2627 39 1276 27 2.06 7 2 5.6 7.4 2702 45 1049 35 2.58 8 2 8.2 10.9 2621 71 1158 96 2.26 9 2 N / AN / A 2350 78 1129 78 2.08 10 Comp 2.3 2.9 1930 20 1160 80 1.66 11 Comp. 4.2 5.4 1430 22 1018 97 1.64

[0132] A person skilled in the art will see from the data provided in Tables 1 and 2 that, under similar copolymerization conditions, the catalysts of Examples of the Invention 1 and 2 provide ethylene copolymers of similar or higher molecular weight compared to the comparative catalyst system, while incorporating a greater amount of comonomer (i.e., 1-octene) as indicated by the amount of short-chain branching per thousand carbon atoms of the main chain. The novel tetradentate catalysts of Examples of the Invention 1 and 2, and especially the hafnium-based catalyst of Example 1, therefore provide ethylene / 1-octene copolymers with good comonomer incorporation and good molecular weight when used in a solution-phase polymerization process. Petition 870240079715, dated 09 / 18 / 2024, pp. 48 / 60 39 / 44

[0133] The non-limiting applications of this description include the following:

[0134] Engine A. A polymerization process comprising polymerizing ethylene with one or more C3-12 alpha olefins in the presence of a polymerization catalyst system comprising: i) a catalyst composition having the formula: THE where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; Each R2 is independently an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; Each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group or a hydrocarbyl group containing an optionally substituted heteroatom; L is an optionally substituted divalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted divalent heteroatom; Optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable output group; and Petition 870240079715, dated 09 / 18 / 2024, pp. 49 / 60 40 / 44 ii) a catalyst activator.

[0135] Modality B. The polymerization process of Mode A, where each R2 has the formula: jwyw\

[0136] Modality C. The polymerization process of Mode A or B, where L is a divalent hydrocarbyl group.

[0137] Modality D. The polymerization process of Modality A, B or C, where L is a divalent n-propyl group having the formula: -CH2CH2CH2-.

[0138] Modality E. The polymerization process of Modality A, B, C or D, where A2 and A8 are each a methyl group.

[0139] Modality F. The polymerization process of Modality A, B, C, D or E, where A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each hydrogen.

[0140] Modality G. The polymerization process of Modality A, B, C, D, E or F, where R1 is a methyl group.

[0141] Modality H. The polymerization process of Modality A, B, C, D, E, F or G, in which the polymerization process is a solution-phase polymerization process carried out in a solvent.

[0142] Modality I. The polymerization process of Modality A, B, C, D, E, F, G or H, wherein the polymerization process comprises polymerizing ethylene with 1-octene.

[0143] Modality J. A prepolymerization catalyst for olefins having the formula: Petition 870240079715, dated 09 / 18 / 2024, pp. 50 / 60 41 / 44 where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; Each R2 is independently an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; Each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group or a hydrocarbyl group containing an optionally substituted heteroatom; L is an optionally substituted divalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted divalent heteroatom; Optionally, two or more adjacent A groups can form part of a ring structure; and each X is independently an activatable output group.

[0144] K-mode. The prepolymerization catalyst of the J-mode, in which each R2 has the formula: Petition 870240079715, dated 09 / 18 / 2024, pp. 51 / 60 42 / 44

[0145] L Mode. The J or K Mode prepolymerization catalyst, where L is a divalent hydrocarbyl group.

[0146] Mode M. The prepolymerization catalyst of Mode J, K or L, where L is a divalent n-propyl group having the formula: -CH2CH2CH2-.

[0147] Modality N. The prepolymerization catalyst of Modality J, K, L or M, where A2 and A8 are each a methyl group.

[0148] Mode O. The prepolymerization catalyst of Mode J, K, L, M or N, where A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each hydrogen.

[0149] Mode P. The prepolymerization catalyst of Mode J, K, L, M, N or O, where R1 is a methyl group.

[0150] Q-Mode. An olefin polymerization catalyst system comprising: i) a catalyst composition having the formula: Petition 870240079715, dated 09 / 18 / 2024, pp. 52 / 60 43 / 44 where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; Each R2 is independently an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; Each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group or a hydrocarbyl group containing an optionally substituted heteroatom; L is an optionally substituted divalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted divalent heteroatom; Optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group; and ii) a catalyst activator. Industrial Application

[0151] Novel polymerization catalysts having a tetradentate ligand are used to copolymerize ethylene with an alpha olefin. The novel polymerization catalysts represent examples of post-metallocene catalysts that Petition 870240079715, dated 09 / 18 / 2024, pp. 53 / 60 44 / 44 can be used in a solution-phase olefin polymerization process.

Claims

1. Polymerization process CHARACTERIZED in that it comprises polymerizing ethylene with one or more C3-12 alpha olefins in the presence of a polymerization catalyst system comprising: i) a catalyst composition having the formula: A wherein M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group or a hydrocarbyl group containing an optionally substituted heteroatom; each R2 is independently an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group or a hydrocarbyl group containing an optionally substituted heteroatom; L is an optionally substituted divalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted divalent heteroatom;Optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group; and Petition 870240079715, dated 09 / 18 / 2024, page 55 / 60 2 / 5 ii) a catalyst activator.; 2. Polymerization process according to claim 1, CHARACTERIZED in that each R2 has the formula: jvvyvvx 3. Polymerization process according to claim 2, CHARACTERIZED in that L is a divalent hydrocarbyl group, wherein optionally L is a divalent n-propyl group having the formula: -CH2CH2CH2-.

4. Polymerization process according to claim 3, CHARACTERIZED in that each A2 and A8 is a methyl group.

5. Polymerization process, according to claim 4, CHARACTERIZED in that each A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 is a hydrogen.

6. Polymerization process according to claim 5, CHARACTERIZED in that R1 is a methyl group.

7. Polymerization process, according to claim 1, CHARACTERIZED in that the polymerization process is a solution-phase polymerization process carried out in a solvent.

8. Polymerization process according to claim 7, CHARACTERIZED in that the polymerization process comprises polymerizing ethylene with 1-octene.

9. Olefin prepolymerization catalyst CHARACTERIZED by the fact that it has the formula: Petition 870240079715, dated 09 / 18 / 2024, page 56 / 60 3 / 5 where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group or a hydrocarbyl group containing an optionally substituted heteroatom; each R2 is independently an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group or a hydrocarbyl group containing an optionally substituted heteroatom; L is an optionally substituted divalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted divalent heteroatom; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group.

10. Pre-polymerization catalyst, according to claim 9, CHARACTERIZED in that each R2 has the formula: Petition 870240079715, dated 09 / 18 / 2024, page 57 / 60 4 / 5 JWVVVX 11. Prepolymerization catalyst, according to claim 10, CHARACTERIZED in that L is a divalent hydrocarbyl group, wherein optionally L is a divalent n-propyl group having the formula: -CH2CH2CH2-.

12. Prepolymerization catalyst, according to claim 11, CHARACTERIZED in that each A2 and A8 is a methyl group.

13. Prepolymerization catalyst, according to claim 12, CHARACTERIZED in that each A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 is a hydrogen.

14. Prepolymerization catalyst, according to claim 13, CHARACTERIZED in that R1 is a methyl group.

15. Olefin polymerization catalyst system CHARACTERIZED in that it comprises: i) a catalyst composition having the formula: Petition 870240079715, dated 09 / 18 / 2024, page.58 / 60 5 / 5 A where M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each R2 is independently an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; each of A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, and A12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom-containing hydrocarbyl group; L is an optionally substituted divalent hydrocarbyl group, or an optionally substituted divalent heteroatom-containing hydrocarbyl group; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an activatable leaving group; and ii) a catalyst activator.