POLYMERIZATION CATALYST HAVING A TETRADENTATE LIGAND

Abstract

A novel olefin polymerization catalyst is linked with a tetradentate ligand having a phenoxy / amino / ether / phenoxy (O / N / O / O) atom donor group. The new zirconium- or hafnium-based polymerization catalyst produces a high-molecular-weight ethylene copolymer with high comonomer incorporation.

Description

A novel polymerization catalyst with a tetradentate ligand is used to copolymerize ethylene with alpha-definin. The novel zirconium- or hafnium-based polymerization catalyst is linked with a ligand having a phenoxy / amino / ether / phenoxy (O / N / O / O) atom donor group. Background of the Invention Since their initial discovery, the use of post-metallocene olefin polymerization catalysts carrying polyvalent aryloxyether ligands has become a well-developed field of technology, with numerous catalyst variants available in the patent literature. These catalysts are particularly notable for their ability to perform well in high-temperature solution polymerization processes. Summary of the Invention In an effort to expand the scope of these post-metallocene catalysts and their use in a solution-phase polymerization process, we have discovered a novel olefin polymerization catalyst linked with a Ref. 335974 tetradentate ligand having a donor set of phenoxy / amino / ether / phenoxy atoms (O / N / O / O). 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 catalytic polymerization system comprising: i) a catalytic composition having the formula: 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 ii) a catalyst activator. One modality of the description is an olefin prepolymerization catalyst that has the 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 a QPCRnn / zznz / E / YiAi optionally substituted bivalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted bivalent heteroatom; optionally, two or more adjacent A groups may form part of a ring structure; and each X is independently an active leaving group. One modality of the description is a catalytic system for the polymerization of olefins comprising: i) a catalytic composition having the 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; and ii) a catalyst activator. Detailed Description of the Invention The olefin polymerization catalysts described herein typically require activation by one or more cocatalytic or activating species to yield polymers from olefins. Therefore, an unactivated olefin polymerization catalyst can be described as an olefin prepolymerization catalyst. The olefin polymerization catalyst employed in the present description is one having a tetradentate ligand, one having a phenoxy / amino / ether / phenoxy (O / N / O / O) atom donor group. The definis 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. The prepolymerization catalyst used in one modality 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 group, 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. 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 in one hydrogen. The term cyclic denotes hydrocarbyl groups or hydrocarbyl groups containing heteroatoms 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 hydrocarbyl groups containing heteroatoms that do not have cyclic moieties such as aromatic or non-aromatic ring structures present within them. As used herein, the term heteroatom includes any atom other than carbon and hydrogen that can bond to carbon. The term containing heteroatoms or hydrocarbyl group containing heteroatoms means that one or more atoms other than carbon 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 hydrocarbyl group containing a heteroatom are N, O, S, P, B, and Si, as well as halides such as Br and metals such as Sn. Some non-limiting examples of hydrocarbyl groups containing heteroatoms include imines, amine fractions, oxide fractions, phosphine fractions, ethers, ketones, heterocyclines, oxazolines, thioethers, and the like. As used herein, the term substituted means that the group to which this term refers has one or more residues that have replaced one or more hydrogen radicals at any position within the group; non-limiting examples of residues 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, naphthyl groups, C1 to C10 alkyl groups, C2 to C10 alkenyl groups and combinations thereof. The use of the term "optional" or "optionally" implies that the circumstance described below may or may not occur or be present, and that the description includes instances where the circumstance occurs and instances where it does not. 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 an unsubstituted hydrocarbyl group. A divalent hydrocarbyl group is a hydrocarbyl group that joins two molecular residues. Divalent hydrocarbyl groups include alkylene, alkenylene, and alguinylene groups, which may be optionally substituted. Divalent hydrocarbyl groups also include aryl residues that are attached at two points to atoms, molecules, or residues; these two points of attachment are covalent bonds. A hydrocarbyl group containing a divalent heteroatom 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 hydrocarbyl group containing a divalent heteroatom are N, O, S, P, and Si, as well as halides such as Br and metals such as Sn. As used herein, an alkyl radical QPCRnn / zznz / E / YiAi The 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. In one form of the description, an alkyl group has from 1 to approximately 50 carbon atoms. In the description, an alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. In one form of the description, an alkyl group contains from 1 to 12 carbon atoms. A substituted alkyl refers to an alkyl substituted with 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 replaced with a heteroatom (e.g., -CH2OCH3 is an example of a heteroalkyl). 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 in a hydrogen radical. In one sense, 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 alkenyl groups include ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, and the like. In one form of the description, an alkenyl group contains from 2 to approximately 12 carbon atoms. A substituted alkenyl refers to an alkenyl substituted with one or more substituent groups, and the terms alkenyl containing a heteroatom, an alkenyl group containing a heteroatom, and heteroalkenyl refer to an alkenyl group in which at least one carbon atom is replaced with a heteroatom. 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 sense, an alkynyl group is a branched or unbranched hydrocarbon group containing 2 to 50 carbon atoms and at least one triple bond. Some non-limiting examples of alkynyl groups include ethynyl, n-propynyl, isopropynyl, n-butynyl, isobutynyl, octinyl, decynyl, and the like. In one form of the description, an alkynyl group has from 2 to 12 carbon atoms. A substituted alkynyl refers to an alkynyl substituted with one or more substituent groups, and the terms heteroatom-containing alkynyl and heteroalkynyl refer to an alkynyl in which at least one carbon atom is replaced with a heteroatom. As used herein, 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 with one or more alkyl groups attached to it; non-limiting examples include benzyl, phenethyl, and tolylmethyl. An arylalkyl group is an aryl group with one or more alkyl groups attached to it; non-limiting examples include tolyl, xylyl, mesityl, and cumyl. Substituted aryl refers to an aryl group substituted with one or more substituent groups (e.g., tolyl, mesityl, and perfluorophenyl) and the terms aryl containing heteroatoms and heteroaryl refer to aryl in which at least one carbon atom is replaced with a heteroatom (e.g., rings such as thiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, etc., or benzo-fused analogues of these rings are included in the term heteroaryl). In some embodiments of this document, the multi-ring moieties are substituents, and in such embodiments, the multi-ring moiety can be attached to an appropriate atom. For example, naphthyl can be 1-naphthyl or 2-naphthyl; anthracenyl can be 1-anthracenyl, 2-anthracenyl, or 9-anthracenyl; and phenanthrenyl can be 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, or 9-phenanthrenyl. The terms halide and halogen are conventionally used 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 with a halogen atom. In one modality of the description, a hydrocarbyl group containing a heteroatom is a hydrocarbyl group containing 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur. The terms hydrocarbyl containing cyclic heteroatom or heterocyclic refer to ring systems having a carbon skeleton that further comprises at least one heteroatom selected from the group consisting, for example, of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur. An alkoxy group is an oxy group that has an alkyl group attached to it; and includes, for example, a methoxy group, an ethoxy group, an isopropoxy group, and the like. An aryloxy group is an oxy group that has an aryl group attached to it; and includes, for example, a phenoxy group and the like. In one modality of the description, a prepolymerization catalyst of definites 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. In one modality of the description, a catalytic polymerization system of defines comprises: i) a catalytic composition having the formula: 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 ii) a catalyst activator. In one embodiment of the description, each R2 is independently an optionally substituted aryl group or an aryl group containing an optionally substituted heteroatom. In one embodiment of the description, each R2 is independently an aryl group containing an optionally substituted heteroatom. In one form of the description, each R2 is independently an aryl group containing a substituted heteroatom. In one form of the description, each R2 is an aryl group containing a substituted heteroatom. In one version of the description, each R2 has the formula: In one embodiment of the description, L is an optionally substituted bivalent hydrocarbyl group. In one form of the description, L is a bivalent hydrocarbon group. In one form of the description, L is a bivalent alkylene group. In one form of the description, L is a bivalent cycloalkylene group. In one form of the description, L is a bivalent aryl group. In one form of the description, L is a bivalent alkylene group that has 2 to 8 carbon atoms. In one form of the description, L is a divalent n-propyl group that has the formula: -CH2CH2CH2-. In one embodiment of the description, A2 and A8 are independently an optionally substituted hydrocarbon group or a hydrocarbon group containing an optionally substituted heteroatom. In one embodiment of the description, A2 and A8 are independently an optionally substituted hydrocarbon group. In one form of the description, A2 and A8 are independently a hydrocarbon group. In one form of the description, A2 and A8 are independently an optionally substituted alkyl group. In one form of the description, A2 and A8 are independently an alkyl group. In one form of the description, A2 and A8 are each an alkyl group having from 1 to 20 carbon atoms. In one form of the description, A2 and A8 are each an alkyl group having from 1 to 8 carbon atoms. In one version of the description, A2 and A8 are each a methyl group. In one form of the description. A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each hydrogen or a halide. In one modality of the description, A1, A3, A4, A5,A A7, A9, A10, A11 and A12 are each hydrogen. In one of the description modes. A1, A3, A4, A5, A A7, A9, A10, A11 and A12 are each hydrogen or fluoride. In one modality of the description, A1, A3, A4, A5,A A7, A9, A10, A11 and A12 are each a halide. In one of the description modes. A1, A3, A4, A5, A A7, A9, A10, A11, and A12 are each a fluoride. In one embodiment of the description, R1 is an optionally substituted hydrocarbyl group or a hydrocarbyl group containing an optionally substituted heteroatom. In one version of the description, R1 is hydrogen. In one form of the description, R1 is an optionally substituted hydrocarbyl group. In one form of the description, R1 is a substituted hydrocarbyl group. In one form of the description, R1 is a hydrocarbyl group. In one form of the description, R1 is an optionally substituted alkyl group. In one form of the description, R1 is a substituted alkyl group. In one form of the description, R1 is a group QPCRnn / zznz / E / YiAi substituted alkyl having one or more halide atoms. In one form of the description, R1 is a substituted alkyl group having one or more fluoride atoms. In one form of the description, R1 is an alkyl group. In one form of the description, R1 is an alkyl group having 1 to 20 carbon atoms. In one form of the description, R1 is an alkyl group having 1 to 8 carbon atoms. In one version of the description, R1 is a methyl group. In the current description, the term "activatable" means that the ligand X can be cleaved from the metal center M via a protonolysis reaction or abstracted from the metal center M by activating compounds of suitable electrophilic catalysts or acids (also known as cocatalyst compounds), respectively, examples of which are described below. The activatable ligand X can also be transformed into another ligand that cleaves or abstracts from the metal center M (e.g., a halide can be converted into an alkyl group). Without intending to limit oneself to any single theory, the protonolysis or abstraction reactions generate an active cationic metal center that can polymerize olefins. 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 hydrocarbyl radical Ci-io; an alkoxy radical Ci-io; and an aryl or aryloxy radical Ce-io, wherein each of the hydrocarbyl, alkoxy, aryl, or aryl oxide radicals may be unsubstituted or further substituted by one or more halogens or another group; an alkyl Ci-s; an alkoxy Ci-s; an aryl or aryloxy Ce-io; an amido or phosphide radical, but wherein X is not a cyclopentadienyl. Two ligands X may also be joined together to 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 selected independently from the group which consists of a halide atom, a C1-4 alkyl radical, and a benzyl radical. In one modality, particularly suitable activatable ligands are monoanionic such as a halide (e.g., chloride) or a hydrocarbyl (e.g., methyl, benzyl). The catalyst activator (or simply the activator for short) used to activate the polymerization catalyst of definis can be any suitable activator that includes one or more activators selected from the group consisting of alkylaluminoxanes and ionic activators, optionally together with an alkylating agent. Without intending to be limited to any theory, alkylaluminoxanes are believed to be complex aluminum compounds of formula: R32A11O (R3A11O) mAl1R32, wherein each R3 is independently selected from the group consisting of C1-20 hydrocarbyl radicals and m is from 3 to 50. Optionally, a hindered phenol can be added to the alkylaluminoxane to provide a molar ratio of Al1:hindered phenol of 2:1 to 5:1 when the hindered phenol is present. In one form of the description, R3 of alkylaluminoxane is a methyl radical and m is from 10 to 40. Alkylluminoxanes are typically used in a substantial molar excess compared to the amount of olefin polymerization catalyst. The molar ratios of Al1:metal in the olefin polymerization catalyst can range from approximately 10:1 to approximately 10,000:1, preferably from approximately 30:1 to approximately 500:1. In one embodiment of the description, the catalyst activator comprises methylaluminoxane (MAO). In one embodiment of the description, the catalyst activator comprises modified methylaluminoxane (MMAO). It is well known in the field that alkylaluminoxane can perform dual functions as an alkylating agent and an activator. Therefore, an alkylaluminoxane activator is often used in combination with activatable ligands such as halogens. Alternatively, the catalyst activator described herein may be a combination of an alkylating agent (which may also serve as a scrubber) with an activator capable of ionizing the group 4 metal of the olefin polymerization catalyst, or a precatalyst (i.e., an ionic activator). In this context, the activator may be selected from one or more alkylaluminoxanes and / or an ionic activator, since an alkylaluminoxane can serve as both an activator and an alkylating agent. When present, the alkylating agent can be selected from the group consisting of (R4)pMgX22-P where X2 is a halide and each R4 is independently selected from the group consisting of Ci-io alkyl radicals and p is 1 or 2; QPCRnn / zznz / E / YiAi R4Li where R4 is as defined above, (R4)qZnX22-q where R4 is as defined above, X2 is a halogen, and q is 1 or 2; and (R4)sAl2X23-s where R4 is as defined above, X2 is a halogen, and s is an integer from 1 to 3. In the embodiments of the description, in the above compounds, R4 is a C1-4 alkyl radical and X2 is chlorine. Commercially available compounds include triethylaluminum (TEAL), trimethylaluminum, triisobutylaluminum, tributylaluminum, diethylaluminum chloride (DEAC), dibutylmagnesium (BuHMg), and butylethylmagnesium (BuEtMg or BuMgEt). Alkylluminoxanes can also be used as alkylating agents. The ionic activator can be selected from the group consisting of: (i) compounds of formula [R5]+[B(R6)4]- where B is a boron atom, R5 is a C5-7 cyclic aromatic cation or a triphenyl methyl cation, and each R6 is independently selected from the group consisting of phenyl radicals that are either unsubstituted or substituted with 3 to 5 substituents selected from the group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical that is either unsubstituted or substituted with a fluorine atom; and a silyl radical of formula -Si-(R7)3; where 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)tZH]+[B(R6)4]- where B is a QPCRnn / zznz / E / YiAi 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 Ci-s alkyl radicals, a phenyl radical that is either unsubstituted or substituted by up to three C1-4 alkyl radicals, or an R8 taken together with the nitrogen atom can form an anilinium radical and R6 is as defined above; and (iii) compounds of formula B(R6)3 wherein R6 is as defined above. In the description, in the above compounds, R6 is a pentafluorophenyl radical and R5 is a triphenylmethyl cation, Z is a nitrogen atom and R8 is a C1-4 alkyl radical or R8 taken together with the nitrogen atom forms an anilinium radical that is substituted by two C1-4 alkyl radicals. 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, and trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,pdimethylphenyl)boron, tributylammonium tetra(m,mdimethylphenyl)boron, tributylammonium tetra(ptrifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o25tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron, N,N QPCRnn / zznz / E / YiAi diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N-2, 4, 6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)amonium tetra(pentafInorophenyl)boron, dicyclohexylamonium tetra(phenyl)boron, triphenylphosphonium tetra)phenyl)boron, tri(methylphenyl))phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, borato de tetrakispentafluorofenilo de tropillo, borato de tetrakispentafluorofenilo de tripenilmetilio, borato de tetrakispentafluorofenilo de benceno(diazonio), borato de feniltris-pentafluorofenilo de tropillo, borato de triphenylmethyl phenyltrispentafluorophenyl, benceno(diazonium) phenyltrispentafluorophenyl borate, triphenylmethyl tetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyl tetrakis(3,4,5-trifluorophenyl)borate, benceno(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate de tropillo, tetrakis(3,4,5-trifluorophenyl)borate de benceno(diazonium), tetrakis(1,2,tropillo 2-trifluoroethenyl)borate, trophenylmethyl tetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium) tetrakis(1,2,2-trifluoroethenyl)borate, tropillo 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., Commercially available activators that are capable of ionizing the phosphinimide catalyst include: N,N-dimethylanilinium tetrakispentafluorophenyl borate ([Me2NHPh][B(CgFs)4]); triphenylmethyl tetrakispentafluorophenyl borate ([PhaC][B(CeFs)4]); and trispentafluorophenyl boron. 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 of 1:1 to 1:6. Optionally, mixtures of alkylaluminoxanes and ionic activators can be used as activators for the olefin polymerization catalyst. The olefin prepolymerization catalysts described herein can be used in any conventional olefin polymerization process, such as gas-phase polymerization, suspension-phase polymerization, or solution-phase polymerization. A heterogenized catalyst system is preferred for gas-phase and suspension-phase polymerization, while a homogeneous catalyst is preferred for solution-phase polymerization. A heterogenized catalyst system supporting a prepolymerization catalyst, optionally along with an activator, can be formed on a support, such as a silica support, as is well known to those skilled in the art. Solution polymerization processes for the polymerization or copolymerization of ethylene are well known in the art (see, for example, U.S. Patents 6,372,864 and 6,777,509). These processes are carried out in the presence of an inert hydrocarbon solvent, typically a C5-12 hydrocarbon that may or may not be substituted with a C1-4 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 (Cg-12 aliphatic solvent, Exxon Chemical Co.). The polymerization temperature in a conventional solution process is approximately 80°C to approximately 300°C. In one embodiment of the description, the polymerization temperature in a solution process is approximately 120°C to approximately 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 approximately 6000 psi (approximately 42,000 kilopascals or kPa). In one embodiment of the description, the polymerization pressure in a solution process can be approximately 10,000 to approximately 40,000 kPa, or approximately 14,000 to approximately 22,000 kPa (i.e., approximately 2000 psi to approximately 3000 psi). Suitable monomers for copolymerization with ethylene include mono- and C3-20 diolefins. Comonomers include C3-12 alpha diolefins that are unsubstituted or substituted with up to two C1-6 alkyl radicals, Cs-12 vinylaromatic monomers that are unsubstituted or substituted with up to two substituents selected from the group consisting of C1-4 alkyl radicals, and linear or cyclic C4-12 diolefins that are unsubstituted or substituted with a C1-4 alkyl radical. Non-limiting illustrative examples of such alpha-olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, styrene, alpha-methylstyrene and the ring-restricted cyclic olefins such as cyclobutene, cyclopentene, dicyclopentadiene, norbornene, alkyl-substituted norbornenes, alkenyl-substituted norbornenes and the like (e.g., 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, bicyclo-(2,2,1)-hepta-2,5-diene). In embodiments, the polyethylene polymers that can be prepared according to the present description are LLDPE and may comprise not less than 60 or not less than 75% by weight of ethylene, with the remainder being one or more C4-10 alpha olefins, such as alpha-olefins selected from QPCRnn / zznz / E / YiAi group consisting of 1-butene, 1-hexene and 1-octene. In the description, the alpha olefin present in a polyethylene polymer may be present in an amount of approximately 3 to 30% by weight, or approximately 4 to 25% by weight. The polyethylene prepared according to this description can be LLDPE with a density of approximately 0.910 to 0.935 g / cm³ or high-density (linear) polyethylene with a density greater than 0.935 g / cm³. This description could also be useful for preparing polyethylene with a density less than 0.910 g / cm³, known as very low and ultra-low density polyethylenes. This description can also be used to prepare copolymers and terpolymers of ethylene, propylene, and optionally one or more diene monomers. Generally, such polymers will contain 50 to 75 wt% ethylene, or 50 to 60 wt% ethylene and correspondingly 50 to 25 wt% propylene. A portion of the monomers, typically the propylene monomer, can be replaced by a conjugated diolefin. The diolefin can be present in amounts up to 10 wt% of the polymer, although it is typically present in amounts of approximately 3 to 5 wt%. The resulting polymer can have a composition comprising 40 to 75 wt% ethylene, 50 to 15 wt% propylene, and up to 10 wt% of a diene monomer to provide 100 wt% 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-2-norbornene and 1,4-hexadiene. In solution polymerization, the 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 to dissolve in the reaction mixture). Before mixing, the solvent and monomers are generally purified to remove potential catalyst poisons, such as water, oxygen, or metallic impurities. Purification of the raw materials follows standard practices in the art; for example, molecular sieves, alumina beds, and oxygen-scavenging catalysts are used for monomer purification. The solvent itself (e.g., methylpentane, cyclohexane, hexane, or toluene) can also be treated similarly. The raw material can be heated or cooled before being fed into the reactor. In general, the catalyst components (the prepolymerization catalyst, an ionic activator, and optionally, an alkylaluminoxane) can be premixed in the solvent for the reaction or fed as separate streams to the reactor. In some cases, it may be QPCAnn / zznz / E / YiAi It is desirable to premix to provide reaction time for the catalyst components before they enter the reaction. The in-line mixing technique is described in a number of patents held by DuPont Canada Inc. (e.g., U.S. Patent No. 5,589,555 issued December 31, 1996). One embodiment of the description is a polymerization process comprising optionally polymerizing ethylene with one or more C3-12 alpha definite bonds in the presence of a catalytic polymerization system comprising: i) a catalytic composition having the formula: 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, 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. In one modality of the description, the polymerization process is a solution-phase polymerization process carried out in a solvent. In one embodiment of the description, the polymerization process comprises polymerizing ethylene with one or more C3-12 alpha definites. In one embodiment of the description, the polymerization process comprises polymerizing ethylene with 1-octene. The following examples provide additional, non-limiting details of the description. These examples are presented to illustrate selected embodiments of this description, it being understood that the examples presented do not limit the claims presented. Examples General Experimental Methods All reactions were performed under nitrogen using standard Schlenk techniques or in an inert atmosphere glovebox. 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 glovebox. 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(pentafluoropheni-1)borate was purchased from Albemarle Corp. and used as received. The deuterated NMR solvents, toluene-δ8 and dichloromethane-δ2, were purchased from Aldrich and stored on 13X molecular sieves prior to use.NMR spectra were recorded on a Bruker 400 MHz spectrometer (:H: 400.1 MHz). Molecular weight (Mw, Mn, Mz, g / mol) and molecular weight distribution (Mw / Mn) and average molecular weight distribution (Mz / Mw) were analyzed by gel permeation chromatography (GPC) using a Waters 150c instrument with 1,2,4-trichlorobenzene as the mobile phase at 140°C. Samples were prepared by dissolving the polymer in this solvent and processed without filtration. Molecular weights are expressed as polyethylene equivalents with a relative standard deviation of 2.9% for number-average molecular weight (Mn) and 5.0% for 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 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 to stabilize the polymer against oxidative degradation.The BHT concentration was 250 ppm. Sample solutions were chromatographically analyzed at 140 °C using a PL 220 high-temperature chromatography unit equipped with four SHODEX columns (HT803, HT804, HT805, and HT806) with TCB as the mobile phase at a flow rate of 1.0 mL / min, and a differential refractive index (DRI) 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 D6474. The branching frequency of the copolymer samples (i.e., short-chain branching, SCB, per 1000 carbon atoms of the backbone) and the C8 comonomer content (in wt.%) were determined by Fourier transform infrared spectroscopy (FTIR) according to ASTM D6645-01. A Thermo-Nicolet 750 Magna-IR spectrophotometer equipped with OMNIC® software version 7.2a was used for the measurements. The branching frequency as a function of molecular weight (and therefore the comonomer distribution) was determined by high-temperature gel permeation chromatography (GPC) and FT-IR spectroscopy of the eluent. Polyethylene standards with known branching content, polystyrene, and hydrocarbons with known molecular weight were used for calibration. Synthesis of catalysts The general synthetic steps and methods used to prepare the ligand, L, and the precatalysts of the Examples 1 and 2 are provided below. QPCRnn / zznz / E / YiAi Compound A: i) NaH, 0°C ¡i) Mel, O°Cata To a 200 mL Schlenk flask charged with 45.7 mmol (10 g) of 2-iodoaniline in 90 mL of dry THE, NaH (2.009 g, 1.1 equiv., 60% in dispensing oil) was slowly added at 0°C. After stirring the resulting pale gray suspension at 0°C for one hour, it was then slowly heated to room temperature, followed by the dropwise addition of Mel (3.2 mL, 1.1 equiv.) at 0°C. After stirring the reaction 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 yield a deep red oil (10.24 g, 94%). The 1H NMR indicates approximately 15% overalkylation product. The crude product was subjected to the following reaction without further purification. 1H NMR (400 MHz, CD2CI2, 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=5Hz). Compound B: 2-Iodophenol (11.0 g, 50 mmol) in 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 then 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 to dryness. An aqueous solution of NaOH (100 mL, 2 M) and diethyl ether (150 mL) was used to process the reaction. The organic layer was dried with MgSO₄ and pumped to dryness. 9.8 g of crystalline solid were obtained by vacuum distillation (140°C). 1H NMR(400 MHz, CD2CI2, 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: A 200 mL two-necked round-bottom flask was filled with 43 mmol (8.71 g) of crude compound A in 65 mL of DMF, and then compound B (13 g, 1.2 equiv.) and diisopropylethylamine (DIPEA, 14 mL, 2.5 equiv.) were added. After the resulting clear orange solution was heated at 120°C for 4 days, it was concentrated under vacuum and diluted in EtzO (150 mL). The organic layer was washed with H₂O (200 mL x 5), then with brine solution, then dried with Na₂SO₄, filtered, and concentrated under vacuum to produce a crude oil. The crude oil was dissolved in 100 mL of Et₂O and filtered to remove some solids. 4.2 mL of 12 M HCl were added to the diethyl ether solution to produce a suspension. The suspension was vigorously shaken for one hour and filtered. The solid was washed with Et2O and dissolved in 100 mL of CH2Cl2. The solution was washed with 1 M NaOH and brine. The organic phase was dried with NazSCg, filtered, and concentrated under vacuum to give a deep red oil. The final product was purified by distillation (125°C at full vacuum) to give 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, 1 H), 7.19 (dd, J=8.0, 1.5 Hz, 1 H), 6.84 (dd, J=8.1, 1.3 Hz, 1 H), 6.81 (dd, 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=6.2 Hz, 2 H), 3.22 (t, J=6.9 Hz, 2 H), 2.71 (s, 3 H), 2.02 (tt, J=6.9, 6.2 Hz, 2 H). QPCRnn / zznz / E / YiAi 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 swirling the mixture, CF3COOH (1.27 g, 20 mol%) was added dropwise to a 10 mL hypovial. The vial was rinsed with 5 mL of dichloromethane, and the rinse solution was added to the flask. The mixture was swirled for 3.5 hours (note: a reaction time longer than 3.5 hours leads to byproducts) and inactivated by the slow addition of 30 mL of a saturated aqueous sodium carbonate solution. 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 NaOH solution (3 x 150 mL) to completely remove any traces of 2-iodo-4-methylphenol. The diethyl ether solution was dried with anhydrous MgSOq.A pentane / ethyl acetate solution (volume ratio 19:1, 400 ml) was filtered through a silica gel buffer solution (diameter 25.4 mm (1 in), height 76.2 mm (3 in)) and GC-MS showed that the product was pure (M+ = 318). The solvents were removed under vacuum to give the product as an almost colorless oil (17.5 g). Compound E: QPCAnn / zznz / E / YiAi H 3,6-di-1erc-butyl-9H-carbazo1 (11.35 g, 40.60 mmol), tetrahydro-2-(2-iodo-4-methyl-1-phenoxy)-2Hpyran (12.92 g, 40.60 mmol; compound D), anhydrous K3PO4 (25.8 g, 121.80 mol), Cul (1.65 g, 8.65 mmol) and CH3NHCH2CH2NHCH3 (1.14 g, 13 mmol) in 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 silica gel plug 20.32 cm (8) in diameter and 2.54 cm (1) in diameter and the plug was rinsed with 300 ml of toluene. The light yellow filtrate was evaporated by rotation to a dry (oily) state, and 60 mL of 1°C acetonitrile was added. The solution was allowed to stand, and crystals began to form after approximately 10 minutes. After 48 hours, the solid product was filtered and rinsed with cold acetonitrile (2 x 30 mL, -20°C). 13.0 g of product were obtained after vacuum drying. 1H NMR (400 MHz, CD2CI2) δ ppm 8.15(d, J=2Hz, 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=3Hz, 1H ), 3.68(td,. J=3Hz, J=llHz, 1H) , 3.44(dt, J=4Hz, J=llHz, 1H), 2.38(s, 3H), 1.46(s, 18H), 1.44-1.34( m, 2H), 1.331.23 (m, 1H) , 1.22-1.03 (m, 3H) . QPCRnn / zznz / E / YiAi 1. nBuLi, 0°C 2. B(O¡Pr)33. H2O / HCI QQCAnn / zznz / E / YiAi A 1 L three-necked round-bottom flask containing compound E (10.0 g, 21.3 mmol) in 400 mL of dry THE was slowly mixed with 1.6 M nBuLi solution (16 mL, 25.55 mmol, 1.2 equiv.) at 0°C. After the resulting mixture was warmed to room temperature and stirred for 3 hours, B(OiPrs) (5.2 g, 27.68 mmol) was added dropwise to the reaction mixture at 0°C. The mixture was then allowed to stir overnight at room temperature. The reaction was concentrated under vacuum and stopped 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 NazSCq and filtered to give the final product (10.1 g, 93%). 1H NMR (400 MHz, CD2CI2) 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=8.6, 1.9 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 H), 4.00 (dd, J=9.0, 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), 1.44 (s, 9 H), 1.31 (dd , J=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), 0.29 (dd, J=13.4, 2.3 Hz, 1 H). Ligand L: A 500 mL three-necked round-bottom flask was charged 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 were added. After refluxing the resulting mixture for 3 days, it was concentrated under vacuum and extracted with DCM (-80 mL). The organic layer was washed with H2O, then with brine solution, then dried with Na2SO4, filtered, and concentrated under vacuum to produce a brown solid. The raw product was added to a 500 ml round-bottom flask QPCRnn / zznz / E / YiAi mi, followed by 200 mi of MeOH and 2 mi of HC1 (12 M). After refluxing the turbid orange solution overnight, it was concentrated under vacuum and diluted in Et2Ü, the organic layer was washed with H2O, then with the brine solution, then dried with Na2SO4, filtered and concentrated under vacuum to produce a pale yellow solid. The final product was purified by filtering through a silica plug, followed by acetonitrile (3.25 g, 70% in two CD2CI2) δ ppm 10.70 (s, 1 H), 8.14 (dd, J=8.6, 7.37 (dd, J=8.6, 7.3 Hz, Hz, 1 H), 7.37 (dd, J=8.7, 2.0 Hz, H), 7.22 - 7.26 (m, 2 H), 7.18 J=1.9 Hz, 1 H), 7.07 (d, J=8.8 Hz, H), 6.81 (d, J=7.3 Hz, 1 H), 6.60 recrystallization in stages). 1H NMR(4 00 MHz, (s, 4 H), 7.49 (dd, J=7.3, 3 Hz, 1 H) , 7.38 (d,J=1.9 1 H) , 7.38 (dd, J=8.5, 7.9 5 H) , 7.30 (d, J=1.9 Hz, 1 7.21 (m, 3 H) , 7.16 (d , H), 7.03 (d, J=8.6 Hz, 2 (d, J=7 . 9 Hz, 1 H) , 5.80 (s, 1 Η), 3.83 (t, J=5.9 Hz, 2 H), 2.86 (dd, J=7.6, 7.4 Hz, 2 H), 2.03 (d, J=7.6 Hz, 2 Hz). 6 H) , 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), H) . Precatalyst, Example 1: A 200 mL Schlenk flask filled with HfC14 (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 vial was rinsed with 5 mL of dry Et2O) at -30°C. After shaking the resulting clear solution at -30°C for 15 minutes, a ligand L solution (700 mg, 0.69 mmol) in 20 mL of dry toluene was slowly added and rinsed with dry toluene (2 x 20 mL). The resulting cloudy whitish mixture was shaken 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 an off-white 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=ll 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=ll.l, 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, 1 H), -1.21 (s, 3 H), -1.52 (s, 3 H). Precatalizador, Ejemplo 2: QPCRnn / zznz / E / YiAi ZrCI4, MeMgBr -30 °C ata tolueno QPCRnn / zznz / E / YiAi A 300 mL Schlenk flask loaded with ZrCl₁₄ (463 mg, 1.98 mmol) in 100 mL of dry toluene was filled with a 3 M MeMgBr solution (3 mL, 4.5 equivalents) at -30°C. After shaking the resulting clear solution at -30°C for 15 minutes, a ligand L solution (2.0 g, 1.98 mmol) in 20 mL of dry toluene (the vial was rinsed with dry toluene) was added very slowly at -30°C (3 x 10 mL). The resulting turbid brown mixture was shaken 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 an off-white solid (1.33 g, 59%). (400 MHz, toluene-ds) δ pprti 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), 1 H), 7.43 (d, J=8.7 Hz, 1 H), 7.49 (d, J=8.7 Hz, 1 H) ,. 7.46 (d, J=8.7 Hz, 1 H) , 7.30 (dd, J= 8.6, 2.0 Hz, 2 H), 7.26 (dd, J=8.7, 2.0 Hz, 1 H) , 7.25 (dd, 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 5 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 =10.8 Hz, 1 H) , 3.53 (br t, J=12.0 Hz, 1 H) , 2.93 (br d, J=9.5 Hz, 1 H) , 2.28 (s,3 H) , 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,9 H) , 0.42 (br d, J=14.0 Hz, 1 H) , -0.99 (s, 3 H) , -1.27 (s,3 H) . Polimerización en solución Continuous solution polymerizations were carried out in a continuous polymerization unit (CPU) using cyclohexane as the solvent. The CPU contained a 71.5 mL stirred reactor and was operated at either 140°C or 160°C for the polymerization experiments. An upstream mixed reactor with a volume of 20 mL was operated at 5°C less than the polymerization reactor. The mixed reactor was used to preheat the ethylene, 1-octene, and some of the solvent streams. The catalyst feeds (xylene or cyclohexane solutions of the precatalyst complex (PhaC) [BICEFsjd as 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 total continuous flow of 27 ml / min was maintained in the polymerization reactor. The copolymers were prepared with an octene / ethylene weight ratio of 0.1 to 0.5. Ethylene was fed into the polymerization reactor at a concentration of 10 wt%. 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: where Q is the ethylene conversion (%) (measured with an online gas chromatograph (GC)), [M] is the catalyst concentration in the reactor (mM) and HUT is the residence time in the reactor (2.6 min). Copolymer samples were typically collected with an ethylene (Q) conversion of 9011%, dried in a vacuum oven, milled, and then analyzed using FTIR (for short-chain branching frequency) and GPC-RI (for molecular weight and distribution). Polymerization conditions are listed in Table 1, and copolymer properties are listed in Table 2. Inventive copolymerizations of ethylene with 1octene with the precatalyst of example No. 1 (the hafnium-based catalyst) were carried out as polymerization runs Nos. 1 to 4. Inventive copolymerizations of ethylene with 1-octene with the precatalyst of Example No. 2 (the zirconium-based catalyst) were carried out as Polymerization Tests Nos. 5 to 9. Comparative copolymerizations of ethylene with 1-octene were carried out using the catalyst (cyclopentadienyl)((t-Bu)3PN)TiCi2 as a comparator in polymerization runs Nos. 10 and 11. Catalyst supplies (xylene solutions of (cyclopentadienyl)((tBu)3PN)TiCi2, (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 upstream of the reactor to ensure that all the phenolic OH had been passivated through the reaction with MMAO-7 before reaching the reactor. QPCAnn / zznz / E / YiAi to the reactor. TABLE 1 Ethylene / l-octene copolymerization conditions QPCRnn / zznz / E / YiAi Polymerization Run No. Example Catalyst [Metal] (μM) B (from borate) / M Al (from MMAO7) / M BHEB / Al Temp. Reactor (°C) C2 Flow (g / min) C8 / C2 C2 Conversion, Q (%) (mM-1· min1) 1 1 Hf, 21.48 1.2 0.93 0.3 160 2.7 0.3 8615 111 2 1 Hf, 13.33 1.2 0.89 0.3 140 2.1 0.3 8916 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 0.15 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 0.15 8989 462 7 2 Zr, 8.89 1.2 2.25 0 140 2.1 0.3 9049 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 4.22 140 2.1 0.15 89 52 18675 11 Comp. Ti, 0.24 0.24 16.30 4.89 140 2.1 0.30 8985 16714 Note: C2=ethylene; C8=l-octene TABLE 2 Copolymer Properties Polymerization Run No. Example Catalyst No. FTIR 1-Octene Content (weight percent, wt%) FTIR Short Chain Branching per 1000 Carbon Atoms (SCB / 1000 C) Mw Mn Mw / Mn 1 1 6.4 8.4 244258 112177 2.18 2 1 6.8 9.0 336756 145174 2.32 3 1 11.4 15.5 300383 104776 2.87 4 1 3.7 4.8 442408 151915 2.91 5 2 1.3 1.6 186733 97269 1.92 6 2 2.8 3.6 262739 127627 2.06 7 2 5.6 7.4 270245 104935 2.58 8 2 8.2 10.9 262171 115896 2.26 9 2 N / AN / A 235078 112978 2.08 10 Comp. 2.3 2.9 193020 116080 1.66 11 Comp. 4.2 5.4 143022 101897 1.64 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 1 and 2 of the invention provide ethylene copolymers of similar or higher molecular weight relative to the comparable catalytic system, while also 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 backbone. The novel tetradentate catalysts of inventive examples 1 and 2, and especially the hafnium-based catalyst of example 1, provide ethylene-1-octene copolymers with good comonomer incorporation and good molecular weight when used in a solution-phase polymerization process. The non-limiting modalities of this description include the following: Mode A. A polymerization process comprising polymerizing ethylene with one or more C3-12 alpha olefins in the presence of a polymerization catalyst system comprising: QPCRnn / zznz / E / YiAi i) a catalyst composition having the 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 bivalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted bivalent 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) an activator of the catalyst. Option B. The polymerization process of the Mode A where each R2 has the formula: Modality C. The polymerization process of the Modality A or B, where L is a divalent hydrocarbyl group. Modality D. The polymerization process of the Modality A, B or C where L is a divalent n-propyl group that has the formula: -CH2CH2CH2-. Modality E. The polymerization process of the Modality A, B, C or D where A2 and A8 are each a methyl group. Modality F. The polymerization process of the Mode A, B, C, D or E where A1, A3, A4, A5, A6, A7,A A10, A11 and A12 are each hydrogen. Modality G. The polymerization process of the Modality A, B, C, D, E or F where R1 is a methyl group. Modality H. The polymerization process of the Modality A, B, C, D, E, F or G, where the polymerization process is a solution-phase polymerization process carried out in a solvent. Modality I. The polymerization process of Modality A, B, C, D, E, F, G or H where the polymerization process comprises polymerizing ethylene with 1-octene. Modality J. An olefin prepolymerization catalyst having the 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, A11y 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 bivalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted bivalent heteroatom; Optionally, two or more adjacent A groups can form part of a ring structure; and each X is independently an activatable outgoing group. Mode K. The prepolymerization catalyst of Mode J where each R2 has the formula: ^ / WWV\ Mode L. The prepolymerization catalyst of Mode J, or K, wherein L is a divalent hydrocarbyl group. Mode M. The prepolymerization catalyst of Mode J, K or L where L is a divalent n-propyl group having the formula: -CH2CH2CH2. Modality N. The prepolymerization catalyst of the Modality J, K, L or M where A2 and A8 are each a methyl group. Mode O. The prepolymerization catalyst of Mode J, K, L, M or N wherein A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each hydrogen. Mode P. The prepolymerization catalyst of Mode J, K, L, M, N or O where R1 is a methyl group. Q-mode. A polymerization catalyst system comprising: i) a catalyst composition having the formula: QPCAnn / zznz / E / YiAi 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 bivalent hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted bivalent 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) an activator of the catalyst. INDUSTRIAL APPLICABILITY Novel polymerization catalysts with a tetradentate ligand are used to copolymerize ethylene with an alpha-defin. These novel polymerization catalysts represent examples of post-metallocene catalysts that can be used in a solution-phase defin polymerization process. It is hereby stated that, as of this date, the best method known to the applicant for putting the aforementioned invention into practice is the one that is clear from the present description of the invention.

Claims

Having described the invention as above, the following claims are claimed as property:

1. A polymerization process, characterized in that it comprises polymerizing ethylene with one or more C3-12 alpha olefins in the presence of a catalytic polymerization system comprising: i) a catalyst composition having the formula: 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 ii) a catalyst activator.

2. The polymerization process according to claim 1, characterized in that each R2 has the formula:

3. The polymerization process according to claim 2, characterized in that L is a divalent hydrocarbyl group.

4. The polymerization process according to claim 3, characterized in that L is a divalent n-propyl group having the formula: -CH2CH2CH2-.

5. The polymerization process according to claim 4, characterized in that A2 and A8 are each a methyl group.

6. The polymerization process according to claim 5, characterized in that A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each hydrogen.

7. The polymerization process according to claim 6, characterized in that R1 is a methyl group.

8. The polymerization process according to claim 1, characterized in that it is a solution-phase polymerization process carried out in a solvent.

9. The polymerization process according to claim 8, characterized in that it comprises polymerizing ethylene with 1-octene.

10. An olefin prepolymerization catalyst, characterized in that it has the formula: QQCRnn / zznz / E / YiAi 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 outgoing group.

11. The prepolymerization catalyst according to claim 10, characterized in that each R2 has the formula: QPCAnn / zznz / E / γΐΛΐ 12. The prepolymerization catalyst according to claim 11, characterized in that L is a divalent hydrocarbyl group.

13. The prepolymerization catalyst according to claim 12, characterized in that L is a divalent n-propyl group having the formula: -CH2CH2CH2.

14. The prepolymerization catalyst according to claim 13, characterized in that A2 and A8 are each a methyl group.

15. The prepolymerization catalyst according to claim 14, characterized in that A1, A3, A4, A5, A6, A7, A9, A10, A11 and A12 are each hydrogen.

16. The prepolymerization catalyst according to claim 15, characterized in that R1 is a methyl group.

17. A polymerization catalyst system of definites, characterized in that it comprises: i) a catalyst composition having the formula: QPCRnn / zznz / E / YiAi wherein M is Hf or Zr; R1 is a hydrogen, an optionally substituted hydrocarbyl group, or a hydrocarbyl group containing an optionally substituted heteroatom; 5 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; 15 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) an activator of the catalyst.;