BR112020019626B1 - OLEFINS POLYMERIZATION PROCESS - Google Patents

Abstract

These are embodiments of this disclosure that include olefin polymerization processes, wherein the process comprises placing ethylene in contact with a (C3-C40) alpha-olefin comonomer in the presence of a catalyst system, wherein the catalyst system comprises a Group IV metal-ligand complex and an ionic metal activator complex, wherein the ionic metal activator complex comprises an anion and a countercation, wherein the anion has a structure according to formula (I):

Description

CROSS REFERENCE TO RELATED ORDERS

[001] The present application claims the priority of Provisional Patent Application serial number US 62/650,412, filed on March 30, 2018, which is incorporated into this document by reference in its entirety.

FIELD OF TECHNIQUE

[002] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes and, more specifically, to olefin polymerization catalyst systems including a group 4 metal-ligand complex and an activator nuclear or cocatalyst.

BACKGROUND

[003] As part of the catalyst composition in α-olefin polymerization reactions, the activator may have characteristics that are beneficial for the production of the α-olefin polymer and for final polymeric compositions, including the α-olefin polymer. Activator characteristics that increase the production of α-olefin polymers include, but are not limited to: rapid procatalyst activation, high catalyst efficiency, high temperature capability, consistent polymer composition, and selective deactivation.

[004] Olefin-based polymers such as ethylene-based polymers and propylene-based polymers are produced using various catalyst systems. The selection of such catalyst systems can be an important factor contributing to the characteristics and properties of olefin-based polymers. Catalyst systems for producing polyethylene-based polymers may include a chromium-based catalyst system, a Ziegler-Natta catalyst system, or a molecular catalyst system (either metallocene or non-metallocene).

[005] As part of the catalyst system, the molecular polymerization procatalyst is activated to generate the catalytically active species for polymerization, and this can be achieved by a number of means. One of these methods employs an activator or cocatalyst that is a Bronsted acid. Bronsted acid salts containing weakly coordinated anions are commonly used to activate molecular polymerization procatalysts, particularly such procatalysts comprising Group IV metal complexes. Br0nsted acid salts that are fully ionized are capable of transferring a proton to form a cationic derivative of such Group IV metal complexes.

[006] For activators, such as Bronsted acid salts, the cationic component may include cations capable of transferring a hydrogen ion, such as ammonium, sulfonium or phosphonium, for example; or oxidizing cations, such as ferrocenium, silver (I) or lead (II) cations, for example; or highly acidic Lewis cations such as carbon or silicon, for example.

[007] However, since the activator or cocatalyst cations activate the procatalyst, the activators can remain in the polymer composition. As a result, cations and anions can affect the composition of the polymer. Because not all ions diffuse equally, different ions affect the polymer composition differently. In particular, the size of the ion and the charge of the ion, the interaction of the ion with the surrounding medium, and the dissociation energy of the ion with available counterions will affect the ability of the ion to diffuse through a surrounding medium such as a solvent, a gel or a polymeric material.

[008] Conventional olefin polymerization activators include weakly coordinated or uncoordinated anions. It has been shown that weak anion coordination leads to increased catalytic efficiency of the cationic catalyst. However, since the non-nucleophilic character of the non-coordinating anion also increases diffusion, the residual activating anion in the produced polymer will decrease the electrical resistance of the polymer, thereby increasing electrical loss and thus decreasing the applicability of the produced polymer.

SUMMARY

[009] Desirable characteristics of activators in polymeric systems include abilities to increase the production of α-olefin polymers, to increase the rate of activation of the procatalyst, to increase the overall efficiency of the catalyst to allow the catalyst system to operate at high temperatures to allow the catalyst system to provide a consistent polymer composition and to allow selective deactivation of activators. Activators derived from the non-coordinating anion tetrakis(pentafluorophenyl)borate (-B(C6F5)4) capture many of these desirable characteristics. However, under typical polymerization reaction conditions, the -B(C6F5)4 anion does not decompose and can remain intact in the final polymer. The presence of an intact activator in the final polymer can be detrimental to the electrical properties of the final polymer.

[0010] Activators based on partially hydrolyzed metal trialkyls, such as methylalumoxane (MAO) or modified methylalumoxane (MMAO), for example, decompose more readily than the -B(C6F5)4 anion, but suffer from low catalyst efficiency in high temperature and wider compositional drift in the final polymer.

[0011] There are ongoing needs for activators that efficiently activate a metal ligand catalyst, that are readily decomposed and that work well at high temperature. The catalyst systems of this disclosure include, in combination with Group IV metal-ligand complexes, activators or cocatalysts that meet such needs. In particular, activators readily react with and activate Group IV metal-ligand complexes in the production of polyolefin resins, and polyolefin resins exhibit useful polymer composition and electrical properties. The activators included in the catalyst systems of this disclosure exhibit characteristics such as, abilities to increase the production of α-olefin polymers, to increase the activation rate of the procatalyst, to increase the overall efficiency of the catalyst to allow the system The catalyst system operates at high temperatures to allow the catalyst system to provide a consistent polymer composition and to allow selective deactivation of activators.

[0012] According to one or more embodiments, an olefin polymerization process includes contacting ethylene and an α-olefin comonomer (C3-C40) in the presence of a catalyst system that includes a metal-ligand complex of the Group IV and an ionic metal activator complex. The ionic metal activator complex includes an anion and a countercation, the anion having a structure according to formula (I):

[0013] The countercation is any cation with a +1 formal charge. In formula (I), each M is independently aluminum, boron or gallium; and n is 2, 3, or 4. Each R is independently selected from the group consisting of radicals with formula (II) and radicals with formula (III):

[0014] In formulas (II) and (III), each Y is independently carbon or silicon; each occurrence of R11, R12, R13, R21, R22, R23, R24, and R25, and R is independently chosen from (C1-C40)alkyl, (C6-C40)aryl, -H, -ORC, -O - or halogen, wherein, when R is a radical according to formula (II), at least one of R11, R12 or R13 is a (C1-C40)alkyl substituted by fluorine, a (C6-C40)substituted aryl by halogen or -F; and, when R is a radical according to formula (III), at least one of R21, R22, R23, R24 and R25 is a halogen-substituted (C1-C40)alkyl, a halogen-substituted (C6-C40)aryl halogen or -F. Furthermore, when M is aluminum and n is 4 and each R is a radical according to formula (II) and Y is carbon, each R11, R12 and R13 of each R is a halogen-substituted (C1-C40)alkyl, a halogen-substituted (C6-C40)aryl or -F, the total number of fluorine atoms in R11, R12 and R13 of each R is greater than six. In some embodiments, the countercation can be chosen from tertiary carbocations, ammonium ions substituted by alkyl, anilinium or ferrocenium.

[0015] In formula (I), each (C6-C40)aryl, -S(O)2CF3 or -S(O)3RC. Optionally, two R groups in formula (I) are covalently connected. Each RC is independently (C1-C30)hydrocarbyl or -H. In one or more embodiments, the ionic metal activator complex has a dissipation factor of less than or equal to 0.1 at a concentration of 200 micromoles of ionic metal activator complex and 20 millimoles of water in a fully saturated high-point hydrocarbon solution. boiling, as measured by the Hydrocarbon Conductivity Test.

[0016] In some embodiments, the ratio of the total number of moles of one or more metal-ligand complexes in the catalyst system to the total number of moles of one or more ionic metal activator complexes in the catalyst system is 1:10,000 to 100:1.

[0017] In one or more embodiments, specifically when two R groups are covalently connected, the cocatalyst has a structure according to formula (IV):

[0018] In formula (IV), M and X are as defined in formula (I). The subscript n is 1 or 2. Each L, representing the two covalently linked groups R, is independently chosen from (C2-C40)alkylene or (C2-C40)heteroalkylene. When n is 1, is a (C1-C20) alkyl.

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] FIGURE is a thermal gradient interaction chromatography (TGIC) spectrum of molecular weight as a function of temperature of two comparative activators and two activators (Activator 1 and Activator 8) that are illustrative embodiments of this disclosure.

DETAILED DESCRIPTION

[0020] Specific embodiments of catalyst systems will now be described. It is to be understood that the catalyst systems of this disclosure may be incorporated in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure.

[0021] Common abbreviations are listed below: R, Y, M, L and n: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; I-Pr: iso-propyl; T-Bu: tert-butyl; T-Oct: tert-octyl (2,4,4-trimethylpentane-2-yl); Tf: trifluoromethane sulfonate; OTf: triflate; (tBuFO)3Al : Al(OC(CF3)3)3; THF: tetrahydrofuran; Et2O: diethyl ether; CH2Cl2: dichloromethane; CV: column volume (used in column chromatography); EtOAc: ethyl acetate; C6D6: deuterated benzene or benzene-d6: CDCl3: deuterated chloroform; Na2SO4: sodium sulfate; MgSO4: magnesium sulfate; HCl: hydrogen chloride; N-BuLi: butyl lithium; T-BuLi: tert-butyl lithium; N,N’-DMEDA: N,N’-dimethylethylenediamine; K3PO4: tribasic potassium phosphate; Pd(AmPhos)Cl2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); Pd(dppf)Cl2: [1,1’-Bis(diphenylphosphine)ferrocene]palladium(II) dichloride; K2CO3: potassium carbonate; Cs2CO3: cesium carbonate; I-PrOBPin: 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; N2: nitrogen gas; PhMe: toluene; PPR: parallel polymerization reactor; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimol; ml: milliliters; M: molar; min: minutes; h: hours; d: days; RF; retention fraction; TLC; thin layer chromatography; rpm: revolutions per minute.

[0022] The term “independently selected” is used herein to indicate that groups R, such as R1, R2, R3, R4 and R5, may be identical or different (e.g., R1, R2, R3, R4 and R5 can be all substituted alkyls or R1 and R2 can be a substituted alkyl and R3 can be an aryl, etc.). A chemical name associated with an R group must convey the chemical structure that is recognized in the art as corresponding to that of the chemical name. Therefore, chemical names should complement and illustrate, not exclude, structural definitions known to those skilled in the art.

[0023] The term “procatalyst” refers to a compound that has catalytic activity when combined with an activator. The term “activator” refers to a compound that chemically reacts with a procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms “cocatalyst” and “activator” are interchangeable terms.

[0024] When used to describe certain chemical groups that contain a carbon atom, an expression in parentheses that has the form “(Cx-Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms , including x and y. For example, a (C1-C50)alkyl is an alkyl group that has 1 to 50 carbon atoms in its unsubstituted form. In some general embodiments and structures, certain chemical groups may be replaced by one or more substituents, such as RS. A chemical group substituted for RS using the “(Cx-Cy)” in parentheses may contain more than y carbon atoms depending on the identity of any RS groups. For example, a “(C1-C50)alkyl substituted exactly by an RS group, where RS is phenyl (-C6H5)”, can contain from 7 to 56 carbon atoms. Thus, in general, when a chemical group defined using “(Cx-Cy)” in parentheses is replaced by substituents RS that contain one or more carbon atoms, the minimum and maximum total number of carbon atoms of the chemical group is determined by adding to x and y the combined sum of the number of carbon atoms of all substituents RS that contain carbon atoms.

[0025] The term “substitution” means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a functional group or corresponding unsubstituted compound is replaced by a substituent (e.g., RS). The term “-H” means a hydrogen or hydrogen radical that is covalently bonded to another atom. “Hydrogen” and “-H” are interchangeable and, unless clearly specified, have identical meanings.

[0026] The term “halogen-substituted” means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of an unsubstituted compound or corresponding functional group is replaced by a halogen. The terms “halogen-substituted” and “halogenated” are interchangeable. The term “persubstitution” means that each hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted functional group or compound is replaced by a substituent. The term “halogen-substituted” means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of an unsubstituted compound or corresponding functional group is replaced by a fluorine atom.

[0027] The term “halogen atom” or “halogen” means the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or iodine atom (I). The term “halide” means the anionic form of halogen atom, for example fluoride (F-) or chloride (Cl-).

[0028] The term “(C1-C50)hydrocabilene” means a hydrocarbon radical of 1 to 50 carbon atoms and the term “(C1-C50)hydrocabilene” means a hydrocarbon diradical of 1 to 50 carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or nonaromatic, saturated or unsaturated, straight-chain or branched, cyclic (having three carbons or more, and including mono- and polycyclic, fused and unfused polycyclic, and bicyclic) or acyclic and substituted by a or more RS or not replaced.

[0029] In this disclosure, a (C1-C50)hydrocarbyl can be an unsubstituted or substituted (C1-C50)alkyl, (C3-C50)cycloalkyl, (C3-C20)cycloalkyl-(C1-C20)alkylene, (C6 -C40)aryl or (C6-C20)aryl-(C1-C20)) alkylene (such as benzyl (-CH2-C6H5)).

[0030] The terms “(C1-C50)alkyl” and “(C1-C18)alkyl” mean a straight or branched saturated hydrocarbon radical of 1 to 50 carbon atoms and a straight or branched saturated hydrocarbon radical of 1 to 18 atoms carbon, respectively, which is substituted or unsubstituted by one or more RS. Examples of unsubstituted (C1-C50)alkyl are (C1-C20)unsubstituted alkyl; (C1-C10)unsubstituted alkyl; (C1-C5)unsubstituted alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2- methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl and 1-decile. Examples of substituted (C1-C4o)alkyl are substituted (C1-C2o)alkyl, substituted (C1-C10)alkyl, trifluoromethyl and [C45]alkyl. The term “[C45]alkyl” means that there is a maximum of 45 carbon atoms in the radical, including substituents and is, for example, a (C27-C40)alkyl substituted by an RS, which is a (C1-Cs)alkyl , respectively. More broadly, the term “[Cz]alkyl” means that there are a maximum of z carbon atoms, where z is a positive integer, in the radical, including substituents. Each (C1-Cs)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl or 1,1-dimethylethyl.

[0031] The term “(C6-C50)aryl” means an unsubstituted or substituted (by one or more RS) monocyclic, bicyclic or tricyclic aromatic hydrocarbon radical of 6 to 40 carbon atoms, of which at least 6 to 14 of the carbon atoms are carbon atoms from the aromatic ring. A monocyclic aromatic hydrocarbon radical includes an aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or unfused and aromatic or non-aromatic. Examples of unsubstituted (C6-C50)aryl include: (C6-C20)unsubstituted aryl, (C6-C18)unsubstituted aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of (C6-C40)substituted aryl include: (C1-C20)substituted aryl; (C6-C18)substituted aryl; 2,4-bis([C20]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; fluoren-9-one-1-yl and biphenyl.

[0032] The term “(C3-C50) cycloalkyl” means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms that is substituted or unsubstituted by one or more RS. Other cycloalkyl groups (e.g., (Cx-Cy)cycloalkyl) are defined in an analogous manner as having from x to y carbon atoms and being unsubstituted or substituted by one or more RS. Examples of unsubstituted (C3-C40)cycloalkyl are (C3-C20)unsubstituted cycloalkyl, (C3-C10)unsubstituted cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl . Examples of substituted (C3-C40)cycloalkyl are substituted (C3-C20)cycloalkyl, substituted (C3-C10)cycloalkyl and 1-fluorocyclohexyl.

[0033] Examples of (C1-C50)hydrocabylene include substituted or unsubstituted (C6-C50)arylene, (C3-C50)cycloalkylene, and (C1-C50)alkylene (e.g., (C1-C20)alkylene). Diradicals may be on the same carbon atom (e.g. -CH2-) or on adjacent carbon atoms (i.e. 1,2-diradicals) or are separated by one, two or more than two intervening carbon atoms (e.g. example, 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or an a,o-diradical. The a,o-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2-C20)alkylene a,o-diradicals include ethan-1,2-diyl (i.e., -CH2CH2-), propan-1,3-di-yl (i.e., -CH2CH2CH2- ), 2-methylpropan-1,3-diyl (i.e. - CH2CH(CH3)CH2-). Some examples of (C6-C50)arylene a,o-diradicals include phenyl-1,4-diyl, naphthalen-2,6-diyl or naphthalen-3,7-diyl.

[0034] The term “(C1-C50)alkylene” means a saturated straight or branched chain diradical (i.e., the radicals are not on ring atoms) of 1 to 50 carbon atoms that is substituted or unsubstituted by a or more RS. Examples of unsubstituted (C1-Cs0)alkylene are unsubstituted (C1-C20)alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -( CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3 and -(CH2)4C*(H)(CH3), where “C*” denotes a carbon atom from from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1-C50)alkylene are (C1-C20)alkylene, -CF2-, -C(O)- and -(CH2)14C(CH3)2(CH2)5- (i.e., a normal-1 6,6-dimethyl substituted ,20-eicosylene). Since, as mentioned previously, two RS can be taken together to form a (C1-C18)alkylene, examples of substituted (C1-C50)alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis( methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane and 2,3-bis(methylene)bicyclo[2.2.2] octane.

[0035] The term “(C3-C50)cycloalkylene” means a cyclic diradical (that is, the radicals are on the ring atoms) of 3 to 50 carbon atoms that is substituted or unsubstituted by one or more RS.

[0036] The term “heteroatom” refers to an atom other than hydrogen or carbon. Examples of groups that contain one or more than one heteroatom include O, S, S(O), S(O)2, Si(RC)2, P(RP), N(RN), -N=C(RCh , -Ge(RC)2-, or -Si(RC)-, wherein each RC and each RP is (C1-C18)unsubstituted hydrocarbyl or -H, and wherein each RN is (C1-C18)unsubstituted hydrocarbyl substituted. The term “heterohydrocarbon” refers to a molecule or molecular structure in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. The term “(C1-C50)heterohydrocarbyl” means a radical of heterohydrocarbon of 1 to 50 carbon atoms, and the term “(C1-C50)heterohydrocarbylene” means a heterohydrocarbon diradical of 1 to 50 carbon atoms. hydrocabylene or (C1-C50)heterohydrocabylene has one or more heteroatoms. The radical of heterohydrocabylene can be on a carbon atom or a heteroatom. The two radicals of heterohydrocabylene can be on a single carbon atom or on a single heteroatom. Additionally, one of the two diradical radicals can be a carbon atom and the other radical can be on a different carbon atom; one of the two radicals can be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the other radical on a different heteroatom. Each (C1-C50)heterohydrocarbyl and (C1-C50)heterohydrocarbylene may be unsubstituted or substituted (by one or more RS), aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including mono- and polycyclic, fused and unfused polycyclic) or acyclic.

[0037] The (C1-C50) heterohydrocabyl can be substituted or unsubstituted. Non-limiting examples of (C1-C50)heterohydrocabyl include (C1-C50)heteroalkyl, (C1-C50)hydrocabyl-O-, (C1-C50)hydrocabyl-S-, (C1-C50)hydrocabyl-S( O)-, (C1-C50)hydrocabil-S(O)2-, (C1-C50)hydrocabil- Si(RC)2-, (Cl-C50)hydrocabil-N(RN)-, (Cl-C50) hydrokabil-P(RP)-, (C2-C50)heterocycloalkyl, (C2-C19)heterocycloalkyl-(C1-C20)alkylene, (C3-C20)cycloalkyl-(C1-C19)heteroalkylene, (C2-C19)heterocycloalkyl- (C1-C20)heteroalkylene, (C1-C50)heteroaryl, (C1-C19)heteroaryl-(C1-C20)alkylene, (C6-C20)aryl-(C1-C19)heteroalkylene or (C1-C19)heteroaryl-( C1- C20)heteroalkylene.

[0038] The term “(C4-C50) heteroaryl” means an unsubstituted or substituted (by one or more RS) monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon radical with a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms . A monocyclic heteroaromatic hydrocarbon radical includes a heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may be independently fused or unfused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (Cx-Cy)heteroaryl, generally such as (C4-C12)heteroaryl) are analogously defined as having from x to y carbon atoms (such as 4 to 12 carbon atoms) and being non replaced or replaced by one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring.

[0039] The monocyclic heteroaromatic hydrocarbon radical with a 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3 or 4; and each heteroatom may be O, S, N or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrole-1-yl; pyrrole-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl and tetrazol-5-yl.

[0040] The 6-membered ring monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2 and the heteroatoms can be N or P. Examples of heteroaromatic hydrocarbon radicals 6-membered rings include pyridin-2-yl; pyrimidin-2-yl and pyrazin-2-yl.

[0041] The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6 or 6,6 ring system. Examples of the bicyclic heteroaromatic hydrocarbon radical of fused 5,6 ring system are indole-1-yl; and benzimidazol-1-yl. Examples of the bicyclic heteroaromatic hydrocarbon radical of fused 6,6 ring system are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical may be a 5,6,5 ring system; 5,6,6; 6,5,6; or 6,6,6 fused. An example of the fused 5,6,5 ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of the fused 5,6,6 ring system is 1H-benzo[f]indol-1-yl. An example of the fused 6,5,6 ring system is 9H-carbazol-9-yl. An example of the fused 6,6,6 ring system is acridin-9-yl.

[0042] The term “(C1-C50) heteroalkyl” means a saturated straight or branched chain radical that contains one to fifteen carbon atoms and one or more heteroatoms. The term “(C1-C50)heteroalkylene” means a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. Heteroalkyl heteroatoms or heteroalkylenes may include Si(RC)3, Ge(RC)3, Si(RC)2, Ge(RC)2, P(RP)2, P(RP), N(RN)2, N(RN), N, O, ORC, S, SRC, S(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups are unsubstituted or are substituted by one or more RS.

[0043] Examples of (C2-C40) unsubstituted heterocycloalkyl include (C2-C20) unsubstituted heterocycloalkyl, (C2-C10) unsubstituted heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3 -yl, pyrrolidin-1-yl, tetrahydrothiophen-S,S-dioxido-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa -cyclo-octyl, 5-thio-cyclononyl and 2-aza-cyclodecyl.

[0044] The term “saturated” means that there are no carbon-carbon double bonds, carbon-carbon triple bonds and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus and carbon-silicon double bonds. When a saturated chemical group is replaced by one or more RS substituents, one or more double and/or triple bonds may optionally be present in RS substituents. The term “unsaturated” means that it contains one or more carbon-carbon double bonds or carbon-carbon triple bonds or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds or carbon-silicon double bonds, not including double bonds that may be present in RS substituents, if any, or in aromatic rings or heteroaromatic rings, if any.

[0045] Embodiments of this disclosure include processes for polymerizing olefins, the processes include contacting ethylene, one or more alpha-olefin comonomer (C3-C40), a catalyst and an ionic metal activator complex. The ionic metal activator complex includes an anion and a countercation. The anion has a structure according to formula (I):

[0046] In formula (I), each (C6-C40)aryl or -S(O)3RC.

[0047] In formula (I), each M is independently aluminum, boron or gallium; the subscript n is 2, 3, or 4. Each R is independently selected from the group consisting of radicals with formula (II) and radicals with formula (III):

[0048] In formula (II), each Y is independently carbon or silicon; each R11, R12, R13, is independently chosen from (Ci-C4o)alkyl, (C6-C4o)aryl, -H, -NRN2, -ORC, -SRC or halogen. In some embodiments of formula (I), when each R is a radical according to formula (II) and Y is carbon, at least one of Rii, Ri2 or Ri3 is a halogen-substituted (Ci-C40)alkyl, a (C6-C40)halogen-substituted aryl or -F. In other embodiments of formula (I), when M is aluminum, n is 4, each R is a radical according to formula (II) and each Y is carbon, (i) each Rii, Ri2 and Ri3 of each R is a halogen-substituted (C1-C40)alkyl, a halogen-substituted (C6-C40)aryl or -F; or (2) the total number of fluorine atoms in Rii, Ri2 and Ri3 of each R is at least six.

[0049] In formula (III), each R2i, R22, R23, R24 and R25 is independently chosen from (Ci-C40) alkyl, (C6-C40) aryl, -H, -NRN2, -ORC, -SRC or halogen. When R is a radical according to formula (III), at least one of R21, R22, R23, R24 or R25 is a halogen-substituted (C1-C40)alkyl, a halogen-substituted (C6-C40)aryl or -F.

[0050] In one or more embodiments of the anion of formula (I), the subscript n is 4 and each R group is independently -C(H)(CF3)2, -C6F5 or -C(CF3)3. In other embodiments, the subscript n is 4 and three of the four R groups are -C(CF3)3 and one of the four R groups is -C6F5. In some embodiments, n is 3 and X is chosen from -OH, triflate (-OTf), methyl or halogen.

[0051] In one or more embodiments of the catalyst system, in the anion of formula (I), two groups X are covalently connected and the anion has a structure according to formula (IV):

[0052] In formula (IV), M and X are as defined in formula (I); the subscript n is 1 or 2. L represents the two R groups that are covalently connected; and each L is independently chosen from (C2-C40) alkylene, (C2-C40) heteroalkylene or -(Si(RC)2-O)z-Si(RC)2-, where the subscript z is 0.1 , 2 or 3; and RC is independently (C1-C30) hydrocarbyl or -H. In formula (IV), when n is 1, X is a monodentate ligand, independently chosen from (C1-C20)halogenated alkyl.

[0053] In one or more embodiments of the catalyst system, including an anion of formula (IV), L is a halogenated diradical biphenyl or halogenated naphthalenediyl ion. The halogenated diradical biphenyl ion can have a single radical on each of the phenyl rings. The diradicals in halogenated naphthalenediyl can be separated by four or more carbon atoms in naphthalene.

[0054] In one or more embodiments, the ionic metal activator complex includes the anion according to formulas (I) or (IV) and the countercation having a formal charge of +1. In some embodiments of the metal ionic complex, the countercation is chosen from a protonated tri[(C1-C40)hydrocarbyl] ammonium cation. In some embodiments, the countercation is a protonated trialkylammonium cation, containing one or two (C14-C20)alkyl groups on the ammonium cation. In one or more embodiments, the countercation is +N(CH3)HRN2, where RN is (C16-C18)alkyl. In other embodiments, the countercation is +N(H)RN3, where each RN is chosen from (C1-C20)alkyl or (C6-C20)aryl. In one or more embodiments, the countercation is +N(H)RN3, in which at least two RN are chosen from (C10-C20)alkyl. In one or more embodiments, the countercation is +N(H)RN3, where RN is (C16-C18)alkyl. In some embodiments, the countercation is chosen from methyldi (octadecyl) ammonium cation, methyl (octadecyl) (hexadecyl) ammonium cation, methyldi (hexadecyl) ammonium cation, or methyldi (tetradecyl) ammonium cation. Methyldi(octadecyl)ammonium cation, methyl(octadecyl)(hexadecyl)ammonium cation, methyldi(hexadecyl)ammonium cation or methyldi(tetradecyl)ammonium cation are collectively referred to herein as Armenian cations. Ionic compounds with Armenian cations are readily formed by protonation (with anhydrous HCl in ether, for example) methyldi(octadecyl)amine, methyl(octadecyl)(hexadecyl)amine, methyldi(hexadecyl)amine or methyldi(tetradecyl)amine which are available from Akzo-Nobel under the trade names Armeen™, for example Armeen™ M2HT. In other embodiments, the countercation is triphenylmethyl carbocation (+C(C6H5)3), also known as trityl. In one or more embodiments, the countercation is a tris-substituted triphenylmethyl carbocation, such as +C(C6H4RC)3, wherein each RC is independently chosen from (C1-C30)alkyl. In other embodiments, the countercation is chosen from anilinium, ferrocenium or aluminocenium. Anilinium cations are protonated nitrogen cations, such as [HN(RS)(RN)2]+, where RN is (C1-C20)alkyl or H and RS is chosen from (C6-C20)aryl, and each alkyl or aryl may be further substituted by -ORC, for example C6H5NMe2H+ or [H3N(C6H5)]+. Aluminocenes are protonated aluminum cations, such as RS2Al(H)(THF)2+ or RSAl(H)(THF)2+, where RS is chosen from (C1-C30)alkyl.

[0055] In one or more embodiments, the ionic metal activator complex in a high boiling point fully saturated hydrocarbon solution containing a concentration of 200 micromoles of metal activator complex and 18 millimoles of water in the high boiling point fully saturated hydrocarbon has a dissipation factor less than or equal to 0.1 as measured by the Hydrocarbon Conductivity Test. In some embodiments, the dissipation factor of the metal activator complex measured in the same manner has a dissipation factor less than or equal to 0.05, less than or equal to 0.03, or less than or equal to 0.025. The high boiling point fully saturated hydrocarbon solution (“hydrocarbon solution”) includes a high boiling point fully saturated hydrocarbon solvent, water, and the ionic metal activator complex. The high boiling point fully saturated hydrocarbon solvent may include a solvent with a boiling point of about 150 °C to about 190 °C. Examples of such high boiling point fully saturated hydrocarbon solvents include squalane, dodecane, eicosane or triacontane, for example.

[0056] The electrical properties of a polyolefin elastomer produced by a polymerization process according to this disclosure, specifically the polyolefin elastomer produced by the ionic metal activator complex according to formula (I) can be evaluated with respect to the electrical properties of other polyolefin elastomers by a Hydrocarbon Conductivity (HC) Test. The HC test simulates differences between the electrical properties of polyolefin elastomers produced by a comparative activator such as methyldi((C14-C20)alkyl) ammonium tetrakis(pentafluorophenyl)borate and the ionic metal complex activators of this disclosure. In the HC test, the activator is dissolved in a fully saturated hydrocarbon solvent with a high boiling point at room temperature. (Ambient temperature is approximately 22.0 ± 2.5 °C.)

[0057] The HC test measures a dissipation factor (at 60 Hz) and a conductivity of hydrocarbon samples. Each of the hydrocarbon samples is measured using a Novocontrol Technologies Broadband Dielectric Spectrometer (Alpha-A) using standard methods. In addition to gentle heating, all sample preparation steps and measurements were performed at room temperature.

[0058] To prepare hydrocarbon samples for the HC Test, an amount of activator is added to approximately 10 ml of hydrocarbon solvent to create samples with a concentration of approximately 200 μm of activator in solution. In a hydrocarbon sample containing water, deionized water is added to obtain a concentration of approximately 20 mM, and an amount of activator is added to obtain a 200 μm hydrocarbon solution. All samples are gently heated to 250°C to remove water and any residual low-boiling solvents. Dissipation factor and conductivity are measured.

[0059] The ratio of the total number of moles of one or more Group IV metal-ligand complexes in the catalyst system to the total number of moles of one or more ionic metal activator complexes in the catalyst system is 1:10,000 to 100:1.

[0060] In illustrative embodiments, catalyst systems may include an ionic metal activator complex comprising an anion and a countercation, in which the anion is in accordance with formula (I). Illustrative embodiments include the anionic structure complexed with a countercation, as described in this disclosure, and have the following structure:

POLYMERIC ELECTRICAL PROPERTIES

[0061] The electrical insulation efficiency of a medium, such as a polymeric material, can be evaluated in view of the electrical resistance of the medium and the electrical loss of the medium. Electrical loss decreases the efficiency by which the aggressive medium insulates electrically in the presence of an electric field. The resistance of the insulating medium must be as high as possible for alternating current (AC) and direct current (DC) systems, as resistance is inversely related to power or electrical loss.

[0062] In a DC system, such as a photovoltaic device encapsulated in an insulating medium such as polymeric material, electrical loss manifests as current leakage from the encapsulated device through the encapsulant to the external environment. This current (I) is directly related to the voltage (V) of the insulating medium and inversely related to the resistance (R) of the insulating medium according to the equation I=VxR-1. Therefore, the higher the resistance, the lower the current and current leakage.

[0063] In an AC system including an insulating medium, such as cable insulation, electrical loss manifests as the absorption of energy by the insulating medium in the presence of an electric field. Measured in power (P), this loss is determined by the equation P = V2 x co x C x ε' x tan δ where co is the angular frequency, ε' is the relative permittivity, C is the capacitance and tan δ is the factor of dissipation, tan δ = (C x R x ®)-1, resulting in the equation P = V2 x ε ' x R-1. Since resistance is inversely related to power loss, the higher the resistance, the lower the power loss.

[0064] The electrical resistance of a medium is generally decreased as a result of ionic diffusion caused by an external electric field. In a system in which ionic diffusion dominates the electrical response, resistance is related to the diffusing ions according to the equation R = 6 x π x ε' x ε0 x i] x r x C-1 x q-2 x N-1 where ε0 is the permittivity of the vacuum (8.854 x 10-12 F-m-1), i] is the dynamic viscosity of the medium, r is the hydrodynamic radius of the ion, q is the charge of the ion, and N is the concentration of the ion. Since increasing resistance decreases energy loss and a decrease in ion concentration increases resistance, a reduction in the concentration of ions diffusing through the medium decreases energy loss.

[0065] The ability of an ion to diffuse through a given medium is influenced by the size of the ion, the charge of the ion, the interaction of the ion with the surrounding medium and the dissociation energy of the ion with the available counterions. Since not all ions diffuse equally through a given medium, when the medium is a polymer, the diffusivity of the ions often affects the insulating ability of the polymer. Without intending to be limited by theory, polymers produced from the catalyst systems of this disclosure are believed to have desirable electrical properties, such as decreased electrical loss, because the anions of the ionic metal activator complex of formula (I) are less capable of to diffuse through the polymer produced.

CATALYST SYSTEM COMPONENTS

[0066] The catalyst system may include a procatalyst. The procatalyst can be made catalytically active by contacting the complex with, or combining the complex with, an activating metal having an anion of formula (I) and a countercation. The procatalyst can be chosen from a Group IV metal-ligand complex (Group IVB according to CAS or Group 4 according to IUPAC nomenclature conventions), such as a titanium metal-ligand complex (Ti ), a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) metal-ligand complex. Non-limiting examples of the procatalyst include catalysts, procatalysts or catalytically active compounds for polymerizing ethylene-based polymers are disclosed in one or more of US 8372927; WO 2010022228; WO 2011102989; US 6953764; US 6900321; WO 2017173080; US 7650930; US 6777509 WO 99/41294; US 6869904; or WO 2007136496, all of which documents are incorporated herein by reference in their entirety.

[0067] In one or more embodiments, the Group IV metal-ligand procatalyst complex includes a Group IV bis(phenylphenoxy) metal-ligand complex or a restricted geometry Group IV metal-ligand complex.

[0068] According to some embodiments, the Group IV metal-ligand procatalyst complex may include a bis(phenylphenoxy) structure according to formula (X):

[0069] In formula (X), M is a metal chosen from titanium, zirconium or hafnium, the metal being in a formal oxidation state of +2, +3 or +4. The subscript n of (X)n of Formula (I) is 0, 1, or 2. When the subscript n is 1, X is a monodentate ligand or a bidentate ligand, and when the subscript n is 2, each X is a ligand monodentate. L is a diradical selected from the group consisting of (C1-C40) hydrocarbylene, (C1-C40) heterohydrocarbylene, -Si(RC)2-, -Si(RC)2OSi(RC)2-, -Si(RC )2C(RC)2-, -Si(RC)2Si(RC)2-, -Si(RC)2C(RC)2Si(RC)2-, -C(RC)2Si(RC)2C(RC)2 -, -N(RN)C(RC)2-, -N(RN)N(RN)-, -C(RC)2N(RN)C(RC)2-, -Ge(RC)2-, - P(RP)-, -N(RN)-, -O-, S-, -S(O)-, -S(O)2-, -N=C(RC)-, -C(O)O -, -OC(O)-, -C(O)N(R)-, and -N(RC)C(O)-. Each Z is chosen independently of -O-, -S-, -N(RN)- or -P(RP)-; R2-R4, R5 to R8, R9 to R12 and R13 to R15 are independently selected from the group consisting of -H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, -Si(RC)3 , -Ge(RC)3, -P(RP)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, -N=C(RC)2, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)- and halogen. R1 and R16 are selected from radicals with formula (XI), radicals with formula (XII) and radicals with formula (XIII):

[0070] In formulas (XI), (XII) and (XIII), each of R31 to R35, R41 to R48 and R51 to R59 is independently chosen from -H, (C1- C40)hydrocarbyl, (C1- C40)heterohydrocarbyl, -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS (O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O) - or halogen.

[0071] In one or more embodiments, each X may be a monodentate ligand that, independently of any other ligands )O- or RKRLN-, wherein each of RK and RL, independently, is an unsubstituted (C1-C20) hydrocarbyl.

[0072] Illustrative bis(phenylphenoxy) metal-ligand complexes according to formula (X) include, for example: (2',2”-(propane-1,3-diylbis(oxy))bis(5' -chloro-3-(3,6-di-tert-octyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol )dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3' -chloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis(3 '-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2- ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3 '-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis( 5'-cyano-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)bipheml-2 - ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis(5'-dimethylamino-3-(3,6-di-tert-butyl-9H-carbazole- 9-yl)-3-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis(3',5'-dimethyl-3-(3,6-di-tert-butyl-9H-carbazol-9-yl) -5-(2,4,4-trimethylpentan-2-yl)bipheml-2-ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis(5'- chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-ethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol) dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'- methyl-5'-tert-butyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium; (2',2”-(propane-1,3-diylbis( oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2- il)biphenyl-2-ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis(3-(9H-carbazol-9-yl)-5-chloro-3 '-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis( 3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2 - ol)dimethylhafnium; (2',2”-(2,2-dimethyl-2-silapropane-1,3-diylbis(oxy))bis(3',5'- dichloro-3-(3,6 -di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium; (2'2”-(2,2-dimethyl-2-silapropane-1-diylbis(oxy))bis(5'-chloro-3- (3,6-di-tert-butyl-9-carbazol-9- yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy ))bis(3'-bromo-5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl )bipheml-2-ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))-(5'-chloro-3-(3,6-di-tert-butyl- 9H-carbazol-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)bipheml-2-ol)-(3",5"-dichloro-3-(3, 6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium; (2',2”-( propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-trifluoromethyl-5-(2, 4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium; (2',2”-(butane-1,4-diylbis(oxy))bis(5-chloro-3-(3, 6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)bipheml-2-ol)dimethylhafnium; (2' ,2”-(ethane-1,2-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl- 5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium; (2',2”-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3' -methyl-5-(2,4,4-trimethylpentan-2-yl)bipheml-2-ol)dimethyl-zirconium; (2',2”-(propane-1,3-diylbis(oxy))bis(3 -(3,6-di-tert-butyl-9H-carbazol-9-yl)-3',5'-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol) dimethyl-titanium; and (2',2”-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9- yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)bipheml-2-ol)dimethyl-titanium.

[0073] Other bis(phenylphenoxy) metal-ligand complexes that can be used in combination with the metal activators in the catalyst systems of this disclosure will be apparent to those skilled in the art.

[0074] According to some embodiments, the Group IV metal-ligand complex may include a cyclopentadienyl procatalyst according to formula (XIV): LpiMXmX'nX”p, or a dimer thereof (XIV).

[0075] In formula (XIV), Lp is an anionic, delocalized group, with π bonds that is linked to M, containing up to 50 non-hydrogen atoms. In some embodiments of formula (XIV), two Lp groups can be joined forming a bridge structure and, optionally, an Lp can be linked to X.

[0076] In formula (XIV), M is a metal from Group 4 of the Periodic Table of Elements in the formal oxidation state +2, +3 or +4. X is an optional divalent substituent of up to 50 non-hydrogen atoms that, together with Lp, forms a metallocycle with M. each X" is independently a monovalent anionic moiety having up to 40 non-hydrogen atoms. Optionally, two covalently bonded to form a neutral, conjugated or unconjugated diene that is π-bonded to M, where M is in the +2 oxidation state. In other embodiments, one or more X" and one or more X' groups may be bonded with each other, thus forming a moiety that is covalently linked to M and coordinated with it through the Lewis base functionality. The subscript i of Lpi is 0, 1, or 2; the subscript n of X'n is 0, 1, 2 or 3; the subscript m of Xm is 0 or 1; and the subscript p of X”p is 0, 1, 2 or 3. The sum of i + m + p is equal to the oxidation state of the M formula.

[0077] Illustrative Group IV metal-ligand complexes may include cyclopentadienyl procatalyst that may be employed in the practice of the present invention include: cyclopentadienyltitaniumtrimethyl; cyclopentadienyltitaniumtriethyl; cyclopentadienyltitaniumtriisopropyl; cyclopentadienyltitaniumtriphenyl; cyclopentadienyltitaniumtribenzyl; cyclopentadienyltitanium-2,4-dimethylpentadienyl; cicl()pentadienyltitani()-2,4-dinietilpeiitadieniHrietilf()sfina; cyclopeiitadieiiiltitaiiio-dd-dinietilpeiiladieniHrinietilphosphine; cyclopentadienyltitaniumdimethylmethoxide; cyclopentadienyl titaniumdimethylchloride; pentamethylcyclopentadienyltitaniumtrimethyl; indenyltitaniumtrimethyl; indenyltitaniumtriethyl; indenyltitaniumtripropyl; indenyltitaniumtriphenyl; tetrahydroindenyltitaniumtribenzyl; pentamethylcyclopentadienyltitaniumtriisopropyl; pentamethylcyclopentadienyltitaniumtribenzyl; pentamethylcyclopentadienyltitanium dimethylmethoxide; pentamethylcyclopentadienyltitaniumdimethylchloride; bis(η5-2,4-dimethylpentadienyl)titanium; bis(η5-2,4-dimethylpentadienyl)titanium^trimethylphosphine; bis(η5-2,4-dimethylpentadienyl)titanium^triethylphosphine; octahydrofluorenyltitaniumtrimethyl; tetrahydroindenyltitaniumtrimethyl; tetrahydrofluorenyltitaniumtrimethyl; (tert-butyl starch)(1,1-dimethyl-2,3,4,9,10-^-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanotitaniumdimethyl; (tert-butyl starch)(1,1,2,3-tetramethyl-2,3,4,9,10-^-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanotitaniumdimethyl; (teix'-biitilamkl())(tetraniethyl-if-cyclopentadienyl)dimethylsilanotitanium dibenzyl; (tcix'-biitilainid())(tctrainethyl-if-cyclopentadienyl)dimethylsilanotitanium dimethyl; Ueix'-biitilainid())(tctrainctyl-if-cycl()pcntadicnyl)-1,2-dimethyl ethanedyl titanium; (tert-butyl starch)(tetramethyl-^5-indenyl)dimethylsilane titanium dimethyl; (tert-butyl starch)(tetramethyl-^5-cyclopentadienyl)dimethylsilane titanium(III)2-(dimethylamine)benzyl; (tert-butyl starch)(tetramethyl-^5-cyclopentadienyl)dimethylsilane titanium (III) allyl; (tert-butyl starch)(tetramethyl-^5-cyclopentadienyl)dimethylsilanotitanium (III) 2,4-dimethylpentadienyl; (tert-butyl starch)(tetramethyl-^5-cyclopentadienyl)dimethylsilane titanium (II) 1,4-diphenyl-1,3-butadiene; (tert-butyl starch)(tetramethyl-^5-cyclopentadienyl)dimethylsilane titanium (II) 1,3-pentadiene; (tert-butyl starch) (2-methylindenyl)dimethylsilanotitanium (IV) 2,3-dimethyl-1,3-butadiene; (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) isoprene; (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV ) 1,3-butadiene; (tert-butyl starch)(2,3-dimethylindenyl)dimethylsilane titanium (IV) 2,3-dimethyl-1,3-butadiene; (tert-butyl starch)(2,3-dimethylindenyl)dimethylsilane titanium (IV ) isoprene; (tert-butyl starch)(2,3-dimethylindenyl)dimethylsilane titanium (IV) dimethyl; (tert-butyl starch)(2,3-dimethylindenyl)dimethylsilane titanium (IV) dibenzyl; (tert-butyl starch)(2,3-dimethylindenyl )dimethylsilane titanium (IV) 1,3-butadiene; (tert-butyl starch)(2,3-dimethylindenyl)dimethylsilane titanium (II) 1,3-pentadiene; (tert-butyl starch)(2,3-dimethylindenyl)dimethylsilane titanium (II) 1 ,4-diphenyl-1,3-butadiene;(tert-butylamido)(2-methylindenyl)dimethylsilane titanium (II) 1,3-pentadiene; (tert-butyl starch)(2-methylindenyl)dimethylsilane titanium (IV) dimethyl; (tert-butyl starch)(2-methylindenyl)dimethylsilane titanium (IV) dibenzyl; (tert-butyl starch)(2-methyl-4-phenylindenyl)dimethylsilane titanium (II) 1,4-diphenyl-1, 3-butadiene; (tert-butyl starch)(2-methyl-4-phenylindenyl)dimethylsilane titanium (II) 1,3-pentadiene; (tert-butyl starch)(2-methyl-4-phenylindenyl)dimethylsilane titanium (II) 2,4-hexadiene; (tert-butyl starch)(tetramethyl-^5-cyclopentadienyl) dimethylsilanotitanium (IV) 1,3-butadiene; (tert-butyl starch)(tetramethyl-^5-cyclopentadienyl) dimethylsilane titanium (IV) 2,3-dimethyl-1,3-butadiene; (teix'-biitilamkl())(tetraniethyl-if-cyclopentadienyl)dimethylsilanotitanium (IV) isoprene; (tcix'-biitilainid())(tctrainectyl-if-cycl()pcntadicnyl) dimethylsilanotitanium (II) 1,4-dibenzyl-1,3-butadiene; (dcix'-biitilainid())(tctrainctyl-if-cyclopntadicnyl)dihynctyl-silanotitanium (II) 2,4-hexadiene; (tert-butyl starch)(tetramethyl-^5-cyclopentadienyl) dimethylsilanotitanium (II) 3-methyl-1,3-pentadiene; (tert-butyl starch)(2,4-dimethylpentadien-3-yl)dimethylsilane titanium dimethyl; (tert-butyl starch)(6,6-dimethylcyclohexadienyl)dimethylsilane titanium dimethyl; (tert-butyl starch)(1,1-dimethyl-2,3,4,9,10-^-1,4,5,6,7,8-hexahydronaphthalen-4-yl) dimethylsilanotitanium dimethyl; (tert-butyl starch)(1,1,2,3-tetramethyl-2,3,4,9,10-^-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitanium dimethyl ; (tert-butyl starch) )-2-(tetramethyl-^5-cyclopentadienyl) ethanediyltitanium (IV) dimethyl; 1-(tert-butylamido)-2-(tetramethyl-^5-cyclopentadienyl)ethanediyl-titanium (II) 1,4-diphenyl- 1,3-butadiene; Each of the illustrative cyclopentadienyl procatalysts may include zirconium or hafnium in place of the titanium metal centers of the cyclopentadienyl procatalyst.

[0078] Other procatalysts, especially procatalysts containing other Group IV metal-ligand complexes, will be evident to those skilled in the art.

[0079] The catalyst systems of this disclosure may include cocatalysts or activators, in addition to the ionic metal activator complex having the anion of formula (I) and a countercation. Such additional cocatalysts may include, for example, tri(hydrocarbyl)aluminum compounds having from 1 to 10 carbons in each hydrocarbyl group, an oligomeric or polymeric alumoxane compound, di(hydrocarbyl)(hydrocarbyloxy)aluminum compound having from 1 to 20 carbons in each hydrocarbyl or hydrocarbyloxy group, or mixtures of the previous compounds. These aluminum compounds are usefully employed for their beneficial ability to eliminate impurities such as oxygen, water and aldehydes from the polymerization mixture.

[0080] The di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds that can be used in conjunction with the activators described in this disclosure correspond to the formula T12AlOT2 or T11Al(OT2)2, where T1 is a (C3-C6) secondary alkyl or tertiary, such as isopropyl, isobutyl or tert-butyl; and T2 is an alkyl-substituted (C6-C30)aryl radical or aryl-substituted (C1-C30)alkyl radical, such as 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert -butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methyltolyl or 4-(3', 5'-di-tert-butyltolyl)-2,6-di-tert-butylphenyl.

[0081] Additional examples of aluminum compounds include [C6]trialkylaluminum compounds, especially those in which the alkyl groups are ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl, dialkyl(arylaxy)aluminum compounds containing 1-6 carbons in the alkyl group and 6 to 18 carbons in the aryl group (especially (3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum), methylalumoxane, modified methylalumoxane and diisobutylalumoxane.

[0082] In catalyst systems according to embodiments of this disclosure, the molar ratio of ionic metal activator complex to Group IV metal-ligand complex can be from 1:10,000 to 1,000:1, such as, for example, from 1: 5,000 to 100:1, from 1:100 to 100:1, from 1:10 to 10:1, from 1:5 to 1:1 or from 1.25:1 to 1:1. Catalyst systems may include combinations of one or more ionic metal activator complexes described in this disclosure.

POLYOLEFINS

[0083] The catalytic systems described in the previous paragraphs are used in the polymerization of olefins, mainly ethylene and propylene. In some embodiments, there is only a single type of olefin or α-olefin in the polymerization scheme, creating a homopolymer. However, additional α-olefins can be incorporated into the polymerization procedure. Additional α-olefin comonomers typically have up to 20 carbon atoms. For example, α-olefin comonomers can have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-l- pentene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. For example, the one or more α-olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene; or alternatively, from the group consisting of 1-hexene and 1-octene.

[0084] Ethylene-based polymers, for example, homopolymers and/or interpolymers (including copolymers) of ethylene and, optionally, one or more comonomers, such as α-olefins, may comprise at least 50 mol percent (% in mol) of ethylene-derived monomer units. All individual values and subranges covered by “from at least 50 mol%” are disclosed herein as separate embodiments; for example, ethylene-based polymers, homopolymers and/or interpolymers (including copolymers) of ethylene and, optionally, one or more comonomers, such as α-olefins, may comprise at least 60 mol% monomer units derived from ethylene; at least 70 mol% ethylene-derived monomer units; at least 80% by weight of ethylene-derived monomer units; or from 50 to 100 mol% ethylene-derived monomer units; or 80 to 100 mol% of ethylene-derived units.

[0085] In some embodiments, ethylene-based polymers may comprise at least 90 mol percent ethylene-derived units. All individual values and subranges of at least 90 mol percent are included herein and disclosed herein as separate embodiments. For example, ethylene-based polymers may comprise at least 93 mole percent ethylene-derived units; at least 96 mole percent units; at least 97 mole percent units derived from ethylene; or alternatively, from 90 to 100 mole percent ethylene-derived units; from 90 to 99.5 mole percent ethylene-derived units; or from 97 to 99.5 mole percent ethylene-derived units.

[0086] In some embodiments of the ethylene-based polymer, the ethylene-based polymers may comprise an amount of (C3-C20)α-olefin. The amount of (C3-C20)α-olefin is less than 50 mol%. In some embodiments, the ethylene-based polymer may include at least 0.5 mol% to 25 mol% (C3-C20)α-olefin; and in other embodiments, the ethylene-based polymer may include at least 5 mole % to 10 mole %. In some embodiments, the additional α-olefin is 1-octene.

[0087] Any conventional polymerization process, in combination with a catalyst system according to embodiments of this disclosure can be used to produce the ethylene-based polymers. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof using one or more conventional reactors, such as loop, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors in parallel, in series or any combination thereof, for example.

[0088] In one embodiment, the ethylene-based polymer can be produced through solution polymerization in a dual reactor system, e.g., a dual cycle reactor system, wherein ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system as described herein, and optionally, one or more cocatalysts. In another embodiment, the ethylene-based polymer may be produced through solution polymerization in a dual reactor system, e.g., a dual cycle reactor system, wherein ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system in the present disclosure and, as described herein, and, optionally, one or more other catalysts. The catalyst system as described herein can be used in the first reactor or in the second reactor, optionally, in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer may be produced through solution polymerization in a dual reactor system, e.g., a dual cycle reactor system, wherein ethylene and, optionally, one or more α-olefins are polymerized in the presence of the catalyst system, as described herein, in both reactors.

[0089] In another embodiment, the ethylene-based polymer can be produced through solution polymerization in a single reactor system, e.g., a single-loop reactor system, in which the ethylene and, optionally, one or more further α-olefins are polymerized in the presence of the catalyst system as described in this disclosure.

[0090] The polymer process may also include the incorporation of one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers and combinations thereof. Ethylene-based polymers can contain any number of additives. Ethylene-based polymers may compromise from about 0 to about 10% by the combined weight of such additives, based on the weight of the ethylene-based polymers and one or more additives. Ethylene-based polymers may additionally comprise fillers, which may include, but are not limited to, organic or inorganic fillers. Ethylene-based polymers may contain about 0 to about 20 weight percent fillers, such as, for example, calcium carbonate, talc or Mg(OH)2, based on the combined weight of the ethylene-based polymers. and all additives or fillers. Ethylene-based polymers can be further blended with one or more polymers to form a blend.

[0091] In some embodiments, a polymerization process for producing an ethylene-based polymer may include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one complex of metal-ligand of formula (I). The polymer resulting from such a catalyst system incorporating the metal-ligand complex of formula (I) may have a density in accordance with ASTM D792 (incorporated herein by reference in its entirety) of 0.850 g/cm3 to 0.950 g/cm3, from 0.870 g/cm3 to 0.920 g/cm3, from 0.870 g/cm3 to 0.910 g/cm3, or from 0.870 g/cm3 to 0.900 g/cm3, for example.

[0092] In another embodiment, the polymer resulting from the catalyst system that includes the metal-ligand complex of the formula has a melt flow ratio (I10/I2) of 5 to 15, where the melt index I2 is measured in accordance with ASTM D1238 (incorporated herein by reference in its entirety) at 190 °C and a load of 2.16 kg, and the melt index I10 is measured in accordance with ASTM D1238 at 190 °C and a load of 10 kg. In other embodiments, the melt flow ratio (I10/I2) is 5 to 10, and in others, the melt flow ratio is 5 to 9.

[0093] In some embodiments, the polymer resulting from the catalyst system that includes the metal-ligand complex and the ionic metal activator complex has a molecular weight distribution (MWD) of 1 to 25, where MWD is defined as Mw/Mn where Mw is a weight average molecular weight and Mn is a number average molecular weight. In other embodiments, the polymers resulting from the catalyst system have an MWD of 1 to 6. Another embodiment includes an MWD of 1 to 3; and other embodiments include MWD of 1.5 to 2.5.

BATCH REACTOR PROCEDURE

[0094] Batch reactor experiments are performed in a 1-gallon continuous stirred tank reactor. The reactor is charged with Isopar-E hydrocarbon solvents, hydrogen, and the appropriate amount of octene comonomer before being heated to the specified temperature and pressurized with ethylene to 450 psi. When the reactor is under pressure, polymerization is initiated by the addition of a catalyst cocktail comprising the procatalyst, ionic metal activator complex, solvent and triethylaluminum sequestrant. Polymerization can continue for 10 minutes while maintaining the reactor temperature and pressure. After the reaction is complete, the polymer is collected and dried in a vacuum oven overnight before being analyzed.

POLYOCTENE SCREENING PROCEDURE

[0095] Pure 1-octene (11 ml) is added to a 40 ml flask equipped with a stir bar. The flask is placed in an insulating polyurethane block that is placed on a magnetic stir plate. The activator is added to the stirring solution. A solution of the procatalyst is added to the stirring solution. The vial is immediately capped with a septum screw cap and a thermometer probe is inserted into the vial so that the tip of the probe is submerged in the 1-octene solution. The thermometer probe is connected to a digital recorder to record time and temperature in 5-second intervals. The solution in the flask is stirred continuously and monitored for 10 minutes.

CONTINUOUS POLYMERIZATION

[0096] Raw materials (ethylene, 1-octene) and the process solvent (a high purity isoparaffinic solvent with a narrow boiling range of the ISOPAR E brand commercially available from ExxonMobil Corporation) are purified with molecular sieves before introduction to the half reaction. Hydrogen is supplied in pressurized cylinders as a high purity grade and further purification is not required. The reactor monomer feed stream (ethylene) is pressurized using a mechanical compressor to a pressure greater than 3.62 MPa (525 psig). The solvent and comonomer (1-octene) feed is pressurized via a mechanical positive displacement pump to reaction pressure above 3.61 MPa (525 psig). Triethylaluminum, commercially available from AkzoNobel, was used as a scavenger. The individual catalyst components (procatalyst/activator/scavenger) are manually batch diluted to specified component concentrations with purified solvent (ISOPAR E) and pressed to above the reaction pressure at 3.62 MPa (525 psig). The activator is used in a molar ratio of 1.2 to the procatalyst. All reaction feed streams are measured with mass flow meters and independently controlled with computer-automated valve control systems.

[0097] Continuous solution polymerizations are carried out in a 1 gallon (3.78541 liter) continuously stirred tank reactor (CSTR). The combined solvent, monomer, comonomer and hydrogen feed to the reactor is temperature controlled between 5°C and 30°C and typically 15°C. All these materials are fed to the polymerization reactor with the solvent. The catalyst is fed to the reactor to achieve a specified ethylene conversion. The cocatalyst is fed based on a calculated specified mole ratio (1.2 mole equivalents) for the catalyst component. The TEA scavenger shares the same line as the activator and flow is based on an Al concentration in the reactor or a specified molar ratio for the catalyst component. The polymerization reactor effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the reactor. When the effluent comes into contact with water, polymerization ends. Additionally, various additives, such as antioxidants, can be added at this time. The stream then passes through a static mixer to evenly disperse the catalyst waste and additives.

[0098] After adding the additive, the effluent passes through a heat exchanger to increase the temperature of the stream in preparation for separating the polymer from the other components of the low boiling point reaction. The current passes through the reactor pressure control valve, through which the pressure is greatly reduced. From there, the effluent enters a two-stage separation system consisting of a devolatizer and a vacuum extruder, where solvent and unreacted hydrogen, monomer, comonomer and water are removed from the polymer. The formed molten polymer yarn exits the extruder and is submerged in a cold water bath, where it solidifies. The wire is then fed through a wire cutter, where the polymer is cut into pellets after being air-dried.

EXAMPLES

[0099] Example 1 is the synthetic procedure for Activator 1 and Example 2 is the synthetic procedure for Activator 8. In Example 3, several activators were used to synthesize polymeric resins. The characteristics of the polymer resin were measured and recorded in Tables 1-3. One or more features of the present disclosure are illustrated with regard to examples according to the following: Example 1: Synthesis of Activator 1

[00100] A solution of nonafluoro-tert-butanol (7.0 g, 30 mmol) in toluene (100 ml) and ARMEEN M2HT, a di(hydrogenated tallow alkyl)(methyl)amine available from Akzo-Nobel, (3 .6 g, 6.7 mmol) was placed in the freezer at -35 °C. In a separate vial, a solution of trimethylaluminum in hexane (6.7 ml, 1 M, 6.7 mmol) in toluene (100 ml) was also placed in the freezer. The trimethylaluminum solution was slowly added to the nonafluoro-tert-butanol solution. Halfway through the addition, both vials were placed back in the glove box freezer and allowed to cool again for 30 minutes. The addition continued until all the aluminum was added. The combined solution was then stirred while warming to room temperature over 30 minutes and continued stirring overnight. The volatiles were then removed under vacuum and the remaining residue was used without further purification to provide 7.8 g of the activator, a 77% yield.

[00101] 19F NMR (376 MHz, CDCI3) δ -75.71. Example 2: Activator 8 Synthesis

[00102] Nonafluoro-tert-butanol (5.0 g, 21 mmol) was weighed into a small vial and dissolved in fluorobenzene (25 ml). AlMe3 (0.51 g, 7.1 mmol) was weighed into a separate flask, which was also dissolved in fluorobenzene (25 ml). Both vials were placed in the freezer (−35 °C) for 30 min. The AlMe3 solution was slowly added to the nonafluoro-tert-butanol solution and then placed in the freezer for 3 hours. During this time, a solution of pentafluorophenol (1.3 g, 7.1 mmol) in fluorobenzene (25 ml) and a solution of ARMEEN M2HT (3.8 g, 7.1 mmol) in fluorobenzene (25 ml) were prepared . The pentafluorophenol solution was slowly added to the cooled reaction mixture. After 3 minutes, the ARMEEN M2HT solution was then added. The reaction was allowed to warm to room temperature and was then stirred for 72 h. The resulting pale yellow solution was placed under vacuum to remove volatiles to yield the product (8.6 g, 84%).

Example 3 - Polymerization results

[00103] The polymerizations were carried out in a batch reactor according to the procedure described previously. Cocatalytic efficiency and resulting polymer characteristics were evaluated for 1.59 activators, each having an anionic structure according to formula (I) and a Group IV bis(phenylphenoxy) metal-ligand complex.

[00104] Each of metal activators 1 to 7 was mixed with Procatalyst A to form a catalyst system. Comparative C1 activator (here “comparative C1”) was mixed with Procatalyst A to form a comparative catalyst system. Comparative C1 had +NH(Me)(C18H37)2 as a countercation.

[00105] The efficiencies of the inventive activators 1 to 7 and the Comparative C1 activator (herein “comparative C1”) and the polymer characteristics of the polymers produced from the inventive activators 1-7 and comparative C1 were determined. The results are summarized in Tables 1 and 2. The Comparative C1 has been used successfully in industrial applications. TABLE 1: POLYOCTENE RESULTS

[00106] The results in Table 1 indicate that Activators 3, 5 and 7 were able to activate Procatalyst A and produce a polyoctene homopolymer. The “Temp. Max.” In Table 1 it was the maximum adiabatic temperature in degrees Celsius in the reactor. Increased adiabatic temperatures would indicate an increase in the amount of polymer produced.

[00107] The data in Table 2 were obtained at a polymerization temperature of 140 °C and the data in Table 3 were obtained at 190 °C. TABLE 2: BATCH REACTOR RESULTS AT 140 °C

[00108] Batch reactor conditions for Tables 2 and 3: 1.47 kg of Isopar™ E; 100 grams of octene, 410 psi of ethylene; the activator:procatalyst ratio was approximately 1.2; MMAO-3A was used as a scavenger at an MMAO-3A:procatalyst molar ratio of approximately 50. TABLE 3: BATCH REACTOR RESULTS AT 190 °C *Efficiency is defined in units of grams of polymer per gram of active metal (Hf or Zr). ELECTRICAL TEST CONDITIONS TABLE 4: RESULTS OF ELECTRICAL EXPERIMENTS CONDUCTED WITH THE SQUALENE TEST

[00109] The Hydrocarbon Conductivity Test, as described in this disclosure, simulates the post-polymerization process when the polymer resins produced are washed with water to remove the catalyst and co-catalyst residue. The results summarized in Table 8 indicate that Activator 1 has a lower dissipation factor than the anion - B(C6F5)4 present in C1 Comparative and therefore indicates that the polymers produced from Activator 1 are superior to the polymers produced from C1 Comparative in relation to its electrical properties.

[00110] Based on the results summarized in Table 4, it is believed that water interacts with the Activators of the invention to reduce the contribution of the Activators to the electrical properties. It is believed, without wishing to be limited by such belief, that water chemically reacts with the activator to form degradation products that do not contribute significantly to charge transport, causing the polymers produced by the inventive activators to exhibit low conductivity. However, it is believed that Comparative C1 does not react with water under HC Test conditions. Because comparative C1 consists of ionic species – anions and cations – it contributes to ionic charge transport before and after water addition.

[00111] As described previously, the hydrocarbon solution in the HC Test is heated to remove water. It is believed, without wishing to be limited by such belief, that water, antioxidant and/or heat from the water removal process degrade the inventive activators, resulting in the formation of degradation products that do not contribute significantly to charge transport. It is assumed that Comparative C1 does not degrade significantly under polymerization conditions and that, as an ionic species, Comparative C1 contributes to ionic charge transport in the elastomer. Since the inventive activators result in the formation of degradation products that do not contribute significantly to charge transport, the inventive activators are capable of producing insulting polymers.

[00112] In FIGURE, the TGIC spectrum for resins generated from activators of the present invention demonstrated that activators 1 and 8 produce polymer resins with narrow monomodal composition distributions similar to those achieved by -B(C6F5)4 anion present in the C1 Comparative. This is in contrast to Comparative C2, which shows a wide distribution of bimodal composition and leads to sticky pellets. Furthermore, the results summarized in Table 4 indicate that Activator 1 has a better dissipation factor than the -B(C6F5)4 anion present in Comparative C1.

HIGH COMMONOMER CONTENT (HCC) METHOD BY TGIC

[00113] A commercial Crystallization Elution Fractionation (CEF) instrument (Polymer Char, Spain) was used to perform high temperature thermal gradient interaction chromatography (TGIC) measurement (Cong, et al., Macromolecules, 2011 , 44 (8), 3,062 to 3,072). A HYPERCARB column (100 x 4.6 mm, Part # 35005-104646, Thermo Scientific) was used for separation. An “8 cm , MO, USA), was installed in front of the IR detector, in the upper oven of the CEF instrument. The experimental parameters are as follows: an upper oven/transfer line/needle temperature at 150 °C, a dissolution temperature at 160 °C, a dissolution stirring setting at 2, a sample loading volume of 0.400 ml , a pump settling time of 15 seconds, a cleaning column pump flow rate at 0.500 ml/m, a column loading pump flow rate at 0.300 ml/min, a settling temperature at 150° C, a stabilization time (pre, before loading onto the column) at 3.0 min, a stabilization time (post, after loading onto the column) at 1.0 min, an SF (Soluble Fraction) time at 3, 0 min, a cooling rate of 3.00 °C/min from 150 °C to 30 °C, a flow rate during the cooling process of 0.01 ml/min, heating rate of 2.00 °C /min from 30 °C to 160 °C, an isothermal time at 160 °C for 10 min, an elution flow rate of 0.500 ml/min and injection cycle size of 140 microliters.

[00114] Samples were prepared by the PolymerChar automatic sampler at 160 °C, for 60 minutes, at a concentration of 4.0 mg/ml in ODCB. Before use, silica gel 40 (particle size 0.2 approximately 0.5 mm, catalog number 10181-3, EMD) was dried in a vacuum oven at 160 °C for about two hours. An amount of 2,5-di-tert-butyl-4-methylphenol (1.6 grams, BHT, catalog number B1378-500G, Sigma-Aldrich) and silica gel (5.0 grams) were added to two liters of ortho-dichlorobenzene (ODCB, Grade 99% anhydrous, Sigma-Aldrich), creating an ODCB solution. The ODCB solution was purged with dry nitrogen (N2) for one hour before use.

[00115] TGIC data was processed on a “GPC One” software platform from PolymerChar (Spain). Temperature calibration was performed with a mixture of about 4 to 6 mg of eicosane, 14.0 mg of iPP isotactic polypropylene homopolymer (polydispersity of 3.6 to 4.0 and molecular weight (Mw) reported as polyethylene equivalent of 150,000 to 190,000 and polydispersity (Mw/Mn) of 3.6 to 4.0), and 14.0 mg of polyethylene HDPE homopolymer (zero comonomer content, Mw reported as polyethylene equivalent as 115,000 to 125,000 and polydispersity of 2.5 to 2.8), in a 10 ml vial filled with 7.0 ml of ODCB. The dissolution time was 2 hours at 160 °C.

[00116] The calibration process (30 °C to 150 °C for eicosane elution and HDPE elution) included the following steps: (1) the elution temperature was extrapolated for each of the isothermal steps during elution according to the heating rate (shown in Figure 1). (2) The delay volume was calculated and the temperature (x-axis) was shifted corresponding to the IR measurement channel chromatogram (y-axis) so that the eicosane peak (y-axis) coincided with the elution temperature at 30.0°C. The delay volume is calculated from the temperature difference (30°C - the actual elution temperature of the eicosane peak) divided by the method heating rate and then multiplied by the elution flow rate. (3) Each recorded elution temperature was adjusted with this same delay volume setting. (4) The heating rate was scaled linearly such that the HDPE reference has a peak elution temperature of 150.0 °C, while maintaining a peak eicosane elution temperature of 30.0 °C. Finally, (5) the peak temperature of polypropylene was observed between 119.3 and 120.2 °C, which is a validation of the calibration method.

DATA PROCESSING FOR TGIC POLYMER SAMPLES

[00117] A solvent blank (pure solvent injection) was run under the same experimental conditions as the polymer samples. Data processing for polymer samples includes: solvent blank subtraction for each detector channel, temperature extrapolation as described in the calibration process, temperature compensation with the delay volume determined by the calibration process, and adjustment on the temperature axis elution range up to the range of 30°C and 160°C as calculated from the calibration heating rate.

[00118] The chromatogram was integrated into the PolymerChar “GPC One” software. A straight baseline was drawn from the visible difference, when the peak falls to a flat baseline (approximately a zero value on the blank subtracted chromatogram) the high elution temperature and the minimum or flat region of the detector signal at the high temperature side of the soluble fraction (SF).

[00119] The upper limit of temperature integration is established based on the visible difference when the peak falls to the flat baseline region (approximately a zero value in the blank subtracted chromatogram). The lowest temperature integration limit is established based on the point of intersection of the baseline with the chromatogram including the soluble fraction.

[00120] “High Comonomer Content (HCC)” is defined as the weight percentage of material eluting at a temperature less than or equal to 65.0 °C. The HCC was calculated by integrating the IR measurement channel, at temperatures less than and including 65.0°C, and dividing this value by the total integration of the IR measurement channel.

Claims (11)

1. Olefin polymerization process, wherein the process is characterized by the fact that it comprises bringing ethylene into contact with a (C3-C40) alpha-olefin comonomer in the presence of a catalyst system to produce an ethylene-based polymer , wherein the catalyst system comprises a procatalyst and an ionic metal activator complex, wherein the ionic metal activator complex comprises an anion and a countercation, wherein the anion has a structure according to formula (I): where: M is aluminum, boron or gallium; n is 3 or 4; each R is independently selected from the group consisting of radicals with formula (II) and radicals with formula (III): each Y is independently carbon or silicon; 11 12 13 21 22 23 24 25 each R, R, R, R, R, R, R and R is independently chosen from (C1-C40)alkyl, (C6-C40)aryl, -ORC, -SRC, -H or -F, wherein, when R is a radical according to formula (III), at least one of R21, R22, R23, R24 or R25 is a halogen-substituted (C1-C40)alkyl, a ( C6-C40)aryl substituted by halogen or -F; and provided that: when each R is a radical according to formula (II) and Y is carbon, at least one of R11, R12 or R13 is a halogen-substituted (C1-C40)alkyl, a (C6-C40) aryl substituted by halogen or -F; and when M is aluminum and n is 4 and each R is a radical according to formula (II), and each Y is carbon: each R11, R12 and R13 of each R is a (C1-C40)alkyl substituted by halogen, a (C6-C40) halogen-substituted aryl, or -F or at least one R11, R12 or R13 is -H and a total number of halogen atoms in R11, R12 and R13 of each R is at least six; each (O)3RC; optionally, two R groups in formula (I) are covalently connected; each RC is independently (Ci-C3o)hydrocarbyl or -H; wherein when n is 4, at most one R is a radical having the formula (III); and the countercation is +N(H)RN3, where each RN is chosen from (Ci-C20)alkyl or (C6-C20)aryl; +C(C6H5)3; or +C(C6H4RC)3, where RC is (Ci-C20)alkyl; The procatalyst is selected from the group consisting of Group IV metal-ligand complexes (Group IVB according to CAS or Group 4 according to IUPAC naming conventions). 2. Polymerization process according to claim i, characterized by the fact that the procatalyst is a bis(phenylphenoxy) metal-ligand complex. 3. Polymerization process according to claim i, characterized by the fact that n is 4 and each R is independently -C(H)(CF3)2, -C6F5 or -C(CF3)3. 4. Polymerization process according to claim 1, characterized by the fact that n is 3 and X is chosen from -OH, triflate (-OTf), methyl or halogen. 5. Polymerization process according to claim 1, characterized by the fact that n is 4 and three of the four R groups are -C(CF3)3 and one of the four R groups is -C6F5. 6. Polymerization process according to claim 1, characterized by the fact that the countercation is +N(H)RN3, wherein each RN is chosen from (C1-C20)alkyl or (C6-C20)aryl. 7. Polymerization process according to claim 1, characterized by the fact that the countercation is +N(H)RaN3, in which at least two RN are chosen from (C10-C20)alkyl. 8. Polymerization process according to claim 1, characterized by the fact that the countercation is +C(C6H5)3. 9. Polymerization process according to claim 1, characterized by the fact that the countercation is +C(C6H4RC)3, where RC is (C1-C20)alkyl. 10. Polymerization process according to claim 1, characterized by the fact that two R groups are covalently connected and the anion has a structure according to formula (IV): where: M and X are defined in formula (I); n is 2; L represents the two R groups that are covalently connected; each L is independently chosen from (C2-C40)alkylene, (C2-C40)heteroalkylene or -(Si(RC)2-O)z-Si(RC)2-, where z is 0, 1, 2 or 3; and wherein RC is independently (C1-C30)hydrocarbyl or -H; and when n is 1, X is a monodentate ligand, independently chosen from halogen, (Ci-C2o)halogenated alkyl or triflate. 11. Polymerization process according to claim 1, characterized by the fact that the ionic metal activator complex in a fully saturated high boiling point hydrocarbon solution having a concentration of 200 micromoles of the ionic metal activator complex and 20 millimoles of water in a fully saturated hydrocarbon solution with a high boiling point has a percent dissipation factor less than or equal to 0.1, as measured by the Hydrocarbon Conductivity Test.