Olefin polymerization activators

Abstract

Processes of polymerizing olefins. The process includes polymerizing ethylene and optionally one or more α-olefin monomers in the presence of a catalyst system. The catalyst system includes a procatalyst and a metallic activator ionic complex. The metallic activator ionic complex comprises a cation and a weakly coordinating anion, the cation having a structure according to formula (I).

Description

84978-WO-PCT / DOW 84978 WO OLEFIN POLYMERIZATION ACTIVATORS CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 516,600 filed July 31, 2023, the contents of which are incorporated in their entirety herein. TECHNICAL FIELD

[0002] Embodiments of the present disclosure generally relate 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 or co-catalyst. BACKGROUND

[0003] Olefin based polymers, such as ethylene-based polymers, are produced via various catalyst systems. Selection of such catalyst systems can be an important factor contributing to the characteristics and properties of olefin-based polymers. The catalyst systems for producing polyethylene-based polymers may include a chromium-based catalyst system, a Ziegler–Natta catalyst system, or a molecular (either metallocene or non-metallocene) catalyst system.

[0004] Often, the catalyst systems used for ^-olefin polymerization reactions include a procatalyst that is activated to generate the catalytically active species for polymerization. The procatalyst can be activated by a number of means, such as by a co-catalyst or an activator. An activator may have characteristics that are beneficial for the production of the α-olefin polymer and for final polymer 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.

[0005] Presently, the number of available activators is very small compared to available procatalysts. Thus, there is a considerable need to expand the number of activators in order to identify the most commercially effective procatalyst / activator pair.84978-WO-PCT / DOW 84978 WO SUMMARY

[0006] One method of procatalyst activation employs a Brønsted acid activator. Brønsted acid salts containing weakly coordinating anions are commonly utilized to activate molecular polymerization procatalysts, particularly such procatalysts comprising Group IV metal complexes. Brønsted acid salts that are fully ionized are capable of transferring a proton to form a cationic derivative of such Group IV metal complexes. The cationic component of such activators may include cations capable of transferring a hydrogen ion, such as ammonium, sulfonium, or phosphonium; oxidizing cations, such as ferrocenium, silver, or lead; or highly Lewis acidic cations, such as carbonium or silylium.

[0007] Conventional olefin polymerization activators include weakly-coordinating or non- coordinating anions. For instance, such activators may include an R2Al+cation (R=hydrocarbon, alkoxides, amines, phosphines) paired with the non-coordinating -B(C6F5)4 anion. However, R2Al+cations have previously been reported to degrade -B(C6F5)4 in the absence of Lewis bases (Bochmann, M.; Sarsfield, M. J. Organometallics 1998, 17, 5908). Disclosed herein are activators comprising Lewis base additives to stabilize the cationic center and, hence, allow for shelf-stable, longer lived materials that still possess a high degree of Lewis acidity so as to be able to activate polyolefin procatalysts.

[0008] According to one or more embodiments disclosed herein, a process of polymerizing olefins includes polymerizing ethylene and optionally one or more α-olefin monomers in the presence of a catalyst system that includes a procatalyst metal-ligand complex and a metallic activator ionic complex. The metallic activator ionic complex includes a cation and a weakly coordinating counteranion, the cation having a structure according to formula (I):

[0009] The counteranion may be any weakly coordinating anion having a formal charge of - 1. In formula (I), M is magnesium, boron, aluminum, gallium, zinc, germanium or silicon. When M is zinc or magnesium, n is 1; when M is boron, aluminum, or gallium, n is 2; and when M is silicon or germanium, n is 3. In formula (I), m is 1, 2, or 3. Each R is a ligand independently selected from the group consisting of (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, –ORC, – SiCR, –CH2Si(ORC)wRCY, –CH2Si(NRN)wRCY, −NRN, and −NRN2; where RCis84978-WO-PCT / DOW 84978 WO (C1−C30)hydrocarbyl, RNis (C1−C30)hydrocarbyl or hydrogen, w is 1, 2, or 3, and y is 0, 1, or 2, provided that the sum of w plus y is 3. Each L is a neutral Lewis base. When n is 2 or 3, each R is optionally covalently connected to form a multidentate ligand. When m is 2 or 3, each L is optionally covalently connected to form a Lewis base having at least two coordinating atoms. DETAILED DESCRIPTION

[0010] Specific embodiments of the process of polymerizing olefins will now be described. It should be understood that the process of polymerizing olefins of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure.

[0011] The term “independently selected” is used herein to indicate that the R groups, such as, R1, R2, R3, R4, and R5, can be identical or different (e.g., R1, R2, R3, R4, and R5may all be substituted alkyls or R1and R2may be a substituted alkyl and R3may be an aryl, etc). A chemical name associated with an R group is intended to convey the chemical structure that is recognized in the art as corresponding to that of the chemical name. Thus, chemical names are intended to supplement and illustrate, not preclude, the structural definitions known to those of skill in the art.

[0012] 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 to a catalytically active catalyst. As used herein, the terms “co-catalyst” and “activator” are interchangeable terms.

[0013] When used to describe certain carbon atom-containing chemical groups, a parenthetical expression having the form “(Cx^Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (C1 ^C50)alkyl is an alkyl group having from 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted by one or more substituents such as RS. An RSsubstituted chemical group defined using the “(Cx ^Cy)” parenthetical may contain more than y carbon atoms depending on the identity of any groups RS. For example, a “(C1^C50)alkyl substituted with exactly one group RS, where RSis phenyl (−C6H5)” may contain from 7 to 56 carbon atoms. Thus, in general when a chemical group defined using the “(Cx^Cy)” parenthetical is substituted by one or more carbon atom-containing substituents RS, the minimum and maximum total number of carbon atoms of the chemical group is determined84978-WO-PCT / DOW 84978 WO by adding to both x and y the combined sum of the number of carbon atoms from all of the carbon atom-containing substituents RS.

[0014] The term “substitution” means that at least one hydrogen atom ( ^H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group 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.

[0015] The term “halogen-substituted” means that at least one hydrogen atom ( ^H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a halogen. The term “halogen-substituted” and “halogenated” are interchangeable. The term “perhalogenated” means that every hydrogen atom (−H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a halogen. The term “halogen-substituted” means that at least one hydrogen atom ( ^H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a halogen atom.

[0016] In this disclosure, the term “halogen atom” or “halogen” means the radical of a fluorine atom (F) or chlorine atom (Cl). The term “halide” means anionic form of the halogen atom: fluoride (F−) or chloride (Cl−).

[0017] The term “(C1 ^C50)hydrocarbyl” means a hydrocarbon radical of from 1 to 50 carbon atoms and the term “(C1 ^C50)hydrocarbylene” means a hydrocarbon diradical of from 1 to 50 carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (having three carbons or more, and including mono- and poly-cyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and substituted by one or more RSor unsubstituted.

[0018] In this disclosure, a (C1 ^C50)hydrocarbyl may 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)).

[0019] The terms “(C1 ^C50)alkyl” and “(C1 ^C18)alkyl” mean a saturated straight or branched hydrocarbon radical of from 1 to 50 carbon atoms and a saturated straight or branched hydrocarbon radical of from 1 to 18 carbon atoms, respectively, that is unsubstituted or substituted by one or more RS. Examples of unsubstituted (C1^C50)alkyl are unsubstituted (C1^C20)alkyl; unsubstituted84978-WO-PCT / DOW 84978 WO (C1^C10)alkyl; unsubstituted (C1^C5)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-decyl. Examples of substituted (C1 ^C40)alkyl are substituted (C1 ^C20)alkyl, substituted (C1 ^C10)alkyl, trifluoromethyl, and [C45]alkyl. The term “[C45]alkyl” means there is a maximum of 45 carbon atoms in the radical, including substituents, and is, for example, a (C27 ^C40)alkyl substituted by one RS, which is a (C1 ^C5)alkyl, respectively. Each (C1 ^C5)alkyl may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0020] The term “(C6 ^C50)aryl” means an unsubstituted or substituted (by one or more RS) monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical of from 6 to 50 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or non-fused and aromatic or non-aromatic.

[0021] The term “(C3 ^C50)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 50 carbon atoms that is unsubstituted or substituted 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 either unsubstituted or substituted with one or more RS.

[0022] Examples of (C1 ^C50)hydrocarbylene include unsubstituted or substituted (C6^C50)arylene, (C3^C50)cycloalkylene, and (C1^C50)alkylene (e.g., (C1^C20)alkylene). The diradicals may be on the same carbon atom (e.g., ^CH2^) or on adjacent carbon atoms (i.e., 1,2- diradicals), or are spaced apart by one, two, or more than two intervening carbon atoms (e.g., 1,3- diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or an α,ω-diradical, and others a 1,2-diradical. The α,ω-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2^C20)alkylene α,ω-diradicals include ethan- 1,2-diyl (i.e. ^CH2CH2^), propan-1,3-diyl (i.e. ^CH2CH2CH2^), 2-methylpropan-1,3-diyl (i.e. ^CH2CH(CH3)CH2^). Some examples of (C6^C50)arylene α,ω-diradicals include phenyl-1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl.

[0023] The term “(C1^C50)alkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 50 carbon atoms that is unsubstituted84978-WO-PCT / DOW 84978 WO or substituted by one or more RS. Examples of unsubstituted (C1^C50)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), in which “C*” denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1^C50)alkylene are substituted (C1^C20)alkylene, ^CF2^, ^C(O) ^, and ^(CH2)14C(CH3)2(CH2)5^ (i.e., a 6,6-dimethyl substituted normal-1,20-eicosylene).

[0024] The term “(C3^C50)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more RS.

[0025] The term “heteroatom,” refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S(O), S(O)2, Si(RC)2, P(RP), N(RN), ^N=C(RC)2, −Ge(RC)2−, or ^Si(RC) ^, where each RCand each RPis unsubstituted (C1^C18)hydrocarbyl or ^H, and where each RNis unsubstituted (C1−C18)hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. The term “(C1−C50)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 50 carbon atoms, and the term “(C1−C50)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 50 carbon atoms. The heterohydrocarbon of the (C1−C50)heterohydrocarbyl or the (C1−C50)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be on a single carbon atom or on a single heteroatom. Additionally, one of the two radicals of the diradical may be on a carbon atom and the other radical may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the ofther 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 poly-cyclic, fused and non-fused polycyclic), or acyclic.

[0026] The term “(C4^C50)heteroaryl” means an unsubstituted or substituted (by one or more RS) monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical of from 4 to 50 total carbon atoms and from 1 to 10 heteroatoms. A monocyclic heteroaromatic hydrocarbon radical includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings;84978-WO-PCT / DOW 84978 WO 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 non-fused and aromatic or non-aromatic.

[0027] The 5-membered ring monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms and may be 1, 2, or 3; and each heteroatom may be O, S, N, or P. The 6-membered ring monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms and may be 1 or 2 and the heteroatoms may be N or P.

[0028] The term “(C1−C50)heteroalkyl” means a saturated straight or branched chain radical containing one to fifty carbon atoms, and one or more heteroatom. The term “(C1−C50)heteroalkylene” means a saturated straight or branched chain diradical containing from 1 to 50 carbon atoms and one or more than one heteroatoms. The heteroatoms of the heteroalkyls or the 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.

[0029] Embodiments of this disclosure include processes for polymerizing olefins, the processes include polymerizing ethylene and optionally one or more α-olefin monomers in the presence of a catalyst system. The catalyst system includes a metallic activator ionic complex and a procatalyst metal-ligand complex.

[0030] Metallic Activator Ionic Complex

[0031] The metallic activator ionic complex of this disclosure includes a cation and a weakly coordinating anion, the cation having a structure according to formula (I):

[0032] In formula (I), M is magnesium, boron, aluminum, gallium, zinc, silicon, or germanium. When M is zinc or magnesium, n is 1; when M is boron, aluminum, or gallium, n is 2; and when M is silicon or germanium, n is 3. In embodiments, m is 1, 2, or 3.84978-WO-PCT / DOW 84978 WO

[0033] In embodiments, each R is a ligand independently selected from the group consisting of (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl –ORC, –SiCR, –CH2Si(ORC)wRCY, −CH2Si(NRN)wRCY, −N(RN)−, and −NRN2. In such embodiments, RCis (C1−C30)hydrocarbyl, RNis (C1−C30)hydrocarbyl or hydrogen, w is 0,1, 2, or 3, and y is 0, 1, 2, or 3, provided that the sum of w plus y is 3.

[0034] In some embodiments disclosed herein, R is (C1−C20)alkyl, −ORC, or –NRN2,. In various embodiments, R is (C1−C12)alkyl, −ORC, wherein RCis (C1−C10)alkyl, or –NRN2, where RNis (C6−C15)aryl or (C1−C12)alkyl. In embodiments, each R is independently octyl, –CH3, – OCH3, or −NPh2. In embodiments, n is 2 and each R is optionally covalently connected to form a multidentate ligand. In embodiments, n is 3 and each R is optionally covalently connected to form a multidentate ligand.

[0035] In some embodiments, each L is a neutral Lewis base. The term “Lewis base” refers to any species that has a filled orbital containing an electron pair which is not involved in bonding; that electron pair may form a dative bond with a Lewis acid. The Lewis base may be neutral or anionic. A neutral Lewis base has a formal charge of zero. In some embodiments, the Lewis base may be a heterohydrocarbon or a hydrocarbon. Examples of neutral heterohydrocarbon lewis bases includes, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. An example of anionic hydrocarbon includes, but is not limited to, cyclopentadiene. An example of a neutral hydrocarbon includes, but is not limited to, 1,3-buta-di-ene.

[0036] In various embodiments, the Lewis base is (C1−C20)heterohydrocarbon, wherein the hetero atom of the heterohydrocarbon is oxygen. In some embodiments, L is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0037] In various embodiments, L is tetrahydrofuran or trimethylamine. In some embodiments, m is 2 and each L is diethyl ether (OEt2). In some embodiments, m is 2 and each L is optionally covalently connected to form a Lewis base having at least two coordinating atoms. In embodiments, m is 3 and each L is optionally covalently connected to form a Lewis base having at least two coordinating atoms.

[0038] In one or more embodiments, the anion of the metallic activator ionic complex has a formal charge of negative one (-1). In embodiments, the anion has the general formula [XQ4]-. In such embodiments, X is boron, aluminum, or gallium. Also in such embodiments, each Q is independently selected from the group consisting of (C6–C40)aryl, (C1–C40)hydrocarbyl, –ORC, −SiRC, −CH2Si(ORC)wRCy, halogen substituted (C6–C40)aryl, halogen substituted84978-WO-PCT / DOW 84978 WO (C1−C40)hydrocarbyl, halogen substituted (–ORC), halogen substituted –SiRC, and halogen substituted −CH2Si(ORC)wRCy, wherein RCis (C1−C30)hydrocarbyl or halogen substituted (C1−C30)hydrocarbyl, w + y is 3 provided that at least three of the four group Q are fluorine atoms or fluorine substituted hydrocarbyl. In embodiments, the anion is [B(C6F5)4]-.

[0039] In embodiments, the anion of the metallic activator ionic complex has the general formula (II):

[0040] In embodiments, each M2in formula (II) is independently aluminum, boron, or gallium. In embodiments, BLis chosen from a species having at least two Lewis basic sites. In embodiments, each Q is independently a monodentate ligand. In embodiments, the subscript x is 0, 1, 2, or 3. In embodiments, when the subscript x is 0, Q of Qx is not present. In embodiments, when the subscript x is 3, (O-R) is not present on the “x” portion connected to M2. In embodiments, subscript n is 0, 1, 2, or 3. In embodiments, when subscript n is 0, Q of Qn is not present. In embodiments, when the subscript n is 3, (O-R) is not present on the “n” portion connected to M2.

[0041] In embodiments, each R in formula (II) is independently selected from the group consisting of radicals having formula (III) and radicals having formula (IV):

[0042] In formula (III), Y is independently carbon or silicon; R11, R12, R13are independently chosen from (C1-C40)alkyl, (C6-C40)aryl, —H, —NRN2, —ORC, —SRC, or halogen. In one or more embodiments, when R is a radical having the formula (III), at least at least one of R11, R12, or R13is perhalogenated (C1-C4)alkyl, perhalogenated (C6-C40)aryl, or —F. In some embodiments, when R is a radical having the formula (III), at least at least one of R11, R12, or R13is a halogen- substituted (C1−C40)alkyl, a halogen-substituted (C6-C40)aryl, or —F; each RNor RCis independently (C1−C30)hydrocarbyl or —H.84978-WO-PCT / DOW 84978 WO

[0043] In formula (IV), R21, R22, R23, R24, and R25are independently chosen from (C1−C40)alkyl, (C6-C40)aryl, —H, —NRN2, —ORC, —SRC, or halogen. In one or more embodiments, when R is a radical having the formula (IV), at least at least one of R21, R22, R23, R24, or R25is perhalogenated (C1-C40)alkyl, perhalogenated (C6-C40)aryl, or —F. In some embodiments, when R is a radical having the formula (IV), at least one of R21, R22, R23, R24, or R25is a halogen-substituted (C1-C40)alkyl, a halogen-substituted (C6-C40)aryl, or —F; each RNor RCis independently (C1-C30)hydrocarbyl or —H.

[0044] In one or more embodiments, in formula (II), BLis a species containing two or more than two Lewis basic sites. In some embodiments, BL is an anionic species containing at least two Lewis basic sites. The anionic species may be polyatomic or monoatomic (such as chloride or fluoride). Each Lewis basic site may be on a different atom of the anionic species or each Lewis basic site may be on the same atom of the anionic species. In some embodiments, BL is chosen from (C1-C20)heterohydrocarbon anion, (C2-C10)heteroaromatic anion,−OC(O)RL,−S(O)3RL,−P(O)3RL, —P(O)2(ORL)3,−NRL2,−ORL,−SRL, or halide, wherein RLis —H, (C1-C30)hydrocarbyl, or halogen-substituted (C1-C30)hydrocarbyl. In some embodiments, BL is−OC(O)RL, RLis chosen from —C6F5, —CH3 (methyl), ethyl, propyl, 2- propyl, n-butyl, tert-butyl, 2,2-dimethylethyl, n-octyl, or tert-octyl (also called 1,1,3,3- tetramethylbutyl). In some embodiments, RLmay be substituted with one or more than one halogen. In other embodiments, BL is —OS(O)2CF3. In some embodiments, BL anionic species containing two or more than two Lewis basic sites and is not a halogen or halide; specifically, L is anionic species containing two or more than two Lewis basic sites and is not fluoride (—F).

[0045] In some embodiments, BL is a anionic compound having the formula (V):

[0046] In formula (V), R1and R2are independently selected from —C(RL)— or —N—, wherein RLis —H, (C1-C30)hydrocarbyl, halogen-substituted (C1-C30)hydrocarbyl, and R3is chosen from —H, (C1-C30)hydrocarbyl, halogen-substituted (C1-C30)hydrocarbyl. In some embodiments, R3is (C2-C3)heterohydrocarbylene connected to R2.84978-WO-PCT / DOW 84978 WO

[0047] In some one or more embodiments, when BLis according to formula (V), R1is — C(C11H23)— and R2is —C(H)—. In some embodiments, R is —C(H)—, R2is —N—, and R3 is —H. In other embodiments, R1is —N—, R2is —C(H)—, and R3is —H.

[0048] In one or more embodiments, when R2and R3are linked together to form a ring, BLis selected from a radical having the formula (VI):

[0049] In formula (VI), each R4is independently a (C1-C30)hydrocarbyl or —H; and R1is as previously defined in formula (V).

[0050] In other embodiments, BL is selected from radicals having a formula (VII):

[0051] In formula (VII), R5, R6, and R7are independently (C1-C30)hydrocarbyl or —H.

[0052] In one or more embodiments, BL is selected from radicals having a formula (VIII):

[0053] In formula (VIII), R10is chosen from the group —H, —NRN2, —SiRC3, —PRP3, (C1−C30)hydrocarbyl; and each of R8and R9is chosen from —H or (C1-C30)alkyl.

[0054] In some embodiments, each R of formula (II) is a radical having the formula (III), wherein Y is carbon, R11, R12, and R13are fluorine.84978-WO-PCT / DOW 84978 WO

[0055] In some embodiments, each Q of formula (II) is independently a monodentate is chosen from unsaturated (C2-C50)hydrocarbon, unsaturated (C2-C50)heterohydrocarbon, (C1- C50)hydrocarbyl, (C6-C50)aryl, (C6-C50)heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C12)diene, halogen, —N(RN)2, and —NCORC, in which each RNand each RCare independently (C1-C20)alkyl. In various embodiments, X is selected from methyl; ethyl; 1- propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chloro. In some embodiments, each Q is identical. In one or more embodiments, subscript x of Qx is 0. In various embodiments, subscript n of Qnis 0.

[0056] In embodiments, the anion of the metallic activator ionic complex has the general formula (IX):

[0057] In formula (IX), each X is a monodentate ligand independently chosen from halogen, halogen-substituted (C1−C20)alkyl, (C1−C20)alkyl, halogen-substituted (C6−C40)aryl, (C6−C40)aryl, or –S(O)3RC.

[0058] In formula (IX), each M3is independently aluminum, boron, or gallium; subscript n is 0, 1, 2, 3, or 4. Each T is independently selected from the group consisting of radicals having formula (X) and radicals having formula (XI):

[0059] In formula (XI), each Y is independently carbon or silicon; each R11, R12, R13, is independently chosen from (C1−C40)alkyl, (C6−C40)aryl, –H, −NRN2, −ORC, –SRC, or halogen. In some embodiments of formula (IX), when each R is a radical according to formula (X) and Y is carbon, at least one of R11-13is a halogen-substituted (C1−C40)alkyl, a halogen-substituted (C6−C40)aryl, or –F. In other embodiments of formula (IX), when M is aluminum, n is 4, each R84978-WO-PCT / DOW 84978 WO is a radical according to formula (X), and each Y is carbon (1) each R11, R12, and R13of each R is a halogen-substituted (C1−C40)alkyl, a halogen-substituted (C6−C40)aryl, or –F; or (2) a total number of fluorine atoms in R11, R12, and R13of each R is at least six (specifically, the number of fluorine atoms on R11, R12, and R13is greater than or equal to six (total number of Fatom= R11+ R12+ R13≥ 6)).

[0060] In formula (XI), each R21, R22, R23, R24, and R25is independently chosen from (C1−C40)alkyl, (C6−C40)aryl, –H, −NRN2, −ORC, –SRC, or halogen. When T is a radical according to formula (XI), at least one of R21-25is a halogen-substituted (C1−C40)alkyl , a halogen-substituted (C6−C40)aryl, or –F.

[0061] In one or more embodiments of anion of formula (IX), subscript n is 4 and each T group is independently −C(H)(CF3)2, −C6F5, or −C(CF3)3. In other embodiments, subscript n is 4, and three of the four T groups are −C(CF3)3 and one of the four T groups is –C6F5. In some embodiments, n is 3 and X is chosen from –OH, triflate (−OTf), methyl, or halogen.

[0062] In one or more embodiments of the anion of formula (IX), two T groups are covalently connected and the anion has a structure according to formula (XII):

[0063] In formula (XII), M4 and X4 are as defined in formula (IX); subscript n is 1 or 2. L represents the two groups R that are covalently connected; and each L is independently chosen from (C2−C40)alkylene, or (C2−C40)heteroalkylene.

[0064] In formula (XII), when n is 1, X4is a monodentate ligand independently chosen from halogenated-(C1−C20)alkyl.

[0065] In one or more embodiments of the anion of formula (XII), L is a halogenated biphenyl diradical ion or halogenated naphthalene-diyl. The halogenated biphenyl diradical ion may have a single radical on each of the phenyl rings. The diradicals on the halogenated naphthalene-diyl may be separated by four or more carbon atoms in the naphthalene.84978-WO-PCT / DOW 84978 WO

[0066] In some embodiments, the anion has a structure according to formula (XXX):

[0067] In formula (XXX), R301and each X300are each independently selected from the following: a halogen, a substituted or unsubstituted (C1‑C40)hydrocarbyl, or a substituted orRCOC(O)−, RCC(O)N(RC)−, (RC)2NC(O)−, or hydrogen. In formula (XXX), at least one of X300or R301is a halogen atom.

[0068] In formula(XXX), each RCis independently a substituted or unsubstituted (C1‑C35)hydrocarbyl, or a substituted or unsubstituted (C1‑C35)heterohydrocarbyl. In some embodiments, two or more of X300may optionally form one or more ring structures. In various embodiments, two or more of X300and R301may optionally form one or more ring structures. One or more hydrogen atoms may optionally be substituted with deuterium.

[0069] In embodiments, halogen atom includes the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). In some embodiments, X300is fluorine. In some embodiments, each X300is chlorine. In other embodiments, each X300is bromine.

[0070] A person of ordinary skill in the art would recognize that the structure of formula (XXX) is a carborane anion. When each X300is chlorine, the structure of formula (XXX) has an empirical formula of−B11CR301Cl11, in which B are boron atoms, C is a carbon atom, Cl are chlorine atoms, and R301is previously defined. Each chlorine atom of formula (XXX) is bonded to the boron atom.

[0071] Procatalyst Metal-Ligand Complex84978-WO-PCT / DOW 84978 WO

[0072] In embodiments of the process disclosed herein, the procatalyst of the catalyst system has the structure according to formula (XIII):

[0073] In formula (XIII), M5is a metal chosen from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4. Subscript n of (X)n is 0, 1, or 2. When subscript n is 1, X5is a monodentate ligand or a bidentate ligand, and when subscript n is 2, each X5is a monodentate ligand. Each Z is independently chosen from −O−, −S−, −N(RN)−, or –P(RP)−; R2−4, R5−8, R9−12and R13−15are 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. In formula (XIII), R1and R16are selected from radicals having formula (XIV), radicals having formula (XV), and radicals having formula (XVI):

[0074] In formulas (XIV), (XV), and (XVI), each of R31–35, R41–48, and R51–59is independently chosen from –H, (C1 ^C40)hydrocarbyl, (C1 ^C40)heterohydrocarbyl, −Si(RC)3, −Ge(RC)3, −P(RP)2,RCOC(O)−, RCC(O)N(RN)−, (RC)2NC(O)−, or halogen.

[0075] In one or more embodiments, each X5of formula (XIII) can be a monodentate ligand that, independently from any other ligands X5, is a halogen, unsubstituted (C1 ^C20)hydrocarbyl, unsubstituted(C1 ^C20)hydrocarbylC(O)O–, or RKRLN−, wherein each of RKand RLindependently is an unsubstituted (C1 ^C20)hydrocarbyl.84978-WO-PCT / DOW 84978 WO

[0076] In embodiments of the process disclosed herein, the procatalyst of the catalyst system has the structure according to formula (XVII):

[0077] In embodiments of the process disclosed herein, the procatalyst of the catalyst system has the structure according to formula (XVIII):

[0078] In embodiments of the process disclosed herein, the procatalyst of the catalyst system has the structure according to formula (XX):

[0079] In formula (XX), M6 is hafnium, titanium or zirconium; n is 0, 1, or 2, m is 0, 1, or 2, provided that when m is 2, n is 0, and when n is 2, m is 0; and each X6 is a monodentate ligand independently chosen from (C1^C50)hydrocarbon, (C1−C50)heterohydrocarbon, (C1−C50)hydrocarbyl, (C6−C50)aryl, (C6−C50)heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4−C12)diene, halogen, hydrogen, −N(RN)2, and −NCORC. The metal–ligand complex is overall charge-neutral.84978-WO-PCT / DOW 84978 WO

[0080] In formula (XX), N is nitrogen; W6is carbon or silicon and is covalently bonded to cyclopentadiene; and R1 and R2 are independently selected from −H, (C1−C40)hydrocarbyl, and (C1−C40)heterohydrocarbyl; R3 are independently selected from (C1−C40)hydrocarbyl, and (C1−C40)heterohydrocarbyl.

[0081] In formula (XX), Y6is independent Lewis base. In some embodiments, Y6is chosen from (C1−C20)heterohydrocarbon, wherein the hetero atom of the heterohydrocarbon is oxygen. In some embodiments, Y6 is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0082] In formula (XX), R4, R5, R6, and R7are independently (C1^C50)hydrocarbyl, (C1^C50)heterohydrocarbyl wherein any of the R4, R5, R6, and R7optionally are connected to form a ring structure.

[0083] In some embodiments, when n is 1, m is 1. In embodiments, m + n is 2.

[0084] In various embodiments, in formula (XX), R4, R5, R6, and R7 are (C1−C12)alkyl; or R4 and R7are (C1−C12)alkyl, or R5and R6are (C1−C12)alkyl or R6and R7are (C1−C12)alkyl.

[0085] In one or more embodiments, in formula (XX), R1and R2are methyl, ethyl, propyl, or phenyl. In some embodiments, R3 is independently (C1−C12)alkyl. In various embodiments, R3 is independently tert-butyl, tert-octyl, or n-octyl.

[0086] In some embodiments, the process includes a procatalyst of formula (XX). An illustrative, non-limiting list of the procatalyst of formula (XX) has the structure according to formula (XXI), (XXI)a, and (XXI)b:

[0087] In embodiments of the process disclosed herein, the procatalyst of the catalyst system has the structure according to formula (XXII):84978-WO-PCT / DOW 84978 WO LpiM7X7mX71nX72p, (XXII) or a dimer thereof (XXIII).

[0088] In formula (XXII), Lp is an anionic, delocalized, π-bonded group that is bound to M7, containing up to 50 non-hydrogen atoms. In some embodiments of formula (XXIII), two Lp groups may be joined together forming a bridged structure, and further optionally one Lp may be bound to X.

[0089] In formulas (XXII) and (XXIII), M7is a metal of Group 4 of the Periodic Table of the Elements in the +2, +3 or +4 formal oxidation state. X7is an optional, divalent substituent of up to 50 non-hydrogen atoms that together with Lp forms a metallocycle with M. X71is a neutral or monoanioic ligand independently selected from (C1−C20)hydrocarbyl or (C1−C20)heterohydrocarbyl; each X72is independently a monovalent, anionic moiety independently selected from (C1−C40)hydrocarbyl or (C1−C40)heterohydrocarbyl. Optionally, two X72groups may be covalently bound together forming a divalent dianionic moiety having both valences bound to M7, or, optionally two X72groups may be covalently bound together to form a neutral, conjugated or nonconjugated diene that is π-bonded to M7, in which M is in the +2 oxidation state. In other embodiments, one or more X72and one or more X71groups may be bonded together thereby forming a moiety that is both covalently bound to M and coordinated thereto by means of Lewis base functionality. Subscript i of Lpiis 0, 1, or 2; subscript n of X71nis 0, 1, 2, or 3; subscript m of X7m is 0 or 1; and subscript p of X72p is 0, 1, 2, or 3. The sum of i + m + p is equal to the formula oxidation state of M7.

[0090] In some embodiments, the process includes a procatalyst of formula (XXII). An illustrative, non-limiting list of the procatalyst of formula (XXII) has the structure according to formulas (XXIV) and (XXV):

[0091] In embodiments of the process disclosed herein, the procatalyst of the catalyst system has the structure according to formula (XXVI):84978-WO-PCT / DOW 84978 WO

[0092] In formula (XXVI), each X is a monodentate ligand independently chosen from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, -CH2Si(RC)3-Q(ORC)Q, −Si(RC)3-Q(ORC)Q, -OSi(RC)3-Q(ORC)Q, −CH2Ge(RC)3-Q(ORC)Q, −Ge(RC)3-Q(ORC)Q, −P(RC)2-W(ORC)W, −P(O)(RC)2-W(ORC)W, −N(RC)2, −NH(RC), −N(Si(RC)3)2, −NRCSi(RC)3, −NHSi(RC)3, −ORC, −SRC, −NO2, −CN, −CF3, −OCF3, a halogen, wherein each RCis independently a (C1−C30)hydrocarbyl, or (C1−C30)heterohydrocarbyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1, or 2; each RYis –H, (C1−C30)hydrocarbyl, or halogen atom, wherein two X ligands can be connected to form a ring, wherein one member of the ring is M8.

[0093] In formula (XXVI), each Y8 is independently Lewis Base; optionally, X and Y can be linked to form a ring. Each subscript m is 1 and 2; and each subscript n is 0, 1 and 2. The metal– ligand complex is overall charge-neutral.

[0094] In formula (XXVI), M8 is titanium, zirconium, or hafnium; R81, R82, R83, R84, and R85are independently (C1 ^C50)hydrocarbyl, (C1 ^C50)heterohydrocarbyl wherein any of the R82, R83, R84, and R85optionally are connected to form a ring structure; R86, R87, and R88are independently (C1^C20)hydrocarbyl, (C1^C20)heterohydrocarbyl, (C6^C30)aryl, (C5^C30)heteroaryl wherein two of R86, R87, and R88are optionally connected to form a ring; and

[0095] In some embodiments, R81, R82, R83, R84, and R85are independently (C1 ^C50)hydrocarbyl, wherein R81and R82are optionally connected to form a ring, or R82and R83are optionally connected to form a ring, R83and R84are optionally connected to form a ring, R84and R55optionally are connected to form a ring. In various embodiments, R86, R87, and R88are independently (C1^C20)hydrocarbyl, (C1^C20)heterohydrocarbyl, (C6^C30)aryl, (C5^C30)heteroaryl wherein two of R56, R57, and R58are optionally connected to form a ring.

[0096] In formula (XXVI), each RC, RP, and RNis independently a (C1^C30)hydrocarbyl, (C1^C30)heterohydrocarbyl, or ^H.84978-WO-PCT / DOW 84978 WO

[0097] In some embodiments, the process includes a procatalyst of formula (XXVI). An illustrative, non-limiting list of the procatalyst of formula (XXVI) has the structure according to formula (XXVII):

[0098] In embodiments of the process disclosed herein, the procatalyst of the catalyst system has the structure according to formula (XXVIII):

[0099] In formula (XXIX), each X is a monodentate ligand independently chosen from (C1−C50)hydrocarbyl or (C1−C50)heterohydrocarbyl, or a halogen. Subscript a is 1 or 2. In formula (XXIX), R91, R92, R93, R94, R95, R96, and R97are independently (C1^C50)hydrocarbyl or (C1^C50)heterohydrocarbyl.

[0100] In one or more embodiments, R92and R93are optionally connected to form a ring structure.

[0101] In some embodiments, the process includes a procatalyst of formula (XXVIII). An illustrative, non-limiting list of the procatalyst of formula (XXVIII) has the structure according to formula (XXIX):

[0102] Polymerization84978-WO-PCT / DOW 84978 WO

[0103] Embodiments of the process described herein may be utilized in the polymerization of ethylene and optionally one or more α-olefin monomers in the presence of the catalyst system described in the previous paragraphs. In some embodiments, there is only a single olefin, ethylene, in the polymerization scheme, creating a polyethylene homopolymer. However, additional α- olefins may be incorporated into the polymerization procedure. The additional α-olefin co- monomers typically have no more than 20 carbon atoms. For example, the α-olefin co-monomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin co-monomers 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-ethyldiene-2-norbornene, and 5-vinyl-2-norbornene. For example, the one or more α-olefin co-monomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or in the alternative, from the group consisting of 1- hexene and 1-octene.

[0104] Ethylene-based polymers, for example homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more co-monomers such as α-olefins, may comprise from at least 50 mole percent (mol%) monomer units derived from ethylene. All individual values and subranges encompassed by “from at least 50 mol%” are disclosed herein as separate embodiments; for example, the ethylene-based polymers, homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more co-monomers such as α-olefins may comprise at least 60 mol% monomer units derived from ethylene; at least 70 mol% monomer units derived from ethylene; at least 80 mol% monomer units derived from ethylene; or from 50 to 100 mol% monomer units derived from ethylene; or from 80 to 100 mol% units derived from ethylene.

[0105] In some embodiments, the ethylene-based polymers may comprise at least 90 mole percent units derived from ethylene. All individual values and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymers may comprise at least 93 mole percent units derived from ethylene; at least 96 mole percent units; at least 97 mole percent units derived from ethylene; or in the alternative, from 90 to 100 mole percent units derived from ethylene; from 90 to 99.5 mole percent units derived from ethylene; or from 97 to 99.5 mole percent units derived from ethylene.

[0106] In some embodiments of the ethylene-based polymer, the ethylene-based polymers may comprise an amount of (C3−C20) ^-olefin. The amount of (C3−C20) ^-olefin is less than 50 mol%. In some embodiments, the ethylene-based polymer may include at least 0.5 mol% to84978-WO-PCT / DOW 84978 WO 25 mol% of (C3−C20) ^-olefin; and in further embodiments, the ethylene-based polymer may include at least 5 mol% to 10 mol%. In some embodiments, the additional ^-olefin is 1-octene.

[0107] Any conventional polymerization process, in combination with a catalyst system according to embodiments of this disclosure may 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 reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors in parallel, series, or any combinations thereof, for example.

[0108] In embodiments of the process disclosed herein, an ethylene-based polymer may be produced in reactor at a reaction temperature. In embodiments, the reaction temperature may be from 100 ℃ to 200 ℃, such as from 100 ℃ to 125 ℃, from 125 ℃ to 150 ℃, from 150 ℃ to 175 ℃, or from 175 ℃ to 200 ℃. In some embodiments, the reactor may be a solution reactor. In such embodiments, the solution reactor may comprise one or more solvents. In embodiments, the one or more solvents may be a hydrocarbon, an aliphatic hydrocarbon, a non-halogenated hydrocarbon, a non-aromatic hydrocarbon, or combinations thereof.

[0109] In one embodiment, an ethylene-based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more ^-olefins are polymerized in the presence of the catalyst system, as described herein, and optionally one or more co-catalysts. In another embodiment, the ethylene- based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more ^-olefins are polymerized in the presence of the catalyst system in this 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 second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more ^-olefins are polymerized in the presence of the catalyst system, as described herein, in both reactors.

[0110] In another embodiment, the ethylene-based polymer may be produced via solution polymerization in a single reactor system, for example a single loop reactor system, in which84978-WO-PCT / DOW 84978 WO ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system, as described within this disclosure.

[0111] The polymer process may further include incorporating 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. The ethylene-based polymers may contain any amounts of additives. The ethylene-based polymers may comprise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene-based polymers and the one or more additives. The ethylene-based polymers may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers. The ethylene-based polymers may contain from 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. The ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0112] In some embodiments, a polymerization process for producing an ethylene-based polymer may include polymerizing ethylene and at least one additional ^-olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one procatalyst metal–ligand complex and a metallic activator ionic complex. The polymer resulting from such a catalyst system that incorporates the procatalyst metal–ligand complex and the metallic activator ionic complex may have a density according to ASTM D792 (incorporated herein by reference in its entirety) from 0.850 g / cm3to 0.967 g / cm3, from 0.870 g / cm3to 0.920 g / cm3, from 0.870 g / cm3to 0.910 g / cm3, or from 0.870 g / cm3to 0.900 g / cm3, for example.

[0113] In another embodiment, the polymer resulting from the catalyst system that includes the procatalyst metal–ligand complex and a metallic activator ionic complex has a melt flow ratio (I10 / I2) from 5 to 15, in which melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190 °C and 2.16 kg load, and melt index I10is measured according to ASTM D1238 at 190 °C and 10 kg load. In other embodiments the melt flow ratio (I10 / I2) is from 5 to 10, and in others, the melt flow ratio is from 5 to 9.

[0114] In some embodiments, the polymer resulting from the catalyst system that includes the procatalyst metal–ligand complex and the metallic activator ionic complex has a molecular-weight distribution (MWD) from 1 to 25, where MWD is defined as Mw / Mn with Mw being a weight- average molecular weight and Mn being a number-average molecular weight. In other84978-WO-PCT / DOW 84978 WO embodiments, the polymers resulting from the catalyst system have a MWD from 1 to 6. Another embodiment includes a MWD from 1 to 3; and other embodiments include MWD from 1.5 to 2.5.

[0115] Compositional Conventional Gel Permeation Chromatography

[0116] The chromatographic system consisted of a Polymer Char GPC-IR (Valencia, Spain) high temperature GPC chromatograph, equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set at 160° Celsius, and the column compartment was set at 150° Celsius. The columns were one Agilent PLgel MIXED 7.5 x 50 mm, 20 µm linear mixed- bed guard column and four Agilent PLgel MIXED-A 7.5 x 300 mm, 20 µm linear mixed-bed columns. The chromatographic solvent was 1,2,4-trichlorobenzene, which contained 300 ppm of butylated hydroxytoluene (BHT) and was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0117] Calibration of the GPC column set was performed using Agilent EasiCal Polystyrene standards (EasiCal PS-1 and EasiCal PS-2). Each EasiCal system consisted of two different spatulas supporting a mixture of 5 polymer standards (approximately 5 mg) to obtain 20 molecular weights points ranging from approximately 580 to 6,570,000 g / mole. Individual spatulas were added to septa-capped vials, sealed, and loaded into the Polymer Char autosampler. Polymer Char Instrument Control Software was utilized to add 8 mL of solvent to each vial and the standards were dissolved for 15 minutes at 160° Celsius under high-speed shaking prior to injection to the chromatography system. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).:where M is the molecular weight, A has a value of 0.41 and B is equal to 1.0.

[0118] A third order polynomial was used to fit the nominal polystyrene standard peak molecular weights to obtain molecular weight equivalent calibration points at each chromatographic slice.

[0119] The total plate count of the GPC column set was performed with decane [3% v / v in 1,2,4-trichlorobenzene (TCB) introduced via micropump]. The plate count for the chromatographic system should be greater than 18,000 for the 4 Agilent “Mixed A” 30 cm 20- micron linear mixed-bed columns.

[0120] Samples were prepared in a semi-automatic manner with the Polymer Char Instrument Control Software, wherein the samples were weight-targeted at 2 mg / ml, and the solvent was84978-WO-PCT / DOW 84978 WO added to a septa-capped sealed vial via the Polymer Char high temperature autosampler. The samples were dissolved for two hours at 160° Celsius under high-speed shaking.

[0121] The calculations of Mn(GPC), Mw(GPC), and Mz(GPC) were based on GPC results using the internal IR5 detector (measurement channel) of the Polymer Char GPC-IR chromatograph according to Equations 2-4. Using Polymer Char GPCOne™ software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i) was converted to the polystyrene equivalent molecular weight, obtained from the narrow standard calibration curve, for the equivalent chromatographic data point (i). Equations 2-4 are as follows:

[0125] In order to monitor the deviations over time, a flowrate marker (3% v / v decane in solvent) was introduced into each sample via a micropump controlled with the Polymer Char GPC-IR system. This flowrate marker (FM) was used to linearly correct the pump flowrate [Flowrate(nominal)] for each sample by RV alignment of the respective decane peak within the sample [RV(FM Sample)] to that of the decane peak within the narrow standards calibration [RV(FM Calibrated)]. Any changes in the time of the decane marker peak were then assumed to be related to a linear-shift in flowrate [Flowrate(effective)] for the entire run. After calibrating the system based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 5. Processing of the flow marker peak was done via the Polymer Char GPCOne™ Software. Acceptable flowrate correction is such that the effective flowrate should be within + / -0.7% of the nominal flowrate. Flowrate(effective) = Flowrate(nominal) * (RV(FM Calibrated) / RV(FM Sample)) (EQ 5)

[0126] Octene Composition Calibration

[0127] A calibration for the IR5 detector was performed using at least ten (co)polymer standards. Homopolyethylene and ethylene / octene copolymers of a narrow short-chain branching (SCB) distribution and known comonomer content (as measured by13C NMR Method, Qiu et al.,84978-WO-PCT / DOW 84978 WO Anal. Chem. 2009, 81, 8585−8589) were prepared using a single-site metallocene catalyst in a single reactor in solution process. SCB ranged from 0 SCB / 1000 total C (homopolyethylene) to approximately 40 SCB / 1000 total C, where total C = carbons in backbone + carbons in branches. Each standard had a weight-average molecular weight from 36,000 g / mole to 126,000 g / mole, as measured by GPC. Each standard had a molecular weight distribution (Mw / Mn) from 2.0 to 2.5. Polymer properties for the SCB standards are shown in Table A.

[0128] Table A: “Copolymer” Standards

[0129] The “IR5 Area Ratio (orbaseline-subtracted area response of the IR5 methyl channel sensor” to “the baseline-subtracted area response of IR5 measurement channel sensor” (standard filters and filter wheel as supplied by Polymer Char: Part Number IR5_FWM01 included as part of the GPC-IR instrument) was calculated for each of the “Copolymer” standards. A linear fit of the wt % comonomer frequency versus the “IR5 Area Ratio” was constructed in the form of the following Equation 6: wt % Comonomer = A0+ [A1x (IR5Methyl Channel Area / IR5Measurement Channel Area)] (EQ 6)

[0130] where A0is the “wt % Comonomer” intercept at an “IR5 Area Ratio” of zero, and A1is the slope of the “wt % Comonomer” versus “IR5 Area Ratio” and represents the increase in the wt % Comonomer as a function of “IR5 Area Ratio.” The IR5 area ratio is equal to the IR5 height ratio for narrow PDI and narrow SCBD standard materials.

[0131] A first aspect of the present disclosure is directed to a process of polymerizing olefins, the process comprising polymerizing ethylene and optionally one or more α-olefin monomers in the presence of a catalyst system, the catalyst system comprising a procatalyst and a metallic activator ionic complex, wherein the metallic activator ionic complex comprises a cation and a weakly coordinating anion, the cation having a structure according to formula (I):84978-WO-PCT / DOW 84978 WOwhere: M is magnesium, boron, aluminum, gallium, zinc, silicon or germanium; when M is zinc or magnesium, n is 1; when M is boron, aluminum, or gallium, n is 2; when M is silicon or germanium, n is 3; m is 1, 2, or 3; each R is a ligand independently selected from the group consisting of (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, –ORC, –SiCR, – CH2Si(ORC)wRCY, –CH2Si(NRN)wRCY, −NRN, and −NRN2; where RCis (C1−C30)hydrocarbyl, RNis (C1−C30)hydrocarbyl or hydrogen, w is 1, 2, or 3, and y is 0, 1, or 2, provided that the sum of w plus y is 3; and each L is a neutral Lewis base; and provided that: when n is 2 or 3, each R is optionally covalently connected to form a multidentate ligand; and when m is 2 or 3, each L is optionally covalently connected to form a Lewis base having at least two coordinating atoms.

[0132] A second aspect may include the first aspect, wherein n is 2 or 3 and at least two groups R in formula (I) are covalently connected.

[0133] A third aspect may include either one of the first aspect or the second aspect, wherein m is 2 or 3 and at least two groups L in formula (I) are covalently connected.

[0134] A fourth aspect may include any one of the first through third aspects, wherein R is (C1−C10)alkyl, −ORC, wherein RCis (C1−C10)alkyl, or –NRN2, where RNis (C6−C15)aryl.

[0135] A fifth aspect may include any one of the first through fourth aspects, wherein L is tetrahydrofuran or trimethylamine or wherein m is 2 and each L is OEt2.

[0136] A sixth aspect may include any one of the first through fifth aspects, wherein L is tetrahydrofuran or trimethylamine or wherein m is 2 and each L is OEt2.84978-WO-PCT / DOW 84978 WO

[0137] A seventh aspect may include any one of the first through sixth aspects, wherein the anion has a formal charge of negative one (-1).

[0138] An eighth aspect may include any one of the first through seventh aspects, wherein the anion has the general formula [XQ4]-, wherein X is boron, aluminum, or gallium and each Q is independently selected from the group consisting of (C6–C40)aryl, (C1–C40)hydrocarbyl, –ORC, – SiCR, −CH2Si(ORC)wRCy, halogen substituted (C6–C40)aryl, halogen substituted (C1– C40)hydrocarbyl, halogen substituted (–ORC), halogen substituted –SiCR, and halogen substituted −CH2Si(ORC)wRCy, wherein RCis (C1−C30)hydrocarbyl, w + y is 3 provided that at least three of the four group Q are fluorine atom or substituted with one or more fluorine atoms.

[0139] A ninth aspect may include any one of the first through eighth aspects, wherein the anion is [B(C6F5)4]-.

[0140] A tenth aspect may include any one of the first through seventh aspects, wherein the anion has a structure according to formula (II):where: each M2 is independently aluminum, boron, or gallium; BL is chosen from a species having at least two Lewis basic sites; each Q is independently a monodentate ligand; n is 0, 1, 2, or 3, wherein when n is 0, Q of Qn is not present; x is 0, 1, 2, or 3, wherein when x is 0, Q of Qx is not present; each R is independently selected from the group consisting of radicals having formula (III) and radicals having formula (IV):each Y is independently carbon or silicon;84978-WO-PCT / DOW 84978 WO each R11, R12, R13, R21, R22, R23, R24, and R25, is independently chosen from (C1−C40)alkyl, (C6−C40)aryl, –H, −NRN2, −ORC, –SRC, or halogen, wherein when R is a radical according to formula (III), at least one of R11, R12, or R13is perhalogenated (C1−C40)alkyl , perhalogenated (C6−C40)aryl, or −F; and when R is a radical according to formula (IV), at least one of R21, R22, R23, R24, and R25is perhalogenated (C1−C40)alkyl , perhalogenated (C6−C40)aryl, or −F; optionally, when n is 0 or 1, two R groups in formula (II) are covalently connected; and each RNor RCis independently (C1−C30)hydrocarbyl or –H.

[0141] An eleventh aspect may include any one of the first through seventh aspects, wherein the anion has a structure according to formula (IX):where: M is aluminum, boron, or gallium; n is 1, 2, 3, or 4; each T is independently selected from the group consisting of radicals having formula (XI) and radicals having formula (XI):where each Y, R11, R12, R13, R21, R22, R23, R24, and R25is defined in claim 10 and each X is a monodentate ligand independently chosen from halogen-substituted (C1−C20)alkyl, (C1−C20)alkyl, halogen-substituted (C6−C40)aryl, (C6−C40)aryl, triflate, or – S(O)3RC; optionally, two groups T in formula (IX) are covalently connected and the anion has a structure according to formula (XII):84978-WO-PCT / DOW 84978 WOeach RCis independently (C1−C30)hydrocarbyl or –H.

[0142] A twelfth aspect may include any one of the first through eleventh aspects, wherein the procatalyst has the structure according to formula (XIII):where: M5 is titanium, zirconium, or hafnium; y is 1, 2, or 3; each X5is a monodentate ligand independently chosen from unsaturated (C2−C50)hydrocarbon, unsaturated (C2−C50)heterohydrocarbon, saturated (C2−C50)heterohydrocarbon, (C1−C50)hydrocarbyl, (C6−C50)aryl, (C6−C50)heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4−C12)diene, halogen, −N(RN)2, and – N(RN)CORC; the metal–ligand complex is overall charge-neutral; each Z is independently chosen from −O−, −S−, −N(RN)−, or –P(RP)−; R1and R16are 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)−, halogen, radicals having formula (XIV), radicals having formula (XV), and radicals having formula (XVI):84978-WO-PCT / DOW 84978 WOwhere each of R31–35, R41–48, and R51–59is 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; R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15are independently selected 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(R)−, (RC)2NC(O)−, and halogen; L is (C1−C40)hydrocarbylene or (C2−C40)heterohydrocarbylene; and each RC, RP, and RNin formula (I) is independently a (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, or −H.

[0143] A thirteenth aspect may include any one of the first through twelfth aspects, wherein the procatalyst has the structure according to formula (XVII):

[0144] A fourteenth aspect may include any one of the first through thirteenth aspects, wherein the procatalyst has the structure according to formula (XVIII):84978-WO-PCT / DOW 84978 WO

[0145] A fifteenth aspect may include any one of the first through fourteenth aspects, wherein the procatalyst has the structure according to formula (XX):where M6is hafnium, titanium or zirconium; n is 0, 1, or 2; m is 0, 1, or 2, provided that when m is 2, n is 0 and when n is 2, m is 0; and each X6 is a monodentate ligand independently chosen from (C1 ^C50)hydrocarbon, (C1−C50)heterohydrocarbon, (C1−C50)hydrocarbyl, (C6−C50)aryl, (C6−C50)heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4−C12)diene, halogen, hydrogen, −N(RN)2, and −NCORC. The metal–ligand complex is overall charge-neutral; each Y6is independently a Lewis base; N is nitrogen; W6is carbon or silicon and is covalently bonded to cyclopentadiene; and R1and R2 are independently selected from −H, (C1−C40)hydrocarbyl, and (C1−C40)heterohydrocarbyl; R3 are independently selected from (C1−C40)hydrocarbyl, and (C1−C40)heterohydrocarbyl; and R4, R5, R6, and R7 are independently (C1 ^C50)hydrocarbyl, (C1 ^C50)heterohydrocarbyl wherein any of the R4, R5, R6, and R7optionally are connected to form a ring structure.

[0146] A sixteenth aspect may include any one of the first through fifteenth aspects, wherein the process further comprises a reactor at a reaction temperature.

[0147] A seventeenth aspect may include the sixteenth aspect, wherein the reactor is a solution reactor comprising one or more solvents.

[0148] An eighteenth aspect may include the seventeenth aspect, wherein the solvent is a hydrocarbon, an aliphatic hydrocarbon, a non-halogenated hydrocarbon, a non-aromatic hydrocarbon or combinations thereof.84978-WO-PCT / DOW 84978 WO

[0149] A nineteenth aspect may include any one of the sixteenth through eighteenth aspects, wherein the reaction temperature is 120 ℃-225 ℃.

[0150] A twentieth aspect may include any one of the first through eleventh aspects, wherein the procatalyst has the structure according to formula (XXVI):each X is a monodentate ligand independently chosen from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, -CH2Si(RC)3-Q(ORC)Q, −Si(RC)3-Q(ORC)Q, -OSi(RC)3-Q(ORC)Q, −CH2Ge(RC)3-Q(ORC)Q, −Ge(RC)3-Q(ORC)Q, −P(RC)2-W(ORC)W, −P(O)(RC)2-W(ORC)W, −N(RC)2, −NH(RC), −N(Si(RC)3)2, −NRCSi(RC)3, −NHSi(RC)3, −ORC, −SRC, −NO2, −CN, −CF3, −OCF3, a halogen, wherein each Q is 0, 1, 2 or 3, and each W is 0, 1, or 2; wherein two X ligands can be connected to form a ring, wherein one member of the ring is M8; each Y8 is independently Lewis Base; optionally, X and Y can be linked to form a ring. Each subscript m is 1 and 2; and each subscript n is 0, 1 and 2. The metal–ligand complex is overall charge-neutral; M8 is titanium, zirconium, or hafnium; R81, R82, R83, R84, and R85are independently (C1^C50)hydrocarbyl, (C1^C50)heterohydrocarbyl wherein any of the R82, R83, R84, and R85optionally are connected to form a ring structure; R86, R87, and R88are independently (C1^C20)hydrocarbyl, (C1^C20)heterohydrocarbyl, (C6^C30)aryl, (C5^C30)heteroaryl wherein two of R86, R87, and R88are optionally connected to form a ring; and R81, R82, R83, R84, and R85are independently (C1 ^C50)hydrocarbyl, wherein R81and R82are optionally connected to form a ring, or R82and R83are optionally connected to form a ring, R83and R84are optionally connected to form a ring, R84and R55optionally are connected to form a ring. In various embodiments, R86, R87, and R88are independently (C1 ^C20)hydrocarbyl, (C1 ^C20)heterohydrocarbyl, (C6 ^C30)aryl,84978-WO-PCT / DOW 84978 WO (C5^C30)heteroaryl wherein two of R56, R57, and R58are optionally connected to form a ring; and each RC, RP, and RNin formula (XXVI) is independently a (C1 ^C30)hydrocarbyl, (C1^C30)heterohydrocarbyl, or ^H.

[0151] A twenty-first aspect may include any one of the first through seventh aspects, wherein the anion has a structure according to formula the anion has a structure according to formula (XXX):R301and each X300are each independently selected from a halogen, a substituted or unsubstituted (C1‑C40)hydrocarbyl, or a substituted or unsubstituted (C1−C40)heterohydrocarbyl, Si(RC)3, Si(N(RC)2)3, Si(O(RC)2)3, Ge(RC)3, Ge(N(RC)2)3, Ge(O(RC)2)3, P(RC)2, P(N(RC)2)2, P(ORC)2, N(RC)2, NH(RC), NH2, OH, SH, ORC, SRC, NO2, CN, −CF3, −CF2RC, −CF(RC)2, RCS(O)−, RCS(O)2−, (RC)2C=N−, RCC(O)O−, RCOC(O)−, RCC(O)N(RC)−, (RC)2NC(O)−, or hydrogen, wherein each RCis independently a substituted or unsubstituted (C1‑C35)hydrocarbyl, or a substituted or unsubstituted (C1‑C35)heterohydrocarbyl; wherein: two or more of X300may optionally form one or more ring structures; two or more of X300and R301may optionally form one or more ring structures; and one or more hydrogen atoms may optionally be substituted with deuterium; and at least one of X300or R301is a halogen atom.84978-WO-PCT / DOW 84978 WO EXAMPLES

[0152] The synthetic protocols for the illustrative embodiments of the activator are disclosed in Examples 1 to 4. In Example 5, the polymerization examples described herein were performed in a two-liter Parr reactor, which was heated via an electrical heating mantle and cooled via an internal serpentine cooling coil containing water. Both the reactor and the heating / cooling system were controlled and monitored by a Camile TG process computer.

[0153] Example 1: Synthesis of alumocenium borate salt (A1):

[0154] In a nitrogen-filled glovebox, a reaction vial was charged with trityl tetrakis(pentafluorophenyl)borate (500 mg, 0.5421 mmol, 1 equiv.) Trioctylaluminum (198.8 mg, 0.5421 mmol, 1 equiv.) in diethyl ether (15 mL) was added to the trityl vial. The vibrant orange trityl solution lost almost all color, but remained a pale yellow. After stirring at room temperature for 30 min, the solution had slightly darkened. The solution was concentrated in vacuo to yield a white solid with a light grey gel. The material was triturated with hexane (5 mL) and concentrated in vacuo (this process was repeated for a total of two times) to afford a white solid with a grey oil (726.9 g). After sitting a room temperature, the grey oil turned light yellow / brown. To remove triphenylmethane, the resulting residue was triturated with hexane (20 mL), resulting in a small amount of light brown oil below the bulk, slightly turbid hexane layer. Stirring was ceased, and the biphasic mixture was allowed to settle. The majority of the hexane layer was carefully pipetted off of the brown oil bottom layer. This process was then repeated a second time with hexanes (20 mL). The resulting brown oil was then concentrated in vacuo to afford the product (579 mg, 98% yield).

[0155] 1H NMR (500 MHz, chlorobenzene-d5) δ 3.72 (q, J = 7.3 Hz, 8H), 1.33 – 1.14 (m, 24H), 1.00 (t, J = 7.1 Hz, 12H), 0.91 – 0.78 (m, 6H), -0.04 (t, J = 7.2 Hz, 4H).11B NMR (160 MHz, chlorobenzene-d5) δ -16.15.13C NMR (126 MHz, chlorobenzene-d5) δ 150.11 – 149.06 (m), 147.99 – 147.19 (m), 139.75 – 139.11 (m), 138.04 – 136.86 (m), 135.92 – 135.22 (m), 69.50, 35.45, 31.94, 29.29 (d, J = 13.5 Hz), 23.98, 22.73, 13.95, 12.77, 6.90.19F NMR (376 MHz, chlorobenzene-d5) δ -132.31 – -132.65 (m), -162.63 – -163.02 (m), -166.54 – -167.05 (m). HRMS (ESI) Calculated for C24H54AlO2[M+] 401.3934; found 401.3923. Calculated for C24B4F20[M-] 678.9779; found 678.9780.

[0156] Example 2: Synthesis zinc borate salt (A2) – (C2H5)Zn(OEt2)3 B(C6F5)4

[0157] In a nitrogen-filled glovebox, a reaction vial was charged with trityl tetrakis(pentafluorophenyl)borate (500 mg, 0.5421 mmol, 1 equiv.) and subsequently dissolved in84978-WO-PCT / DOW 84978 WO toluene (3 mL). A 1 M solution of diethylzinc in hexane (0.5421 mL, 66.95 mg diethylzinc, 0.5421 mmol, 1 equiv.) was added to diethyl ether (15 mL). The trityl solution was added dropwise to the stirring diethylzinc solution. Residual trityl borate was further extracted by washing the trityl vial with additional toluene and added to the diethylzinc solution. The vibrant orange trityl solution changed to a pale yellow when added to the reaction. The solution was concentrated in vacuo to yield a light beige solid. The material was triturated with hexane (6 mL) and concentrated in vacuo (this process was repeated for a total of two times) to afford a white solid. To remove triphenylmethane, the resulting residue was triturated with hexane (20 mL). Stirring was ceased, and the biphasic mixture was allowed to settle. Most of the hexane layer was carefully pipetted off of the bottom layer. This process was then repeated a second time with hexanes (20 mL). The resulting material was then concentrated in vacuo for 24 h to afford the product as a white powder (406.0 mg, 75% yield).

[0158] 1H NMR (500 MHz, bromobenzene-d5) δ 3.60 (q, J = 7.1 Hz, 12H), 1.21 (t, J = 8.1 Hz, 3H), 1.12 (t, J = 7.1 Hz, 18H), 0.54 (q, J = 8.1 Hz, 2H).13C NMR (126 MHz, bromobenzene-d5) δ 148.77 (d, J = 241.4 Hz), 140.42 – 134.77 (m), 68.49, 14.14, 11.36, 2.21.19F NMR (471 MHz, bromobenzene-d5) δ -131.60 (q, J = 10.0 Hz), -161.83 (t, J = 21.0 Hz), -165.84 (t, J = 19.7 Hz).11B NMR (160 MHz, bromobenzene-d5) δ -15.98.

[0159] Example 3: Synthesis of bis(dodecyl)magnesium

[0160] In a nitrogen-filled glovebox, a solution of 1.0 M solution of dodecylMgBr (70 mL, 70 mmol, 1 equiv.) was cooled in a -30°C freezer for 1 h. A small amount of solid precipitated from solution. The vessel was removed from the freezer and dioxane (6.0 mL) was added dropwise to the vigorously stirring solution, resulting in the precipitation of copious amounts of a white solid. The reaction was allowed to stir at room temperature for 30 min. A thick paste was obtained. Additional diethyl ether (approximately 40 mL) was added to thin out the mixture. The majority of the slurry was transferred to a set of four centrifuge tubes, sealed, and removed from the glovebox. Centrifugation at 14,000 rpm for 10 min allowed for clean separation of the solid magnesium salts from the supernatant solution. The tubes were transferred back into the glovebox and the supernate was decanted into a jar to afford an amber solution. The resulting material was titrated in triplicate against solutions of iodine in 0.5 M LiCl in THF and found to be 0.36 M.1H NMR (400 MHz, THF-d8) δ 1.52 (p, J = 7.7 Hz, 4H), 1.38 – 1.17 (m, 36H), 0.88 (t, J = 6.9 Hz, 6H), -0.67 (t, J = 8.0 Hz, 4H).13C NMR (101 MHz, THF-d8) δ 40.05, 33.02, 31.48, 31.25, 31.10, 31.01, 30.93, 30.82, 30.48, 23.69, 14.59, 8.64.84978-WO-PCT / DOW 84978 WO

[0161] Example 4: Synthesis of magnesium borate salt (A3) – (C12H25)Mg(OEt2)3B(C6F5)4

[0162] In a nitrogen-filled glovebox, a reaction vial was charged with trityl tetrakis(pentafluorophenyl)borate (500 mg, 0.5421 mmol, 1 equiv.) Bis(dodecyl)magnesium in diethyl ether (0.36 M, 1.51 mL, 0.5421 mmol, 1 equiv.) was further diluted with diethyl ether (15 mL) and added to the trityl vial. Immediately, the bright yellow color of the trityl disappeared and yielded a pale tan solution with some brown / yellow solids. The solution was stirred at room temperature for 1 h. A small amount of solid remained in the light tan solution. Stirring was ceased for 1 h. The solution was filtered through a 0.45 μm PTFE syringe filter in line with a 0.2 μm PFTE syringe filter. The filters were washed with diethyl ether (3 mL), and the combined filtrates were concentrated in vacuo to afford an off-white solid in an oil. The material was triturated with hexane (5 mL) and all volatiles were removed in vacuo (this process was repeated for a total of two times) to afford an off-white solid in an oil. The resulting residue was triturated with hexane (20 mL), resulting in a small amount of oil below the bulk, slightly turbid hexane layer. Stirring was ceased, and the biphasic mixture was allowed to settle. The majority of the hexane layer was carefully pipetted off of the pale yellow oil bottom layer. This process was then repeated a second time with hexanes (20 mL). The resulting solution was then concentrated in vacuo to afford a thick pale yellow oil with a small amount of residual solids at the top of the vial (545.9 mg). The material was triturated with toluene (5 mL). A second liquid phase was present at the bottom. The material was passed through a 0.2 μm PTFE syringe filter. The vial and filters were washed with toluene (3x2 mL), and the combined filtrates were concentrated in vacuo to afford a thick pale yellow oil. The material was triturated with hexane (3 mL) and all volatiles were removed in vacuo (this process was repeated for a total of two times) to afford the product as a pale yellow oil (504.6 mg, 85% yield).1H NMR (500 MHz, chlorobenzene-d5) δ 3.48 (s, 12H), 1.53 – 1.13 (m, 20H), 0.98 (t, J = 7.2 Hz, 18H), 0.90 – 0.79 (m, 3H), -0.49 (d, J = 4.7 Hz, 2H).11B NMR (160 MHz, chlorobenzene-d5) δ -16.15.19F NMR (471 MHz, chlorobenzene-d5) δ -132.00 (q, J = 10.1 Hz, 8F), -162.41 (t, J = 20.7 Hz, 4F), -166.45 (t, J = 19.4 Hz, 8F).13C NMR (126 MHz, chlorobenzene- d5) δ 151.53 – 146.28 (m), 139.91 – 135.19 (m), 66.17, 38.88, 32.00, 30.14, 30.06, 29.94, 29.84, 29.66, 29.50, 29.08, 22.77, 14.02, 13.16, 6.20.

[0163] Example 5 - Polymerization

[0164] All chemicals used for polymerization or for the catalyst were purified before introduction into the reaction environment. Specifically, 1-octene, toluene, and ISOPAR E (a mixed alkanes solvent available from ExxonMobil, Inc.) were passed through an A2 alumina84978-WO-PCT / DOW 84978 WO column then through a column containing Q5 reactant (available from Engelhard Chemicals Inc.). Ethylene gas was passed through a first column containing A204 alumina and activated 4Å molecular sieves and a second column containing Q5 reactant. Hydrogen gas was passed through Q5 reactant and A2 alumina. Nitrogen gas was passed through a single column containing A204 alumina, activated 4Å molecular sieves, and Q5 reactant. Procatalyst and activator solutions were handled in a nitrogen-filled glovebox.

[0165] The load column was filled with ISOPAR E and 1-octene to the load set points by use of an Ashcroft differential pressure cell, and the material was transferred into the reactor. Once complete, the reactor immediately began heating toward the reaction temperature set point. Hydrogen was loaded into the reactor, via a shot tank with an internal volume of approximately 75 milliliters (“mL”), immediately following the solvent / comonomer addition. A solution containing a modified methylaluminoxane (“MMAO”) scavenger was optionally added to the reactor via the shot tank once the reactor temperature reached 25 degrees Celsius (°C) under the reaction temperature set point. At 10°C under the reaction temperature set point, ethylene was added to the specified pressure as monitored via a micro-motion flow meter. Finally, at this same time, dilute toluene solutions (or chlorobenzene for A2) of the activator (Table 1) and the procatalyst (Table 2) were mixed, transferred to the shot tank, and added to the reactor to begin the polymerization reaction.

[0166] The polymerization conditions were typically maintained for 10 minutes with supplemental ethylene added on demand to maintain the specified pressure. Exothermic heat was continuously removed from the reaction vessel via the internal cooling coil. The resulting solution was removed from the reactor and stabilized by addition of 5 mL of a toluene solution containing approximately 33.5 milligrams (“mg”) of a hindered phenol antioxidant (Irganox 1010 from Ciba Geigy Corp.) and 66.5 mg of a phosphorus stabilizer (Irgafos 168 from Ciba Geigy Corp.). Polymer resins were recovered by evaporating in a hood overnight and then drying for about 12 h in a temperature-ramped vacuum oven with a final set point of 140 °C. Between polymerization runs, at least one wash cycle was conducted in which ISOPAR E (850 g) was added and the reactor was heated to a setpoint between 160 °C and 190 °C. The reactor was then emptied of the heated solvent immediately before beginning a new polymerization run.

[0167] For Examples 1-6, Inventive Activators A1-A3 and Comparative Activator C1, shown in Table 1, were used to synthesize ethylene-based polymers according to the procedure described above. The procatalysts used for the polymerization reactions are shown in Table 2.84978-WO-PCT / DOW 84978 WOProcatalyst 1 Procatalyst 2Procatalyst 4 Procatalyst 584978-WO-PCT / DOW 84978 WOProcatalyst 6

[0168] Most polymerizations were performed at 140 °C with 288 psi of ethylene and 300 g of 1-octene. The polymerizations were performed in 605 g ISOPAR E. The ratio of procatalyst to activator ratio was 1:1.2; or the polymerizations were performed at temperature of 190 °C with 400 psi ethylene, 300 g 1-octene, and 520 g Isopar-E. The ratio of procatalyst to activator ratio was 1:1.2.

[0169] Each polymerization reaction using an Inventive Activator A1-A3 was compared to the same polymerization under the same reaction conditions using Comparative Activator C1. The polymerizations using C1 were each performed three times and the data for each run is reported. The efficiency with respect to C1 was calculated according to Equation 7: ^^^^^^^^^^ ^^ ^^^^^^^^^^ ^^^ ^^^^^^^ ^^^^^^^^^^ ^^ ^ ^^ ^^^^ × 100 (EQ. 7) Table 3 – Batch Reactor Polymerization Results with Procatalyst 1

[0170] Batch reactor conditions for Table 3 includes temperature of 190 °C, 400 psi C2H4, 520 g Isopar-E, 300 g 1-octene, 10 µmol MMAO-3A, The Procatalyst:Activator ratio is 1:1.2, with the catalyst loading of 1.8 µmol. Table 4 – Batch Reactor Polymerization Results with Procatalyst 284978-WO-PCT / DOW 84978 WO

[0171] Batch reactor conditions in Table 4 is: Temperature was 190 °C, 400 psi C2H4, 520 g Isopar-E, 300 g 1-octene, 0 µmol MMAO-3A, Procatalyst:Activator ratio = 1:1.2; catalyst loading was 0.03 µmol. Table 5 – Batch Reactor Polymerization Results with Procatalyst 2

[0172] Batch reactor conditions in Table 5 is: Temperature was 140 °C, 288 psi C2H4, 605 g Isopar-E, 300 g 1-octene, 0 µmol MMAO-3A, Procatalyst:Activator ratio = 1:1.2; catalyst loading was 0.6 µmol. Table 6 – Batch Reactor Polymerization Results with Procatalyst 3

[0173] Batch reactor conditions in Table 6 is: Temperature was 140 °C, 288 psi C2H4, 605 g Isopar-E, 300 g 1-octene, 0 µmol MMAO-3A, Procatalyst:Activator ratio = 1:1.2; catalyst loading was 0.6 µmol. Table 7 – Batch Reactor Polymerization Results with Procatalyst 484978-WO-PCT / DOW 84978 WO

[0174] Batch reactor conditions in Table 7 is: Temperature was 190 °C, 400 psi C2H4, 520 g Isopar-E, 300 g 1-octene, 0 µmol MMAO-3A, Procatalyst:Activator ratio = 1:1.2. The procatalyst loading was 0.2 µmol. Table 8 – Batch Reactor Polymerization Results with Procatalyst 1

[0175] Batch reactor conditions for Table 8 includes a temperature of 190 °C, 400 psi C2H4, 520 g Isopar-E, 300 g 1-octene, 0 µmol MMAO-3A, Procatalyst:Activator ratio = 1:1.2 with the procatalyst loading of 1.5 µmol. Table 9 – Batch Reactor Polymerization Results with Procatalyst 3

[0176] The batch reactor conditions for Table 9 includes a temperature of 140 °C, 288 psi C2H4, 605 g Isopar-E, 300 g 1-octene, and 0 µmol MMAO-3A, The Procatalyst:Activator ratio is 1:1.2 with a procatalyst loading of 0.3 µmol. Table 10 – Batch Reactor Polymerization Results with Procatalyst 484978-WO-PCT / DOW 84978 WO

[0177] The batch reactor conditions for Table 10 includes a temperature of 190 °C, 400 psi C2H4, 520 g Isopar-E, 300 g 1-octene, 0 µmol MMAO-3A, The Procatalyst:Activator ratio is 1:1.2 with a procatalyst loading of 0.2 µmol. Table 11 – Batch Reactor Polymerization Results with Procatalyst 1

[0178] The batch reactor conditions for Table 11 includes a temperature of 190 °C, 400 psi C2H4, 520 g Isopar-E, 300 g 1-octene, 0 µmol MMAO-3A, The Procatalyst:Activator ratio is 1:1.2 with a procatalyst loading of 1.5 µmol. Table 12 – Batch Reactor Polymerization Results with Procatalyst 2

[0179] The batch reactor conditions for Table 12 includes a temperature of 190 °C, 400 psi C2H4, 520 g Isopar-E, 300 g 1-octene, 0 µmol MMAO-3A, The Procatalyst:Activator ratio is 1:1.2 with a procatalyst loading of 0.06 µmol. Table 13 – Batch Reactor Polymerization Results with Procatalyst 384978-WO-PCT / DOW 84978 WO

[0180] The batch reactor conditions for Table 13 includes a temperature of 140 °C, 288 psi C2H4, 605 g Isopar-E, 300 g 1-octene, and 0 µmol MMAO-3A, The Procatalyst:Activator ratio is 1:1.2 with a procatalyst loading of 0.3 µmol. Table 14 – Batch Reactor Polymerization Results with Procatalyst 4

[0181] The batch reactor conditions for Table 14 includes a temperature of 190 °C, 400 psi C2H4, 520 g Isopar-E, 300 g 1-octene, 0 µmol MMAO-3A, The Procatalyst:Activator ratio is 1:1.2 with a procatalyst loading of 0.2 µmol. Table 15 – Batch Reactor Polymerization Results with Procatalyst 5

[0182] The batch reactor conditions for Table 15 includes a temperature of 140 °C, 288 psi C2H4, 605 g Isopar-E, 300 g 1-octene, and 0 µmol MMAO-3A, The Procatalyst:Activator ratio is 1:1.2 with a procatalyst loading of 0.1 µmol. Table 16 – Batch Reactor Polymerization Results with Procatalyst 684978-WO-PCT / DOW 84978 WO

[0183] The batch reactor conditions for Table 16 includes a temperature of 190 °C, 400 psi C2H4, 520 g Isopar-E, 300 g 1-octene, and 0 µmol MMAO-3A, The Procatalyst:Activator ratio is 1:1.2 with a procatalyst loading of 0.5 µmol.

[0184] In each of the Examples in Tables 1-16, there is a steady ethylene uptake, which indicates that the activators in combination with the procatalysts provide a high catalyst efficiency as supported by the data in the Tables.

[0185] In several Examples the polymerization efficiencies of Inventive Activators A1, A2, and A3 were comparable or superior to that of Comparative Activator C1. The data in Tables 3 and 9 indicates that A1 and A2 out-performed C1 when used in conjunction with Procatalyst 1 and Procatalyst 3. The performance of the Inventive Activator A3 was also notably superior to C1 when used in conjunction with Procatalyst 1, as shown by Table 11. In Table 7, the Activator A1 was more than double the efficiency of the Comparative Activator C1 when coupled with Procatalyst 4.

Claims

84978-WO-PCT / DOW 84978 WO CLAIMS1. A process of polymerizing olefins, the process comprising polymerizing ethylene and optionally one or more α-olefin monomers in the presence of a catalyst system, the catalyst system comprising a procatalyst and a metallic activator ionic complex, wherein the metallic activator ionic complex comprises a cation and a weakly coordinating anion, the cation having a structure according to formula (I):where: M is magnesium, boron, aluminum, gallium, zinc, silicon or germanium; when M is zinc or magnesium, n is 1; when M is boron, aluminum, or gallium, n is 2; when M is silicon or germanium, n is 3; m is 1, 2, or 3; each R is a ligand independently selected from the group consisting of (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, –ORC, –SiCR, – CH2Si(ORC)wRCY, –CH2Si(NRN)wRCY, −NRN, and −NRN2; where RCis (C1−C30)hydrocarbyl, RNis (C1−C30)hydrocarbyl or hydrogen, w is 1, 2, or 3, and y is 0, 1, or 2, provided that the sum of w plus y is 3; and each L is a neutral Lewis base; and provided that: when n is 2 or 3, each R is optionally covalently connected to form a multidentate ligand; and when m is 2 or 3, each L is optionally covalently connected to form a Lewis base having at least two coordinating atoms.

2. The process of claim 1, wherein n is 2 or 3 and at least two groups R in formula (I) are covalently connected.

3. The process of claim 1 or claim 2, wherein m is 2 or 3 and at least two groups L in formula (I) are covalently connected.84978-WO-PCT / DOW 84978 WO 4. The process of any previous claim, wherein R is (C1−C10)alkyl, −ORC, wherein RCis (C1−C10)alkyl, or –NRN2, where RNis (C6−C15)aryl.

5. The process of any previous claim, wherein L is tetrahydrofuran or trimethylamine or wherein m is 2 and each L is OEt2.

6. The process of any previous claim, wherein each R is octyl, –CH3, –OCH3, or −NPh2.

7. The process of any previous claim, wherein the anion has a formal charge of negative one (-1).

8. The process of any previous claim, wherein the anion has the general formula [XQ4]-, wherein X is boron, aluminum, or gallium and each Q is independently selected from the group consisting of (C6–C40)aryl, (C1–C40)hydrocarbyl, –ORC, –SiCR, −CH2Si(ORC)wRCy, halogen substituted (C6–C40)aryl, halogen substituted (C1–C40)hydrocarbyl, halogen substituted (–ORC), halogen substituted –SiCR, and halogen substituted −CH2Si(ORC)wRCy, wherein RCis (C1−C30)hydrocarbyl, w + y is 3 provided that at least three of the four group Q are fluorine atom or substituted with one or more fluorine atoms.

9. The process of any previous claim, wherein the anion is [B(C6F5)4]-.

10. The catalyst system of any one of claims 1 to 7, wherein the anion has a structure according to formula (II):where: each M2 is independently aluminum, boron, or gallium; BLis chosen from a species having at least two Lewis basic sites; each Q is independently a monodentate ligand; n is 0, 1, 2, or 3, wherein when n is 0, Q of Qn is not present; x is 0, 1, 2, or 3, wherein when x is 0, Q of Qx is not present; each R is independently selected from the group consisting of radicals having formula (III) and radicals having formula (IV):84978-WO-PCT / DOW 84978 WOeach Y is independently carbon or silicon; each R11, R12, R13, R21, R22, R23, R24, and R25, is independently chosen from (C1−C40)alkyl, (C6−C40)aryl, –H, −NRN2, −ORC, –SRC, or halogen, wherein when R is a radical according to formula (III), at least one of R11, R12, or R13is perhalogenated (C1−C40)alkyl , perhalogenated (C6−C40)aryl, or −F; and when R is a radical according to formula (IV), at least one of R21, R22, R23, R24, and R25is perhalogenated (C1−C40)alkyl , perhalogenated (C6−C40)aryl, or −F; optionally, when n is 0 or 1, two R groups in formula (II) are covalently connected; and each RNor RCis independently (C1−C30)hydrocarbyl or –H.

11. The process of any one of claims 1 to 7, wherein the anion has a structure according to formula (IX):where: M is aluminum, boron, or gallium; n is 1, 2, 3, or 4; each T is independently selected from the group consisting of radicals having formula (XI) and radicals having formula (XI):where each Y, R11, R12, R13, R21, R22, R23, R24, and R25is defined in claim 10 and84978-WO-PCT / DOW 84978 WO each X is a monodentate ligand independently chosen from halogen-substituted (C1−C20)alkyl, (C1−C20)alkyl, halogen-substituted (C6−C40)aryl, (C6−C40)aryl, triflate, or –S(O)3RC; optionally, two groups T in formula (IX) are covalently connected and the anion has a structure according to formula (XII):each RCis independently (C1−C30)hydrocarbyl or –H.

12. The process of any one previous claims, wherein the procatalyst has the structure according to formula (XIII):where: M5is titanium, zirconium, or hafnium; y is 1, 2, or 3; each X5is a monodentate ligand independently chosen from unsaturated (C2−C50)hydrocarbon, unsaturated (C2−C50)heterohydrocarbon, saturated (C2−C50)heterohydrocarbon, (C1−C50)hydrocarbyl, (C6−C50)aryl, (C6−C50)heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4−C12)diene, halogen, −N(RN)2, and –N(RN)CORC; the metal–ligand complex is overall charge-neutral; each Z is independently chosen from −O−, −S−, −N(RN)−, or –P(RP)−;84978-WO-PCT / DOW 84978 WO R1and R16are 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)−, halogen, radicals having formula (XIV), radicals having formula (XV), and radicals having formula (XVI):where each of R31–35, R41–48, and R51–59is 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; R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15are independently selected 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(R)−, (RC)2NC(O)−, and halogen; L is (C1−C40)hydrocarbylene or (C2−C40)heterohydrocarbylene; and each RC, RP, and RNin formula (I) is independently a (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, or −H.

13. The process of any previous claim, wherein the procatalyst has the structure according to formula (XVII):84978-WO-PCT / DOW 84978 WO 14. The process of any previous claim, wherein the procatalyst has the structure according to formula (XVIII):

15. The process of any one of claims 1 to 11, wherein the procatalyst has the structure according to formula (XX):where M6is hafnium, titanium or zirconium; n is 0, 1, or 2; m is 0, 1, or 2, provided that when m is 2, n is 0 and when n is 2, m is 0; and each X6 is a monodentate ligand independently chosen from (C1 ^C50)hydrocarbon, (C1−C50)heterohydrocarbon, (C1−C50)hydrocarbyl, (C6−C50)aryl, (C6−C50)heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4−C12)diene, halogen, hydrogen, −N(RN)2, and −NCORC. The metal–ligand complex is overall charge-neutral; each Y6 is independently a Lewis base; N is nitrogen; W6is carbon or silicon and is covalently bonded to cyclopentadiene; and R1and R2 are independently selected from −H, (C1−C40)hydrocarbyl, and (C1−C40)heterohydrocarbyl; R3 are independently selected from (C1−C40)hydrocarbyl, and (C1−C40)heterohydrocarbyl; and84978-WO-PCT / DOW 84978 WO R4, R5, R6, and R7are independently (C1^C50)hydrocarbyl, (C1^C50)heterohydrocarbyl wherein any of the R4, R5, R6, and R7optionally are connected to form a ring structure.

16. The process according to any previous claim, wherein the process further comprises a reactor at a reaction temperature.

17. The process of claim 16, wherein the reactor is a solution reactor comprising one or more solvents.

18. The process of claim 17, wherein the solvent is a hydrocarbon, an aliphatic hydrocarbon, a non-halogenated hydrocarbon, a non-aromatic hydrocarbon or combinations thereof.

19. The process according to any one of claims 16-18, wherein the reaction temperature is 120 ℃-225 ℃.

20. The process of any one of claims 1 to 11, wherein the procatalyst has the structure according to formula (XXVI):each X is a monodentate ligand independently chosen from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, -CH2Si(RC)3-Q(ORC)Q, −Si(RC)3-Q(ORC)Q, -OSi(RC)3-Q(ORC)Q, −CH2Ge(RC)3-Q(ORC)Q, −Ge(RC)3-Q(ORC)Q, −P(RC)2-W(ORC)W, −P(O)(RC)2-W(ORC)W, −N(RC)2, −NH(RC), −N(Si(RC)3)2, −NRCSi(RC)3, −NHSi(RC)3, −ORC, −SRC, −NO2, −CN, −CF3, −OCF3, a halogen, wherein each Q is 0, 1, 2 or 3, and each W is 0, 1, or 2; wherein two X ligands can be connected to form a ring, wherein one member of the ring is M8;84978-WO-PCT / DOW 84978 WO each Y8is independently Lewis Base; optionally, X and Y can be linked to form a ring. Each subscript m is 1 and 2; and each subscript n is 0, 1 and 2. The metal–ligand complex is overall charge-neutral; M8is titanium, zirconium, or hafnium; R81, R82, R83, R84, and R85are independently (C1^C50)hydrocarbyl, (C1^C50)heterohydrocarbyl wherein any of the R82, R83, R84, and R85optionally are connected to form a ring structure; R86, R87, and R88are independently (C1 ^C20)hydrocarbyl, (C1 ^C20)heterohydrocarbyl, (C6 ^C30)aryl, (C5 ^C30)heteroaryl wherein two of R86, R87, and R88are optionally connected to form a ring; and R81, R82, R83, R84, and R85are independently (C1 ^C50)hydrocarbyl, wherein R81and R82are optionally connected to form a ring, or R82and R83are optionally connected to form a ring, R83and R84are optionally connected to form a ring, R84and R55optionally are connected to form a ring. In various embodiments, R86, R87, and R88are independently (C1 ^C20)hydrocarbyl, (C1 ^C20)heterohydrocarbyl, (C6 ^C30)aryl, (C5 ^C30)heteroaryl wherein two of R56, R57, and R58are optionally connected to form a ring; and each RC, RP, and RNin formula (XXVI) is independently a (C1 ^C30)hydrocarbyl, (C1 ^C30)heterohydrocarbyl, or ^H.

21. The process of any one of claims 1 to 7, wherein the anion has a structure according to formula the anion has a structure according to formula (XXX):84978-WO-PCT / DOW 84978 WO R301and each X300are each independently selected from a halogen, a substituted or unsubstituted (C1‑C40)hydrocarbyl, or a substituted or unsubstituted (C1−C40)heterohydrocarbyl, Si(RC)3, Si(N(RC)2)3, Si(O(RC)2)3, Ge(RC)3, Ge(N(RC)2)3, Ge(O(RC)2)3, P(RC)2, P(N(RC)2)2, P(ORC)2, N(RC)2, NH(RC), NH2, OH, SH, ORC, SRC, NO2, CN, −CF3, −CF2RC, −CF(RC)2, RCS(O)−, RCS(O)2−, (RC)2C=N−, RCC(O)O−, RCOC(O)−, RCC(O)N(RC)−, (RC)2NC(O)−, or hydrogen, wherein each RCis independently a substituted or unsubstituted (C1‑C35)hydrocarbyl, or a substituted or unsubstituted (C1‑C35)heterohydrocarbyl; wherein: two or more of X300may optionally form one or more ring structures; two or more of X300and R301may optionally form one or more ring structures; and one or more hydrogen atoms may optionally be substituted with deuterium; and at least one of X300or R301is a halogen atom.

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