Borate cocatalyst for polyolefin production

Abstract

An embodiment relates to a catalyst system comprising a metal-ligand complex procatalyst and an activator, the activator comprising an anion and a cation, the anion having a structure according to formula (I). [Case 1] JPEG2024535749000028.jpg45170

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 242,751, filed Sep. 10, 2021, the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THEINVENTION SUMMARY OF THE DISCLOSURE Embodiments of the present disclosure relate generally to borate anionic cocatalysts. [Background technology]

[0003] Since the discovery of heterogeneous olefin polymerization by Ziegler and Natta, worldwide polyolefin production reached approximately 150 million tons per year in 2015, which is rising due to increasing market demand. This success is based in part on a series of important breakthroughs in cocatalyst technology. The cocatalysts discovered include aluminoxanes, boranes, and borates containing triphenylcarbenium or ammonium cations. These cocatalysts activate homogeneous single-site olefin polymerization catalysts, and polyolefins are produced using these cocatalysts in industry.

[0004] In particular, borate-based cocatalysts have contributed significantly to the fundamental understanding of olefin polymerization mechanisms and improved the ability to precisely control polyolefin microstructure by deliberately tailoring catalyst structure and process, which has led to increased interest in mechanistic studies and the development of novel homogeneous olefin polymerization catalyst systems that provide precise control over polyolefin microstructure and performance.

[0005] As part of the catalyst composition in an α-olefin polymerization reaction, the activator may have beneficial characteristics for the production of α-olefin polymers and for the final polymer composition comprising the α-olefin polymer. Activator characteristics that increase the production of α-olefin polymers include, but are not limited to, rapid activation of the procatalyst, high catalyst efficiency, high temperature performance, consistent polymer composition, and selective deactivation.

[0006] Olefin-based polymers, such as ethylene-based polymers and propylene-based polymers, are produced through various catalyst systems. The selection of such catalyst systems can be an important factor that contributes to the characteristics and properties of olefin-based polymers. Catalyst systems for producing polyethylene-based polymers can include chromium-based catalyst systems, Ziegler-Natta catalyst systems, or molecular (either metallocene or non-metallocene) catalyst systems.

[0007] To generate catalytically active species for polymerization, the molecular polymerization procatalyst as part of the catalyst system is activated, which can be accomplished by any of a number of means. One such method uses an activator or cocatalyst that is a Bronsted acid. To activate molecular polymerization procatalysts, particularly those that contain Group IV metal complexes, Bronsted acid salts containing weakly coordinating anions are typically utilized. The fully ionized Bronsted acid salts are capable of transferring protons to form cationic derivatives of such Group IV metal complexes.

[0008] In the case of activators such as Bronsted acid salts, the cationic component may include a cation capable of transferring a hydrogen ion, such as, for example, ammonium, sulfonium, or phosphonium, or an oxidizing cation, such as, for example, ferrocenium, silver, or lead, or a highly Lewis acidic cation, such as, for example, carbonium or silylium.

[0009] However, when a cation activates a procatalyst, the activator may remain in the polymer composition. As a result, cations and anions may affect the polymer composition. Since not all ions diffuse equally, various ions affect the polymer composition differently. Specifically, the size and charge of the ion, the interaction of the ion with the surrounding medium, and the dissociation energy of the ion with the available counter ions will affect the ability of the ion to diffuse through the surrounding medium, such as a solvent, gel, or polymeric material.

[0010] Traditional olefin polymerization activators include weakly coordinating or non-coordinating anions. It has been shown that the weak coordination of anions leads to increased catalytic efficiency of cationic catalysts.However, the non-nucleophilic character of non-coordinating anions also increases diffusion, so that the activator anions remaining in the produced polymer will reduce the electrical resistance of the polymer, thereby increasing electrical loss, and thus reducing the applicability of the produced polymer. Summary of the Invention

[0011] Desirable characteristics of an activator in a polymerization reaction include the ability to increase the production of α-olefin polymers, the ability to increase the rate of procatalyst activation, the ability to increase the overall efficiency of the catalyst allowing the catalyst system to operate at higher temperatures, the ability to allow the catalyst system to provide consistent polymer composition, and the ability to allow selective deactivation of the activator. The non-coordinating anion tetrakis(pentafluorophenyl)borate ( - B(C 6 F 5 ) 4 ) activators achieve many of these desirable characteristics. Nevertheless, under typical polymerization reaction conditions, - B(C 6 F 5 ) 4 The anion is not decomposed and can remain intact in the final polymer. The presence of the activator intact in the final polymer can be detrimental to the electrical properties of the final polymer.

[0012] Activators based on partially hydrolyzed metal trialkyls, such as methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), can be used, for example, - B(C 6 F 5 ) 4 They are more easily decomposed than the anions, but suffer from poorer high temperature catalyst efficiency and wider composition drift in the final polymer.

[0013] There is an ongoing need for an activator that efficiently activates the procatalyst, is easily decomposed, and performs well at high temperatures. The catalyst system of the present disclosure includes a combination of a Group IV metal-ligand complex as a catalyst and an activator or cocatalyst that addresses such needs. In particular, in the production of polyolefin resins, when the activator easily reacts with the Group IV metal-ligand complex and activates the Group IV metal-ligand complex, the polyolefin resin exhibits useful polymer composition and electrical properties. The activator included in the catalyst system of the present disclosure exhibits features such as the ability to increase the production of α-olefin polymers, the ability to increase the rate of procatalyst activation, the ability to increase the overall efficiency of the catalyst and allow the catalyst system to operate at high temperatures, the ability to allow the catalyst system to provide a consistent polymer composition, and the ability to selectively deactivate the activator.

[0014] According to some embodiments, the polymerization process comprises contacting ethylene and optionally one or more α-olefin monomers in a solution polymerization reactor in the presence of a catalyst system at a temperature between 120° C. and 200° C., the catalyst system comprising a procatalyst and an activator, the activator comprising an anion and a cation, the anion having a structure according to formula (I).

[0015] [ka]

[0016] In formula (I), B is a boron atom. 1 and each R 5 is selected from -H or -F; each R 2 , R 3 , and R 4 -H, -F, (C 1 ~C 10 ) hydrocarbyl, (C 1 ~C 10 ) heterohydrocarbyl; R 6 , R 7 , R 8 , R 9 and R 10 are independently -H, -F, (C 1 ~C 10 ) hydrocarbyl, (C 1 ~C 10 ) heterohydrocarbyl, -OR C , -SiR C 3 where R C is -H or (C 1 ~C 20 ) hydrocarbyl, optionally R 7 and R 8 are linked to form a ring.

[0017] In formula (I), the structure according to formula (I) has a fluorine to carbon ratio (F / C) of 0.86 or less, where F is the total number of fluorine atoms in the structure according to formula (I) and C is the total number of carbon atoms in the structure according to formula (I).

[0018] In formula (II), M 2 is nitrogen or phosphorus, R N1 (C 1 ~C 30 ) hydrocarbyl, R N2 (C 2 ~C 30 ) hydrocarbyl, R N3 (C 3 ~C 30 ) hydrocarbyl. [Brief description of the drawings]

[0019] [Figure 1] 1 is a Thermogravimetric analysis (TGA) isothermal plot for cocatalyst samples of percent loss as a function of time at 250° C. [Diagram 2] 1 is a thermogravimetric analysis (TGA) isothermal plot for cocatalyst samples of percent loss as a function of time at 260° C. [Diagram 3] 1 is a thermogravimetric analysis (TGA) isothermal plot for cocatalyst samples of percent loss as a function of time at 210° C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as being limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0021] Common abbreviations are listed below.

[0022] Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: iso-propyl, t-Bu: tert-butyl, t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl), Tf: trifluoromethanesulfonate, THF: tetrahydrofuran, Et 2 O: Diethyl ether, CH 2 Cl 2 : dichloromethane, CV: column volume (if used in column chromatography), EtOAc: ethyl acetate, C 6 D 6 : Deuterated benzene or benzene-d6, CDCl 3 : Deuterated chloroform, Na 2 SO 4 : Sodium sulfate, MgSO 4: magnesium sulfate, HCl: hydrogen chloride, n-BuLi: butyl lithium, t-BuLi: tert-butyl lithium, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: molar concentration, min or mins: minutes, h or hrs: hours, d: days.

[0023] The term "independently selected" means 1 , R 2 , R 3 , R 4 , and R 5 The R groups, such as R 1 , R 2 , R 3 , R 4 , and R 5 may all be substituted alkyl, or R 1 and R 2 may be substituted alkyl, R 3 R may be aryl, etc. Chemical names associated with R groups are intended to convey chemical structures that are recognized in the art as corresponding to the chemical structure of the chemical name. Thus, the chemical names are intended to supplement and illustrate, not preclude, structural definitions known to those of skill in the art.

[0024] The term "procatalyst" refers to a transition metal compound that has olefin polymerization catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with the procatalyst to convert it into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0025] When used to describe a chemical group that contains a particular carbon atom, "(C x ~C yA bracketed expression having the form "(C)" means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive. For example, (C 1 ~C 50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S The parenthetical "(C x ~C y )" S The substituted chemical group can be any group R S For example, "R S is phenyl (-C 6 H 5 ) exactly one group R S Replaced by (C 1 ~C 50 "(C)alkyl" can contain from 7 to 56 carbon atoms. Thus, the parenthetical "(C)alkyl" is generally used. x ~C y )" is a substituent R S When a chemical group is substituted by x, the minimum and maximum total number of carbon atoms in the group is determined by the presence of both x and y in the substituent R S It is determined by adding the total number of carbon atoms from

[0026] The term “substituted” refers to at least one hydrogen atom (—H) bonded to a carbon atom of the corresponding unsubstituted compound or functional group, replaced by a substituent (e.g., R S The term "-H" means a hydrogen or hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0027] "(C 1 ~C 50 The term "(C)hydrocarbyl" means a hydrocarbon radical of 1 to 50 carbon atoms. 1 ~C50 The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 50 carbon atoms, each of which may be aromatic or non-aromatic, saturated or unsaturated, straight or branched, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and may be selected from the group consisting of one or more R S is or is not replaced by

[0028] In this disclosure, 1 ~C 50 ) Hydrocarbyl is unsubstituted or substituted (C 1 ~C 50 ) alkyl, (C 3 ~C 50 ) cycloalkyl, (C 3 ~C 20 )Cycloalkyl-(C 1 ~C 20 ) alkylene, (C 6 ~C 40 ) aryl, or (C 6 ~C 20 )Aryl-(C 1 ~C 20 ) alkylene (benzyl (-CH 2 ~C 6 H 5 ) etc.

[0029] "(C 1 ~C 50 The term "(C)alkyl" means a saturated linear or branched hydrocarbon radical containing 1 to 50 carbon atoms. 1 ~C 30 The term "alkyl" means a saturated linear or branched hydrocarbon radical of 1 to 30 carbon atoms. 1 ~C 50 ) alkyl and (C 1 ~C 30 ) Alkyl can be unsubstituted or can have one or more R S In some instances, each hydrogen atom in a hydrocarbon radical can be substituted with R, such as trifluoromethyl. S It can be substituted with unsubstituted (C1 ~C 50 Examples of alkyl groups include unsubstituted (C 1 ~C 20 ) Alkyl, unsubstituted (C 1 ~C 10 ) Alkyl, unsubstituted (C 1 ~C 5 ) 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. 1 ~C 40 Examples of substituted (C 1 ~C 20 ) Alkyl, Substituted (C 1 ~C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" means that there are up to 45 carbon atoms in the radical, including the substituents, such as methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl. 1 ~C 5 ) one R S is replaced by (C 27 ~C 40 ) alkyl.

[0030] (C 3 ~C 50 The term alkenyl refers to an alkyl group containing 3 to 50 carbon atoms, at least one double bond, and is unsubstituted or substituted with one or more R S means a branched or unbranched, cyclic or acyclic monovalent hydrocarbon radical substituted with unsubstituted (C 3 ~C 50 ) Examples of alkenyl are: n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, and cyclohexadienyl. 3 ~C 50Examples of alkenyl are (2-trifluoromethyl)pent-1-enyl, (3-methyl)hex-1-enyl, (3-methyl)hexa-1,4-dienyl, and (Z)-1-(6-methylhept-3-en-1-yl)cyclohex-1-enyl.

[0031] "(C 3 ~C 50 The term "cycloalkyl" refers to an unsubstituted or substituted cycloalkyl group. S means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms, substituted with other cycloalkyl groups, such as (C x ~C y )Cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S The unsubstituted (C 3 ~C 40 Examples of cycloalkyl are unsubstituted (C 3 ~C 20 ) Cycloalkyl, unsubstituted (C 3 ~C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 3 ~C 40 Examples of cycloalkyl are substituted (C 3 ~C 20 ) Cycloalkyl, substituted (C 3 ~C 10 ) cycloalkyl, and 1-fluorocyclohexyl.

[0032] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O) 2 , Si(R C ) 2 , P(R P ), N(R N ), -N=C(R C ) 2 , -Ge(R C ) 2 -, -Si(RC )-, boron (B), aluminum (Al), gallium (Ga), or indium (In), C and each R P is a non-substituted (C 1 ~C 18 ) hydrocarbyl or -H, and each R N is non-substituted (C 1 ~C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 1 ~C 50 The term "heterohydrocarbyl" means a heterohydrocarbon radical having 1 to 50 carbon atoms, and 1 ~C 50 The term "heterohydrocarbylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. 1 ~C 50 ) heterohydrocarbyl or (C 1 ~C 50 The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be on a carbon atom or on 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 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 other radical on a different heteroatom. Each (C 1 ~C 50 ) heterohydrocarbyl and (C 1 ~C 50 ) Heterohydrocarbylene may be unsubstituted, (one or more R S and may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0033] (C 1 ~C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. 1 ~C 50 Non-limiting examples of heterohydrocarbyls include (C 1 ~C 50 )heteroalkyl, (C 1 ~C 50 ) hydrocarbyl-O-, (C 1 ~C 50 ) hydrocarbyl-S-, (C 1 ~C 50 ) hydrocarbyl-S(O)-, (C 1 ~C 50 ) Hydrocarbyl-S(O) 2 -, (C 1 ~C 50 ) Hydrocarbyl-Si(R C ) 2 -, (C 1 ~C 50 )hydrocarbyl-N(R N )-, (C 1 ~C 50 ) hydrocarbyl-P(R P )-, (C 2 ~C 50 )heterocycloalkyl, (C 2 ~C 19 )Heterocycloalkyl-(C 1 ~C 20 ) alkylene, (C 3 ~C 20 )Cycloalkyl-(C 1 ~C 19 ) heteroalkylene, (C 2 ~C 19 )Heterocycloalkyl-(C 1 ~C 20 ) heteroalkylene, (C 1 ~C 50 ) heteroaryl, (C 1 ~C 19 ) Heteroaryl-(C 1 ~C 20 ) alkylene, (C 6 ~C 20 )Aryl-(C 1 ~C19 ) heteroalkylene, or (C 1 ~C 19 ) Heteroaryl-(C 1 ~C 20 ) heteroalkylene.

[0034] "(C 1 ~C 50 The term "heteroaryl" refers to an unsubstituted or heteroaryl group having a total of 1 to 50 carbon atoms and 1 to 10 heteroatoms (one or more R S (C) or (D). Monocyclic heteroaromatic hydrocarbon radicals contain one heteroaromatic ring, bicyclic heteroaromatic hydrocarbon radicals have two rings, and tricyclic heteroaromatic hydrocarbon radicals have three rings. When bicyclic or tricyclic heteroaromatic hydrocarbon radicals are 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. Other heteroaryl groups (such as, generally, (C) x ~C y ) heteroaryl, for example (C 1 ~C 12 ) Heteroaryl) similarly has x to y carbon atoms (e.g., 1 to 12 carbon atoms) and is unsubstituted or has one or more R SIt is defined that the monocyclic heteroaromatic hydrocarbon radical is substituted by. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms, which may be 1, 2, 3, or 4, and each heteroatom may be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. A 6-membered monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2, and the heteroatom may be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. A bicyclic heteroaromatic hydrocarbon radical may be a fused 5,6- or 6,6-ring system. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. A tricyclic heteroaromatic hydrocarbon radical may be a fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring system. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0035] "(C 1 ~C 50The term "(C)heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms and one or more heteroatoms. 1 ~C 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a heteroalkyl or heteroalkylene include Si(R C ) 3 , Ge(R C ) 3 , Si(R C ) 2 , Ge(R C ) 2 , P(R P ) 2 , P(R P ), N(R N ) 2 , N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O) 2 wherein each of the heteroalkyl and heteroalkylene groups can be unsubstituted or can include one or more R S has been replaced by

[0036] Unsubstituted (C 2 ~C 40 Examples of heterocycloalkyl include unsubstituted (C 2 ~C 20 )Heterocycloalkyl, unsubstituted (C 2 ~C 10 ) heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0037] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom, fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I - )

[0038] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double or triple bonds may optionally be replaced by a substituent R S The term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, and may be present in the substituent R S (if present), or in an aromatic or heteroaromatic ring (if present).

[0039] Embodiments of the present disclosure include catalyst systems comprising a procatalyst and an activator, the activator comprising an anion and a cation, the anion having a structure according to formula (I).

[0040] [ka]

[0041] In formula (I), B is a boron atom. 1 and each R 5 is selected from -H or -F; each R 2 , R 3 , and R 4 -H, -F, (C 1 ~C 10 ) hydrocarbyl, (C 1~C 10 ) heterohydrocarbyl; R 6 , R 7 , R 8 , R 9 and R 10 are independently -H, -F, (C 1 ~C 10 ) hydrocarbyl, (C 1 ~C 10 ) heterohydrocarbyl, -OR C , -SiR C 3 where R C is -H or (C 1 ~C 20 ) hydrocarbyl, optionally R 7 and R 8 In one or more embodiments, in formula (I), R C is -H or (C 1 ~C 10 ) hydrocarbyl, or -H or (C 1 ~C 10 ) alkyl.

[0042] In formula (I), the structure according to formula (I) has a fluorine to carbon ratio (F / C) of 0.86 or less, where F is the total number of fluorine atoms in the structure according to formula (I) and C is the total number of carbon atoms in the structure according to formula (I).

[0043] In one or more embodiments, the activator has a percent thermal decomposition of greater than 10% as measured by thermogravimetric analysis.

[0044] In some embodiments, in formula (I), R 6 , R 7 , R 8 , R 9 , and R 10 When three or more of R are fluorine atoms, R 1 , R 2 , R 3 , R 4 , and R 5At least one of R is -H. 6 , R 7 , R 8 , R 9 , and R 10 If none of the groups is a fluorine atom, R 1 , R 2 , R 3 , R 4 , and R 5 At least four of the are fluorine atoms.

[0045] In some embodiments, R 1 , R 2 , R 3 , R 4 , and R 5 Each of R is a fluorine atom. 2 , R 3 , R 4 , and R 5 Each of R is a fluorine atom. 2 , R 3 , and R 4 is a fluorine atom. In various embodiments, R 1 , R 3 , and R 5 is a fluorine atom. In some embodiments, R 2 and R 5 -CF 3 or a fluorine atom. In one or more embodiments, R 2 , R 3 , and R 5 is a fluorine atom.

[0046] In one or more embodiments, R 6 , R 7 , R 8 , R 9 , and R 10 is a fluorine atom. In some embodiments, R 7 , R 8 , R 9 , and R 10 is a fluorine atom, or R 8 , and R 9 is a fluorine atom. In various embodiments, R7 and R 9 -CF 3 In some embodiments, R 6 and R 10 is a fluorine atom. In one or more embodiments, R 6 , R 8 , and R 10 is a fluorine atom.

[0047] In some embodiments, in formula (I), the total number of fluorine atoms is 4 to 18. In one or more embodiments, the value of the fluorine to carbon ratio (F / C) is 0.81 or less. In various embodiments, the value of the fluorine to carbon ratio (F / C) is 0.80 or less.

[0048] In an embodiment, the polymerization process comprises polymerizing ethylene and optionally one or more α-olefin monomers in a solution polymerization reactor in the presence of a catalyst system. The polymer produced is obtained and heated to a pyrolysis temperature for at least one minute.

[0049] In an embodiment, the catalyst system in the polymerization process comprises a procatalyst and an activator, the activator comprising an anion and a cation, the anion having a structure according to formula (I).

[0050] [ka]

[0051] In formula (II), B is a boron atom. 11 and each R 15 is selected from -H or a fluorine atom. 12 , R 13 , and R 14 is -H, fluorine atom, (C 1 ~C 40 ) hydrocarbyl, (C 1 ~C 40 ) heterohydrocarbyl, provided that (1) R on each individual ring 11 , R 12 , R 13 , R14 , and R 15 at least three of R on each individual ring are fluorine atoms, or 11 , R 12 , R 13 , R 14 , and R 15 At least one of the following is -CF 3 R 16 , R 17 , R 18 , R 19 , and R 20 are independently -H, a fluorine atom, (C 1 ~C 40 ) hydrocarbyl, (C 1 ~C 40 ) heterohydrocarbyl, -OR C , -SiR C 3 and optionally R 7 and R 8 In one or more embodiments, in formula (II), R C -H, (C 1 ~C 20 ) hydrocarbyl, (C 1 ~C 20 ) hydrocarbyl, or (C 1 ~C 10 ) alkyl.

[0052] The structure according to formula (II) does not include:

[0053] [ka]

[0054] In some embodiments, in formula (II), R 16 , R 17 , R 18 , R 19 , and R 20 When three or more of R are fluorine atoms, R 11 , R 12 , R 13 , R 14 , and R 15At least one of R is -H. 16 , R 17 , R 18 , R 19 , and R 20 If none of the groups is a fluorine atom, R 11 , R 12 , R 13 , R 14 , and R 15 At least four of the are fluorine atoms.

[0055] In some embodiments, in formula (II), R 11 , R 12 , R 13 , R 14 , and R 15 Each of R is a fluorine atom. 12 , R 13 , R 14 , and R 15 Each of R is a fluorine atom. 12 , R 13 , and R 14 is a fluorine atom. In various embodiments, R 11 , R 13 , and R 15 is a fluorine atom. In some embodiments, R 12 and R 15 -CF 3 or a fluorine atom. In one or more embodiments, R 2 , R 3 , and R 5 is a fluorine atom.

[0056] In one or more embodiments, in formula (II), R 16 , R 17 , R 18 , R 19 , and R 20 is a fluorine atom. In some embodiments, R 17 , R 18 , R 19 , and R 20 is a fluorine atom, or R 18 and R 19is a fluorine atom. In various embodiments, R 17 and R 19 -CF 3 In some embodiments, R 6 and R 10 is a fluorine atom. In one or more embodiments, R 16 , R 18 , and R 20 is a fluorine atom.

[0057] In some embodiments, the total number of fluorine atoms in formula (II) is 4 to 18. In one or more embodiments, the value of the fluorine to carbon ratio (F / C) is 0.81 or less. In various embodiments, the value of the fluorine to carbon ratio (F / C) is 0.80 or less.

[0058] In one or more embodiments, the pyrolysis temperature is greater than 200° C. or at least 250° C. In some embodiments, the pyrolysis temperature is between 200° C. and 500° C.

[0059] In some embodiments of the polymerization process, the formed polymer is heated to the pyrolysis temperature for at least 5 minutes or at least 10 minutes, in some embodiments, the formed polymer is heated to the pyrolysis temperature for 5 to 30 minutes.

[0060] In embodiments, the catalyst system comprises an anion of formula (I) and a cation. The cation is any cation having a formal charge of +1. In some embodiments, the cation is selected from the group consisting of a tertiary carbocation, an alkyl-substituted ammonium ion, anilinium, an alkyl-substituted alumocenium, or a ferrocenium.

[0061] In some embodiments of the metal ion complex, the counter cation is a protonated tri[(C 1 ~C 40 In some embodiments, the counter cation is selected from one or two (C 14 ~C 20) alkyl-containing protonated trialkylammonium cation. In one or more embodiments, the countercation is + N(CH 3 )HR N 2 where R N is (C 16 ~C 18 ) alkyl. In some embodiments, the countercation is selected from methyldi(octadecyl)ammonium cation or methyldi(tetradecyl)ammonium cation. The methyldi(octadecyl)ammonium cation or methyldi(tetradecyl)ammonium cation are collectively referred to herein as armeenium cation. Ionic compounds having armeenium cations are available from Nouryon under the trade name Armeen™ M2HT. In other embodiments, the countercation is triphenylmethyl carbocation (Ph), also known as trityl. 3 C + In one or more embodiments, the counter cation is + C(C 6 H 4 R C ) 3 and the like, wherein + C(C 6 H 4 R C ) 3 Each R in C are independent, (C 1 ~C 30 ) alkyl. In other embodiments, the counter cation is selected from anilinium, ferrocenium, or aluminocenium. The anilinium cation is selected from [HMe 2 N(C 6 H 5 )] + Aluminocenium is a protonated nitrogen cation such as R S 2 Al(THF) 2 + and the like, wherein R S is (C 1~C 30 ) alkyl.

[0062] In an exemplary embodiment, the catalyst system may include an activator having an anion and a cation, where the anion conforms to formula (I) and the activator has any of the following structures:

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] Catalyst System Components The catalyst system may include a procatalyst. The procatalyst may be made catalytically active by contacting the complex with or combining the complex with a metal activator having an anion of formula (I) and a countercation. The procatalyst may be selected from metal-ligand complexes such as Group IV metal-ligand complexes (Group IVB according to CAS, or Group 4 according to IUPAC nomenclature), such as titanium (Ti) metal-ligand complexes, zirconium (Zr) metal-ligand complexes, or hafnium (Hf) metal-ligand complexes. Non-limiting examples of procatalysts include catalysts, procatalysts, or catalytically active compounds for polymerizing ethylene-based polymers and are disclosed in one or more of U.S. Pat. No. 8,372,927, WO 2010022228, WO 2011102989, U.S. Pat. No. 6,953,764, U.S. Pat. No. 6,900,321, WO 2017173080, U.S. Pat. No. 7,650,930, U.S. Pat. No. 6,777,509, WO 99 / 41294, U.S. Pat. No. 6,869,904, or WO 2007136496, all of which documents are incorporated herein by reference in their entirety.

[0068] In one or more embodiments, the catalyst system includes a metal-ligand complex procatalyst, where the catalyst is ionic. Examples of homogeneous catalysts include, but are not limited to, metallocene complexes, constrained geometry metal-ligand complexes (Li, H.; Marks, TJ, Proc. Natl. Acad. Sci. USA 2006, 103, 15295-15302; Li, H.; Li, L.; Schwartz, DJ; Metz, MV; Marks, TJ; Liable-Sands, L.; Rheingold, AL, J. Am. Chem.Soc. 2005,127,14756-14768, McInnis,JP;Delferro,M.;Marks,TJ,Acc.Chem.Res. 2014,47,2545-2557, Delferro,M.;Marks,TJ,Chem.Rev. 2011,111,2450-2485.), pyridylamide Hf (or Zr, Ti) complexes (Arriola,DJ;Carnahan,EM ;Hustad,PD;Kuhlman,RL;Wenzel,TT,Science,2006,312,714-719.,Arriola,DJ;Carnahan,EM;Cheung,YW;De vore, DD; Graf, DD; Hustad, PD; Kuhlman, RL; Shan, CLP; Poon, BC; Roof, GR, U.S. Patent No. 9243090 (B2), 2016.), phenoxyimide See, for example, phenylalanine metal complexes (Makio, H.; Terao, H.; Iwashita, A.; Fujita, T., Chem. Rev. 2011, 111, 2363-2449.), bis-biphenylphenoxy metal-ligand complexes (Arriola, DJ; Bailey, BC; Klosin, J.; Lysenko, Z.; Roof, GR; Smith, AJWO2014209927A1, 2014.).The following references summarize metal complexes as olefin polymerization catalysts in both industrial and academic fields: Sturzel, M.; Mihan, S.; Mulhaupt, R., Chem. Rev. 2016, 116, 1398-1433.; Busico, V., Dalton Transactions 2009, 8794-8802.; Klosin, J.; Fontaine, PP; Figueroa, R., Acc. Chem. Res. 2015, 48, 2004-2016. All references cited in the detailed description of the present disclosure are incorporated herein.

[0069] In one or more embodiments, the Group IV metal-ligand complexes include bis(phenylphenoxy) Group IV metal-ligand complexes, or constrained geometry Group IV metal-ligand complexes.

[0070] According to some embodiments, the Group IV metal-ligand procatalyst complex may comprise a bis(phenylphenoxy) structure according to formula (X).

[0071] [ka]

[0072] In formula (X), M is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4. (X) n The subscript n in is 0, 1, or 2. When the subscript n is 1, X is a monodentate or bidentate ligand, and when the subscript n is 2, each X is a monodentate ligand. L is (C 1 ~C 40 ) hydrocarbylene, (C 1 ~C 40 ) heterohydrocarbylene, -Si(R C ) 2 -, -Si(R C ) 2 OSi(R C ) 2 -, -Si(R C ) 2 C(RC ) 2 -, -Si(R C ) 2 Si(R C ) 2 -, -Si(R C ) 2 C(R C ) 2 Si(R C ) 2 -, -C(R C ) 2 Si(R C ) 2 C(R C ) 2 -, -N(R N )C(R C ) 2 -, -N(R N )N(R N )-, -C(R C ) 2 N(R N )C(R C ) 2 -, -Ge(R C ) 2 -, -P(R P )-, -N(R N )-, -O-, -S-, -S(O)-, -S(O) 2 -, -N=C(R C )-, -C(O)O-, -OC(O)-, -C(O)N(R)-, and -N(R C Each Z is independently selected from the group consisting of -O-, -S-, -N(R N )- or -P(R P )-, R 2 -R 4 , R 5 -R -8 , R 9 -R 12 , and R 13 -R 15 are independently -H, (C 1 ~C 40 ) hydrocarbyl, (C 1 ~C 40 ) heterohydrocarbyl, -Si(R C ) 3 , -Ge(R C ) 3 , -P(RP ) 2 , -N(R N ) 2 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , R C S(O)-, R C S(O) 2 -, -N=C(R C ) 2 , R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) 2 R is selected from the group consisting of NC(O)-, and halogen. 1 and R 16 is selected from a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII).

[0073] [ka]

[0074] In formulas (XI), (XII), and (XIII), R 31 -R 35 , R 41 -R 48 , and R 51 -R 59 each independently represents -H, (C 1 ~C 40 ) hydrocarbyl, (C 1 ~C 40 ) heterohydrocarbyl, -Si(R C ) 3 , -Ge(R C ) 3 , -P(R P ) 2 , -N(R N ) 2 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , R C S(O)-, R CS(O) 2 -, (R C ) 2 C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) 2 NC(O)-, or halogen.

[0075] In one or more embodiments, each X, independently of any other ligand X, is halogen, unsubstituted (C 1 ~C 20 ) hydrocarbyl, unsubstituted (C 1 ~C 20 ) hydrocarbyl C(O)O-, or R K R L N-, where R K and R L Each of 1 ~C 20 ) hydrocarbyl.

[0076] According to some embodiments, the Group IV metal-ligand complex may include a cyclopentadienyl procatalyst according to formula (XIV): Lp i MX m X' n X” p , or a dimer thereof (XIV).

[0077] In formula (XIV), Lp is an anionic delocalized π-bonded group containing up to 50 non-hydrogen atoms and attached to M. In some embodiments of formula (XIV), two Lp groups may be bonded together to form a bridged structure, and further optionally one Lp may be bonded to X.

[0078] In formula (XIV), M is a Group 4 metal of the Periodic Table of Elements in a formal oxidation state of +2, +3, or +4. X is an optional divalent substituent of up to 50 non-hydrogen atoms that together with Lp forms a metallocycle containing M. X' is an optional neutral ligand having up to 20 non-hydrogen atoms, and each X'' is independently a monovalent anionic moiety having up to 40 non-hydrogen atoms. Optionally, two X'' groups may be covalently bonded together to form a divalent dianionic moiety with both valencies bonded to M, or optionally, two X'' groups may be covalently bonded together to form a neutral, conjugated, or non-conjugated diene π-bonded to M, where M is in the +2 oxidation state. In other embodiments, one or more X'' and one or more X' groups may be bonded together, thereby forming a moiety that is covalently bonded to M and coordinated by a Lewis base functional group. Lp i The subscript i in X' is 0, 1, or 2; n The subscript n is 0, 1, 2, or 3; m The subscript m in X" is 0 or 1, p The subscript p is 0, 1, 2, or 3. The sum of i+m+p equals the formula oxidation state of M.

[0079] Other procatalysts, particularly those containing other Group IV metal-ligand complexes, will be apparent to those skilled in the art.

[0080] The catalyst system of the present disclosure may include a cocatalyst or activator in addition to the ionic metal activator complex having the anion and countercation of formula (I). Such additional cocatalysts may include, for example, tri(hydrocarbyl)aluminum compounds having 1-10 carbons in each hydrocarbyl group, oligomeric or polymeric aluminoxane compounds, di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds having 1-20 carbons in each hydrocarbyl or hydrocarbyloxy group, or mixtures of the foregoing compounds. It is useful to use these aluminum compounds due to their beneficial ability to scavenge impurities such as oxygen, water, and aldehydes from the polymerization mixture.

[0081] Di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds that may be used in conjunction with the activators described in this disclosure have the formula T 1 2 AlOT 2 Or T 1 1 Al(OT 2 ) 2 (In the formula, T 1 Class 2 or 3 (C 3 ~C 6 ) alkyl, for example, isopropyl, isobutyl, or tert-butyl; T 2 is alkyl substituted (C 6 ~C 30 ) aryl radical or aryl substituted (C 1 ~C 30 ) alkyl radicals, such as 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methyltolyl, or 4-(3',5'-di-tert-butyltolyl)-2,6-di-tert-butylphenyl).

[0082] Additional examples of aluminum compounds include [C 6 ]Trialkylaluminum compounds, specifically those in which the alkyl group is ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl, dialkyl(aryloxy)aluminum compounds containing 1 to 6 carbons in the alkyl group and 6 to 18 carbons in the aryl group (specifically, (3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum), methylaluminoxane, modified methylaluminoxane, and diisobutylaluminoxane.

[0083] In catalyst systems according to embodiments of the present disclosure, the molar ratio of ionic metal activator complex to Group IV metal-ligand complex can be from 1:10,000 to 1000:1, e.g., from 1:5000 to 100:1, from 1:100 to 100:1, from 1:10 to 10:1, from 1:5 to 1:1, or from 1.25:1 to 1:1. The catalyst systems can include a combination of one or more ionic metal activator complexes described herein.

[0084] Polyolefin The catalyst system described in the preceding paragraphs is utilized for the polymerization of olefins, primarily ethylene and propylene, to form ethylene-based or propylene-based polymers. In some embodiments, there is only one type of olefin or α-olefin in the polymerization scheme, so that homopolymers are produced. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomer typically has 20 or fewer carbon atoms. For example, the α-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, the one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0085] An ethylene-based polymer, e.g., a homopolymer of ethylene and / or an interpolymer (including a copolymer) of ethylene and, optionally, one or more comonomers, such as an α-olefin, can include at least 50 mole percent (mol %) of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 mole percent" are disclosed herein as separate embodiments, for example, an ethylene-based polymer, a homopolymer of ethylene and / or an interpolymer (including a copolymer) of ethylene and, optionally, one or more comonomers, such as an α-olefin, can include at least 60 mole percent of monomer units derived from ethylene, at least 70 mole percent of monomer units derived from ethylene, at least 80 mole percent of monomer units derived from ethylene, or from 50 to 100 mole percent of monomer units derived from ethylene, or from 80 to 100 mole percent of monomer units derived from ethylene.

[0086] In some embodiments, the polymerization process according to the present disclosure produces an ethylene-based polymer. In one or more embodiments, the ethylene-based polymer can comprise at least 90 mole percent of 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 polymer can comprise at least 93 mole percent of units derived from ethylene, at least 96 mole percent of units, at least 97 mole percent of units derived from ethylene, or alternatively, 90 to 100 mole percent of units derived from ethylene, 90 to 99.5 mole percent of units derived from ethylene, or 97 to 99.5 mole percent of units derived from ethylene.

[0087] In some embodiments of the ethylene-based polymer, the amount of the additional α-olefin is less than 50 mol %, other embodiments include at least 1 mole percent (mol %) to 25 mol %, and in further embodiments the amount of the additional α-olefin includes at least 5 mol % to 103 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0088] Any conventional polymerization process may be used to produce the ethylene-based polymers, including, but 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, and the like, in parallel, in series, or any combination thereof.

[0089] In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor, e.g., a dual loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more cocatalysts. In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and herein and optionally one or more other catalysts. The catalyst system described herein can be used in the first reactor or the second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of the catalyst system described herein.

[0090] In another embodiment, the ethylene-based polymer can be produced by solution polymerization in a single reactor system, such as a single loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system, as described within this disclosure, and optionally in the presence of one or more cocatalysts, as described in the preceding paragraphs.

[0091] The ethylene-based polymer may further comprise 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 polymer may comprise any amount of additives. The ethylene-based polymer may comprise from about 0 to about 10 percent by weight of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may comprise, but is not limited to, calcium carbonate, talc, or Mg(OH), based on the weight of the ethylene-based polymer and all additives or fillers. 2 The ethylene-based polymer may contain from about 0 to about 20 weight percent of a filler such as, for example, a tertiary olefin copolymer ... or a tertiary olefin copolymer. The ethylene-based polymer may be further blended with one or more polymers to form a blend.

[0092] In some embodiments, a polymerization process for producing an ethylene-based polymer may comprise polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system according to the present disclosure. The polymer obtained from such a catalyst system incorporating a metal-ligand complex of formula (X) may have a molecular weight of, for example, 0.850 g / cm according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.950g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm 3 , or 0.880 g / cm3 ~0.900g / cm 3 The density may be

[0093] In another embodiment, the polymer resulting from the catalyst system according to the present disclosure has a melt flow ratio (I 10 / I 2 ) and has a melt index I 2 is measured at 190° C. and a load of 2.16 kg in accordance with ASTM D1238, which is incorporated herein by reference in its entirety, and the melt index I 10 is measured at 190° C. and a load of 10 kg according to ASTM D1238. In another embodiment, the melt flow ratio (I 10 / I 2 ) is 5-10, and in other embodiments the melt flow ratio is 5-9.

[0094] In some embodiments, the polymers obtained from the catalyst system according to the present disclosure have a molecular-weight distribution (MWD) of 1 to 25, w / M n is defined as M w is the weight average molecular weight, M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1 to 6. Another embodiment has an MWD of 1 to 3, and another embodiment has an MWD of 1.5 to 2.5.

[0095] Embodiments of the catalyst systems described in this disclosure result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0096] Procedure for continuous process reactor polymerization: Feedstocks (ethylene, 1-octene) and process solvent (high purity narrow boiling range isoparaffinic solvent commercially available from ExxonMobil Corporation under the trademark ISOPAR E) are purified with molecular sieves and then introduced into the reaction environment. Hydrogen is supplied in a pressurized cylinder as a high purity grade with no further purification. The reactor monomer feed stream (ethylene) is pressurized above the reaction pressure. The solvent and comonomer feeds are pressurized above the reaction pressure. The individual catalyst components (metal-ligand complex and cocatalyst) are manually batch diluted with purified solvent to the specified component concentrations and pressurized to a pressure above the reaction pressure. All reaction feed streams are metered with mass flow meters and independently controlled by computer automated valve control systems.

[0097] Continuous solution polymerization is carried out in a continuously circulated loop-reactor. The feed to the reactor, which combines solvent, monomer, comonomer, and hydrogen, is temperature controlled between 5°C and 50°C, typically 15-25°C. All components are fed to the polymerization reactor along with the solvent feed. Catalyst is fed to the reactor to reach a specific conversion of ethylene. Cocatalyst components are fed separately based on a calculated specified molar ratio or ppm amount. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and polymer) exits the reactor and contacts water. In addition, various additives such as antioxidants can be added at this point. The stream is then passed through a static mixer to uniformly disperse the mixture.

[0098] Following the addition of the additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the temperature of the stream to approximately 250° C. in preparation for separation of the polymer from other low boiling components. The polymer stream remains in the heat exchanger segment for approximately 2 minutes. It then passes the stream through a reactor pressure control valve where the pressure is greatly reduced throughout. From there, it enters a separation system consisting of two devolatilizers in series followed by a vacuum extruder. In this section, the solvent and unreacted hydrogen, monomer, comonomer, and water are removed from the polymer. The residence time in this section is at least 1 hour per devolatilizer section. The first devolatilizer was maintained at approximately 180° C. and the second devolatilizer was maintained at approximately 230° C. At the exit of the extruder, the strands of molten polymer formed pass through a cold water bath where they solidify. The strands are then fed through a strand chopper to cut the polymer into pellets which are then air dried.

[0099] Procedure for batch reactor polymerization. The feedstocks (ethylene, 1-octene) and process solvent (ISOPAR E) are purified with molecular sieves and then introduced into the reaction environment. A stirred autoclave reactor was charged with ISOPAR E and 1-octene. The reactor was then heated to a certain temperature and charged with ethylene to reach the desired pressure. Optionally, hydrogen was also added. The catalyst system was prepared by mixing the metal-ligand complex and, optionally, one or more additives with additional solvent in a dry box under an inert atmosphere. The catalyst system was then injected into the reactor. The reactor pressure and temperature were kept constant by feeding ethylene during the polymerization and cooling the reactor as necessary. After 10 minutes, the ethylene feed was stopped and the solution was transferred to a nitrogen-purged resin kettle. The polymer was thoroughly dried in a vacuum oven and the reactor was thoroughly rinsed with hot ISOPAR E between polymerization runs.

[0100] Unless otherwise indicated herein, the following analytical methods are used in describing the embodiments of the present disclosure.

[0101] Melt Index Melt index I of polymer sample 2 (or I2) and I 10 (or I10) were measured according to ASTM D-1238 (Method B) at 190° C. and loads of 2.16 kg and 10 kg, respectively, and the values ​​are reported in g / 10 min.

[0102] density Samples for density measurements were prepared according to ASTM D4703. Measurements were performed according to ASTM D792, Method B, within 1 hour of sample pressing.

[0103] Gel Permeation Chromatography (GPC) The chromatography system consisted of a PolymerChar (Valencia, Spain) GPC-IR high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set at 160°C and the column compartment was set at 150°C. The columns used were four Agilent "Mixed A" 30 cm 20 micron linear mixed bed columns and a 20 um precolumn. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume employed was 200 microliters and the flow rate was 1.0 milliliters / min.

[0104] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in six "cocktail" mixtures with at least 10-fold spacing between individual molecular weights. Standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and at 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M_polyethylene = A × (M_polystyrene)^B (Equation 1) where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0105] A fifth order polynomial was used to fit each of the polyethylene equivalent calibration points, with a small adjustment to A (approximately 0.375 to 0.445) to correct for column resolution and band broadening effects for a linear homopolymer polyethylene standard obtained at 120,000 Mw.

[0106] A total plate count of the GPC column set was performed using decane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation). Plate count (Equation 2) and symmetry (Equation 3) were measured with a 200 microliter injection according to the following equations: Plate count = 5.54 * (((RV_(peak maximum value)) / (peak width at 1 / 2 height))^2 (Equation 2) where RV is the retention volume in milliliters, PeakWidth is in milliliters, PeakMax is the maximum height of the peak, and ½Height is half the height of the PeakMax.

[0107]

number

[0108] Samples were prepared in a semi-automated fashion using PolymerChar's "Instrument Control" software to target sample weights of 2 mg / ml and add solvent (containing 200 ppm BHT) via a PolymerChar high temperature autosampler to pre-nitrogen sparged capped vials with septa. Samples were dissolved at 160° C. for 2 hours under "slow" shaking.

[0109] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on GPC results using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph according to Equations 4-6 using PolymerChar GPCOne™ software, baseline-subtracted IR chromatograms at each equally spaced data collection point (i), and polyethylene equivalent molecular weights obtained from a narrow standard calibration curve for point (i) of Equation 1.

[0110]

number

[0111]

number

[0112]

number

[0113] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate (apparent)) of each sample by RV matching the respective decane peak in the sample (RV (FM sample)) with that of the decane peak in the narrow standard calibration (RV (FM calibrated)). Any change in time of the decane marker peak is then assumed to be related to a linear shift in flow rate (flow rate (effective)) throughout the run. To facilitate the highest accuracy of the RV measurement of the flow rate marker peak, a least squares fitting routine is used to fit the peaks of the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on the flow rate marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated as per Equation 7. Processing of flow marker peaks was performed via GPCOne™ software from PolymerChar, Inc. Acceptable flow correction is such that the effective flow rate should be within ±0.5% of the apparent flow rate. Flow (effective) = Flow (apparent) * (RV(FM calibrated) / RV(FM sample)) (Equation 7)

[0114] Short chain branches per 1000 total carbons (SCB / 1000C) are measured according to the method described in the "Molecular Weighted Comonomer Distribution Index (MWCDI)" section of WO2015200743(A1).

[0115] Plaque preparation for electrical testing For all samples, the resin is placed in a 420 mL Brabender mixer bowl, the cam blade set at 80°C, and fluxed for 1 minute once melted. If the sample contains a partitioning agent, add it to the resin and flux until the powder is visibly incorporated. Slowly add the antioxidant and once melted, flux the blend for 3 minutes. Perkadox BC-FF is melted in a sealed vial using a water bath set at 60°C, the liquid peroxide is added, and mixed at 40 rpm for 3 minutes. The polymer melt temperature should not exceed 125°C. The mixture is removed from the mixing bowl and cold pressed into a "pancake".

[0116] For plaque preparation, the samples are first pressed at 120°C under low pressure (500 psi) for 3 minutes. After 3 minutes, compression is switched to high pressure (2500 psi) for an additional 3 minutes at the same temperature. The samples are cut into uniform specimens and reloaded into the press. The samples are then pressed at 120°C under low pressure for 3 minutes. The temperature is then increased to 182°C and the pressure increased to the high pressure condition. Once the press has reached the desired temperature, the samples are cured at high pressure for an additional 12 minutes. Following the cure period, the samples are cooled to approximately 30°C under high pressure.

[0117] Using the plaque preparation and curing method described above, 50 mil and 20 mil plaques are made from cold press. The plaques are then placed in a vacuum oven and degassed at 65°C under house vacuum for 3 days. Sample discs are then punched out and tested for DC / DF and VR. Duplicate samples are punched out from the same plaques.

[0118] Electrical properties of polymers The electrical insulating efficiency of a medium, such as a polymeric material, can be evaluated by considering the electrical resistance of the medium and the electrical losses in the medium. Electrical losses reduce the efficiency with which an insulating medium electrically insulates in the presence of an electric field. Because resistance is inversely related to power or electrical losses, the resistance of an insulating medium should be as high as possible in both alternating current (AC) and direct current (DC) systems.

[0119] In DC systems, such as photovoltaic devices encapsulated in an insulating medium, such as a polymeric material, electrical losses appear as leakage current from the encapsulated device through the encapsulant to the external environment. This current (I) is related to the voltage (V) of the insulating medium by the equation I=V×R -1 It is inversely related to the resistance (R) of the insulating medium according to: Thus, the higher the resistance, the lower the current and leakage current.

[0120] In AC systems that contain insulating media, such as cable insulation, electrical losses appear as the absorption of energy by the insulating medium in the presence of an electric field. This loss, measured in power (P), is expressed by the equation P=V 2 ×ω×C×ε'×tan δ, where ω is the angular frequency, ε' is the relative permittivity, C is the capacitance, and tan δ is the dielectric tangent, tan δ=(C×R×ω) -1 and the equation P=V 2 ×ε'×R -1 Resistance is inversely related to power dissipation, so the higher the resistance, the lower the power dissipation.

[0121] The electrical resistance of a medium generally decreases as a result of ionic diffusion induced by an external electric field. In systems where ionic diffusion dominates the electrical response, the resistance is given by the equation R = 6 × π × ε' × ε 0 ×η×r×C -1 ×q -2 ×N -1 For diffusing ions according to the formula: 0 is the dielectric constant of a vacuum (8.854×10 -12 F m -1 ), η is the kinematic viscosity of the medium, r is the hydrodynamic radius of the ion, q is the charge of the ion, and N is the concentration of the ion. Reducing the concentration of ions diffusing through a medium reduces the energy loss because increasing the resistance reduces the energy loss and decreasing the ion concentration increases the resistance.

[0122] The ability of an ion to diffuse through a given medium is influenced by the size of the ion, the charge of the ion, the interaction of the ion with the surrounding medium, and the dissociation energy of the ion with available counterions. Since not all ions diffuse equally through a given medium, when the medium is a polymer, the diffusivity of the ion generally affects the insulating ability of the polymer. Without intending to be bound by theory, it is believed that the anion of the ionic bimetallic activator complex of formula (I) has a low ability to diffuse through the resulting polymer, so that the resulting polymer of the catalyst system of the present disclosure has desirable electrical properties, such as reduced electrical losses.

[0123] [B(C 6 F 5 ) 4 The presence of [B(C 6 F 5 ) 4 Polymers made using activators based on the ]-anion often retain the anion after polymerization. The thermal stability of this anion allows them to withstand high temperatures such as those commonly found prior to devolatilization in a solution polymerization asset or during post-polymerization processing such as those experienced in an extruder or other activity downstream of the polymerization activity.

[0124] Scheme 1. Thermal decomposition of ammonium borate

[0125] [ka]

[0126] The relative thermal stability of a series of anions can be evaluated by comparing a series of anions using a common cation moiety. For example, but not limited to, the ammonium cation can be used. In this example, the thermal decomposition of the borate anion is believed to proceed by protonation of the aromatic substituent by the ammonium cation. This produces triarylboranes, aromatic hydrocarbons, and neutral amines. Depending on the volatility of these species and the temperature at which the thermal decomposition experiment is performed, one or more of these species may be volatile and mass loss from the sample is observed.

[0127] The theoretical percent decomposition of each borate species can be determined by evaluation of the starting structure and the volatile components expected to be present upon decomposition. From these values, the expected mass loss at 100% decomposition can be assigned and then compared to the observed mass loss. This general approach is described in Equation 1.

[0128]

number

[0129] In the formula, m 0 is the initial mass of the sample, m t is the mass of the sample at time t, and wf is the molecular weight of the expected volatile fragment divided by the molecular weight of the parent compound. For the calculation of equation (1), the amine is considered to be the only non-volatile component after decomposition.

[0130] One or more features of the present disclosure will be illustrated in light of the following examples. EXAMPLES

[0131] Example 1 is a procedure for the synthesis of intermediates and isolated activators.

[0132] Example 1 - Representative Procedure for the Synthesis of Sodium Boric Acid Salt - Synthesis A In a glove box, magnesium turnings were suspended in diethyl ether and activated by the addition of 2 drops of dibromoethane. Bromofluorobenzene compound was added slowly as a 33 wt% solution in diethyl ether. The solution was stirred for 4-6 hours and then quenched by the addition of solid sodium tetrafluoroborate. The quenched solution was stirred for 24 hours. The solution was removed from the glove box and poured into a saturated solution of sodium bicarbonate and stirred for 30 minutes. The mixture was filtered through Celite. The organic solution was isolated and the aqueous solution was extracted with diethyl ether. The combined organic fractions were dried over anhydrous sodium sulfate. The solution was filtered and then concentrated using a rotary evaporator. The resulting residue was redissolved in dichloromethane and concentrated using a rotary evaporator. The residue was triturated using dichloromethane to give an off-white solid and a pale yellow to brown solution. The solid was isolated by filtration and rinsed with additional dichloromethane. The solid was dried under vacuum to give the desired product.

[0133] Representative Procedure for the Synthesis of Sodium Boric Acid Salt - Synthesis B In a glove box, the desired bromofluorobenzene compound was dissolved in diethyl ether. Isopropylmagnesium chloride (2M) in diethyl ether was then added dropwise. The solution was stirred for 4-6 hours at which point the reaction was quenched by the addition of solid sodium tetrafluoroborate. The resulting mixture was stirred for 18-24 hours. The solution was removed from the glove box and poured into a saturated solution of sodium bicarbonate and stirred for 30 minutes. The organic solution was isolated and the aqueous solution was extracted with diethyl ether. The combined organic fractions were dried over anhydrous sodium sulfate. The solution was filtered and then concentrated using a rotary evaporator. The resulting residue was redissolved in dichloromethane and concentrated using a rotary evaporator. The residue was triturated with dichloromethane to give a white solid and a yellow solution. The solid was isolated by filtration and rinsed with additional dichloromethane. The solid was dried under vacuum to give the desired material.

[0134] Representative Procedure for Cation Exchange to Form Aluminum Borate Under an inert atmosphere, Armeen HCl and sodium borate salt were added together in a 1:1 molar ratio in dry degassed toluene. The suspension was stirred overnight, filtered and concentrated under vacuum at 50° C. to give the desired product.

[0135] [ka]

[0136] Table 1 lists the theoretical decomposition of Comparative Example C1 and Compounds A through I.

[0137] [Table 1]

[0138] Figure 1 is a thermogravimetric analysis (TGA) isothermal plot of percent loss as a function of time at 250°C for activator compounds A and B and comparative compound C1. Compounds A and B are representative of compounds A-I in that each compound has greater than 10 percent weight loss, which is identified in the TGA isothermal plot of Figure 1 and summarized in Table 1. For compound B, the weight loss is greater than 40% in 30 minutes.

[0139] Figure 2 is a TGA isothermal plot of percent loss as a function of time at 260°C for activator compounds A and B and comparative compound C1. As in Figure 1, compounds A and B are representative of compounds A-I in Figure 2. For compound B, the weight loss is over 43% in 30 minutes.

[0140] Figure 3 is a TGA isothermal plot of percent loss as a function of time at 210°C for activator compounds A and B and comparative compound C1. As in Figure 1, compounds A and B are representative of compounds A-I in Figure 3. For compound B, the weight loss is over 26% in 30 minutes.

[0141] Ethylene-co-1-octene polymerization experiment

[0142] [ka]

[0143] Comparative Example C2 (Comp. C2) has a methyl:n-octyl ratio of about 6:1 and AlR 3 Comp. C3 is an aluminoxane modified with n-octyl substituents to contain about 15 mol% Al as a species. 3 The species is an aluminoxane modified with an iso-butyl substituent to contain approximately 40 mol % Al.

[0144] [Table 2] * Runs using Comp. C1 and A activators were performed using Comp. C3 as a scavenger with an Al:M ratio of 50:1, where M is the molar amount of metal associated with the procatalyst.

[0145] [Table 3] [A] Polymerizations were conducted using procatalyst Cat. 1 at a reactor temperature of 165°C with feed flows of 240 lbs / hr ethylene, 83 lbs / hr 1-octene, and 525 lbs / hr ISOPAR E. Activator was added at a ratio of 1.2 to the procatalyst. Comp. C2 was added at an Al:Zr ratio of 10:1. [B] Efficiency (eff.) is 10 6 (Measured as g polymer / g metal in catalyst component). Ethylene conversion is measured as the difference between the ethylene fed to the reactor and the amount leaving the reactor, expressed as a percentage. [C] The % solids is the polymer concentration in the reactor. [D] H 2 (mol%) is defined as the mole fraction of hydrogen relative to ethylene fed to the reactor.

[0146] All manipulation of air-sensitive materials was performed using a high vacuum line (10 -6 in oven-dried Schlenk-type glassware on a dual manifold Schlenk line interfaced with a 1000 rpm (2.5 Torr) or N 2 Filled MBraun glove box (less than 1 ppm O 2 ) in O 2 and with rigorous removal of moisture. Argon (Airgas, prepurified grade) was purified by passage through a supported MnO oxygen scavenging column and an activated Davison 4Å molecular sieve column. Ethylene (Airgas) was purified by passage through an oxygen / moisture trap (Matheson, model MTRP-0042-XX). Hydrocarbon solvents (n-pentane, n-hexane, 1-hexene, methylcyclohexane, and toluene) were dried using activated alumina columns according to the method described by Grubbs (see Pangborn, AB; Giardello, MA; Grubbs, RH; Rosen, RK; Timmers, FJ, Safe and Convenient Procedure for Solvent Purification. Organometallics 1996, 15(5), 1518-1520) and then vacuum transferred from Na / K alloys. Benzene-d6 and toluene-d8 (Cambridge Isotope Laboratories, 99+ atomic % D) were stored in vacuum over Na / K alloy and vacuum transferred immediately before use. 1,2-Difluorobenzene and chlorobenzene-d5 were stored in CaH 2 The solution was dried at 40° C. and distilled under vacuum. Chloroform-d3 and 1,1,2,2-tetrachloroethane-d2 were used as received (Cambridge Isotope Laboratories, 99+ atom % D).

[0147] Equipment standards All solvents and reagents were obtained from commercial sources and used as received unless otherwise stated. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether are purified by passing through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments performed in a nitrogen-filled glove box are further dried by storage over activated 4 Å molecular sieves. Glassware for moisture-sensitive reactions is dried overnight in an oven before use. NMR spectra are recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis is performed using a Waters e2695 separations module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a 5:95 to 100:0 gradient of acetonitrile and water (with 0.1% formic acid as the ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1 H NMR data are reported as follows: chemical shifts (multiplicities (br=broadline, s=singlet, d=doublet, t=triplet, q=quartet, p=quintet, sex=sexet, sept=septet, and m=multiplet), integrals, and assignments). 1 Chemical shifts for H NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as the reference. 13 C NMR data is 1 Determined using 1 H decoupling and chemical shifts are reported in ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the reference.

Claims

1. 1. A polymerization process comprising contacting ethylene and optionally one or more α-olefin monomers in a solution polymerization reactor in the presence of a catalyst system at a temperature from 120° C. to 200° C., said catalyst system comprising a procatalyst and an activator, said activator comprising an anion and a cation, said anion having a structure according to formula (I): 【Chemical 1】 During the ceremony, B is a boron atom, Each R １ and each R ５ is selected from —H or a fluorine atom; Each R ２ , R ３ , and R ４ is —H, fluorine atom, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, wherein R on each individual ring is １ , R ２ , R ３ , R ４ , and R ５ at least three of which are fluorine atoms; R ６ , R ７ , R ８ , R ９ , and R １０ are independently —H, a fluorine atom, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —OR Ｃ , -SiR Ｃ ３ where R Ｃ However, (C １ ~C ２０ ) hydrocarbyl or —H, and optionally R ７ and R ８ are bonded to form a ring, where: A polymerization process wherein the structure according to formula (I) has a fluorine to carbon ratio (F / C) of 0.83 or less, where F is the total number of fluorine atoms in the structure according to formula (I) and C is the total number of carbon atoms in the structure according to formula (I).

2. 10. The process of claim 1, wherein the anion of formula (I) has a percent thermal decomposition of greater than 10% as measured by thermogravimetric analysis.

3. R ６ , R ７ , R ８ , R ９ , and R １０ When three or more of R １ , R ２ , R ３ , R ４ , and R ５ The process of claim 1 , wherein at least one of

4. R ６ , R ７ , R ８ , R ９ , and R １０ When none of R １ , R ２ , R ３ , R ４ , and R ５ 10. The process of claim 1, wherein at least four of

5. 2. The process of claim 1, wherein the total number of fluorine atoms is 4 to 18.

6. 10. The process of claim 1, wherein the fluorine to carbon ratio (F / C) value is less than or equal to 0.

81.

7. 10. The process of claim 1, wherein the fluorine to carbon ratio (F / C) value is less than or equal to 0.

80.

8. A process comprising: Polymerizing ethylene and optionally one or more α-olefin monomers in a solution polymerization reactor in the presence of a catalyst system, said catalyst system comprising a procatalyst and an activator, said activator comprising an anion and a cation, said anion having a structure according to formula (II): 【Chemistry 2】 During the ceremony, B is a boron atom, Each R １１ and each R １５ is —H, a fluorine atom, or —CF ３ is selected from Each R ２ , R ３ , and R ４ is —H, fluorine atom, (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, provided that (1) R on each individual ring １１ , R １２ , R １３ , R １４ , and R １５ are fluorine atoms, or (2) at least three of R on each individual ring １１ , R １２ , R １３ , R １４ , and R １５ At least one of the groups is -CF ３ and R １６ , R １７ , R １８ , R １９ , and R ２０ are independently —H, a fluorine atom, or —CF ３ , (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, —OR Ｃ , -SiR Ｃ ３ and optionally R １７ and R １８ are joined to form a ring, where R Ｃ is -H or (C １ ~C ２０ ) hydrocarbyl, polymerizing the structure according to formula (II) so as not to include: 【Chemistry 3】 Obtaining the produced polymer; and heating the produced polymer to a pyrolysis temperature for at least 1 minute.

9. The polymerization process of any one of claims 1 to 8, wherein the counter cation has a formal variable of positive one (+1).

10. The cation is ＋ N(H)R Ｎ ３ where each R Ｎ However, (C １ ~C ２０ ) alkyl or (C ６ ~C ２０ 9. The polymerization process of claim 1, wherein the aryl is selected from the group consisting of aryl, aryl, aryl, aryls ...

11. 9. The process of claim 8, wherein the pyrolysis temperature is greater than 200°C.

12. 9. The process of claim 8, wherein the pyrolysis temperature is at least 250°C.

13. 9. The process of claim 8, wherein the pyrolysis temperature is between 200°C and 500°C.

14. 9. The process of claim 8, wherein the produced polymer is heated at the pyrolysis temperature for at least 5 minutes.

15. 9. The process of claim 8, wherein the produced polymer is heated at the pyrolysis temperature for 5 to 30 minutes.

16. 9. The process of claim 8, wherein the produced polymer is heated at the pyrolysis temperature for at least 10 minutes.

17. The process of claim 1 or 8, wherein the procatalyst is a metal-ligand complex.

18. 10. The process of claim 1 or 8, wherein the procatalyst is a bis(phenylphenoxy) metal-ligand complex, a constrained geometry metal-ligand complex, a pyridylamide metal complex, or a phenoxyimine metal complex.

19. an activator selected from: 【Chemistry 4】 【Chemistry 5】

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