# US 2019/0169322 A1 · Dual Metallocene Catalyst Copolymer Compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0169322 A1 - Document ID: US20190169322A1 - Status: Published application - Kind: A1 - Application number: 16/315,722 - Filed: 2017-06-14 - Published: 2019-06-06 - Earliest claimed: 2016-07-13 - Assignees: ExxonMobil Chemical Patents Inc. - Applicants: ExxonMobil Chemical Patents Inc. - Inventors: Francis C. Rix; Rhutesh K. Shah; Rainer Kolb; Jo Ann M. Canich; Peijun Jiang; Periagaram S. Ravishankar; Syamal Tallury - Web page: https://patentgrep.com/patent/US20190169322A1 ## CPC - C08F 4/65904: {in combination with another component of C08F4/64} - B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls} - C08F 4/61927: {two cyclopentadienyl rings being mutually bridged} - C08F 110/06: Propene - C08F 210/18: with non-conjugated dienes, e.g. EPT rubbers - B01J 2231/122: Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type - C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+} - C08F 2420/09: Cyclic bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is part of a cyclic group - C08F 2420/10: Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom - C08F 2500/17: Viscosity - C08F 2500/19: Shear ratio or shear ratio index - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract Processes are provided which include copolymerization using two different metallocene catalysts, one capable of producing high Mooney-viscosity polymers and one suitable for producing lower Mooney-viscosity polymers having at least a portion of vinyl terminations. The two catalysts may be used together in polymerization to produce copolymer compositions of particularly well-tuned properties. For instance, polymerizations are contemplated to produce high-Mooney metallocene polymers that exhibit excellent processability and elasticity, notwithstanding their high Mooney viscosity. Other polymerizations are also contemplated in which lower-Mooney metallocene polymers are produced, which also exhibit excellent processability and elasticity, while furthermore having excellent cure properties suitable in curable elastomer compound applications. Many of the contemplated polymerizations include controlling the ratio of the two metallocene catalysts used in the polymerization so as to obtain the desired Mooney viscosity and desired rheology (indicated by Mooney Relaxation Area) of the copolymer compositions. ## Claims ### Claim 1 A process comprising: (a) carrying out a polymerization reaction that comprises polymerizing a plurality of monomers comprising (i) a first C2-C20 α-olefin monomer; (ii) a second C2-C20 α-olefin monomer different from the first; and optionally (iii) one or more dienes in the presence of both a first metallocene catalyst and a second metallocene catalyst in a polymerization reaction zone; wherein the first metallocene catalyst has structure in accordance with Formula (I): where (1) J is a divalent bridging group comprising C, Si, or both; (2) M is a group 4 transition metal; (3) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) each R″1-R″10 is independently hydrogen, C1-C50 hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl provided that any one or more of the pairs R″1 and R″2, R″3 and R″4, R″5 and R″6, R″6 and R″7, R″8 and R″9, and R″9 and R″10, may optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure; further wherein the second metallocene catalyst has structure in accordance with Formula (II): where: (1) J is a divalent bridging group comprising C, Si, or both; (2) M is Hf; (3) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) each R2-R7 is independently hydrogen, C1-C50 substituted or unsubstituted hydrocarbyl, or C1-C50 substituted or unsubstituted halocarbyl, provided that any one or more of the pairs R4 and R5, R5 and R6, and R6 and R7 may be bonded together to form a saturated or partially saturated cyclic or fused ring structure; (b) controlling the polymerization reaction so as to obtain a copolymer composition having Mooney viscosity within the range from 20 to 59 MU (MST, 5+4 @ 200° C.) and comprising units derived from the first C2-C20 α-olefin monomer, the second C2-C20 α-olefin monomer, and optionally the one or more dienes; and (c) controlling the polymerization such that the copolymer composition has Mooney Relaxation Area (MSTRA) within the range from 300 to 750 MU-sec, wherein the controlling (c) is based at least in part upon the molar ratio of the first metallocene catalyst to the second metallocene catalyst in the polymerization reaction. ### Claim 2 (depends on 1) The process of claim 1, wherein the first C2-C20 α-olefin monomer is ethylene, and the second C2-C20 α-olefin monomer is one of propylene and 1-butene. ### Claim 3 (depends on 1) The process of claim 1, wherein the plurality of monomers comprises one or more dienes selected from the group consisting of: 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), 1,4-hexadiene, dicyclopentadiene, and any combination thereof. ### Claim 4 (depends on 1) The process of claim 1, wherein the molar ratio of the first metallocene catalyst to the second metallocene catalyst is controlled within the range from 0.8 to 6. ### Claim 5 (depends on 4) The process of claim 4, wherein the molar ratio of the first metallocene catalyst to the second metallocene catalyst is controlled within the range from 1.5 to 2.0. ### Claim 6 (depends on 1) The process of claim 1, wherein the controlling (b) is based at least in part upon one or more of: (i) temperature of the polymerization reaction zone; (ii) monomer concentration in the polymerization reaction zone; and (iii) an amount of chain transfer agent fed to the polymerization reaction zone. ### Claim 7 (depends on 6) The process of claim 6, wherein the temperature of the polymerization reaction zone is maintained within the range from 95° C. to 150° C. ### Claim 8 (depends on 6) The process of claim 6, wherein the polymerization reaction is continuous, and the amount of chain transfer agent fed to the polymerization reaction zone is 500 wppm or less on the basis of mass of monomers, catalyst, and solvent fed to the polymerization reaction zone. ### Claim 9 (depends on 1) The process of claim 1, wherein, in Formula (I): (1) R″6 and R″9 are each C1 to C4 alkyl; (2) R″1-R″4, R″5, R″7, R″8, and R″10 are each independently methyl, ethyl, or H; (3) J is p-(Et)3SiPh)2C; (4) M is Hf; and (5) each X is C1-C3 alkyl or halide. ### Claim 10 (depends on 9) The process of claim 9, wherein the first metallocene catalyst comprises 1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-fluoren-9-yl)hafnium dimethyl. ### Claim 11 (depends on 1) The process of claim 1, wherein, in Formula (II): (1) each R4 and R7 is independently C1-C5 alkyl; (2) each R2 is H or C1-C5 alkyl; (3) R3, R5, and R6 are each independently H or C1-C5 alkyl; (4) J is cyclopentamethylenesilylene, cyclotetramethylenesilylene, cyclotrimethylenesilylene, cyclopropandiyl, cyclobutandiyl, cyclopentandiyl, or cyclohexandiyl; (5) M is Hf; and (6) each X is independently a halide or C1-C3 alkyl. ### Claim 12 (depends on 11) The process of claim 11, wherein the second metallocene catalyst comprises cyclotetramethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dimethyl. ### Claim 13 (depends on 1) The process of claim 1, wherein the first monomer is ethylene, and wherein the copolymer composition comprises from 45 wt % to 60 wt % ethylene-derived units (corrected for diene content, if any). ### Claim 14 (depends on 1) The process of claim 1, wherein the copolymer composition exhibits one or more of the following properties: (i) phase angle (δ) at complex modulus G*=1.1×105 within the range from 15° to 40°; (ii) tan(δ) at 0.245 Rad/s within the range from 0.350 to 0.800; and (iii) shear thinning ratio (STR) within the range from 200 to 500. ### Claim 15 (depends on 1) The process of claim 1, wherein the copolymer composition has Mooney viscosity within the range from 30 to 40 MU (MST, 5+4 @ 200° C.) and Mooney Relaxation Area (MSTRA) within the range from 350 to 550 MU-sec. ### Claim 16 A process comprising: (a) polymerizing a plurality of monomers comprising (i) a first C2-C20 α-olefin monomer; (ii) a second C2-C20 α-olefin monomer different from the first; and optionally (iii) one or more dienes in the presence of both a first metallocene catalyst and a second metallocene catalyst in a polymerization reaction zone; wherein the first metallocene catalyst has structure in accordance with Formula (I): where (1) J is a divalent bridging group comprising C, Si, or both; (2) M is a group 4 transition metal; (3) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) each R″1-R″10 is independently hydrogen, C1-C50 hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl provided that any one or more of the pairs R″1 and R″2, R″3 and R″4, R″5 and R″6, R″6 and R″7, R″8 and R″9, and R″9 and R″10, may optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure; further wherein the second metallocene catalyst has structure in accordance with Formula (II): where: (1) J is a divalent bridging group comprising C, Si, or both; (2) M is Hf; (3) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) each R2-R7 is independently hydrogen, C1-C50 substituted or unsubstituted hydrocarbyl, or C1-C50 substituted or unsubstituted halocarbyl, provided that any one or more of the pairs R4 and R5, R5 and R6, and R6 and R7 may be bonded together to form a saturated or partially saturated cyclic or fused ring structure; and (b) obtaining a copolymer composition having Mooney viscosity within the range from 20 to 59 MU (MST, 5+4 @ 200° C.), Mooney Relaxation Area (MSTRA) within the range from 300 to 750 MU-sec, and comprising units derived from the first C2-C20 α-olefin monomer, the second C2-C20 α-olefin monomer, and optionally the one or more dienes. ### Claim 17 (depends on 1) A copolymer composition formed by the process of claim 1. ### Claim 18 A copolymer composition comprising 45 wt % to 60 wt % ethylene-derived units, 1 wt % to 10 wt % units derived from one or more dienes, and the balance of units derived from one or more C3 to C8 α-olefins, said wt % based upon the combined weight of monomer-derived units in the copolymer composition; wherein the polymer composition has Mooney Viscosity within the range from 20 to 59 MU (MST, 5+4 @ 200° C.) and Mooney Relaxation Area (MSTRA) within the range from 300 to 750 MU-sec; further wherein the copolymer composition exhibits one or more of the following properties: (i) phase angle (δ) at complex modulus G*=1.1×105 within the range from 15° to 40°; (ii) tan(δ) at 0.245 Rad/s within the range from 0.350 to 0.800; and (iii) shear thinning ratio (STR) within the range from 200 to 500. ### Claim 19 (depends on 18) The copolymer composition of claim 18, wherein the copolymer composition exhibits: (i) phase angle (δ) at complex modulus G*=1.1×105 within the range from 15° to 250; (ii) tan(δ) at 0.245 Rad/s within the range from 0.350 to 0.500; and (iii) STI within the range from 350 to 500. ### Claim 20 (depends on 18) A thermoplastic vulcanizate comprising an at least partially vulcanized rubber dispersed in a continuous thermoplastic phase comprising a thermoplastic resin, wherein the at least partially vulcanized rubber is formed from a copolymer composition according to claim 18. ### Claim 21 (depends on 20) The thermoplastic vulcanizate of claim 20, wherein the thermoplastic resin comprises homopolypropylene.