# US 5,705,569 A · Block copolymers of monovinylarenes and conjugated dienes and preparation thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,705,569 A - Document ID: US5705569A - Status: Granted - Kind: A - Application number: 08/651,082 - Filed: 1996-05-22 - Granted: 1998-01-06 - Earliest claimed: 1993-09-30 - Assignees: Phillips Petroleum Company - Inventors: George A. Moczygemba; Larry L. Nash; William J. Trepka; Craig D. DePorter; Nathan E. Stacy; Ralph C. Farrar; Charles M. Selman - Web page: https://patentgrep.com/patent/US5705569A ## CPC - C08F 297/044: {using a coupling agent} - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract A method for preparing resinous polymodal monovinylarene-conjugated diene block copolymers and polymers produced thereby are provided. The method comprises sequentially contacting under polymerization conditions: (a) a monovinylarene monomer and initiator; (b) initiator and a monovinylarene monomer; (c) a sequence of at least two charges selected from the group consisting of (i) initiator and a monovtnylarene monomer, (ii) a mixture of monovtnylarene monomer and conjugated diene monomor, (iii) a conjugated diene monomer, (iv) a monovinylarene monomer; (d) a coupling agent; wherein the sequence of at least two charges in step (c) can be made in any order. In a preferred embodiment, at least three Initiator charges are provided. In another preferred embodiment, at least three monovinylarene charges precede the first charge containing conjugated diene. In another preferred embodiment, at least four monovinylarene charges precede the first charge containing conjugated diene. ## Claims ### Claim 1 A method for preparing a block copolymer, said method comprising polymerizing under polymerization conditions by sequentially charging at least one monovinylarene monomer, an organomono alkali metal initiator, and at least one conjugated diene monomer, thereafter coupling with a polyfunctional coupling agent; and recovering said block copolymer; wherein the step of polymerizing is conducted using a charge sequence of the following charges in the following order: (a) a monovinylarene monomer and initiator; (b) initiator and a monovinylarene monomer; (c) a mixture of monovinylarene monomer and conjugated diene monomer; and (d) a monovinylarene monomer; wherein steps (a)-(b) are the only monomer and initiator charges used in the process; wherein said at least one monovinylarene monomer contains from about 8 to about 18 carbon atoms and is provided in at least three monovinylarene charges; and wherein said at least one conjugated diene monomer contains from about 4 to about 12 carbon atoms and is provided in at least one conjugated diene monomer charge. ### Claim 2 A method for preparing a block copolymer, said method comprising polymerizing under polymerization conditions by sequentially charging at least one monovinylarene monomer, an organoalkali metal initiator, and at least one conjugated diene monomer, thereafter coupling with a polyfunctional coupling agent; and recovering said block copolymer; wherein the step of polymerizing is conducted using a charge sequence of the following charges in the following order: (a) a monovinylarene monomer and initiator; (b) initiator and a monovinylarene monomer; (c) a mixture of monovinylarene monomer and conjugated diene monomer; (d) a monovinylarene monomer and initiator; and (e) a mixture of monovinylarene monomer and conjugated diene monomer; wherein steps (a)-(e) are the only monomer and initiator charges used in the process; wherein said at least one monovinylarene monomer contains from about 8 to about 18 carbon atoms and is provided in at least three monovinylarene charges; and wherein said at least one conjugated diene monomer contains from about 4 to about 12 carbon atoms and is provided in at least one conjugated diene monomer charge. ### Claim 3 (depends on 1) A method according to claim 1 wherein said monomers are added in an amount in the range of about 55 to about 95 weight percent monovinylarene monomer and about 5 to about 45 weight percent conjugated diene monomer. ### Claim 4 (depends on 3) A method according to claim 3 wherein said monomers are added in an amount in the range of about 60 to about 95 weight percent monovinylarene monomer and about 5 to about 40 weight percent conjugated diene monomer. ### Claim 5 (depends on 4) A method according to claim 4 wherein said monomers are added in an amount in the range of about 80 to about 95 weight percent monovinylarene monomer and about 5 to about 20 weight percent conjugated diene monomer. ### Claim 6 (depends on 1) A method according to claim 1 wherein the first monovinylarene monomer charge contains monovinylarene monomer in an amount in the range of from about 30 weight percent to about 50 weight percent based on the total weight of the final block copolymer. ### Claim 7 (depends on 6) A method according to claim 6 wherein the second monovinylarene monomer charge contains monovinylarene monomer in an amount in the range of from about 15 weight percent to about 30 weight percent based on the total weight of the final block copolymer. ### Claim 8 (depends on 7) A method according to claim 7 wherein the third monovinylarene monomer charge contains monovinylarene monomer in the range of from about 5 weight percent to about 30 weight percent based on the total weight of the final block copolymer. ### Claim 9 (depends on 8) A method according to claim 8 wherein said conjugated diene monomer is 1,3-butadiene and said monovinylarene monomer is styrene. ### Claim 10 A monovinylarene/conjugated diene block copolymer consisting essentially about 55 to about 95 weight percent polymerized monovinylarene based on total weight of said copolymer and about 5 to about 45 weight percent polymerized conjugated diene based on total weight of said copolymer; wherein said copolymer results from coupling block copolymer chains S.sub.1 -S.sub.2 -B.sub.1 /S.sub.3 -S.sub.4 -Li.sub.1 S.sub.2 -B.sub.1 /S.sub.3 -S.sub.4 -Li.sub.2 wherein S=monovinylarene block B/S=tapered block of conjugated diene/monovinylarene Li=living polymer site or coupling site where subscripts 1 and 2 refer to the imitator charge sequence and said block copolymer chains are the only block copolymer chains present during the coupling. ### Claim 11 A monovinylarene/conjugated diene block copolymer consisting essentially of; about 55 to about 95 weight percent polymerized monovinylarene based on total weight of said copolymer and about 5 to about 45 weight percent polymerized conjugated diene based on total weight of said copolymer; wherein said copolymer results from coupling block copolymer chains S.sub.1 -S.sub.2 -B.sub.1 /S.sub.3 -S.sub.4 -B.sub.2 /S.sub.5 -Li.sub.1 S.sub.2 -B.sub.1 /S.sub.3 -S.sub.4 -B.sub.2 /S.sub.5 -Li.sub.2 S.sub.4 -B.sub.2 /S.sub.5 -Li.sub.3 wherein S=monovinylarene block B/S=tapered block of conjugated diene/monovinylarene Li=living polymer site or coupling site where subscripts 1, 2 and 3 refer to the initiator charge sequence. ### Claim 12 (depends on 2) A method according to claim 2 wherein said monomers are added in an amount in the range of about 55 to about 95 weight percent monovinylarene monomer and about 5 to about 45 weight percent conjugated diene monomer. ### Claim 13 (depends on 12) A method according to claim 12 wherein said monomers are added in an amount in the range of about 60 to about 95 weight percent monovinylarene monomer and about 5 to about 40 weight percent conjugated diene monomer. ### Claim 14 (depends on 13) A method according to claim 13 wherein said monomers are added in an amount in the range of about 80 to about 95 weight percent monovinylarene monomer and about 5 to about 20 weight percent conjugated diene monomer. ### Claim 15 (depends on 2) A method according to claim 2 wherein the first monovinylarene monomer charge contains monovinylarene monomer in an amount in the range of from about 30 weight percent to about 50 weight percent based on the total weight of the final block polymer. ### Claim 16 (depends on 15) A method according to claim 15 wherein the second monovinylarene monomer charge contains monovinylarene monomer in an amount in the range of from about 15 weight percent to about 30 weight percent based on the total weight of the final block polymer. ### Claim 17 (depends on 16) A method according to claim 16 wherein the third monovinylarene monomer charge contains monovinylarene monomer in an amount in the range of from about 5 weight percent to about 30 weight percent based on the total weight of the final block polymer. ### Claim 18 (depends on 17) A method according to claim 17 wherein said conjugated diene monomer is 1,3-butadiene and said monovinylarene monomer is styrene.