Claims
- 1. A hydrogenated block copolymer having the general configuration A-B, A-B-A, (A-B)n, (A-B-A)n, (A-B-A)nX, (A-B)nX or mixtures thereof, where n is an integer from 2 to about 30, and X is coupling agent residue and wherein:
a. prior to hydrogenation each A block is a mono alkenyl arene polymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene; b. subsequent to hydrogenation about 0-10% of the arene double bonds have been reduced, and at least about 90% of the conjugated diene double bonds have been reduced; c. each A block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 30,000 and about 300,000; d. each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units; e. the total amount of mono alkenyl arene in the hydrogenated block copolymer is about 20 percent weight to about 80 percent weight; and f. the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent.
- 2. The copolymer according to claim 1 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
- 3. The copolymer according to claim 2 wherein said conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration prior to hydrogenation.
- 4. The copolymer according to claim 3 wherein the styrene blockiness index of the block B is less than about 40 percent.
- 5. The copolymer according to claim 4 wherein each block B has a center region with a minimum ratio of butadiene units to styrene units.
- 6. The copolymer according to claim 3 wherein the weight percentage of styrene in the B block is between about 10 percent and about 40 percent, and the styrene blockiness index of the block B is less than about 10 percent, said styrene blockiness index being the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
- 7. A block copolymer having the general configuration A-B, A-B-A, (A-B)n, (A-B-A)n, (A-B-A)nX, (A-B)nX or mixtures thereof, where n is an integer from 2 to about 30, and X is coupling agent residue and wherein
a. each A block is a mono alkenyl arene homopolymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene; b. each A block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 30,000 and about 300,000; c. each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units; d. the total amount of mono alkenyl arene in the block copolymer is about 20 percent weight to about 80 percent weight; and e. the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent.
- 8. The copolymer according to claim 7 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
- 9. The copolymer according to claim 8 wherein said conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.
- 10. The copolymer according to claim 9 wherein the styrene blockiness index of the block B is less than about 40 percent.
- 11. The copolymer according to claim 10 wherein each block B has a center region with a minimum ratio of butadiene units to styrene units.
- 12. The copolymer according to claim 9 wherein the weight percentage of styrene in the B block is between about 10 weight percent and 40 weight percent, and the styrene blockiness index of the block B is less than about 10 percent, said styrene blockiness index being the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
- 13. A process for the preparation of a block copolymer having one or more mono alkenyl arene polymer blocks and one or more controlled distribution copolymer blocks of a conjugated diene and a mono alkenyl arene, comprising the steps:
a. polymerizing a mono alkenyl arene in a first reactor in the presence of an inert hydrocarbon solvent and an organolithium initiator whereby a living polymer block Al terminated with a lithium ion is formed; b. adding to a second reactor an inert hydrocarbon solvent, 80 to 100% of the mono alkenyl arene monomer desired in the copolymer block B1, between 30 and 60% of the conjugated diene monomer desired in the copolymer block B1, and an effective amount of a distribution agent; c. transferring the living homopolymer block A1 to the second reactor and starting the polymerization of the mono alkenyl arene monomer and conjugated diene monomer added in step b; d. after about 10 to about 60 mol percent of the monomers of step c have been polymerized, continuously adding the remaining amount of conjugated diene monomer and mono alkenyl arene to the second reactor at a rate that maintains the concentration of the conjugated diene monomer at no less than about 0.1% weight until about 90% of the monomers in block B1 have been polymerized, thereby forming a living block copolymer A1B1.
- 14. The process of claim 13 wherein 100% of the monoalkenyl arene monomer and about 50% of the conjugated diene monomer is added to the reactor in step b.
- 15. The process of claim 13 wherein said distribution agent is selected from the group consisting of cyclic ethers and aliphatic monoethers.
- 16. The process of claim 13 wherein said monoalkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
- 17. The process of claim 16 wherein said conjugated diene is butadiene.
- 18. The process of claim 13 including the additional step wherein additional mono alkenyl arene monomer is added to the second reactor, thereby forming a living block copolymer A1B1A2, wherein the A1 block and the A2 block each have a number average molecular weight of about 3,000 to about 60,000 and the B1 block has a number average molecular weight of about 30,000 to about 300,000.
- 19. The process of claim 13 including the additional step where the living block copolymer A1B1 is contacted with a coupling agent to form the block copolymer (A1B1)nX where n is an integer from 2 to about 30 and X is the coupling agent residue.
- 20. The process of claim 18 wherein said living copolymer A1B1A2 is contacted with a terminating agent to form a terminated copolymer.
- 21. The process of claim 20 wherein said terminated copolymer is hydrogenated.
- 22. The polymer formed by the process of claim 20.
- 23. A process for the preparation of a linear A1B1A2 block copolymer having two monoalkenyl arene polymer blocks and one controlled distribution copolymer block of a conjugated diene and a mono alkenyl arene, comprising the steps:
a. polymerizing a mono alkenyl arene in a reactor in the presence of an inert hydrocarbon solvent and an organolithium initiator whereby a living polymer block Al terminated with a lithium ion is formed; b. prior to the completion of the polymerization in step a, adding to the reactor in one aliquot between 40 and 60% of the conjugated diene monomer desired in the copolymer block B1, and a distribution agent and continuing the polymerization of the mono alkenyl arene monomer and conjugated diene monomer; c. after about 20 to about 60 mol % of the monomers in step b has been polymerized, gradually adding the remaining amount of conjugated diene monomer and mono alkenyl arene monomer to the reactor at a rate that maintains the concentration of the conjugated diene at no less than about 0.1% weight until about 90% of the monomers in block B1 have been polymerized, thereby forming a living copolymer block copolymer A1B1; d. adding additional mono alkenyl arene monomer to the reactor, thereby forming a living copolymer A1B1A2, wherein the A1 block and the A2 block each has a number average molecular weight of about 3,000 to about 60,000 and the B1 block has a number average molecular weight of about 30,000 to about 300,000.
- 24. The process of claim 23 wherein said living copolymer A1B1A2 is contacted with a terminating agent to form a terminated polymer.
- 25. The process of claim 24 wherein said terminated polymer is hydrogenated.
- 26. The process of claim 15 wherein said distribution agent is an aliphatic monoether.
- 27. The process of claim 26 wherein said aliphatic monoether is diethyl ether.
- 28. A hydrogenated block copolymer having the general configuration A-B, A-B-A, (A-B)n, (A-B-A)n, (A-B-A)nX, (A-B)nX or mixtures thereof, where n is an integer from 2 to about 30, and X is coupling agent residue and wherein
a. prior to hydrogenation each A block is a mono alkenyl arene homopolymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene; b. subsequent to hydrogenation at least about 90% of the arene double bonds have been reduced, and at least about 90% of the conjugated diene double bonds have been reduced; c. each A block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 30,000 and about 300,000; d. each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units; e. the total amount of mono alkenyl arene in the hydrogenated block copolymer is about 20 percent weight to about 80 percent weight; and f. the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent.
- 29. The copolymer of claim 28 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
- 30. The copolymer of claim 29 wherein said conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration prior to hydrogenation.
- 31. The copolymer of claim 30 wherein the styrene blockiness index of the block B is less than about 40 percent.
- 32. A functionalized selectively hydrogenated block copolymer wherein the block copolymer of claim 1 has been grafted with an acid compound or its derivative.
- 33. The block copolymer of claim 32 wherein said acid compound or its derivative is selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, and their derivatives.
- 34. A functionalized selectively hydrogenated block copolymer wherein the block copolymer of claim 1 has been reacted with a silicon or boron-containing compound.
- 35. The block copolymer of claim 34 wherein the block copolymer of claim 1 has been reacted with a silicon compound containing at least one alkoxy group, acetoxy group, or oximido-containing group.
- 36. A functionalized selectively hydrogenated block copolymer wherein the block copolymer of claim 1 has been reacted with at least one ethylene oxide molecule.
- 37. A functionalized selectively hydrogenated block copolymer wherein the block copolymer of claim 1 has been reacted with at least one carbon dioxide molecule.
- 38. A functionalized selectively hydrogenated block copolymer wherein the block copolymer of claim 1 has been metallated with an alkali metal alkyl.
- 39. A functionalized selectively hydrogenated block copolymer wherein the block copolymer of claim 1 has been grafted with sulfonic functional groups.
- 40. The block copolymer of claim 39 wherein at least 50 percent of the sulfonic functional groups are present as zinc salts.
- 41. A block copolymer comprising at least one polymer block A and at least one polymer block B wherein
a. each A block is a mono alkenyl arene polymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene; b. each A block independently having a number average molecular weight between about 3,000 and about 60,000 and each B block independently having a number average molecular weight between about 30,000 and about 300,000; c. each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units; d. the total amount of mono alkenyl arene in the block copolymer is about 20 percent weight to about 80 percent weight; and e. the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent.
- 42. The copolymer according to claim 41 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
- 43. The copolymer according to claim 42 wherein said conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.
- 44. The copolymer according to claim 43 wherein the styrene blockiness index of the block B is less than about 40 percent.
- 45. The copolymer according to claim 43 wherein the weight percentage of styrene in the B block is between about 10 weight percent and 40 weight percent, and the styrene blockiness index of the block B is less than about 10 percent, said styrene blockiness index being the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
- 46. The copolymer according to claim 41 wherein either polymer block A, polymer block B or both polymer blocks A and B are hydrogenated.
- 47. The copolymer according to claim 46 wherein subsequent to hydrogenation about 0 to 10% of the arene double bonds have been reduced and at least about 90% of the conjugated diene double bonds have been reduced.
- 48. The copolymer according to claim 46 wherein subsequent to hydrogenation at least about 90% of the arene double bonds have been reduced and at least about 90% of the conjugated diene double bonds have been reduced.
- 49. A block copolymer having at least one A block, at least one B block and at least one C block, wherein:
a. each A block is a mono alkenyl arene polymer block, each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene, and each C block is a polymer block of one or more conjugated dienes; b. each A block having a number average molecular weight between about 3,000 and about 60,000, each B block having a number average molecular weight between about 30,000 and about 300,000, and each C block having a number average molecular weight between about 2,000 and about 200,000; c. each B block comprises terminal regions adjacent to the A block that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units; d. the total amount of mono alkenyl arene in the block copolymer is about 20 percent weight to about 80 percent weight; and e. the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent.
- 50. The copolymer according to claim 49 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
- 51. The copolymer according to claim 50 wherein said conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.
- 52. The copolymer according to claim 51 wherein the styrene blockiness index of the block B is less than about 40 percent.
- 53. The copolymer according to claim 51 wherein the weight percentage of styrene in the B block is between about 10 weight percent and 40 weight percent, and the styrene blockiness index of the block B is less than about 10 percent, said styrene blockiness index being the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
- 54. The copolymer according to claim 49 wherein either polymer block A, polymer block B, polymer block C or any of polymer blocks A, B or C are hydrogenated.
- 55. The copolymer according to claim 54 wherein subsequent to hydrogenation about 0 to 10% of the arene double bonds have been reduced and at least about 90% of the conjugated diene double bonds have been reduced.
- 56. The copolymer according to claim 46 wherein subsequent to hydrogenation at least about 90% of the arene double bonds have been reduced and at least about 90% of the conjugated diene double bonds have been reduced.
- 57. A tetrablock copolymer having the structure A1-B1-A2-B2, wherein:
a. each A1 and A2 block is a mono alkenyl arene polymer block, each B1 block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene, and each B2 block is selected from the group consisting of (I) a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene (ii) a homopolymer block of a conjugated diene and (iii) a copolymer block of two or more different conjugated dienes; b. each A1 and A2 block having a number average molecular weight between about 3,000 and about 60,000, each B1 block having a number average molecular weight between about 30,000 and about 300,000, and each B2 block having a number average molecular weight between 2,000 and 40,000; c. each B1 block comprises terminal regions adjacent to the A block that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units; d. the total amount of mono alkenyl arene in the block copolymer is about 20 percent weight to about 80 percent weight; and e. the weight percent of conjugated diene to mono alkenyl arene in each B1 block is between about 10 percent and about 75 percent.
- 58. The copolymer according to claim 57 wherein one or more of the polymer blocks are hydrogenated.
- 59. The copolymer according to claim 58 wherein subsequent to hydrogenation about 0 to 10% of the arene double bonds have been reduced and at least about 90% of the conjugated diene double bonds have been reduced.
- 60. The copolymer according to claim 57 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
- 61. The copolymer according to claim 60 wherein said B1 block is a copolymer of styrene and butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B1 have 1,2-configuration.
- 62. The copolymer according to claim 61 wherein said B2 block is a butadiene homopolymer block, and wherein about 5 to about 80 mol percent of the condensed butadiene units in block B2 have 1,2-configuration.
- 63. The copolymer according to claim 60 wherein the styrene blockiness index of the block B1 is less than about 40 percent.
- 64. The copolymer according to claim 60 wherein the weight percentage of styrene in the B1 block is between about 10 weight percent and 40 weight percent, and the. styrene blockiness index of the block B1 is less than about 10 percent, said styrene blockiness index being the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
- 65. The copolymer according to claim 61 wherein about 40 to about 60 mol percent of the condensed units in said B1 and B2 blocks have 1,2-configuration.
- 66. The copolymer according to claim 61 wherein said B2 block is an isoprene polymer block
- 67. A block copolymer or hydrogenated block copolymer having at least one block A and at least one block B wherein each block A is a polymer block of one or more mono alkenyl arenes having a number average molecular weight between 3,000 and 60,000 and each block B is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene, wherein the total amount of mono alkenyl arene in the block copolymer is between 20 and 80 percent by weight, the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent, and wherein each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units.
- 68. The block copolymer as claimed in claim 67, comprising at least two blocks A, preferably of general configuration A-B-A, (A-B-A)nX or (A-B)nX, where n is an integer from 2 to 30, and X is coupling agent residue.
- 69. The block copolymer as claimed in claim 67, wherein each block B is partially or fully hydrogenated, and wherein each block A is either unhydrogenated, partially hydrogenated or fully hydrogenated.
- 70. The block copolymer as claimed in claim 67, wherein the conjugated diene is butadiene, isoprene or a mixture thereof.
- 71. The block copolymer as claimed in claim 70, wherein each block B has a vinyl content between 20 and 80 percent by mol.
- 72. The block copolymer as claimed in claim 67, wherein the mono alkenyl arene is styrene.
- 73. The block copolymer as claimed in claim 72, wherein each block B has a styrene blockiness index of less than 40 mol %, said styrene blockiness index being the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
- 74. The block copolymer as claimed in claim 67, wherein at least one of block A or block B is a functionalized polymer block.
- 75. The block copolymer according to claim 1 wherein said A block has a glass transition temperature of plus 80° C. to plus 110° C. and said B block has a glass transition temperature of at least above about minus 60° C.
- 76. The block copolymer of claim 75 wherein said B block has a glass transition temperature of between minus 40° C. and plus 30° C.
- 77. The block copolymer according to claim 7 wherein said A block has a glass transition temperature of plus 80° C. to plus 110° C. and said B block has a glass transition temperature of at least above about minus 60° C.
- 78. The block copolymer of claim 77 wherein said B block has a glass transition temperature of between minus 40° C. and plus 30° C.
- 79. The block copolymer according to claim 28 wherein said A block has a glass transition temperature of plus 80° C. to plus 110° C. and said B block has a glass transition temperature of at least above about minus 60° C.
- 80. The block copolymer of claim 79 wherein said B block has a glass transition temperature of between minus 40° C. and plus 30° C.
- 81. The block copolymer according to claim 41 wherein said A block has a glass transition temperature of plus 80° C. to plus 110° C. and said B block has a glass transition temperature of at least above about minus 60° C.
- 82. The block copolymer of claim 81 wherein said B block has a glass transition temperature of between minus 40° C. and plus 30° C.
- 83. The block copolymer according to claim 41 wherein said block copolymer has at least two blocks A and has the general configuration AB, A-B-A, (A-B)n, (A-B)nA, (A-B-A)nX, (A-B)nX or mixtures thereof, where n is an integer from 2 to about 30 and X is coupling agent residue.
- 84. The block copolymer according to claim 83 wherein said block copolymer is a linear block copolymer and has the general configuration A-B-A.
- 85. The block copolymer according to claim 83 wherein said block copolymer has the general configuration (A-B)n or (A-B)nA where n is between 2 and 6.
- 86. The block copolymer according to claim 83 wherein said block copolymer has the general configuration (A-B)nX.
- 87. The block copolymer according to claim 86 wherein said block copolymer is a radial polymer and the coupling agent is divinyl benzene.
- 88. The block copolymer according to claim 86 wherein said block copolymer is a mixture of linear polymers and radial polymers, n is between 2 and about 6 and said coupling agent is a tetra-alkoxy silane.
- 89. The block copolymer according to claim 88 wherein said tetra-alkoxy silane is tetra-ethoxy silane.
- 90. The block copolymer according to claim 86 wherein said block copolymer is a radial polymer, n is between 2 and about 6 and said coupling agent is a diester of a carboxylic acid.
- 91. The block copolymer according to claim 90 wherein said diester is dimethyl adipate.
- 92. The block copolymer according to claim 41 wherein the Young's modulus is less than 20 MPa and the rubber modulus between 100% and 300% elongation is greater than 0.5 MPa.
- 93. A block copolymer having the general configuration (A1-B)dXe(B-A2), where d is an integer from 1 to about 30, e is an integer from 1 to 30, and X is coupling agent residue and wherein
a. each A1 and A2 block is a mono alkenyl arene homopolymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene; b. each A1 and each A2 block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 30,000 and about 300,000, the molecular weight of the each Al block being at least 1.2 times the molecular weight of each A2 block; c. each B block comprises terminal regions adjacent to the A1 and A2 blocks that are rich in conjugated diene units and one or more regions not adjacent to the A1 and A2 blocks that are rich in mono alkenyl arene units; d. the total amount of mono alkenyl arene in the block copolymer is about 20 percent weight to about 80 percent weight; and e. the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent.
- 94. The block copolymer according to claim 93 wherein each block B is partially or fully hydrogenated, and wherein each block A1 and A2 is either unhydrogenated, partially hydrogenated or fully hydrogenated.
- 95. The block copolymer as claimed in claim 93, wherein the conjugated diene is butadiene, isoprene or a mixture thereof.
- 96. The block copolymer as claimed in claim 95, wherein each block B has a vinyl content between 20 and 80 percent by mol.
- 97. The block copolymer as claimed in claim 96, wherein the mono alkenyl arene is styrene.
- 98. The block copolymer as claimed in claim 97, wherein each block B has a styrene blockiness index of less than 40 mol %, said styrene blockiness index being the proportion of styrene units in the block B having two styrene neighbors on the polymer chain
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority from copending, commonly assigned U.S. patent application Serial No. 60/355,210, filed Feb. 7, 2002, entitled Novel Block Copolymers and Method for Making Same.
Provisional Applications (1)
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Number |
Date |
Country |
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60355210 |
Feb 2002 |
US |