Granted Patent B2

US 7,625,979 · App. 10/454,237 · Granted Dec 1, 2009

Abstract

Claims (144)

1. A block copolymer composition comprising:

a. a tetra-branched black copolymer (IV) having a number avenge molecular weight of 100,000 to 800,000 represented by the general formula (A-B)4X;

b. a tri-branched block copolymer (III) having a number avenge molecular weight of from 75,000 to 600,000 represented by the general formula (A-B)3X;

c. a di-branched block copolymer (II) having a number average molecular weight of from 50,000 to 400,000 represented by the general formula (A-B)2X; and

d. a linear diblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula A-B; where:

i. A represents a polymer block of a mono alkenyl arene;

ii. B represents a polymer block of a conjugated diene selected from the group consisting essentially of butadiene and mixtures of isoprene and butadiene;

iii. X represents the residue of an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals; and

iv. the relative amounts of copolymers I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and from 2 to 10 weight percent 1, where the total of I, II, III and IV equals 100 weight percent.

2. The black copolymer composition of claim 1 wherein said conjugated diene is butadiene and said mono alkenyl arene is styrene.

3. The block copolymer composition of claim 2 wherein about 10 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.

4. A hydrogenated block copolymer composition comprising:

a. a tetra-branched block copolymer (IV) having a number average molecular weight of 100,000 to 800,000 represented by the general formula (A-B)4X;

b. a tri-branched block copolymer (III) having a number average molecular weight of from 75,000 to 600,000 represented by the general formula (A-B)3X;

c. a di-branched block copolymer (II) having a number average molecular weight of from 50,000 to 400,000 represented by the general formula (A-B)2X; and

d. a linear diblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula A-B; where:

i. A represents a polymer block of a mono alkenyl arene;

ii. B represents a polymer block of a conjugated diene;

iii. X represents the residue of an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, ft is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals; and

iv. the relative amounts of copolymers I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and from 2 to 10 weight percent I, where the total of I, II, III and IV equals 100 weight percent.

5. The hydrogenated block copolymer composition of claim 4 wherein said hydrogenated block copolymer composition is a selectively hydrogenated block copolymer composition.

6. The block copolymer composition of claim 5 wherein said conjugated diene is selected from the group consisting of butadiene, isoprene and mixtures thereof and said mono alkenyl arene is styrene.

7. The block copolymer composition of claim 6 wherein said conjugated diene is butadiene and wherein about 10 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.

8. The block copolymer composition of claim 6 wherein said conjugated diene is isoprene and wherein about 5 to about 80 mol percent of the condensed isoprene units in block B have 3,4-configuration.

9. The block copolymer composition of claim 6 wherein said conjugated diene is a random mixture of isoprene and butadiene and wherein about 5 to about 80 mol percent of the condensed isoprene/butadiene units in block B have 3,4-configuration.

10. The block copolymer composition of claim 6 wherein said block copolymer is selectively hydrogenated such that greater than 95% of the olefinic unsaturation in the B blocks have been reduced.

11. The block copolymer composition of claim 10 wherein said alkoxy silane coupling agent is selected from the group consisting of tetraethoxy silane, tetramethoxy silane, tetrabutoxy silane, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane and isobutyl trimethoxy silane.

12. The block copolymer composition of claim 11 wherein the amount of selectively hydrogenated diblock I is from 4 to 8 percent.

13. The block copolymer composition of claim 12 wherein the weight ratio of polymer block A to polymer block B is from 5/95 to 50/50.

14. A block copolymer composition comprising:

a. a tetra-branched block copolymer (IV) having a number average molecular weight of from 100,000 to 800,000 represented by the general formula (C-D-E)4X;

b. a tri-branched block copolymer (III) having a number average molecular weight of from 75,000 to 600,000 represented by the general formula (C-D-E)3X;

c. a di-branched block copolymer (II) having a number average molecular weight of from 50,000 to 400,000 represented by the general formula (C-D-E)2X; and

d. a linear diblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula C-D-E; where:

i. D represents a polymer block of a mono alkenyl arene;

ii. C and E represent polymer blocks of a conjugated diene;

iii. X represents the residue of an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals; and

iv. the relative amounts of copolymers I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and from 2 to 10 weight percent I, where the total of I, II, III and IV equals 100 weight percent.

15. The block copolymer composition of claim 14 wherein said conjugated diene is selected from the group consisting of butadiene and isoprene and said mono alkenyl arene is styrene.

16. The block copolymer composition of claim 15 wherein said D blocks are styrene polymer blocks and said C and E blocks are butadiene polymer blocks, and wherein about 10 to about 80 mol percent of the condensed butadiene units in blocks C and E have 1,2-configuration.

17. The block copolymer composition of claim 15 wherein said D blocks are styrene polymer blocks, said C blocks are isoprene polymer blocks where about 5 to about 80 mol percent of the condensed isoprene units have 3,4-configuration, and said E blocks are butadiene polymer blocks where about 10 to about 80 mol percent of the condensed butadiene units have 1,2-configuration.

18. The block copolymer composition of claim 15 wherein said block copolymers I, II, III and IV are selectively hydrogenated such that greater than 90% of the olefinic unsaturation in the C and E blocks have been reduced and the relative amounts of hydrogenated block copolymer I, II, III and IV are from 0 to 5 weight percent IV from 0 to 60 weight percent III from 40 to 95 weight percent II and from 2 to 10 weight percent I, where the total of I, II, III and IV equals 100 weight percent.

19. The block copolymer composition of claim 18 wherein said alkoxy silane is selected from the group consisting of tetraethoxy silane, tetramethoxy silane, tetrabutoxy silane, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane and isobutyl triethoxy silane.

20. The block copolymer composition of claim 17 wherein said block copolymers I, II, III and IV are selectively hydrogenated such that greater than 90% of the olefinic unsaturation in the C and E blocks have been reduced and the relative amounts of block copolymer I, II, III and IV after hydrogenation are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and from 2 to 10 weight percent I, where the total of I, II, III and IV equals 100 weight percent.

21. The block copolymer composition of claim 20 wherein the weight percent of D polymer blocks in the block copolymer composition is from 5 weight percent to 50 weight percent.

22. The block copolymer composition of claim 21 wherein the weight ratio of C blocks to E blocks is from 10:90 to 90:10.

23. A block copolymer composition comprising:

a. a tetra-branched block copolymer (IV) having a number average molecular weight of from 100,000 to 800,000 represented by the general formula (F-G-H)4X;

b. a tri-branched block copolymer (III) having a number average molecular weight of from 75,000 to 600,000 represented by the general formula (F-G-H)3X;

c. a di-branched black copolymer (II) having a number avenge molecular weight of from 50,000 to 400,000 represented by the general formula (F-G-H)2X; and

d. a linear diblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula F-G-H; where:

i. F represents a polymer block of a mono alkenyl arene;

ii. G and H represent polymer blocks of different conjugated dienes;

iii. X represents the residue of an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched hydrocarbon radicals; and

iv. the relative amounts of copolymers I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and from 2 to 10 weight percent I, where the total of I, II, III and IV equals 100 weight percent.

24. The block copolymer composition of claim 23 wherein said conjugated diene is selected from the group consisting of butadiene and isoprene and said mono alkenyl arene is styrene.

25. The block copolymer composition of claim 24 wherein said F blocks are styrene polymer blocks, said G blocks are butadiene polymer blocks wherein about 10 to about 80 mol percent of the condensed butadiene units in the G blocks have 1,2-configuration, and said H blocks are isoprene polymer blocks wherein about 5 to about 80 mol percent of the condensed isoprene units in the H blocks have 3,4-configuration.

26. The block copolymer composition of claim 24 wherein said F blocks are styrene polymer blocks, said H blocks are butadiene polymer blocks wherein about 10 to about 80 mol percent of the condensed butadiene units in the H blocks have 1,2-configuration, and said G blocks are isoprene polymer blocks wherein about 5 to about 80 mol percent of the condensed isoprene units in the G blocks have 3,4-configuration.

27. The block copolymer composition of claim 24 wherein said block copolymers I, II, III and IV are selectively hydrogenated such that greater than 95% of the olefinic unsaturation in the G and H blocks have been reduced and the relative amounts of hydrogenated block copolymer I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and from 2 to 10 weight percent I, where the total of I, II, III and IV equals 100 weight percent.

28. The block copolymer composition of claim 27 wherein said alkoxy silane is selected from the group consisting of tetraethoxy silane, tetramethoxy silane, tetrabutoxy silane, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane and isobutyl triethoxy silane.

29. The block copolymer composition of claim 28 wherein the amount of selectively hydrogenated diblock IV is from 2 to 8 percent.

30. The block copolymer composition of claim 29 wherein the weight percent of the F blocks in the block copolymer composition is from 5 weight percent to 50 weight percent.

31. The block copolymer composition of claim 30 wherein the weight ratio of G blocks to H blocks is from 10:90 to 90:10.

32. The block copolymer composition of claim 2 wherein said B block comprises a random mixture of isoprene and butadiene monomers.

33. The block copolymer composition of claim 32 wherein the weight ration of isoprene to butadiene is between about 1:4 and 4:1.

34. A hydrogenated block copolymer composition comprising:

a. a tetra-branched block copolymer (IV) having a number average molecular weight of 100,000 to 800,000 represented by the general formula (A-B)4X;

b. a tri-branched block copolymer (III) having a number average molecular weight of from 75,000 to 600,000 represented by the general formula (A-B)3X;

c. a di-branched block copolymer (II) having a number average molecular weight of from 50,000 to 400,000 represented by the general formula (A-B)2X; and

d. a linear diblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula A-B; where:

i. A represents a polymer block of a mono alkenyl arene;

ii. B represents a hydrogenated polymer block of a conjugated diene;

iii. the relative amounts of copolymers I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and from 2 to 10 weight percent I, where the total of I, II, III and IV equals 100 weight percent;

said hydrogenated block copolymers prepared by the process of:

1. reacting a living lithium-terminated polymer having the formula P—Li where P is a copolymer chain of one or more conjugated dienes having from 4 to 12 carbon atoms and one or more mono alkenyl arenes having from 8 to 18 carbon atoms with an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals and where the molar ratio of Si to Li is from about 0.35 to about 0.7, thereby forming a coupled polymer;

2. hydrogenating the coupled polymer under hydrogenation conditions to substantially saturate at least the olefinically derived double bonds of said coupled polymer without substantial degradation of the coupled polymer; and

3. recovering the resulting hydrogenated polymer.

35. The block copolymer composition of claim 34 , wherein in the process for preparing the block copolymers, the coupled polymer is contacted with an alcohol prior to hydrogenation.

36. The block copolymer composition of claim 34 wherein said block copolymer is hydrogenated such that greater than 95% of the olefinic unsaturation in the B blocks have been reduced.

37. The block copolymer composition of claim 35 wherein the molar ratio of alcohol to Li is from 0.05 to 0.5 moles of alcohol per mole of Li.

38. A hydrogenated block copolymer composition comprising:

a. a tetra-branched block copolymer (IV) having a number average molecular weight of from 100,000 to 800,000 represented by the general formula (C-D-E)4X;

b. a tri-branched block copolymer (III) having a number average molecular weight of from 75,000 to 600,000 represented by the general formula (C-D-E)3X;

c. a di-branched block copolymer (II) having a number average molecular weight of from 50,000 to 400,000 represented by the general formula (C-D-E)2X; and

d. a linear diblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula C-D-E; where:

i. D represents a polymer block of a mono alkenyl arene;

ii. C and E represent hydrogenated polymer blocks of a conjugated diene;

iii. the relative amounts of copolymers I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and from 2 to 10 weight percent I, where the total of I, II, III and IV equals 100 weight percent;

said hydrogenated block copolymers prepared by the process of:

1. reacting a living lithium-terminated polymer having the formula P—Li where P is a copolymer chain of one or more conjugated dienes having from 4 to 12 carbon atoms and one or more mono alkenyl arenes having from 8 to 18 carbon atoms with an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals and where the molar ratio of Si to Li is from about 0.35 to about 0.7, thereby forming a coupled polymer;

2. hydrogenating the coupled polymer under hydrogenation conditions to substantially saturate at least the olefinically derived double bonds of said coupled polymer without substantial degradation of the coupled polymer; and

3. recovering the resulting hydrogenated polymer.

39. The block copolymer composition of claim 38 , wherein in the process for preparing the block copolymers, the coupled polymer is contacted with an alcohol prior to hydrogenation.

40. The block copolymer composition of claim 38 wherein said block copolymer is hydrogenated such that greater than 95% of the olefinic unsaturation in the B blocks have been reduced.

41. The block copolymer composition of claim 39 wherein the molar ratio of alcohol to Li is from 0.05 to 0.5 moles of alcohol per mole of Li.

42. A hydrogenated block copolymer composition comprising:

a. a tetra-branched block copolymer (IV) having a number average molecular weight of from 100,000 to 800,000 represented byte general formula (F-G-H)4X;

b. a tri-branched block copolymer (III) having a number avenge molecular weight of from 75,000 to 600,000 represented by the general formula (F-G-H)3X;

c. a di-branched block copolymer (II) having a number avenge molecular weight of from 50,000 to 400,000 represented by the general formula (F-G-H)2X; and

d. a linear diblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula F-G-H; where:

i. F represents a polymer block of a mono alkenyl arene;

ii. G and H represent hydrogenated polymer blocks of different conjugated dienes;

iii. the relative amounts of copolymers I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and from 2 to 10 weight percent I, where the total of I, II, III and IV equals 100 weight percent;

said hydrogenated block copolymers prepared by the process of:

1. reacting a living lithium-terminated polymer having the formula P—Li where P is a copolymer chain of one or more conjugated dienes having from 4 to 12 carbon atoms and one or more mono alkenyl arenes having from 8 to 18 carbon atoms with an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals and where the molar ratio of Si to Li is from about 0.35 to about 0.7, thereby forming a coupled polymer;

2. hydrogenating the coupled polymer under hydrogenation conditions to substantially saturate at least the olefinically derived double bonds of said coupled polymer without substantial degradation of the coupled polymer; and

3. recovering the resulting hydrogenated polymer.

43. The block copolymer composition of claim 42 , wherein in the process for preparing the block copolymers, the coupled polymer is contacted with an alcohol prior to hydrogenation.

44. The block copolymer composition of claim 42 wherein said block copolymer is hydrogenated such that greater than 95% of the olefinic unsaturation in the B blocks have been reduced.

45. The block copolymer composition of claim 43 wherein the molar ratio of alcohol to Li is from 0.05 to 0.5 moles of alcohol per mole of Li.

46. The block copolymer of composition of claim 1 wherein a coupling efficiency is from 90% to 98%.

47. The block copolymer of composition of claim 14 wherein a coupling efficiency is from 90% to 98%.

48. The block copolymer of composition of claim 23 wherein a coupling efficiency of said block copolymer composition is from 90% to 98%.

49. The block copolymer of composition of claim 4 wherein a coupling efficiency of said block copolymer composition is from 90% to 98%.

50. The block copolymer of composition of claim 34 wherein a coupling efficiency of said block copolymer composition is from 90% to 98%.

51. The block copolymer of composition of claim 38 wherein a coupling efficiency of said block copolymer composition is from 90% to 98%.

52. The block copolymer of composition of claim 42 wherein a coupling efficiency of said block copolymer composition is from 90% to 98%.

53. A block copolymer composition comprising:

a. a tetra-branched block copolymer (IV) having a number avenge molecular weight of 100,000 to 800,000 represented by the general formula (A-B)4X;

b. a tri-branched block copolymer (III) having a number avenge molecular weight of from 75,000 to 600,000 represented by the general formula (A-B)3X;

c. a di-branched block copolymer (II) having a number average molecular weight of from 50,000 to 400,000 represented by the general formula (A-B)2X; and

d. a linear diblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula A-B; where:

i. A represents a polymer block of a mono alkenyl arene;

ii. B represents a polymer block of a conjugated diene selected from the group consisting essentially of butadiene and mixtures of isoprene and butadiene

iii. X represents the residue of an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals; and

iv. the relative amounts of copolymers I, II, III, and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and wherein the coupling efficiency is greater than 90% and where the total of I, II, III and IV equals 100 weight percent.

54. A block copolymer composition comprising:

a. a tetra-branched block copolymer (IV) having a number average molecular weight of from 100,000 to 800,000 represented by the general formula (C-D-E)4X;

b. a tri-branched block copolymer (III) having a number average molecular weight of from 75,000 to 600,000 represented by the general formula (C-D-E)3X;

c. a di-branched block copolymer (II) having a number average molecular weight of from 50,000 to 400,000 represented by the general formula (C-D-13)2X; and

d. a linear diblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula C-D-E; where:

i. D represents a polymer block of a mono alkenyl arene;

ii. C and E represent polymer blocks of a conjugated diene;

iii. X represents the residue of an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals; and

iv. the relative amounts of copolymers I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and wherein the coupling efficiency is greater than 90% and where the total of I, II, III and IV equals 100 weight percent.

55. A block copolymer composition comprising:

a. a tetra-branched block copolymer (IV) having a number avenge molecular weight of from 100,000 to 800,000 represented by the general formula (F-G-H)4X;

b. a tri-branched block copolymer (III) having a number average molecular weight of from 75,000 to 600,000 represented by the general formula (F-G-H)3X;

c. a di-branched block copolymer (II) having a number avenge molecular weight of from 50,000 to 400,000 represented by the general formula (F-G-H)2X; and

d. a linear diblock copolymer (1) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula F-G-H; where:

i. F represents a polymer block of a mono alkenyl arene;

ii. G and H represent polymer blocks of different conjugated dienes;

iii. X represents the residue of an alkoxy silane coupling agent having the formula Rx-Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched hydrocarbon radicals; and

iv. the relative amounts of copolymers I, II, III and IV are from 0 to 5 weight percent IV, from 0 to 60 weight percent III, from 40 to 95 weight percent II and wherein the coupling efficiency is greater than 90% and where the total of I, II, III and IV equals 100 weight percent.

Assignments (11)