Gels from silane-coupled block copolymers
View Patent ↗The present invention relates to gels prepared from novel anionic block copolymers of mono alkenyl arenas and conjugated dienes, and to blends of such block copolymers with such polymers. The block copolymers are selectively hydrogenated and have A polymer blocks and B polymer blocks wherein A represents a polymer block of a mono alkenyl arene and B represents a polymer block of a conjugated diene. The block copolymer may be combined with tackifying resins, oils and other components to form the gel of the present invention.
1. An oil gel composition comprising 100 parts by weight of at least one hydrogenated block copolymer composition and about 1000 to about 2000 parts by weight of an extending oil, said hydrogenated block copolymer comprising:
a. 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;
b. 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) 2 X;
c. 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) 3 X; and
d. 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) 4 X where:
i. A represents a polymer block of a mono alkenyl arene;
ii. B represents a polymer block of a hydrogenated conjugated diene;
iii. X represents the residue of an alkoxy silane coupling agent having the formula R x —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 2 to 10 weight percent I , from 40 to 95 weight percent II, from 0 to 60 weight percent III, from 0 to 5 weight percent IV, and where the total of I, II, III and IV equals 100 weight percent.
2. The oil gel composition 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 oil gel composition according to claim 2 wherein said conjugated diene is butadiene, and wherein prior to hydrogenation about 10 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.
4. The oil gel composition according to claim 2 wherein said conjugated diene is isoprene, and wherein prior to hydrogenation about 5 to about 80 mol percent of the condensed isoprene units in block B have 3,4-configuration.
5. The oil gel composition according to claim 3 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.
6. The oil gel composition according to claim 5 wherein the amount of diblock I is from 4 to 8 percent.
7. The oil gel composition according to claim 3 wherein said A blocks have a number avenge molecular weight of between about 3,000 and about 60,000, and wherein said B blocks have a number average molecular weight of between about 20,000 and about 200,000.
8. The oil gel composition according to claim 7 wherein the weight ratio of polymer block A to polymer block B is from 5/95 to 50/50.
9. The oil gel composition according to claim 8 wherein said extending oil is a paraffinic processing oil.
10. An article prepared from the gel of claim 1 .
11. The oil gel composition according to claim 1 also comprising up to 30 percent by weight of a filler, based on the amount of hydrogenated block copolymer.
12. An oil gel composition comprising 100 parts by weight of at least one hydrogenated block copolymer composition and about 1000 to about 2000 parts by weight of an extending oil, said hydrogenated block copolymer comprising:
a. a linear triblock copolymer (I) having a number average molecular weight of from 25,000 to 200,000 represented by the general formula C-D-E;
b. 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) 2 X;
c. 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) 3 X; and
d. a tetra-branched block copolymer (IV) having a number average molecular weight of 100,000 to 800,000 represented by the general formula (C-D-E) 4 X where:
i. C represents a polymer block of a hydrogenated conjugated diene;
ii. D represents a polymer block of a mono alkenyl arene;
in. E represents a polymer block of a hydrogenated conjugated diene;
iv. X represents the residue of an alkoxy silane coupling agent having the formula R—Si—(OR′) y , where x is 0 or 1, x+y =4, and 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 2 to 10 weight percent I, from 40 to 95 weight percent II, from 0 to 60 weight percent III, from 0 to 5 weight percent IV, and where the total of I, II, III and IV equals 100 weight percent.
13. The oil gel composition according to claim 12 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
14. The oil gel composition according to claim 13 wherein said conjugated diene is butadiene, and wherein prior to hydrogenation about 10 to about 80 mol percent of the condensed butadiene units in block C and/or block E have 1,2-configuration.
15. The oil gel composition of claim 13 wherein the amount of 1,2 configuration in block C is 5 to 45% and the amount of 1,2 configuration in block E is 25 to 80%.
16. The oil gel composition according to claim 12 wherein said conjugated diene is isoprene, and wherein prior to hydrogenation about 5 to about 80 mol percent of the condensed isoprene units in block C and/or block E have 3,4-configuration.
17. The oil gel composition according to claim 12 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.
18. The oil gel composition according to claim 12 wherein the amount of triblock I is from 4 to 8 percent.
19. The oil gel composition according to claim 12 wherein said C blocks have a number average molecular weight of between about 3,000 and about 25,000, D blocks have a number average molecular weight of between about 3,000 and about 60,000, and wherein said E blocks have a number average molecular weight of between about 20,000 and about 200,000.
20. The oil gel composition according to claim 12 wherein the weight ratio of polymer block D to the sum of polymer blocks C+E is from 5/95 to 50/50.
21. The oil gel composition according to claim 12 wherein said extending oil is paraffinic processing oil.
22. The oil gel composition according to claim 12 also comprising up to 30 percent by weight of a filler, based on the amount of hydrogenated block copolymer.
23. An article prepared from the gel of claim 12 .