Articles prepared from hydrogenated block copolymers
View Patent ↗The present invention relates to articles prepared from novel anionic block copolymers of mono alkenyl arenes and conjugated dienes, and to blends of such block copolymers with other polymers. The block copolymers are selectively hydrogenated and have mono alkenyl arene end blocks and conjugated diene mid blocks. The block copolymer may be blended with at least one other polymer selected from the group consisting of olefin polymers, styrene polymers, amorphous resins and engineering thermoplastic resins.
1. An article comprising at least one hydrogenated block copolymer composition and at least one other component selected from the group consisting of olefin polymers, styrene polymers, tackifying resins, polymer extending oils and engineering thermoplastic resins, said 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) 4 X;
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) 3 X;
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) 2 X; 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 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, 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 IV, III, II and I 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.
2. The article 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 article 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 article 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 article 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 article according to claim 5 wherein the amount of diblock copolymer I is from 4 to 8 percent.
7. The article according to claim 5 wherein said A blocks have a number average molecular weight of between about 3,000 and about 60,000, wherein said B blocks have a number average molecular weight of between about 20,000 and about 200,000, and wherein the weight ratio of polymer block A to polymer block B is from 5/95 to 50/50.
8. The article according to claim 7 comprising 100 parts by weight of said hydrogenated block copolymer composition and about 5 to about 300 parts by weight of a polymer extending oil.
9. The article according to claim 7 comprising 100 parts by weight of said hydrogenated block copolymer composition and about 5 to about 100 parts by weight of an olefin polymer selected from the group consisting of ethylene homopolymers, ethylene/alpha olefin copolymers, propylene homopolymers, propylene/alpha olefin copolymers, high impact polypropylene, and ethylene/vinyl acetate copolymers.
10. The article according to claim 7 comprising 100 parts by weight of said hydrogenated block copolymer composition and about 5 to about 100 parts by weight of a tackifying resin.
11. The article according to claim 7 comprising 100 parts by weight of said hydrogenated block copolymer composition and about 5 to about 100 parts by weight of a styrene polymer selected from the group consisting of crystal polystyrene, high impact polystyrene, syndiotactic polystyrene and acrylonitrile/butadiene/styrene terpolymer.
12. The article according to claim 8 also comprising about 5 to about 100 parts by weight of an olefin polymer selected from the group consisting of ethylene homopolymers, ethylene/alpha olefin copolymers, propylene homopolymers, propylene/alpha olefin copolymers, high impact polypropylene, and ethylene/vinyl acetate copolymers.
13. The article according to claim 12 wherein said prior to hydrogenation about 60 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuation.
14. The article according to claim 12 also comprising about 5 to about 100 parts by weight of a tackifying resin.
15. The article according to claim 12 also comprising about 5 to about 100 parts by weight of a styrene polymer selected from the group consisting of crystal polystyrene, high impact polystyrene, syndiotactic polystyrene and acrylonitrile/butadiene/styrene terpolymer.
16. The article according to claim 15 also comprising about 5 to about 100 parts by weight of a tackifying resin.
17. The article according to claim 12 also comprising about 2 to about 80 percent by weight of a filler based on the total weight of the article.
18. The article according to claim 10 wherein said tackifying resin is a midblock compatible resin or a polystyrene block compatible resin.
19. The article according to claim 10 wherein said tackifying resin includes both a midblock compatible resin and a polystyrene block compatible resin.
20. The article according to claim 7 comprising about 5 to about 95 percent by weight of said hydrogenated block copolymer composition and about 95 to about 5 percent by weight of an olefin polymer selected from the group consisting of ethylene homopolymers, ethylene/alpha olefin copolymers, propylene homopolymers, propylene/alpha olefin copolymers, high impact polypropylene, and ethylene/vinyl acetate copolymers.
21. The article according to claim 20 wherein said olefin polymer is selected from the group consisting of propylene homopolymers, propylene/alpha olefin copolymers, propylene/vinyl aromatic copolymers, and high impact polypropylene.
22. The article according to claim 7 wherein said conjugated diene is butadiene, and wherein prior to hydrogenation about 10 to about 45 mol percent of the condensed butadiene units in block B have 1,2-configuration.
23. The article according to claim 22 comprising 100 parts by weight of said hydrogenated block copolymer composition and about 5 to about 100 parts by weight of an olefin polymer selected from the group consisting of ethylene homopolymers, ethylene/alpha olefin copolymers, ethylene/vinyl aromatic copolymers, propylene homopolymers, propylene/alpha olefin copolymers, propylene/vinyl aromatic copolymers, high impact polypropylene, and ethylene/vinyl acetate copolymers.
24. The article according to claim 23 also comprising about 5 to about 100 parts by weight of a tackifying resin.
25. The article according to claim 24 wherein said olefin polymer is selected from the group consisting of propylene homopolymers, propylene/alpha olefin copolymers, propylene/vinyl aromatic copolymers, and high impact polypropylene, and said tackifying resin is a polystyrene block compatible resin.
26. The article according to claim 7 also comprising about 2 to about 80 percent by weight of a filler based on the total weight of the article.
27. The article according to claim 26 wherein said filler is calcium carbonate.
28. The article according to claim 1 wherein the article is in the form of a film, sheet, coating, band, strip, profile, molding, foam, tape, fabric, thread, filament, ribbon, fiber, plurality of fibers or fibrous web.
29. The article according to claim 1 wherein said article is formed in a process selected from the group consisting of injection molding, over molding, dipping, extrusion, roto molding, slush molding, fiber spinning, film making or foaming.
30. The article according to claim 1 also comprising an S-EB-S block copolymer.
31. The article according to claim 30 comprising 100 parts by weight of said hydrogenated blocky copolymer composition and about 5 to about 100 parts by weight of said S-EB-S block copolymer.
32. The article according to claim 7 comprising about 5 to about 95 percent by weight of a styrene polymer and about 95 to about 5 percent by weight of said hydrogenated block copolymer composition.
33. An article comprising at least one hydrogenated block copolymer composition and at least one other component selected from the group consisting of olefin polymers, styrene polymers, tackifying resins, polymer extending oils, fillers, reinforcements, lubricants and engineering thermoplastic resins, said 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) 4 X;
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) 3 X;
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) 2 X; 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 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 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.
34. The article according to claim 33 wherein said conjugated diene is selected from the group consisting of butadiene and isoprene and said mono alkenyl arene is styrene.
35. The article according to claim 34 wherein said D blocks are styrene polymer blocks and said C and E blocks are butadiene polymer blocks, and wherein prior to hydrogenation about 10 to about 80 mol percent of the condensed butadiene units in blocks C and E have 1,2-configuration.
36. The article according to claim 34 wherein said D blocks are styrene polymer block, said C blocks are isoprene polymer blocks where prior to hydrogenation about 5 to about 80 mol percent of the condensed isoprene units have 3,4-configuration, and said D blocks are butadiene polymer blocks where prior to hydrogenation about 10 to about 80 mol percent of the condensed butadiene units have 1,2-configuration.
37. The article according to claim 35 wherein said block copolymer composition is selectively hydrogenated such that greater than 95% of the olefinic unsaturation in the C and E blocks have been reduced.
38. The article according to claim 37 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.
39. The article according to claim 38 wherein the weight percent of D polymer blocks in the block copolymer composition is from 5 weight percent to 50 weight percent.
40. The article according to claim 39 wherein the weight ratio of C blocks to E blocks is from 10:90 to 90:10.
41. The article according to claim 40 comprising 100 parts by weight of said hydrogenated block copolymer composition and about 5 to about 300 parts by weight of a polymer extending oil.
42. The article according to claim 40 comprising 100 parts by weight of said hydrogenated block copolymer composition and about 5 to about 100 parts by weight of an olefin polymer selected from the group consisting of ethylene homopolymers, ethylene/alpha olefin copolymers, propylene homopolymers, propylene/alpha olefin copolymers, high impact polypropylene, and ethylene/vinyl acetate copolymers.
43. The article according to claim 40 comprising 100 parts by weight of said hydrogenated block copolymer composition and about 5 to about 100 parts by weight of a tackifying resin.
44. The article according to claim 40 comprising 100 parts by weight of said hydrogenated block copolymer composition and about 5 to about 100 parts by weight of a styrene polymer selected from the group consisting of crystal polystyrene, high impact polystyrene, syndiotactic polystyrene and acrylonitrile/butadiene/styrene terpolymer.
45. The article according to claim 41 also comprising about 5 to about 100 parts by weight of an olefin polymer selected from the group consisting of ethylene homopolymers, ethylene/alpha olefin copolymers, propylene homopolymers, propylene/alpha olefin copolymers, high impact polypropylene, and ethylene/vinyl acetate copolymers.
46. The article according to claim 42 wherein said prior to hydrogenation about 60 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuation.
47. The article according to claim 46 also comprising about 5 to about 100 parts by weight of a tackifying resin.
48. The article according to claim 47 also comprising about 5 to about 100 parts by weight of a styrene polymer selected from the group consisting of crystal polystyrene, high impact polystyrene, syndiotactic polystyrene and acrylonitrile/butadiene/styrene terpolymer.
49. The article according to claim 46 wherein said tackifying resin is a midblock compatible resin.
50. The article according to claim 46 wherein said tackifying resin is a polystyrene block compatible resin.
51. The article according to claim 46 wherein said tackifying resin includes both a midblock compatible resin and a polystyrene block compatible resin.
52. The article according to claim 2 wherein the conjugated dienes in said block B comprise a mixture of butadiene and isoprene.
53. The article according to claim 52 wherein the weight ratio of isoprene to butadiene is between about 1:4 to about 4:1.