Articles prepared from hydrogenated controlled distribution 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 controlled distribution blocks of mono alkenyl arenes and conjugated dienes. 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 selected from the group consisting of personal hygiene films and fibers, blown films for medical devices, extruded films, extruded tubes, extruded profiles, overmolded grips, airbags, steering wheels, toys, cap seals, automotive skins, thermal spray coatings, trays, and gloves, consisting essentially of at least one hydrogenated block copolymer 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, wherein said hydrogenated block copolymer has at least one block A and at least one block B, 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 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 a region not adjacent to the A blocks that is 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 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 about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.
4. The article according to claim 3 wherein the styrene blockiness of block B is less than 40 percent.
5. The article according to claim 4 wherein the polymer is an ABA polymer and each block B has a center region with a minimum ratio of butadiene units to styrene units.
6. The article according to claim 2 wherein the weight percent 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 defined to be the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
7. The article according to claim 1 wherein said hydrogenated block copolymer has the general configuration ABA, (A-B) n , (A-B-A) n , (A-B) n X or mixtures thereof where n is an integer between 2 and about 30, X is the residue of a coupling agent, each A block has a number average molecular weight of about 5,000 to about 20,000, each B block has a number average molecular weight of about 30,000 to about 100,000, and the total molecular weight is about 50,000 to about 140,000.
8. The article according to claim 7 comprising 100 parts by weight of said hydrogenated block copolymer and about 5 to about 50 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 and about 5 to about 50 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 9 also comprising about 5 to about 50 parts by weight of a tackifying resin.
11. The article according to claim 8 also comprising about 5 to about 40 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 7 comprising about 5 to about 95 percent by weight of said hydrogenated block copolymer and about 95 to about 5 percent by weight of an ethylene/vinyl aromatic copolymer or propylene/vinyl aromatic copolymer.
13. The article according to claim 12 wherein said ethylene/vinyl aromatic copolymer is a substantially random ethylene/styrene copolymer.
14. The article according to claim 1 wherein said hydrogenated block copolymer has the general configuration ABA, (A-B) n , (A-B-A) n , (A-B) n X or mixtures therof where n is an integer between 2 and about 30, X is the residue of a coupling agent, each A block has a number average molecular weight of about 10,000 to about 40,000, each B block has a number average molecular weight of about 60,000 to about 140,000, and the total molecular weight is about 140,000 to about 280,000.
15. The article according to claim 14 comprising 100 parts by weight of said hydrogenated block copolymer and about 10 to about 50 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.
16. The article according to claim 15 also comprising about 20 to about 150 parts by weight of a polymer extending oil.
17. The article according to claim 14 comprising about 5 to about 95 percent by weight of said hydrogenated block copolymer and about 95 to about 5 percent by weight of at least one polymer selected from the group consisting of poly(phenylene oxides), syndiotactic polystyrene, cyclic olefin copolymers and acrylonitrile/butadiene/styrene terpolymers.
18. The cap seal of claim 1 , comprising 100 parts by weight of said hydrogenated block copolymer and about 50 to about 125 parts by weight of a polymer extending oil, 20 to 50 parts by weight of polypropylene and optionally 10 to 60 parts by weight silica.
19. 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.
20. 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.
21. The article according to claim 1 comprising about 5 to 20 percent weight of said hydrogenated block copolymer and about 80 to about 95 percent weight of an engineering thermoplastic resin.
22. The article according to claim 21 wherein said engineering thermoplastic resin is selected from the group consisting of thermoplastic polyester, thermoplastic polyurethane, poly(arylether), poly(aryl sulfone), polycarbonate, acrylic resins, acetal resin, polyamide, halogenated thermoplastic, cyclic olef in copolymers and nitrile barrier resin.
23. The article according to claim 1 wherein said hydrogenated block copolymer is a functionalized block copolymer.
24. The article according to claim 23 wherein said hydrogenated block copolymer has been grafted with an acid compound or its derivative.
25. The article according to claim 24 wherein said acid compound or its derivative is selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, and its derivatives.
26. The article according to claim 24 wherein said acid compound or its derivative is maleic anhydride or maleic acid.
27. The article according to claim 26 containing 75 to 95 weight percent of an engineering thermoplastic selected from the group consisting of polyamides and polyurethanes and 5 to 25 weight percent of the functionalized block polymer.
28. The article according to claim 1 comprising about 5 to 40 percent weight of said hydrogenated block copolymer and about 60 to about 95 percent weight of a polystyrene homopolymer or copolymer.
29. The article according to claim 1 wherein said hydrogenated block copolymer has the general configuration A-B-A, (A-B) n , (A-B) n -A, (A-B) n X, or mixtures thereof where n is an integer from 2 to about 30 and X is coupling agent residue.
30. The article according to claim 29 wherein said A block is a polystyrene block, said B block prior to hydrogenation is a controlled distribution copolymer block of 1,3-butadiene and styrene, wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration, and wherein the styrene blockiness of block B is less than 40 percent.
31. The article according to claim 30 comprising said hydrogenated block copolymer and a cyclic olef in copolymer.
32. The article according to claim 31 wherein said cyclic olefin copolymer is a norbornene/ethylene copolymer.
33. The article according to claim 31 comprising about 5 to about 95 weight percent hydrogenated block copolymer and about 95 to about 5 weight percent cyclic olefin copolymer.
34. The article according to claim 31 comprising said hydrogenated block copolymer and at least one olefin polymer.
35. The article according to claim 34 wherein said olefin polymer is selected from the group consisting of ethylene homopolymers, ethylene/alpha olef in copolymers, ethylene/vinyl aromatic copolymers, propylene homopolymers, propylene/alpha olefin copolymers, propylene/vinyl aromatic copolymers, high impact polypropylene, and ethylene/vinyl acetate copolymers.
36. The article according to claim 30 comprising said hydrogenated block copolymer and at least one styrene polymer.
37. The article according to claim 36 wherein said styrene polymer is selected from the group consisting of crystal polystyrene, high impact polystyrene, syndiotactic polystyrene and acrylonitrile/butadiene/styrene terpolymer.
38. The article according to claim 30 comprising said hydrogenated block copolymer and a tackifying resin.
39. The article according to claim 30 also comprising a polystyrene block compatible resin.
40. The article according to claim 30 comprising said hydrogenated block copolymer and an engineering thermoplastic resin.
41. The article according to claim 40 wherein said engineering thermoplastic resin is selected from the group consisting of thermoplastic polyesters, thermoplastic polyurethanes, poly(aryl ethers), poly(aryl sulfones), polycarbonates, acetal resins, polyamides, halogenated thermoplastics, nitrile barrier resins, cyclic olef in copolymers and poly(methyl methacrylates).
42. The article according to claim 30 comprising said hydrogenated block copolymer and an S-EB-S block copolymer.
43. The article according to claim 1 wherein said hydrogenated block copolymer has the general configuration A-B-A, (A-B) n , (A-B) n -A, (A-B) n X, or mixtures thereof where n is an integer from 2 to about 30 and X is coupling agent residue.
44. The tray according to claim 1 comprising:
a. an unsaturated, crosslinkable thermosetting resin;
b. an ethylenically unsaturated monomer;
c. an additive selected from the group consisting of reinforcing agents, fillers and mixtures thereof; and
d. said block copolymer.
45. The composition according to claim 44 wherein said thermosetting resin is a polyester resin.
46. The composition according to claim 44 wherein said unsaturated monomer is styrene.
47. The article according to claim 1 comprising 1 to 99 percent weight of said hydrogenated block copolymer and 99 to 1 percent weight of said other component.
48. An article selected from the group consisting of personal hygiene films and fibers, blown films for medical devices, extruded films, extruded tubes, extruded profiles, overmolded grips, airbags, steering wheels, toys, cap seals, automotive skins, trays, and gloves consisting essentially of at least one hydrogenated block copolymer and at least one other component selected from the group consisting of olef in polymers, styrene polymers, tackifying resins, polymer extending oils and engineering thermoplastic resins, wherein said hydrogenated block copolymer has at least one block A and at least one block B, 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 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 a region not adjacent to the A blocks that is 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
f. the weight ratio of conjugated diene to mono alkenyl arene in the B block is between about 5:1 and about 1:2.
49. The article according to claim 48 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
50. The article according to claim 49 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.
51. The article according to claim 50 wherein the styrene blockiness of block B is less than 40 percent.
52. The article according to claim 51 wherein the polymer is an ABA polymer and each block B has a center region with a minimum ratio of butadiene unites to styrene units.
53. The article according to claim 49 wherein the weight percent 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 defined to be the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
54. The article according to claim 48 wherein said hydrogenated block copolymer has the general configuration ABA, (A-B) n , (A-B-A) n , (A-B) n X or mixtures thereof where n is an integer between 2 and about 30, X is the residue of a coupling agent, each A block has a number average molecular weight of about 5,000 to about 20,000, each B block has a number average molecular weight of about 30, 000 to about 100,000, and the total molecular width is bout 50,000 to about 140,000.
55. The article according to claim 48 wherein said hydrogenated block copolymer has the general configuration ABA, (A-B) n , (A-B-A) n , (A-B) n X or mixtures thereof where n is an integer between 2 and about 30, X is the residue of a coupling agent, each A block has a number average molecular weight of about 10,000 to about 40,000, each B block has a number average molecular weight of about 60,000 to about 140,000, and the total molecular weight is about 140,000 to about 280,000.