High 1,2 content thermoplastic elastomer/oil/polyolefin composition

• US 5,777,031 A
• Filed: 07/25/1997
• Issued: 07/07/1998
• Est. Priority Date: 07/03/1996
• Status: Expired due to Term

• Current Assignee: Kraton Polymers US LLC (DL Holdings Co., Ltd.)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Djiauw, Lie Khong, Modic, Michael John
• Primary Examiner(s): Zitomer, Fred
• Application Number:
  US08/898,001
• Time in Patent Office: 347 Days
• Field of Search: 525/88, 525/98, 525/95, 525/232, 525/240, 525/241
• US Class Current: 525/98
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 53/02 of vinyl-aromatic monomers and conjugated dienes
• CPC Class Codes: C08L 53/025 modified

Abstract

A thermoplastic elastomer composition comprising a block copolymer having at least two resinous endblocks and a high 1,2-addition butadiene midblock, a paraffin oil and a crystalline polyolefin. The composition exhibits greater softness, better processability and better elastic properties as compared with similar compositions made with normal amounts of a 1,2-addition. Compositions are useful for utilities such as overmolding into hard substrates, grips, medical tubing and miscellaneous rubbery articles.

Claims

1. A thermoplastic elastomer composition comprising:

(a) a base composition comprising;

(i) 15 to 55 weight percent of a block copolymer having at least two resinous polymerized monovinyl aromatic endblocks and a nidblock of hydrogenated polymerized butadiene wherein at least 51 mole percent of said butadiene has polymerized at the 1,2-position,

(ii) 5 to 80 weight percent of a paraffinic oil, and

(iii) 5 to 20 weight percent of a crystalline polyolefin; and

(b) a stabilizer, such stabilizer being present in an amount within the range of 0.01 to 4 weight percent based on the weight of said base composition.

2. A composition according to claim 1 wherein said end-blocks each have a molecular weight of at least 20,000 and wherein said block copolymer has a molecular weight of at least 130,000.

3. A composition according to claim 2 wherein said block copolymer comprises 20-48 weight percent of said monovinyl aromatic compound.

4. A composition according to claim 3 wherein said block copolymer is an A-B-A block copolymer wherein each A represents polymerized styrene and wherein said crystalline polyolefin is polypropylene, said block copolymer further being defined by a molecular weight within the range of 180,000-250,000.

5. A composition according to claim 4 wherein said block copolymer has a styrene content within the range of 25-35 weight percent.

6. A composition according to claim 1 wherein said block copolymer is an A-B-A block copolymer having a molecular weight within the range of 150,000-300,000.

7. A composition according to claim 1 wherein said block copolymer has a monovinyl aromatic content within the range of 22-45 weight percent.

8. A composition according to claim 1 wherein said monovinyl aromatic compound is styrene.

9. A composition according to claim 1 wherein said polyolefin is polypropylene.

10. A composition according to claim 1 wherein said block copolymer has a monovinyl aromatic content within the range of 25-35 weight percent.

11. A composition according to claim 1 wherein said stabilizer comprises a hindered phenol antioxidant and a thiosynergist.

12. A composition according to claim 11 wherein said hindered phenol is tetrakis methylene(3,5-di-t-butyl-4-hydroxyhydrocinnaniate)! methane and said thiosynergist is dilaurylthiodipropropionate.

13. A composition according to claim 1 comprising in addition a flame retardant.

14. A composition according to claim 1 comprising in addition a filler.

15. A composition according to claim 1 wherein said oil is a white mineral oil having a specific gravity within the range of 0.864-0.878 at 60°

C. and a viscosity of 370-420 sus at 100°

F. and wherein said polyolefin is polypropylene.

16. A composition comprising 25 to 45 weight percent of a styrene-ethylenebutylene-styrene block copolymer wherein at least 51 mole percent of said butylene block is derived from 1,2-butadiene polymerization;

35 to 60 weight percent of a paraffinic oil; and

10 to 15 weight percent of a crystalline polyolefin.

17. A composition according to claim 16 wherein said ethylene-butylene block is derived from butadiene in which 65-80 mole percent polymerized at the 1,2 position.

18. A process comprising:

combining a block copolymer having at least two resinous polymerized monovinyl aromatic compound endblocks and a midblock of hydrogenated polymerized butadiene wherein at least 51 mole percent of said butadiene has polymerized at the 1,2-position with a paraffinic oil;

allowing time for said block copolymer to absorb said paraffinic oil to give an oil-containing block copolymer composition;

tumble blending said oil-containing block copolymer composition with a crystalline polyolefin to give a block copolymer/oil/polyolefin mixture;

melt extruding said mixture, wherein said block copolymer is present in an amount within the range of 15 to 55 weight percent, said oil is present in an amount within the range of 5 to 80 weight percent, and said crystalline polyolefin is present in an amount within the range of 5 to 20 weight percent based on the total weight of said block copolymer, oil and polyolefin.

19. A method according to claim 18 wherein said monovinyl aromatic compound is styrene, said block copolymer is of a linear A-B-A configuration, 65-80 mole percent of said butadiene has polymerized at the 1,2-position, and wherein said block copolymer is present in an amount within the range of 25 to 45 weight percent, said oil is present in an amount within the range of 35 to 60 weight percent and said crystalline polyolefin is poly-propylene present in an amount within the range of 10 to 15 weight percent, and wherein a stabilizer is also present during said tumble blending.