Grafted near-gelation polymers having high damping properties

• US 6,476,117 B1
• Filed: 06/05/2000
• Issued: 11/05/2002
• Est. Priority Date: 06/05/2000
• Status: Expired due to Fees

• Current Assignee: Bridgestone Corporation
• Original Assignee: Bridgestone Corporation
• Inventors: Foltz, Victor J., Wang, Xiaorong, Hall, James E., Hogan, Terrence E.
• Primary Examiner(s): Woodward, Ana
• Application Number:
  US09/586,873
• Time in Patent Office: 883 Days
• Field of Search: 525/66, 525/64, 525/69, 525/71, 525/74, 525/77, 525/78, 525/79, 524/504, 524/506, 524/514, 524/515, 524/517, 524/522
• US Class Current: 524/504
• CPC Class Codes: C08F 297/00 Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C

Abstract

Thermoplastic elastomers containing hard segments formed from polyalkylenes and soft segments formed from elastomeric polymers near their gelation point are formed. Compositions containing these materials are elastomeric and exhibit excellent damping capabilities over a wide range of temperatures and frequencies.

Claims

1. A thermoplastic elastomer comprising a multi-block polymer including hard segments and soft segments, said hard segments comprising polymeric chains of a crystalline polyalkylene and said soft segments comprising a near gelation polymer, wherein said hard segments and said soft segments are connected via covalent bonds, said near-gelation polymer having at least one functional group capable of being linked to a functional group on the polyalkylene and being the reaction product of a prepolymer and a crosslinking agent, said near-gelation polymer having a physical state relative to its gelation point defined by 0≦

|(r−

r_g)/r_g|≦

0.5 where r is the weight ratio of said crosslinking agent to said prepolymer and r_g is the weight ratio of said crosslinking agent to said prepolymer at the gelation point.

2. The thermoplastic elastomer of claim 1 wherein said prepolymer and said crosslinking agent each contain at least two reactive functional groups independently selected from the group consisting of hydroxy, amino, carboxylic acid, isocyanate, oxirane and succinyl oxide groups.

3. The thermoplastic elastomer of claim 1 wherein said crystalline polyalkylene comprises monomer units derived from at least one of the group consisting of ethylene and C₃ to C₇ α

-olefins.

4. The thermoplastic elastomer of claim 3 wherein said crystalline polyalkylene comprises a maleated polypropylene.

5. The thermoplastic elastomer of claim 4 wherein said maleated polypropylene has a molecular weight below about 10,000.

6. The thermoplastic elastomer of claim 7 wherein said maleated polypropylene has a maleic anhydride content above about 0.2%.

7. The thermoplastic elastomer of claim 1 wherein said crystalline polyalkylene is functionalized by reaction with at least one of the group consisting of acid anhydrides, unsaturated carboxylic acids, primary amines, and secondary amines.

8. The thermoplastic elastomer of claim 7 wherein said crystalline polyalkylene is functionalized by reaction with at least one of the group consisting of:

phthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric anhydride, itaconic anhydride, pyromellitic anhydride, trimellitic anhydride, succinic anhydride, citraconic anhydride, cyclohexane dicarboxylic anhydride, madic anhydride, and alkyl and alkenyl derivatives thereof;

acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, and itaconic acid.

9. The thermoplastic elastomer of claim 1 wherein said prepolymer has functional groups selected from the group consisting of primary amino, secondary amino, hydroxyl, carboxyl, vinyl, epoxy, anhydride, aryl halide, carboxylic acid anhydride, carboxamide, and isocyanate groups.

10. The thermoplastic elastomer of claim 1 wherein said prepolymer comprises hydrogenated styrene/butadiene rubber, hydrogenated nitrile rubber, ethylene/propylene rubber, ethylene/propylene/diene rubber, ethylene/butene rubber, ethylene/butene/diene rubber, acrylic rubber, chlorinated polyethylene rubber, fluororubber, silicone rubber, urethane rubber, polysulfide rubber, hydrogenation product of styrene/butadiene block polymer, α

,β

-unsaturated nitrile/acrylate/conjugated diene copolymer rubber, styrene/butadiene copolymers, polyisoprene, nitrile rubber, chloroprene rubber or butyl rubber.

11. The thermoplastic elastomer of claim 1 wherein said thermoplastic elastomer has a tan δ

ranging between about 0.1 to about 1.0 from about −

20°

to about 100°

C.

12. The thermoplastic elastomer of claim 1 wherein said thermoplastic elastomer has a Shore A hardness at about 20°

to 25°

C. of from 0 to about 40.

13. The thermoplastic elastomer of claim 1 wherein said thermoplastic elastomer has a 100°

C. compression set of from about 30 to about 65%.

14. The thermoplastic elastomer of claim 1 wherein said hard segments and soft segments are randomly distributed.

15. The thermoplastic elastomer of claim 1 further comprising a plasticizer.

16. A thermoplastic elastomer made by reacting a near-gelation saturated polymer with a crystalline polyalkylene for a time sufficient to form said elastomer, said near gelation saturated polymer having at least one functional group capable of being linked with at least one functional group on the crystalline polyalkylene, said near gelation saturated polymer being the reaction product of a prepolymer and a crosslinking agent and having a physical state relative to its gelation point defined by 0≦

|(r−

r_g)/r_g|≦

0.5 where r is the weight ratio of said crosslinking agent to said prepolymer and r_g is the weight ratio of said crosslinking agent to said prepolymer at the gelation point.

17. A method of making a thermoplastic elastomer comprising:

a) subjecting a composition comprising a liquid, crosslinkable polymer having low or no unsaturation to the action of a crosslinking agent so as to form a near-gelation elastomer, said near-gelation elastomer having a physical state relative to its gelation point defined by 0≦

|(r−

r_g)/r_g|≦

0.5, in which r is the weight ratio of the crosslinking agent to the crosslinkable polymer, and r_g is the weight ratio of the crosslinking agent to the crosslinkable polymer at the gelation point; and

b) allowing a covalent bond to form between at least one functional group on each of said near-gelation elastomer and a crystalline polyalkylene.

18. A method of making a thermoplastic elastomer comprising:

a) crosslinking a polymer whose gelation point is known with a crosslinking agent, the crosslinking agent being added in sufficient amount to form a near-gelation polymer, said near-gelation polymer having a physical state relative to the gelation point defined by 0≦

|(r−

r_g)/r_g|≦

0.5, in which r is the weight ratio of the crosslinking agent to polymer, and r_g is the weight ratio of the crosslinking agent to the polymer at the gelation point; and

b) linking the near-gelation polymer to a crystalline polyalkylene via at least one functional group on the near-gelation polymer and at least one functional group on the crystalline polyalkylene to form the thermoplastic elastomer.

19. The method of claim 18 wherein the near-gelation polymer has a physical state relative to the gelation point defined by 0≦

|(r−

r_g)/r_g|≦

0.2.