Compositions containing free radical capping additives and uses therefor

• US 6,194,509 B1
• Filed: 04/13/1999
• Issued: 02/27/2001
• Est. Priority Date: 04/13/1999
• Status: Expired due to Term

• Current Assignee: Bridgestone Corporation
• Original Assignee: Bridgestone Corporation
• Inventors: Hayes, Michael W., Hergenrother, William L., Lin, Chen-Chy
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): RAJGURU, UMAKANT K
• Application Number:
  US09/290,292
• Time in Patent Office: 686 Days
• Field of Search: 524/492, 524/493, 524/494, 524/495, 524/496, 524/506
• US Class Current: 524/493
• CPC Class Codes: B60C 1/0016 Compositions of the tread
• CPC Class Codes: C08K 3/013 Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 5/3435 Piperidines
• CPC Class Codes: C08L 21/00 Compositions of unspecified rubbers

Abstract

A vulcanizable filler-reinforced, elastomer-containing composition comprises 100 parts by weight of an elastomer; from about 5 to about 100 parts by weight of a reinforcing filler, per 100 parts of elastomer; from about 0.1 to about 10 parts by weight of a free radical capping additive; and from about 0.2 to about 5 parts by weight of a cure agent, per 100 parts of elastomer. A process for the preparation of a vulcanized composition comprising the composition and a pneumatic tire comprising a tread stock manufactured from the composition are also provided.

Claims

1. A vulcanizable composition comprising:

100 parts by weight of an elastomer;

from about 5 to about 100 parts by weight of at least one reinforcing filler, per 100 parts of said elastomer, selected from the group consisting of carbon black, silica and combinations thereof,

from about 0.1 to about 10 parts by weight of a free radical-capping additive, per 100 parts of the elastomer wherein said free radical-capping additive is selected from the group consisting of galvanoxyl, diphenyl picrylhydrazyl (DPPH), hexaphenyl ethane, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and compatible, free radical capping derivatives thereof; and

from about 0.2 to about 5 parts by weight of a cure agent, per 100 parts of the elastomer.

2. The vulcanizable composition, as set forth in claim 1, wherein said elastomer includes a diene monomer, homopolymer or a copolymer or terpolymer of a diene monomer and a monomer selected from the group consisting of a monovinyl aromatic monomer and a triene monomer.

3. The vulcanizable composition, as set forth in claim 1, wherein said elastomer includes a copolymer of at least one diene and at least one monovinyl aromatic monomer.

4. The vulcanizable composition, as set forth in claim 1, wherein said elastomer includes styrene butadiene rubber.

5. The vulcanizable composition, as set forth in claim 1, wherein said composition includes natural rubber.

6. The vulcanizable composition, as set forth in claim 1, wherein said free radical-capping additive is selected from the group consisting of, 2,2,6,6,-tetramethyl-1-piperidinyloxy, 4-hydroxyl-, and 4-amino-2,2,6,6,-tetra methyl-1-piperidinyloxy.

7. The vulcanizable composition, as set forth in claim 1, wherein said reinforcing filler includes silica and said composition includes a silane coupling agent selected from the group consisting of trialkoxyorganosilane polysulfides and alkylalkoxysilanes of the formula (R₁)₂Si(OR₂)₂ or R₁Si(OR₂)₃, wherein the alkoxy groups are the same or are different;

each R₁ independently comprising C1 to about C18 aliphatic, about C6 to about C12 cyclo-aliphatic, or about C6 to about C 18 aromatic, preferably C1 to about C10 aliphatic, about C6 to about C10 cyclo-aliphatic, or about C6 to about C12 aromatic; and

each R₂ independently containing from one to about 6 carbon atoms.

8. The vulcanizable composition, as set forth in claim 7, wherein said silane is bis-[3-(triethoxysilyl) propyl] tetrasulfide.

9. The vulcanizable composition, as set forth in claim 7, wherein said silica filler has a surface area of about 32 to about 400 m²/gram.

10. The vulcanizable composition, as set forth in claim 7, wherein said silica filler has a surface area of about 100 to about 250 m²/gram.

11. The vulcanizable composition, as set forth in claim 7, wherein said silica filler has a pH of about 5.5 to about 7.

12. The vulcanizable composition, as set forth in claim 1, wherein said reinforcing filler includes carbon black and said carbon black filler has a surface area of about 20 to about 200 m²/gram.

13. The vulcanizable composition, as set forth in claim 1, wherein the composition has a non-functional polymer wherein the change in storage modulus is reduced at least 20 percent as compared to compositions containing no free radical capping additives.

14. The vulcanizable composition, as set forth in claim 1, wherein the composition has a lowered hysteresis loss (tan δ

) as compared to composition containing no free radical-capping additives.

25. A pneumatic tire comprising tread stock manufactured from the vulcanizable composition of claim 1.

15. A process for the preparation of a vulcanized composition comprising:

mixing 100 parts by weight of an elastomer with

from about 5 to about 100 parts by weight of a reinforcing filler, per 100 parts of said elastomer, selected from the group consisting of carbon black, silica and combinations thereof;

from about 0.1 to about 10 parts by weight of a free radical-capping additive, per 100 parts of the elastomer wherein said free radical additive is aselected from the group consisting of galvanoxyl, diphenyl picrylhydrazyl (DPPH), hexaphenyl ethane, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and compatible free radical capping derivatives thereof; and

from about 0.2 to about 5 parts by weight of a cure agent, per 100 parts of said elastomer.

16. The process, as set forth in claim 15, wherein said elastomer includes a diene monomer, homopolymer or a copolymer of a diene monomer and a monomer selected from the group consisting of a monovinyl aromatic monomer and a triene monomer.

17. The process, as set forth in claim 15, wherein said elastomer includes a copolymer of at least one diene and at least one monovinyl aromatic monomer.

18. The process, as set forth in claim 15, wherein said elastomer includes styrene butadiene rubber.

19. The process, as set forth in claim 15, wherein said composition includes a natural rubber.

20. The process, as set forth in claim 15, wherein said free radical-capping additive is selected from the group consisting 4-hydroxyl-2,2,6,6,-tetramethyl-1-piperidinyloxy, and 4-amino-2,2,6,6,-tetra methyl-1-piperidinyloxy.

21. The process, as set forth in claim 15, wherein said reinforcing filler includes silica and said composition includes a silane coupling agent selected from the group consisting of trialkoxyorganosilane polysulfides and alkylalkoxysilanes of the formula (R₁)₂Si(OR₂)₂ or R₁Si(OR₂)₃, wherein the alkoxy groups are the same or are different;

each R₁ independently comprising C1 to about C18 aliphatic, about C6 to about C12 cyclo-aliphatic, or about C6 to about C18 aromatic, preferably C1 to about C10 aliphatic, about C6 to about C10 cyclo-aliphatic, or about C6 to about C12 aromatic; and

each R₂ independently containing from one to about 6 carbon atoms.

22. The process, as set forth in claim 20, wherein said silane is bis-[3-(triethoxysilyl) propyl] tetrasulfide.

23. The process, as set forth in claim 15, wherein said step of mixing includes heating said composition to a temperature of at least 155°

C.

24. The process, as set forth in claim 15, wherein said step of mixing includes heating said composition to a temperature of at least 185°

C.