Granted Patent B2

US 7,560,513 · App. 11/305,450 · Granted Jul 14, 2009

Abstract

Claims (104)

1. A rubber composition, comprising an unsaturated elastomer and a sulfur-functional linear polyorganosiloxane comprising a chemically-protected sulfur group capable of reacting with the unsaturated elastomer, with the proviso that the sulfur-functional linear polyorganosiloxane does not further comprise a functional group capable of chemical coupling with a filler surface.

2. The rubber composition as defined in claim 1 , wherein the sulfur-functional linear polyorganosiloxane has a molecular weight in a range greater than about 250 grams per mole.

3. The rubber composition as defined in claim 1 , wherein the chemically-protected sulfur group is terminally-connected to the linear polyorganosiloxane.

4. The rubber composition as defined in claim 1 , further comprising a filler.

5. The rubber composition as defined in claim 1 , further comprising a curing agent.

6. The rubber composition as defined in claim 1 , further comprising a deblocking agent that is capable of activating the chemically-protected sulfur groups.

7. The rubber composition as defined in claim 1 , wherein the unsaturated elastomer comprises one or both of natural rubber or synthetic rubber.

8. The rubber composition as defined in claim 7 , wherein the synthetic rubber is diene-based.

9. The rubber composition as defined in claim 4 , wherein the filler comprises one or both of carbon or silicon.

10. The rubber composition as defined in claim 4 , wherein the filler comprises one or both of metal oxide or metal hydroxide.

11. The rubber composition as defined in claim 4 , wherein the filler comprises one or more of silica, synthetic silicate, natural silicate, or glass fiber.

12. The rubber composition as defined in claim 4 , wherein the filler comprises carbon black.

13. The rubber composition as defined in claim 1 , wherein the unsaturated elastomer is present in an amount greater than about 10 weight percent.

14. A vulcanized rubber composition comprising a vulcanized product of the rubber composition of claim 1 .

15. The vulcanized rubber composition as defined in claim 14 , comprising a sulfur-functional linear polyorganosiloxane cross-linked to an unsaturated elastomer.

16. The vulcanized rubber composition of claim 14 , having a tensile strength greater than about 19.5 megaPascal according to ASTM D412.

17. The vulcanized rubber composition of claim 14 , having an elongation at break greater than about 400 percent according to ASTM D412.

18. The vulcanized rubber composition of claim 14 , having a modulus at 300 percent strain greater than about 7 megaPascal according to ASTM D412.

19. The vulcanized rubber composition of claim 14 , having a modulus at 100 percent strain greater than about 1.5 megaPascal according to ASTM D412.

20. The vulcanized rubber composition of claim 14 , having a hardness greater than about 56 Shore A according to ASTM 2240.

21. An article comprising the vulcanized rubber composition of claim 14 , wherein the article is one or more of cable sheath, hose, transmission belt, conveyor belt, roller coating, packing ring, damping element, or shoe sole.

22. A tire comprising the vulcanized rubber composition of claim 14 .

23. A rubber composition comprising an unsaturated elastomer and a sulfur-functional linear polyorganosiloxane chosen from those of formulae (I), (II) and (III)

wherein A is a polyvalent radical ((R 27 OC(═O) t —(L) j ) k —(Q) z J(═E);

R 1 -R 27 are independently at each occurrence a hydrogen atom, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

G is a bond, a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical;

R 28 is a hydroxyl group, a halogen, a silyl alkoxy group, an alkoxy group, or an aryloxy group;

S is one or more sulfur atoms;

L is independently at each occurrence a monovalent or a polyvalent group derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

Q is oxygen, sulfur or an NR 29 group, R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

J is carbon, sulfur, phosphorus, or a sulfinyl group;

E is oxygen or sulfur;

“m” and “n” are independently equal to 0 or are an integer greater than 0; “p” is greater than 0; “t” is an integer that is equal to 0, 1, 2, 3, 4, or 5; “j” is equal to 0 or 1; “k” is equal to 1 if J is carbon, sulfur or sulfinyl, “k” is 2 if J is phosphorus; and “z” is an integer that is equal to 0, 1, or 2, and further wherein “m+n+p” is greater than or equal to 10.

24. The rubber composition as defined in claim 23 , wherein A—S— is a chemically-protected sulfur group.

25. The rubber composition of claim 23 , further comprising an ingredient chosen from fillers, curing agents, and deblocking agents capable of activating the chemically-protected sulfur groups.

26. The rubber composition of claim 25 , wherein the fillers are chosen from those comprising carbon, silicon, metal oxide, metal hydroxide, silica, synthetic silicate, natural silicate, glass fiber, and carbon black.

27. The rubber composition of claim 23 , wherein the unsaturated elastomer comprises one or both of natural rubber or synthetic rubber.

28. The rubber composition of claim 23 , wherein the unsaturated elastomer is present in an amount greater than about 10 weight percent.

29. The rubber composition of claim 23 , wherein the rubber composition is in the form of a vulcanized product.

30. The rubber composition of claim 29 , wherein the rubber composition is in the form of a tire.

31. A method for producing a tire composition, comprising:

producing a sulfur-functional linear polyorganosiloxane comprising a chemically-protected sulfur group by reacting a linear polyorganosiloxane comprising an alkene group, and a thio acid and having a structure as defined in formula (IV):

((R 27 OC(═O)) t —(L) j ) k —(Q) z J(═E)SH  (IV)

wherein R 27 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical; L is independently at each occurrence a monovalent group or a polyvalent group that is derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

Q is oxygen, sulfur, or an NR 29 group, wherein R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

J is carbon, sulfur, phosphorus, or a sulfinyl group;

E is oxygen or sulfur;

S comprises one or more sulfur atoms;

“t” is an integer that is equal to 0, 1, 2, 3, 4, or 5; “j” is equal to 0 or 1, “k” is equal to 1 if J is carbon, sulfur or sulfinyl, “k” is 2 if J is phosphorus; and “z” is equal to 0, 1, or 2; and

mixing the sulfur-functional linear polyorganosiloxane with an unsaturated elastomer, with the proviso that the sulfur-functional linear polyorganosiloxane comprising a chemically-protected sulfur group does not further comprise a functional group capable of chemical coupling with a filler surface.

32. The method as defined in claim 31 , further comprising adding a filler.

33. The method as defined in claim 32 , further comprising coupling the sulfur-functional linear polyorganosiloxane to the filler surface.

34. The method as defined in claim 31 , further comprising adding a curing agent.

35. The method as defined in claim 34 , further comprising cross linking the unsaturated elastomer.

36. The method as defined in claim 31 , further comprising adding a deblocking agent, wherein the deblocking agent is responsive to activate the chemically-protected sulfur groups.

37. A tire formed from a composition comprising the reaction product of a linear polyorganosiloxane comprising an alkene group, and a thio acid having a structure defined by formula (IV):

((R 27 OC(═O)) t —(L) j ) k —(Q) z J(═E)SH  (IV)

wherein R 27 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical; L is independently at each occurrence a monovalent group or a polyvalent group that is derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

Q is oxygen, sulfur, or an NR 29 group, wherein R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

J is carbon, sulfur, phosphorus, or a sulfinyl group;

E is oxygen or sulfur;

S comprises one or more sulfur atoms;

“t” is an integer that is equal to 0, 1, 2, 3, 4, or 5; “j” is equal to 0 or 1, “k” is equal to 1 if J is carbon, sulfur or sulfinyl, “k” is 2 if J is phosphorus; and “z” is equal to 0, 1, or 2, wherein the reaction product is a sulfur-functional linear polyorganosiloxane comprising a chemically-protected sulfur group does not further comprise a functional group capable of chemical coupling with a filler surface.

38. The tire as defined in claim 37 , wherein the reaction product comprises one or more of a thiocarboxylate ester; dithiocarboxylate; thiocarbonate ester; dithiocarbonate ester; trithiocarbonate ester; thiosulfonate ester; thiosulfate ester; thiosulfamate ester; thiosulfinate ester; thiosulfite ester; thiosulfimate ester; thiophosphate ester; dithiophosphate ester; trithiophosphate ester; tetrathiophosphate ester; thiophosphamate ester; dithiophosphamate ester; thiophosphoramidate ester; dithiophosphoramidate ester; or trithiophosphoramidate ester.

39. A method for producing a tire composition, comprising: producing a sulfur-functional linear polyorganosiloxane comprising a chemically-protected sulfur group by reacting a linear polyorganosiloxane comprising an alkene group, and a thio acid and having a structure as defined in formula (IV):

((R 27 OC(═O)) t —(L) j ) k —(Q) z J(═E)SH  (IV)

wherein R 27 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical; L is independently at each occurrence a monovalent group or a polyvalent group that is derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

Q is oxygen, sulfur, or an NR 29 group, wherein R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

J is carbon, sulfur, phosphorus, or a sulfinyl group;

E is oxygen or sulfur;

S comprises one or more sulfur atoms;

“t” is an integer that is equal to 0, 1, 2, 3, 4, or 5; “j” is equal to 0 or 1, “k” is equal to 1 if J is carbon, sulfur or sulfinyl, “k” is 2 if J is phosphorus; and “z” is equal to 0, 1, or 2; and

mixing the sulfur-functional linear polyorganosiloxane with an unsaturated elastomer,

wherein the sulfur-functional linear polyorganosiloxane comprising a chemically-protected sulfur group is chosen from those of formulae (I), (II), and (III);

wherein A is a polyvalent radical ((R 27 OC(═O)) t —(L) j ) k —(Q) z J(═E);

R 1 -R 27 are independently at each occurrence a hydrogen atom, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

G is a bond, a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical;

R 28 is a hydroxyl group, a halogen, a silyl alkoxy group, an alkoxy group, or an aryloxy group;

S is one or more sulfur atoms;

L is independently at each occurrence a monovalent or a polyvalent group derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

Q is oxygen, sulfur or an NR 29 group, R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

J is carbon, sulfur, phosphorus, or a sulfinyl group;

E is oxygen or sulfur;

“m” and “n” are independently equal to 0 or are an integer greater than 0; “p” is greater than 0; “t” is an integer that is equal to 0, 1, 2, 3, 4, or 5; “j” is equal to 0 or 1; “k” is equal to 1 if J is carbon, sulfur or sulfinyl, “k” is 2 if J is phosphorus; and “z” is an integer that is equal to 0, 1, or 2.

40. The method as defined in claim 39 , further comprising cross linking the unsaturated elastomer.

41. A tire formed from a composition comprising the reaction product of a linear polyorganosiloxane comprising an alkene group, and a thio acid having a structure defined by formula (IV):

((R 27 OC(═O)) t —(L) j ) k —(Q) z J(═E)SH  (IV)

wherein R 27 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical; L is independently at each occurrence a monovalent group or a polyvalent group that is derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

Q is oxygen, sulfur, or an NR 29 group, wherein R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

J is carbon, sulfur, phosphorus, or a sulfinyl group;

E is oxygen or sulfur;

S comprises one or more sulfur atoms;

“t” is an integer that is equal to 0, 1, 2, 3, 4, or 5; “j” is equal to 0 or 1, “k” is equal to 1 if J is carbon, sulfur or sulfinyl, “k” is 2 if J is phosphorus; and “z” is equal to 0, 1, or 2,

wherein the reaction product includes a sulfur-functional linear polyorganosiloxane, comprising a chemically-protected sulfur group, chosen from those of formulae (I), (II), and (III);

wherein A is a polyvalent radical ((R 27 OC(═O)) t —(L) j ) k —(Q) z J(═E);

R 1 -R 27 are independently at each occurrence a hydrogen atom, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

G is a bond, a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical;

R 28 is a hydroxyl group, a halogen, a silyl alkoxy group, an alkoxy group, or an aryloxy group;

S is one or more sulfur atoms;

L is independently at each occurrence a monovalent or a polyvalent group derived by substitution of an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

Q is oxygen, sulfur or an NR 29 group, R 29 is an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

J is carbon, sulfur, phosphorus, or a sulfinyl group;

E is oxygen or sulfur;

“m” and “n” are independently equal to 0 or are an integer greater than 0; “p” is greater than 0; “t” is an integer that is equal to 0, 1, 2, 3, 4, or 5; “j” is equal to 0 or 1; “k” is equal to 1 if J is carbon, sulfur or sulfinyl, “k” is 2 if J is phosphorus; and “z” is an integer that is equal to 0, 1, or 2.

Assignments (8)