Polyorganosiloxane composition for use in unsaturated elastomer, article made therefrom, and associated method
View Patent ↗A tire composition is provided that may include a sulfur-functional linear polyorganosiloxane and an unsaturated elastomer. The sulfur-functional linear polyorganosiloxane may include a chemically protected sulfur group, which includes a thiocarbamate, a dithiocarbamate, or a derivative or analog of thiocarbamate or dithiocarbamate. Under certain conditions, the sulfur group may react with the unsaturated elastomer. The invention includes embodiments that may relate to methods of making and using the sulfur-functional linear polyorganosiloxane in tire compositions.
1. A tire composition, comprising:
an unsaturated elastomer; and
a sulfur-functional linear polyorganosiloxane comprising a chemically-protected sulfur group capable of reacting with the unsaturated elastomer, wherein the sulfur-functional linear polyorganosiloxane has a formula of (I), (II) or (III):
wherein A is a ((R 27 OC(═O)) t -(L) j ) k -(Q) z J(=E) group;
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 divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical;
R 28 is a hydroxyl group, a halogen atom, 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” is equal to an integer greater than 0; “n” is equal to 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.
2. The composition as defined in claim 1 , wherein the sulfur-functional linear polyorganosiloxane further comprises a functional group capable of coupling with a filler surface.
3. The composition as defined in claim 2 , wherein -G-R 28 is the functional group capable of coupling to a filler surface.
4. The composition as defined in claim 1 , wherein R 28 is one or more of a hydroxyl group, a methoxy group, an ethoxy group, an isopropyloxy group, an isobutoxy group, or an acetoxy group.
5. The 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.
6. The composition as defined in claim 1 , wherein G is one or more of (—CH 2 CH 2 —), (—CH 2 CH 2 CH 2 —), (—CH 2 CH 2 CH 2 CH 2 —), (—CH(CH 3 )—), (—CH 2 CH(CH 3 )—), (—C(CH 3 ) 2 —), (—CH(C 2 H 5 )—), (—CH 2 CH 2 CH(CH 3 )—), (—CH 2 CH(CH 3 )CH 2 —), (—CH 2 CH 2 (C 6 H 4 )CH 2 CH 2 —), diethylene cyclohexane, or 1,2,4-triethylene cyclohexane.
7. The composition as defined in claim 1 , further comprising a filler.
8. The composition as defined in claim 7 , wherein the filler comprises one or both of metal oxide or metal hydroxide.
9. The composition as defined in claim 7 , wherein the filler comprises one or both of carbon or silicon.
10. The composition as defined in claim 9 , wherein the filler comprises carbon black.
11. The composition as defined in claim 7 , wherein the filler comprises one or more of silica, synthetic silicate, natural silicate, or glass fiber.
12. The composition as defined in claim 1 , wherein the unsaturated elastomer comprises natural rubber.
13. The composition as defined in claim 1 , wherein the unsaturated elastomer comprises synthetic rubber.
14. The composition as defined in claim 13 , wherein the synthetic rubber is diene-based.
15. The composition as defined in claim 1 , further comprising a deblocking agent that is capable of activating the chemically-protected sulfur groups.
16. The composition as defined in claim 1 , wherein the unsaturated elastomer is present in an amount greater than about 10 weight percent.
17. The composition as defined in claim 1 , further comprising a curing agent.
18. A vulcanized tire composition comprising a vulcanized product of the composition of claim 17 .
19. The vulcanized rubber composition of claim 18 , having a tensile strength greater than about 19.5 megaPascal according to ASTM D412.
20. The vulcanized rubber composition of claim 18 , having an elongation at break greater than about 400 percent according to ASTM D412.
21. The vulcanized tire composition of claim 18 , having a modulus at 300 percent strain greater than about 7 megaPascal according to ASTM D412.
22. The vulcanized tire composition of claim 18 , having a modulus at 100 percent strain greater than about 1.5 megaPascal according to ASTM D412.
23. The vulcanized tire composition of claim 18 , having a hardness greater than about 56 Shore A according to ASTM 2240.
24. A tire comprising the vulcanized tire composition of claim 18 .
25. 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 —R 28 group bonded to the linear polyorganosiloxane through a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical, d a —R, 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 a C 1 -C 20 aliphatic radical, a C 3 -C 40 cycloaliphatic radical, or a C 3 -C 40 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;
S comprises one or more sulfur atoms;
R 28 is a hydroxyl group, an alkoxy group, or an aryloxy group;
“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 comprises one or more of a thiocarbamate, dithiocarbamate, or a derivative or analog of thiocarbamate or dithiocarbamate.
26. The method as defined in claim 25 , further comprising adding a filler.
27. The method as defined in claim 26 , wherein the sulfur-functional linear polyorganosiloxane comprises a functional group capable of reacting with the filler surface, and the method further comprising coupling the sulfur-functional linear polyorganosiloxane to the filler surface.
28. The method as defined in claim 25 , further comprising adding a curing agent.
29. The method as defined in claim 28 , further comprising cross linking the unsaturated elastomer.
30. The method as defined in claim 25 , further comprising adding a deblocking agent, wherein the deblocking agent is responsive to activate the chemically-protected sulfur groups.
31. A tire formed from a composition comprising the reaction product of a linear polyorganosiloxane comprising an alkene group and a —R 28 group bonded to the linear polyorganosiloxane through a divalent aliphatic radical, a divalent cycloaliphatic radical, or a divalent aromatic radical, 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 a C 1 -C 20 aliphatic radical, a C 3 -C 40 cycloaliphatic radical, or a C 3 -C 40 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 sulfonyl sulfinyl group;
E is oxygen or sulfur;
S comprises one or more sulfur atoms;
R 28 is a hydroxyl group, an alkoxy group, or an aryloxy group;
“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; and “z” is equal to 0, 1, or 2;
wherein the reaction product comprises one or more of a thiocarbamate, dithiocarbamate, or a derivative or analog of thiocarbamate or dithiocarbamate.
32. The tire as defined in claim 31 , wherein the reaction product further comprises one or more of a hydroxyl group, a methoxy group, an ethoxy group, an isopropyloxy group, an isobutoxy group, or an acetoxy group.