Rubber composition for a tire comprising a coupling agent having a polythiosulfenamide function
View Patent ↗An elastomeric composition usable for the manufacture of tires, based on at least (i) a diene elastomer, (ii) an inorganic filler as reinforcing filler and (iii), as (inorganic filler/diene elastomer) coupling agent, a polysilylated organosilicon compound which is at least bifunctional and can be grafted onto the elastomer by means of a sulfur group having a polythiosulfenamide function, of formula: ≡Si—A—S x —NR 1 R 2 , (I) in which: A is a divalent bond group, whether straight-chain or branched, which makes it possible to join the polythiosulfenamide group to a first silicon atom of the organosilicon compound; x is an integer or fractional number of from 2 to 4; R 1 represents hydrogen, a monovalent hydrocarbon group, or R 2 ; and R 2 represents the grouping: —B—Si≡, in which: B is a divalent bond group, whether straight-chain or branched; Si represents a second silicon atom of the organosilicon compound. The invention also concerns tires and tire treads comprising a composition of this type.
1. A tire comprising an elastomeric composition based on a diene elastomer, an inorganic filler as reinforcing filler and a coupling agent comprising a polysilylated organosilicon compound which is at least bifunctional and is grafted on to the elastomer by means of a sulfur group having a polythiosulfenamide function, of formula:
≡Si-A-S x —NR 1 R 2 , (I)
in which:
A is a straight-chain or branched divalent bond group, which is capable of joining the polythiosulfenamide group to a first silicon atom of the organosilicon compound;
x is an integer or fractional number of from 2 to 4;
R 1 represents hydrogen, a monovalent hydrocarbon group or R 2 ;
R 2 represents the grouping:
—B—Si≡,
in which:
B is a straight-chain or branched divalent bond group;
Si represents a second silicon atom of the organosilicon compound.
2. The tire according to claim 1 , wherein R 1 is selected from the group consisting of hydrogen, C 1 -C 8 alkyls, C 5 -C 10 cycloalkyls, C 6 -C 18 aryls, (C 6 -C 18 )aryl-(C 1 -C 8 )alkyls, and R 2 .
3. The tire according to claim 2 , wherein R 1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, benzyl, cyclohexyl, phenyl, and R 2 .
4. The tire according to claim 1 , wherein R 2 represents the grouping:
—B—SiR 3 (3-a) (OR 4 ) a ,
in which:
R 3 represents a monovalent hydrocarbon group;
R 4 represents hydrogen or a monovalent hydrocarbon group, which is identical to or different from R 3 , and
a is an integer equal to 1, 2 or 3.
5. The tire according to claim 4 , wherein the radicals R 3 and R 4 are selected from the group consisting of C 1 -C 8 alkyls, C 5 -C 10 cycloalkyls, and phenyl.
6. The tire according to claim 5 , wherein the radicals R 3 and R 4 are C 1 -C 4 alkyls.
7. The tire according to claim 1 , wherein A and B, which are identical or different, represent a group consisting of carbon, hydrogen and optionally one or more heteroatoms, and comprising from 1 to 18 carbon atoms.
8. The tire according to claim 7 , wherein A and B, which are identical or different, are selected from the group consisting of C 1 -C 18 alkylenes and C 6 -C 12 arylenes.
9. The tire according to claim 8 , wherein the sulfur group satisfies the formula:
≡Si-Z-S x —NR 1 -Z-Si≡, (II)
wherein the groupings Z, which are identical or different, represent a C 1 -C 8 alkylene.
10. The tire according to claim 8 , wherein the sulfur group satisfies the formula:
≡Si-Z-S x —NR 1 —S y -Z-Si≡, (III)
wherein the groupings Z, which are identical or different, represent a C 1 -C 8 alkylene, and y, which is identical to or different from x, is an integer or fractional number from 2 to 4.
11. The tire according to claim 1 , wherein the diene elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
12. The tire according to claim 1 , wherein said composition comprises between 10 and 200 phr (parts by weight per hundred parts of elastomer) of the inorganic filler.
13. The tire according to claim 1 , wherein the quantity of coupling agent is between 1 and 20 phr.
14. The tire according to claim 1 , wherein the organosilicon compound is a silane-polythiosulfenamide of formula:
(R 6 O) b R 5 (3-b) Si-A-S x —NR 1 —B—SiR 3 (3-a) (OR 4 ) a , (IV)
in which:
R 5 represents a monovalent hydrocarbon group;
R 6 hydrogen or a monovalent hydrocarbon group, which is identical to or different from R 5 ;
b is an integer equal to 1, 2 or 3; and
R 5 , R 6 and b are, respectively, identical to or different from R 3 , R 4 and a.
15. The tire according to claim 14 , wherein the silane satisfies the formula:
(R 6 O) b R 5 (3-b) Si-Z-S x —NR 1 -Z-SiR 3 (3-a) (OR 4 ) a , (V)
in which the groupings Z, which are identical or different, represent a C 1 -C 4 alkylene, the radicals R 3 , R 4 , R 5 and R 6 representing a C 1 -C 3 alkyl.
16. The tire according to claim 15 , wherein Z is propylene, and R 3 , R 4 , R 5 and R 6 are selected from the group consisting of methyl and ethyl.
17. The tire according to claim 14 , wherein the silane satisfies the symmetrical formula:
[(R 4 O) a R 3 (3-a) Si-Z-S x —] 2 NR 1 (VII)
18. The tire according to claim 17 , wherein Z is propylene, and R 3 , R 4 , R 5 and R 6 are selected from among methyl and ethyl.
19. The tire according to claim 15 , wherein x is an integer or fractional number of from 2 to 3.
20. The tire according to claim 19 , wherein x is equal to 2.
21. The tire according to claim 14 , wherein the silane satisfies the formula:
(R 6 O) b R 5 (3-b) Si-Z-S x —NR 1 —S y -Z-SiR 3 (3-a) (OR 4 ) a (VI)
in which the groupings Z, which are identical or different, represent a C 1 -C 4 alkylene, the radicals R 3 , R 4 , R 5 and R 6 represent a C 1 -C 3 alkyl, and y, which is identical to or different from x, is an integer or fractional number of from 2 to 4.
22. The tire according to claim 21 , wherein Z is propylene, and R 3 , R 4 , R 5 and R 6 are selected from the group consisting of methyl and ethyl.
23. The tire according to claim 21 , wherein x and y are integers or fractional numbers of from 2 to 3.
24. The tire according to claim 23 , wherein x and y are equal to 2.
25. The tire according to claim 14 , wherein R 1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, hexyl, benzyl, cyclohexyl and phenyl.
26. The tire according to claim 1 , wherein the inorganic filler is silica.
27. The tire according to claim 1 having a tread, wherein said elastomeric composition is present in the tread of the tire.
28. The tire according to claim 9 having a tread, wherein said elastomeric composition is present in the tread of the tire.
29. The tire according to claim 10 having a tread, wherein said elastomeric composition is present in the tread of the tire.
30. The tire according to claim 14 having a tread, wherein said elastomeric composition is present in the tread of the tire.
31. The tire according to claim 15 having a tread, wherein said elastomeric composition is present in the tread of the tire.
32. The tire according to claim 17 having a tread, wherein said elastomeric composition is present in the tread of the tire.
33. The tire according to claim 21 having a tread, wherein said elastomeric composition is present in the tread of the tire.