Rubber composition, process of preparing same and articles made therefrom
View Patent ↗There is provided herein a rubber composition comprising (a) at least one rubber component; (b) at least one silane-reactive filler; (c) optionally, at least one activating agent and, (d) at least one silane of the general Formula (1): [X 1 X 2 X 3 Si—] d (G) a [—Y—(CR 3-e -Z e ) b ] c (1) wherein X 1 is selected hydrolyzable groups; X 2 and X 3 are independently hydrocarbons or selected hydrolyzable groups; G is a hydrocarbon group of from 1 to 18 carbon atoms that can optionally contain at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphous and silicon; each Y can independently be an unsaturated group; each Z can independently be a halogen atom; and, each R can independently be hydrogen, alkyl, alkenyl, aryl or aralkyl. There is also provided a process of preparing a rubber composition comprising mixing (a), (b), optionally (c), and (d). There are also provided articles (e.g., tires) made from the rubber composition.
1. A rubber composition comprising:
(a) at least one rubber component;
(b) at least one silane-reactive filler;
(c) optionally, at least one activating agent; and,
(d) at least one hydrolyzable silane of the general Formula (1):
[X 1 X 2 X 3 Si—] d (G) a [—Y—(CR 3-e -Z e ) b ] c (1)
wherein
each occurrence of X 1 is independently selected from a hydrolyzable group consisting of Cl—, Br—, I—, R 1 O—, R 1 (═O)O—, R 1 2 C═NO—, and R 1 2 NO—, wherein each R 1 is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl, alkenyl, aryl and aralkyl groups wherein each R 1 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur;
each occurrence of X 2 and X 3 is independently selected from X 1 and R 2 — groups wherein each R 2 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl groups wherein each R 2 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur;
each occurrence of G is independently a divalent or polyvalent hydrocarbon group of from 1 to 18 carbon atoms that can optionally contain at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphorous and silicon;
each occurrence of Y is independently an unsaturated group;
each occurrence of Z is independently a halogen atom selected from the groups consisting of F—, Cl—, Br—and I—;
each occurrence of R is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl or aralkyl wherein each R, other than hydrogen, contains from 1 to 30 carbon atoms; and
each occurrence of subscripts a, b and c are integers independently given by a is 1; b is an integer of from 1 to about 5; c is an integer of from 1 to 3, with the provisos that when a is zero, c is 1, and when a is 1, c is an integer of from 1 to 3; d is an integer of from 1 to 5 and e is an integer of from 1 to 3.
2. The rubber composition of claim 1 wherein rubber component (a) is an organic polymer selected from the group consisting of at least one diene based elastomer or rubber.
3. The rubber composition of claim 1 wherein rubber component (a) is made from monomers selected from the group consisting of conjugated dienes, vinyl aromatic compounds and combinations thereof.
4. The rubber composition of claim 1 wherein rubber component (a) is a sulfur curable rubber.
5. The rubber composition of claim 1 wherein rubber component (a) is at least one selected from the group consisting of natural rubber, synthetic polyisoprene, polybutadiene, copolymers of butadiene, copolymers of isoprene, solution styrene-butadiene rubber, emulsion styrene-butadiene rubber, ethylene-propylene terpolymers, and acrylonitrile-butadiene rubber.
6. The rubber composition of claim 1 wherein the silane-reactive filler (b) is at least one metal oxide.
7. The rubber composition of claim 1 wherein the silane-reactive filler (b) is at least one selected from the group consisting of silica, alumina, titanium dioxide, aluminosilicate materials and alumina siliceous materials.
8. The rubber composition of claim 1 wherein the silane-reactive filler (b) is pyrogenic and/or precipitated silica.
9. The rubber composition of claim 1 wherein the silane-reactive filler (b) is a combination of silica and carbon black.
10. The rubber composition of claim 1 wherein the [Y—(CR 3-e —Z e ) b ] moiety of the silane (d) of general Formula (1) is selected from the group consisting of −CH 2 ═CH—CH 2 —Z; —C≡C—CH 2 —Z; and —Ar—CH 2 —Z, where Z is a halogen atom and Ar represents an aromatic ring.
11. A rubber composition comprising:
(a) at least one rubber component;
(b) at least one silane-reactive filler;
(c) optionally, at least one activating agent; and,
(d) at least one hydrolyzable silane;
wherein the silane (d) is at least one silane selected from the group consisting of 3-chloroprop-1-ynyltriethoxysilane, 3-chloroprop-1-enyltriethoxysilane, 3-chloroprop-1-enyltrimethoxysilane, 3-chloroprop-1-enylmethyldiethoxysilane, 3-chloroprop-1-enyldimethylethoxysilane, 3-chloroprop-1-enyltributoxysilane, 3-bromoprop-1-enyltriethoxysilane, 3-bromoprop-1-enyltrimethoxysilane, 3-bromoprop-1-enyltributoxysilane, 3-iodoprop-1-enyltriethoxysilane, 3-iodoprop-1-enyltrimethoxysilane, 3-iodoprop-1-enyltributoxysilane, (p-chloromethylphenylethyl)triethoxysilane, (p-dichloromethylphenylethyl)triethoxysilane, (p-trichloromethylphenylethyl)triethoxysilane, (p-chloromethylphenylethyl)methyldiethoxysilane, (p-chloromethylphenylethyl)dimethylethoxysilane, (p-α-chloroethylphenylethyl)triethoxysilane, (p-α-chloropropylphenylethyl)triethoxysilane, (p-chloromethylphenylethyl)trimethoxysilane, (p-α-chloroethylphenylethyl)trimethoxysilane, (m-bromomethylphenylethyl)triethoxysilane, (m-α-bromoethylphenylethyl)triethoxysilane, (m-α-bromopropylphenylethyl)triethoxysilane, (m-bromomethylphenylethyl)trimethoxysilane, (m-α-bromoethylphenylethyl)trimethoxysilane, (m-α-bromopropylphenylethyl)trimethoxysilane, (m-bromomethylphenylethyl)tributoxysilane, (m-α-bromoethylphenylethyl)tributoxysilane, (m-α-bromopropylphenylethyl)tributoxysilane, (m-iodomethylphenylethyl)triethoxysilane, (m-α-iodoethylphenylethyl)triethoxysilane, (m-α-iodopropylphenylethyl)triethoxysilane, (m-iodomethylphenylethyl)trimethoxysilane, (m-α-iodoethylphenylethyl)trimethoxysilane, (m-α-iodopropylphenylethyl)trimethoxysilane, (m-iodomethylphenylethyl)tributoxysilane, (m-α-iodoethylphenylethyl)tributoxysilane, (m-αt-iodopropylphenylethyl)tributoxysilane, 2, 2-bis-(triethoxysilyl)-1-(p-chloromethylphenyl)ethane, 2, 3-bis-(triethoxysilyl)-1-(p-chloromethylphenyl)propane, (CH 3 CH 2 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CH═CHCH 2 Cl, and mixtures thereof.
12. The rubber composition of claim 1 wherein the rubber composition comprises the mixture and/or reaction product of (a), (b), optionally (c) and (d).
13. The rubber composition of claim 1 wherein silane (d) bonds to the silane reactive filler (b) through one functionality and to the rubber component (a) through a different functionality.
14. A process for preparing a rubber composition comprising mixing
(a) at least one rubber component; (p-α-chloropropylphenylethyl)trimethoxysilane, (p-chloromethylphenylethyl)tributoxysilane, (p-α-chloroethylphenylethyl)tributoxysilane, (p-α-chloropropylphenylethyl)tributoxysilane, (p-bromomethylphenylethyl)triethoxysilane, (p-α-bromoethylphenylethyl)triethoxysilane, (p-α-bromopropylphenylethyl)triethoxysilane, (p-bromomethylphenylethyl)trimethoxysilane, (p-α-bromoethylphenylethyl)trimethoxysilane, (p-α-bromopropylphenylethyl)trimethoxysilane, (p-bromomethylphenylethyl)tributoxysilane, (p-α-bromoethylphenylethyl)tributoxysilane, (p-α-bromopropylphenylethyl)tributoxysilane, (p-iodomethylphenylethyl)triethoxysilane, (p-α-iodoethylphenylethyl)triethoxysilane, (p-α-iodopropylphenylethyl)triethoxysilane, (p-iodomethylphenylethyl)trimethoxysilane, (p-α-iodoethylphenylethyl)trimethoxysilane, (p-α-iodopropylphenylethyl)trimethoxysilane, (p-iodomethylphenylethyl)tributoxysilane, (p-α-iodoethylphenylethyl)tributoxysilane, (p-α-iodopropylphenylethyl)tributoxysilane. (m-chloromethylphenylethyl)triethoxysilane, (m-α-chloroethylphenylethyl)triethoxysilane, (m-α-chloropropylphenylethyl)triethoxysilane, (m-chloromethylphenylethyl)trimethoxysilane, (m-α-chloroethylphenylethyl)trimethoxysilane, (m-α-chloropropylphenylethyl)trimethoxysilane, (m-chloromethylphenylethyl)tributoxysilane, (m-α-chloroethylphenylethyl)tributoxysilane, (m-α-chloropropylphenylethyl)tributoxysilane,
(b) at least one silane-reactive filler;
(c) optionally, at least one activating agent; and,
(d) at least one hydrolyzable silane of the general Formula (1):
[X 1 X 2 X 3 Si—] d (G) a [—Y—(CR 3-e —Z e )b] c (1)
wherein
each occurrence of X 1 is independently selected from a hydrolyzable group consisting of Cl—, Br—, I—, R 1 O—, R 1 (═O)O—, R 1 2 C═NO—, and R 1 2 NO—, wherein each R 1 is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl, alkenyl, aryl and aralkyl groups wherein each R 1 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur;
each occurrence of X 2 and X 3 is independently selected from X 1 and R 2 — groups wherein each R 2 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl groups wherein each R 2 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur;
each occurrence of G is independently a divalent or polyvalent hydrocarbon group of from 1 to 18 carbon atoms that can optionally contain at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphorous and silicon;
each occurrence of Y is independently an unsaturated group;
each occurrence of Z is independently a halogen atom selected from the groups consisting of F—, Cl—, Br— and I—;
each occurrence of R is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl or aralkyl wherein each R, other than hydrogen, contains from 1 to 30 carbon atoms; and
each occurrence of subscripts a, b and c are integers independently given by a is 1; b is an integer of from 1 to about 5; c is an integer of from 1 to 3, with the provisos that when a is zero, c is 1, and when a is 1, c is an integer of from 1 to 3; d is an integer of from 1 to 5 and e is an integer of from 1 to 3; wherein (a), (b), optionally (c) and (d) are present in an effective amount.
15. The process of claim 14 wherein rubber component (a) is an organic polymer selected from the group consisting of at least one diene based elastomer or rubber.
16. The process of claim 14 wherein rubber component (a) is made from monomers selected from the group consisting of conjugated dienes, vinyl aromatic compounds and combinations thereof.
17. The process of claim 14 wherein rubber component (a) is a sulfur curable rubber.
18. The process of claim 14 wherein rubber component (a) is at least one selected from the group consisting of natural rubber, synthetic polyisoprene, polybutadiene, copolymers of butadiene, copolymers of isoprene, solution styrene-butadiene rubber, emulsion styrene-butadiene rubber, ethylene-propylene terpolymers, and acrylonitrile-butadiene rubber.
19. The process of claim 14 wherein the silane-reactive filler (b) is at least one metal oxide.
20. The process of claim 14 wherein the silane-reactive filler (b) is at least one selected from the group consisting of silica, alumina, titanium dioxide, aluminosilicate materials and alumina siliceous materials.
21. The process of claim 14 wherein the silane-reactive filler (b) is pyrogenic and/or precipitated silica.
22. The process of claim 14 wherein the silane-reactive filler (b) is a combination of silica and carbon black.
23. The process of claim 14 wherein the [—Y—(CR 3-e —Z e ) b ] moiety of the silane (d) of general Formula (1) is selected from the group consisting of —CH 2 ═CH—CH 2 —Z; —C≡C—CH 2 —Z; and —Ar—CH 2 —Z, where Z is a halogen atom and Ar represents an aromatic ring.
24. A process for preparing a rubber composition comprising mixing
(a) at least one rubber component;
(b) at least one silane-reactive filler;
(c) optionally, at least one activating agent; and,
(d) at least one hydrolyzable silane
wherein the silane (c) is at least one silane selected from the group consisting of 3-chloroprop-1-ynyltriethoxysilane, 3-chloroprop-1-enyltriethoxysilane, 3-chloroprop-1-enyltrimethoxysilane, 3-chloroprop-1-enylmethyldiethoxysilane, 3-chloroprop-1-enyldimethylethoxysilane, 3-chloroprop-1-enyltributoxysilane, 3-bromoprop-1-enyltriethoxysilane, 3-bromoprop-1-enyltrimethoxysilane, 3-bromoprop-1-enyltributoxysilane, 3-iodoprop-1-enyltriethoxysilane, 3-iodoprop-1-enyltrimethoxysilane, 3-iodoprop-1-enyltributoxysilane, (p-chloromethylphenylethyl)triethoxysilane, (p-dichloromethylphenylethyl)triethoxysilane, (p-trichloromethylphenylethyl)triethoxysilane, (p-chloromethylphenylethyl)methyldiethoxysilane, (p-chloromethylphenylethyl)dimethylethoxysilane, (p-α-chloroethylphenylethyl)triethoxysilane, (p-α-chloropropylphenylethyl)triethoxysilane, (p-chloromethylphenylethyl)trimethoxysilane, (p-α-chloroethylphenylethyl)trimethoxysilane, (p-α-chloropropylphenylethyl)trimethoxysilane, (p-chloromethylphenylethyl)tributoxysilane, (p-α-chloroethylphenylethyl)tributoxysilane, (p-α-chloropropylphenylethyl)tributoxysilane, (p-bromomethylphenylethyl)triethoxysilane, (p-α-bromoethylphenylethyl)triethoxysilane, (p-α-bromopropylphenylethyl)triethoxysilane, (p-bromomethylphenylethyl)trimethoxysilane, (p-α-bromoethylphenylethyl)trimethoxysilane, (p-α-bromopropylphenylethyl)trimethoxysilane, (p-bromomethylphenylethyl)tributoxysilane, (p-α-bromoethylphenylethyl)tributoxysilane, (p-α-bromopropylphenylethyl)tributoxysilane, (p-iodomethylphenylethyl)triethoxysilane, (p-α-iodoethylphenylethyl)triethoxysilane, (p-α-iodopropylphenylethyl)triethoxysilane, (p-iodomethylphenylethyl)trimethoxysilane, (p-α-iodoethylphenylethyl)trimethoxysilane, (p-α-iodopropylphenylethyl)trimethoxysilane, (p-iodomethylphenylethyl)tributoxysilane, (p-α-iodoethylphenylethyl)tributoxysilane, (p-α-iodopropylphenylethyl)tributoxysilane. (m-chloromethylphenylethyl)triethoxysilane, (m-α-chloroethylphenylethyl)triethoxysilane, (m-α-chloropropylphenylethyl)triethoxysilane, (m-chloromethylphenylethyl)trimethoxysilane, (m-α-chloroethylphenylethyl)trimethoxysilane, (m-α-chloropropylphenylethyl)trimethoxysilane, (m-chloromethylphenylethyl)tributoxysilane, (m-α-chloroethylphenylethyl)tributoxysilane, (m-α-chloropropylphenylethyl)tributoxysilane, (m-bromomethylphenylethyl)triethoxysilane, (m-α-bromoethylphenylethyl)triethoxysilane, (m-α-bromopropylphenylethyl)triethoxysilane, (m-bromomethylphenylethyl)trimethoxysilane, (m-α-bromoethylphenylethyl)trimethoxysilane, (m-α-bromopropylphenylethyl)trimethoxysilane, (m-bromomethylphenylethyl)tributoxysilane, (m-α-bromoethylphenylethyl)tributoxysilane, (m-α-bromopropylphenylethyl)tributoxysilane, (m-iodomethylphenylethyl)triethoxysilane, (m-α-iodoethylphenylethyl)triethoxysilane, (m-α-iodopropylphenylethyl)triethoxysilane, (m-iodomethylphenylethyl)trimethoxysilane, (m-α-iodoethylphenylethyl)trimethoxysilane, (m-α-iodopropylphenylethyl)trimethoxysilane, (m-iodomethylphenylethyl)tributoxysilane, (m-α-iodoethylphenylethyl)tributoxysilane, (m-α-iodopropylphenylethyl)tributoxysilane, 2,2-bis-(triethoxysilyl)-1-(p-chloromethylphenyl)ethane, 2,3-bis-(triethoxysilyl)-1-(p-chloromethylphenyl)propane, (CH 3 CH 2 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CH═CHCH 2 Cl, and mixtures thereof.
25. The process of claim 14 wherein the rubber composition comprises the mixture and/or reaction product of (a), (b), optionally (c) and (d).
26. The process of claim 14 wherein silane (d) bonds to the silane-reactive filler (b) through one functionality and to the rubber component (a) through a different functionality.
27. The process of claim 14 further comprising curing the rubber composition.
28. An article of which at least one component is the cured rubber composition of claim 1 .
29. An article of which at least one component is the cured rubber composition of claim 27 .
30. A tire at least one component of which comprises the cured rubber composition of claim 28 .
31. A tire at least one component of which comprises the cured rubber composition of claim 29 .
32. The rubber composition of claim 1 , wherein the silane (d) is pre-mixed or pre-reacted with the silane-reactive filler (b).
33. The rubber composition of claim 32 , wherein the silane-reactive filler (b) is at least one selected from the group consisting of silica, alumina, titanium dioxide, aluminosilicate materials and alumina siliceous materials.
34. The rubber composition of claim 33 , wherein the silane-reactive filler (b) is pyrogenic and/or precipitated silica.
35. The process of claim 14 , wherein the silane-reactive filler (b) and the silane (d) are pre-mixed or pre-reacted prior to mixing with the rubber component (a) and optionally the activating agent (c).