Rubber composition and articles therefrom both comprising mercapto-functional silane
View Patent ↗The disclosure herein relates to organofunctional silanes and mixtures of organofunctional silanes possessing mercaptan and hydrocarbyl and/or heterocarbyl functionality. These silanes reduce or eliminate the generation of volatile organic compounds (VOC's) during use, aid in the processing of filled elastomeric materials and enhance the end-use properties of the filled elastomer. The present disclosure relates to a rubber composition and article comprising these silanes.
1. A rubber composition comprising:
(a) at least one rubber component, (b) at least one particulate filler and (c) at least one mercaptofunctional silane composition comprising at least one organofunctional silane selected from the group consisting of:
(i) mercaptosilane possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,
(ii) hydrocarbyl and/or heterocarbyl silane possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,
(iii) mercaptosilane dimer in which the silicon atoms of the mercaptosilane units are bonded to each other through a bridging dialkoxy group, each silane unit optionally possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,
(iv) hydrocarbyl and/or heterocarbyl silane dimer in which the silicon atoms of the hydrocarbyl and/or heterocarbyl silane units are bonded to each other through a bridging dialkoxy group, each silane unit optionally possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,
(v) silane dimer possessing a mercaptosilane unit the silicon atom of which is bonded to the silicon atom of a hydrocarbyl and/or heterocarbyl silane unit through a bridging dialkoxy group, each silane unit optionally possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,
(vi) mercaptosilane oligomer in which the silicon atoms of adjacent mercaptosilane units are bonded to each other through a bridging dialkoxy group, the terminal mercaptosilane units possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,
(vii) hydrocarbyl and/or heterocarbyl silane oligomer in which the silicon atoms of adjacent hydrocarbyl and/or heterocarbyl silane units are bonded to each other through a bridging dialkoxy group, the terminal mercaptosilane units possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group, and
(viii) silane oligomer possessing at least one mercaptosilane unit and at least one hydrocarbyl and/or heterocarbyl silane unit, the silicon atoms of adjacent silane units being bonded to each other through a bridging dialkoxy group, the terminal silane units possessing at least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group, with the provisio that,
where the composition contains one or more of (i), (iii) and (vi), the composition additionally contains one or more of (ii), (iv), (v), (vii) and (viii), and where the composition contains one or more of (ii), (iv) and (vii), the composition additionally contains one or more of (i), (iii), (v), (vi) and (viii).
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. A process for preparing a rubber composition comprising adding to a rubber composition reaction-forming mixture in an effective amount of at least one mercaptofunctional silane composition of claim 1 .
6. The process of claim 5 wherein rubber composition reaction forming mixture further comprises at least one filler.
7. The process of claim 5 wherein rubber composition reaction-forming mixture further comprises a rubber component.
8. The process of claim 7 wherein the rubber component is an organic polymer selected from the group of at least one diene based elastomer or rubber.
9. The process of claim 7 wherein the rubber component is made from monomers selected from the group consisting of conjugated dienes, vinyl aromatic compounds and combinations thereof.
10. The process of claim 7 wherein rubber component is a sulfur curable rubber.
11. The rubber composition of claim 1 wherein at least one mercaptofunctional silane composition is at least one selected from the group consisting of structures (10) and (11):
[G 1 -(SiX α u Z β v Z θ w ) s ] m [(HS) r -G 2 -(SiX α u Z β v Z θ w ) s ] n (10)
[[G 3 -(YG 2 ) k Y] j G 2 -(SiX α u Z β v Z θ w ) s ] m [(HS) r -G 2 -(SiX α u Z β v Z θ w ) s ] n (11)
wherein:
each occurrence of Y is independently selected from a polyvalent species (-Q) a [C(=E)] b (A-) c , wherein the atom (E) is attached to an unsaturated carbon atom;
each occurrence of G 1 is independently selected from the group consisting of monovalent and polyvalent groups derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein G 1 can have from 1 to about 30 carbon atoms;
each occurrence of G 2 is independently selected from the group consisting of divalent or polyvalent group derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein G 2 can have from 1 to 30 carbon atoms;
each occurrence of G 3 is independently selected from the group consisting of monovalent and polyvalent groups derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein G 3 can have from 1 to about 30 carbon atoms, with the proviso that if G 3 is monovalent, G 3 can be hydrogen;
each occurrence of X α is independently selected from the group consisting of —Cl, —Br, RO—, RC(═O)O—, R 2 C═NO—, R 2 NO—, R 2 N—, —R, (HO) d-1 G 4 O—, HO(CR 0 2 ) f O—, and HO(CR 0 2 CR 0 2 O) e — wherein each R is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl that can or can not contain unsaturation, alkenyl groups, aryl groups, and aralkyl groups, wherein each R, other than hydrogen, contains from 1 to 18 carbon atoms, G 4 is independently a substituted hydrocarbon group of from about 2 to about 15 carbon atoms or a substituted heterocarbon group of from about 4 to 15 carbon atoms and contains one or more etheric oxygen atoms, R 0 is independently given by one of the members listed for R, f is from about 2 to about 15, and e is from about 2 to about 7;
each occurrence of Q is independently selected from the group consisting of oxygen, sulfur, and (—NR—) and with the proviso that when Q is sulfur, b is 0;
each occurrence of A is independently selected from the group consisting of oxygen, sulfur, and (—NR—) and with the proviso that when A is sulfur, b is 0;
each occurrence of E is independently selected from the group consisting of oxygen, sulfur, and (—NR—);
each occurrence of Z β , which forms a bridging structure between two silicon atoms, is independently selected from the group consisting of, [—OG 4 (OH) d-2 O—] 0.5 , [—O(CR 0 2 CR 0 2 O) e —] 0.5 and [—O(R 0 CR 0 ) f O—] 0.5 , wherein each occurrence of R 0 is independently given by one of the members listed above for R; and, each occurrence of G 4 is independently selected form the group consisting of a substituted hydrocarbon group from 2 to 15 carbon atoms or a substituted hetercarbon from 4 to 15 carbon atoms and contain one or more etheric oxygen atoms;
each occurrence of Z θ , which forms a cyclic structure with a silicon atom, is independently given by —OG 4 (OH) d-2 O—, —O(CR 0 2 CR 0 2 O) f — and —O(R 0 CR 0 ) f O— wherein each occurrence of R 0 is independently given by one of the members listed above for R;
each occurrence of the subscripts, a, b, c, d, e, f, j, k, m, n, r, s, u, v, and w are integers independently given by a is 0 or 1; b is 0 or 1; c is 0 or 1; d is from about 2 to about 8; e is from about 2 to about 7; f is from about 2 to about 15; j is from 1 to about 3; k is from 0 to about 15; m is from about 1 to about 20; n is from about 1 to about 20; r is from 1 to about 3; and s is from 1 to about 3; u is from 0 to 3; v is from 0 to 3; w is from 0 to about 1; with the proviso that u+v+2w=3; and with the proviso that the each of the above structures (10) and/or (11) contains at least one hydrolysable group, Z β or Z θ .
12. The rubber composition of claim 11 wherein rubber component (a) is an organic polymer selected from the group of at least one diene based elastomer or rubber.
13. The rubber composition of claim 11 wherein rubber component (a) is made from monomers selected from the group consisting of conjugated dienes, vinyl aromatic compounds and combinations thereof.
14. The rubber composition of claim 11 wherein rubber component (a) is a sulfur curable rubber.
15. The rubber composition of claim 1 wherein mercaptofunctional silane (a) is selected from the group consisting of 3-{4-methyl-2-[2-(4-methyl-2-pentyl-[1,3,2]dioxasilolan-2-yloxy)-propoxy]-[1,3,2]dioxasilolan-2-yl}-propane-1-thiol; 3-{2-[2-(2-methyl-[1,3,2]dioxasilolan-2-yloxy)-ethoxy]-[1,3,2]dioxasilolan-2-yl}-propane-1-thiol; mixture of 3-[2-(3-mercapto-propyl)-[1,3,2]dioxasilinan-2-yloxy]-propan-1-ol and 3-(2-butyl-[1,3,2]dioxasilinan-2-yloxy)-propan-1-ol; 4-{2-[3-(2-butyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-[1,3,2]dioxasilinan-2-yl}-butane-1-thiol; 4-[2-(3-{2-[3-(2-methoxy-ethoxy)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-butane-1-thiol; 4-[5-methyl-2-(2-methyl-3-{5-methyl-2-[3-(2-methylamino-ethylamino)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-butane-1-thiol; 2-acetylamino-N-[3-(2-{3-[2-(4-mercapto-butyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-acetamide; (2-{3-[3-(2-{3-[2-(4-mercapto-butyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-ureido}-ethyl)-urea; 4-acetoxy-butyric acid 3-(2-{3-[2-(4-mercapto-butyl)-5,5-dimethyl-[1,3,2]dioxasilinan-2-yloxy]-2,2-dimethyl-propoxy}-5,5-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl ester; carbonic acid 2-[3-(2-{3-[2-(4-mercapto-butyl)-5,5-dimethyl-[1,3,2]dioxasilinan-2-yloxy]-2,2-dimethyl-propoxy}-5,5-dimethyl-[1,3,2]dioxasilinan-2-yl)-propoxycarbonyloxy]-ethyl ester methyl ester; 4-{[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-dimethyl-silanyl}-butane-1-thiol; 4-{[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-diethoxy-silanyl}-butane-1-thiol; 4-[butyl-[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-(4-mercapto-butyl)-silanyloxy]-2-methyl-pentan-2-ol; 4-{(3-hydroxy-2-methyl-propoxy)-(4-mercapto-butyl)-[2-methyl-3-(5-methyl-2-octyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-silanyl}-2-methyl-butan-1-ol; 3-{(3-hydroxy-2-methyl-propoxy)-(4-mercapto-butyl)-[2-methyl-3-(5-methyl-2-octyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-silanyloxy}-2-methyl-propan-1-ol; 4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(4-mercapto-butyl)-silanyl]-2-methyl-butan-1-ol; 3-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(4-mercapto-butyl)-silanyloxy]-2-methyl-propan-1-ol; 3-[{3-[(3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-methyl-octyl-silanyloxy]-3-methyl-butyl}-(3-mercapto-propyl)-silanyloxy]-2-methyl-propoxy}-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propan-1-ol; 4-((3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyl]-2-methyl-butoxy}-octyl-silanyl)-2-methyl-butan-1-ol; 3-((3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyl]-2-methyl-butoxy}-octyl-silanyl)-2-methyl-propan-1-ol; 4-(benzyl-(3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-phenethyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyl]-2-methyl-butoxy}-silanyl)-2-methyl-butan-1-ol; 4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-pent-4-enyl-silanyl]-2-methyl-butan-1-ol; 4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyl]-2-methyl-butan-1-ol; 4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyl]-2-methyl-butan-1-ol; 4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-octyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyl]-2-methyl-butan-1-ol; and combinations thereof.
16. An article of which at least one component is the cured rubber composition of claim 1 .
17. An article of which at least one component is the cured rubber composition of claim 11 .
18. A tire at least one component of which comprises the cured rubber composition of claim 1 .
19. The tire of claim 18 wherein rubber component (a) is an organic polymer selected from the group of at least one diene based elastomer or rubber.
20. The tire of claim 18 wherein rubber component (a) is made from monomers selected from the group consisting of conjugated dienes, vinyl aromatic compounds and combinations thereof.
21. The tire of claim 18 wherein rubber component (a) is a sulfur curable rubber.
22. A tire at least one component of which comprises the cured rubber composition of claim 11 .
23. The tire of claim 22 wherein rubber component (a) is an organic polymer selected from the group of at least one diene based elastomer or rubber.
24. The tire of claim 22 wherein rubber component (a) is made from monomers selected from the group consisting of conjugated dienes, vinyl aromatic compounds and combinations thereof.
25. The tire of claim 22 wherein rubber component (a) is a sulfur curable rubber.