Diol-derived organofunctional silane and compositions containing same
View Patent ↗Described are diol-derived organofunctional silanes in which the silanes contain cyclic and bridged alkoxy groups derived from hydrocarbon-based diols and methods for the preparation of the silanes. Also described are rubber compositions containing the diol-derived organofunctional silanes, methods for the preparation of the rubber compositions and articles of manufacture containing the rubber compositions, in particular, automotive tires and components thereof.
1. A silane of the general formula:
wherein
each occurrence of G is independently a polyvalent group derived from an alkyl, alkenyl, aryl or aralkyl group with G containing from 1 to 30 carbon atoms;
each occurrence of R 10 and R 11 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms;
each occurrence of Y is independently a monovalent organofunctional group chosen from the group consisting of mercapto, acryloxy, methacryloxy, —O—CH 2 —C 2 H 3 O, —C 6 H 9 O, —CR 6 (—O—)CR 4 R 5 , —NH 2 , —NHR 4 , —NR 4 R 5 , —NR 4 -L 1 -NR 5 R 6 , —NR 4 -L l (-NR 5 R 6 ) 2 , —NR 4 -L 1 -NR 5 -L 2 -NR 6 R 7 , —NR 4 -L 1 (-NR 5 R 6 ) 3 , —NR 4 -L 1 -NR 5 -L 2 -NR 6 -L 3 -NR 7 R 8 , and —NR 4 -L 1 -N(-L 2 NR 5 R 6 ) 2 , wherein each occurrence of L 1 , L 2 and L 3 is selected independently from the meanings given for G and each occurrence of R 4 , R 5 , R 6 , R 7 and R 8 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms;,
each occurrence of X is independently selected from the group consisting of —Cl, —Br, R 1 O—, R 2 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO—, R 1 R 2 N—, —R 1 , -(OSiR 1 R 2 ) t (OSiR 1 R 2 R 3 ), and —O(R 10 CR 11 ) f OH, wherein each occurrence of R 1 , R 2 , and R 3 is independently selected from the group consisting of straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, aralkyl group containing from 1 to 20 carbon atoms, and hydrogen;
each occurrence of the subscript f is independently an integer from 1 to 15;
each occurrence of the subscript t is independently an integer from 0 to 50; and
the subscript n is an integer from 3 to 100.
2. The silane of claim 1 wherein G is selected from the group consisting of diethylene cyclohexane, diethylene benzene, phenylene, —(CH 2 ) m - wherein m is an integer from 1 to 12, and —CH 2 (CH 2 ) q CH(CH 3 )- wherein q is an integer from zero to 17.
3. The silane of claim 1 wherein each occurrence of —O(R 10 CR 11 ) f O— is independently selected from divalent alkoxy groups derived from 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol and 2-methyl-2,4-pentanediol.
4. The silane of claim 1 wherein R 10 and R 11 is each independently selected from a group consisting of hydrogen, methyl, ethyl and propyl.
5. The silane of claim 1 wherein Xis R 1 O— or —O(R 10 CR 11 ) f OH, wherein R 1 is independently selected from the group consisting of straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, aralkyl group containing from 1 to 20 carbon atoms and hydrogen; each occurrence of R 10 and R 11 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms; and each occurrence of the subscript f is independently an integer from 1 to 15.
6. A silane of the general formula:
wherein
each occurrence of G is independently a polyvalent group derived from an alkyl, alkenyl, aryl or aralkyl group with G containing from 1 to 30 carbon atoms;
each occurrence of R 10 and R 11 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms;
each occurrence of Y is independently a monovalent organofunctional group chosen from the group consisting of —OH, —NR 4 C(═O)OR 5 , —OC(═O)NR 4 R 5 , —NR 4 C(═O)SR 5 , —SC(═O)NR 4 R 5 , —NR 4 C(═S)OR 5 , —OC(═S)NR 4 R 5 , —NR 4 C(═S)SR 5 , —SC(═S)NR 4 R 5 , maleimide, maleate, substituted maleate, fumurate, substituted fumurate, —CN, citraconimide, —OCN, —N═C═O, —SCN, —N═C═S, —OR 4 —SR 4 , —S—SR 4 , —S—S—SR 4 , —S—S—S—SR 4 ,—S—S—S—S—SR 4 , —S—S—S—S—S—SR 4 , —S x R 4 , —SC(═S)OR 4 , —SC(═S)SR 4 , —SC(═O)SR 4 , —NR 4 C(═O)NR 5 R 6 , —NR 4 C(═S)NR 5 R 6 , R 4 C(═O)NR 5 —, —C(═O)NR 4 R 5 —, R 4 C(═S)NR 4 —, melamine and cyanurato wherein each occurrence of R 4 , R 5 , and R 6 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms; and
each occurrence of X is independently selected from the group consisting of —Cl, —Br, R 1 O—, R 2 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO—, R 1 R 2 N—, —R 1 , —(OSiR 1 R 2 ) t (OSiR 1 R 2 R 3 ), and —O(R 10 CR 11 ) f OH, wherein each occurrence of R 1 , R 2 , and R 3 is independently selected from the group consisting of straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, aralkyl group containing from 1 to 20 carbon atoms, and hydrogen;
each occurrence of the subscript f is independently an integer from 1 to 15;
each occurrence of the subscript t is independently an integer from 0 to 50; and
the subscript n is an integer from 3 to 100.
7. The silane of claim 6 wherein G is selected from the group consisting of diethylene cyclohexane, diethylene benzene, phenylene, —(CH 2 ) m — wherein m is an integer from 1 to 12 and —CH 2 (CH 2 ) q CH(CH 3 )— wherein q is an integer from zero to 17.
8. The silane of claim 6 wherein each occurrence of —O(R 10 CR 11 ) f O— is independently selected from divalent alkoxy groups derived from 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, and 2-methyl-2,4-pentanediol.
9. The silane of claim 6 wherein X is R 1 O— or —O(R 10 CR 11 ) f OH, wherein R 1 is independently selected from the group consisting of straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, aralkyl group containing from 1 to 20 carbon atoms and hydrogen; each occurrence of R 10 and R 11 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms; and each occurrence of the subscript f is independently an integer from 1 to 15.
10. A silane of the general formula:
wherein
each occurrence of G is independently a polyvalent group derived from an alkyl, alkenyl, aryl or aralkyl group with G containing from 1 to 30 carbon atoms;
each occurrence of R 10 and R 11 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms;
each occurrence of Y is independently a monovalent organofunctional group chosen from the group consisting of mercapto, acryloxy, methacryloxy, —O—CH 2 —C 2 H 3 O, —C 6 H 9 O, —CR 6 (—O—)CR 4 R 5 , —NH 2 , —NHR 4 , —NR 4 R 5 , —NR 4 -L 1 -NR 5 R 6 , —NR 4 -L 1 (-NR 5 R 6 ) 2 , —NR 4 -L 1 -NR 5 -L 2 -NR 6 R 7 , —NR 4 -L 1 (-NR 5 R 6 ) 3 , —NR 4 -L 1 -NR 5 -L 2 -NR 6 -L 3 -NR 7 R 8 , and —NR 4 -L 1 -N(-L 2 NR 5 R 6 ) 2 , wherein each occurrence of L 1 , L 2 and L 3 is selected independently from the meanings given for G and each occurrence of R 4 , R 5 , R 6 , R 7 and R 8 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms;
each occurrence of X is independently selected from the group consisting of —Cl, —Br, R 1 O—, R 2 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO—, R 1 R 2 N—, —R 1 , —(OSiR 1 R 2 ) t (OSiR 1 R 2 R 3 ), and —O(R 10 CR 11 ) f OH, wherein each occurrence of R 1 , R 2 , and R 3 is independently selected from the group consisting of straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, aralkyl group containing from 1 to 20 carbon atoms and hydrogen;
each occurrence of the subscript f is independently an integer from 1 to 15;
each occurrence of the subscript t is independently and integer from 0 to 50; and
the subscript n is an integer from 3 to 100.
11. The silane of claim 10 wherein G is selected from the group consisting of diethylene cyclohexane, diethylene benzene, phenylene, —(CH 2 ) m — wherein m is 1 to 12 and —CH 2 (CH 2 ) q CH(CH 3 )— wherein q is zero to 17.
12. The silane of claim 10 wherein each occurrence of —O(R 10 CR 11 ) f O— is independently selected from divalent alkoxy groups derived from 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol and 2-methyl-2,4-pentanediol.
13. The silane of claim 10 wherein R 10 and R 11 is each independently selected from a group consisting of hydrogen, methyl, ethyl and propyl.
14. The silane of claim 10 wherein X is R 1 O— or —O(R 10 CR 11 ) f OH, wherein R 1 is independently selected from the group consisting of straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, aralkyl group containing from 1 to 20 carbon atoms and hydrogen; each occurrence of R 10 and R 11 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms; and each occurrence of the subscript f is independently an integer from 1 to 15.
15. A silane of the general formula:
wherein
each occurrence of G is independently a polyvalent group derived from an alkyl, alkenyl, aryl or aralkyl group with G containing from 1 to 30 carbon atoms;
each occurrence of R 10 and R 11 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms;
each occurrence of Y is independently a monovalent organofunctional group chosen from the group consisting of —OH, —NR 4 C(═O)OR 5 , —OC(═O)NR 4 R 5 , —NR 4 C(═O)SR 5 , —SC(═O)NR 4 R 5 , —NR 4 C(═S)OR 5 , —OC(═S)NR 4 R 5 , —NR 4 C(═S)SR 5 , —SC(═S)NR 4 R 5 , maleimide, maleate, substituted maleate, fumurate, substituted fumurate, —CN, citraconimide, —OCN, —N═C═O, —SCN, —N═C═S, —OR 4 —SR 4 , —S—SR 4 , —S—S—SR 4 , —S—S—S—SR 4 , —S—S—S—S—SR 4 , —S—S—S—S—S—SR 4 , —S x R 4 , —SC(═S)OR 4 , —SC(═S)SR 4 , —SC(═O)SR 4 , —NR 4 C(═O)NR 5 R 6 , —NR 4 C(═S)NR 5 R 6 , R 4 C(═O)NR 5 —, —C(═O)NR 4 R 5 —, R 4 C(═S)NR 4 —, melamine and cyanurato wherein each occurrence of R 4 , R 5 , and R 6 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms; and
each occurrence of X is independently selected from the group consisting of —Cl, —Br, R 1 O—, R 2 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO—, R 1 R 2 N—, —R 1 , —(OSiR 1 R 2 ) t (OSiR 1 R 2 R 3 ), and —O(R 10 CR 11 ) f OH, wherein each occurrence of R 1 , R 2 , and R 3 is independently selected from the group consisting of straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, aralkyl group containing from 1 to 20 carbon atoms, and hydrogen;
each occurrence of the subscript f is independently an integer from 1 to 15;
each occurrence of the subscript t is independently an integer from 0 to 50; and
the subscript n is an integer from 3 to 100.
16. The silane of claim 15 wherein G is selected from the group consisting of diethylene cyclohexane, diethylene benzene, phenylene, —(CH 2 ) m — wherein m is an integer from 1 to 12 and —CH 2 (CH 2 ) q CH(CH 3 )— wherein q is an integer from zero to 17.
17. The silane of claim 15 wherein each occurrence of —O(R 10 CR 11 ) f O— is independently selected from divalent alkoxy groups derived from 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, and 2-methyl-2,4-pentanediol.
18. The silane of claim 15 wherein X is R 1 O— or —O(R 10 CR 11 ) f OH, wherein R 1 is independently selected from the group consisting of straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, aralkyl group containing from 1 to 20 carbon atoms and hydrogen; each occurrence of R 10 and R 11 is independently a hydrogen, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a monovalent heterocarbon group containing 1 to about 20 carbon atoms; and each occurrence of the subscript f is independently an integer from 1 to 15.
19. A sizing for fiberglass comprising the silane of claim 1 .
20. A sizing for fiberglass comprising the silane of claim 16 .
21. A sizing for fiberglass comprising the silane of claim 10 .
22. A sizing for fiberglass comprising the silane of claim 15 .
23. A rubber composition comprising
(a) at least one sulfur vulcanizable rubber selected from the group consisting of a conjugated diene homopolymer and a copolymer, a copolymer of at least one conjugated diene and aromatic vinyl compound, and mixtures thereof;
(b) at least one particulate filler;
(c) least one silane of claim 1 ; and, optionally, at least one curing agent.
24. A rubber composition comprising
(a) at least one sulfur vulcanizable rubber selected from the group consisting of a conjugated diene homopolymer and a copolymer, a copolymer of at least one conjugated diene and aromatic vinyl compound, and mixtures thereof;
(b) at least one particulate filler;
(c) least one silane of claim 6 ; and, optionally, at least one curing agent.
25. A rubber composition comprising
(a) at least one sulfur vulcanizable rubber selected from the group consisting of a conjugated diene homopolymer and a copolymer, a copolymer of at least one conjugated diene and aromatic vinyl compound, and mixtures thereof;
(b) at least one particulate filler;
(c) east one silane of claim 10 ; and, optionally, at least one curing agent.
26. A rubber composition comprising
(a) at least one sulfur vulcanizable rubber selected from the group consisting of a conjugated diene homopolymer and a copolymer, a copolymer of at least one conjugated diene and aromatic vinyl compound, and mixtures thereof;
(b) at least one particulate filler;
(c) east one silane of claim 15 ; and, optionally, at least one curing agent.
27. The cured rubber composition of claim 23 .
28. The cured rubber composition of claim 24 .
29. The cured rubber composition of claim 25 .
30. The cured rubber composition of claim 26 .