IP Library › Granted Patent US 7,960,576

Granted Patent B2

US 7,960,576 · App. 11/104,103 · Granted Jun 14, 2011

Diol-derived organofunctional silane and compositions containing same

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Quick Facts

Patent No.: US 7,960,576
App. No.: 11/104,103
Granted: Jun 14, 2011
Kind: B2

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Abstract

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.

Claims (214)

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, —CR 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; and

each occurrence of the subscript f is independently an integer from 1 to 15.

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 1 to 12 and —CH 2 (CH 2 ) q CH(CH 3 )— wherein q is 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 and ethyl.

5. The silane of claim 1 wherein R 10 and R 11 is each independently selected from the group consisting of hydrogen, methyl, ethyl and propyl.

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 group obtained from a heterocarbon containing 1 to 20 carbon atoms;

each occurrence of Y is independently a monovalent organofunctional group of 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 , —SJSR 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 the subscript f is independently an integer from 1 to 15.

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 1 to 12 and —CH 2 (CH 2 ) q CH(CH 3 )— wherein q is 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. 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 X is independently selected from the group consisting of R 1 O—, R 1 C(═O)O—, R 1 — and —O(R 10 CR 11 ) f OH, wherein each occurrence of R 10 , R 11 , and R 1 , is independently a hydrogen, an alkyl group, an alkenyl group, an arvl group, or an aralkyl group containing 1 to 20 carbon atoms;

each occurrence of Y is independently a divalent organofunctional group selected from the group consisting of —NH—,

—NR 4 —, —N-L 3 -NR 4 R 5 , —NR 4 -L 3 -NR 5 , —NR-L 1 -NR 4 R 5 , —(—)N-L 3 -NR 5 -L 2 -NR 6 R 7 , —NR 4 -L 1 -N(-)-L 2 -NR 5 R 6 , —NR 4 -L 1 -NR 5 -L 2 -NR 6 —,

—(—)C(—O—)CR 4 R 5 , —CR 5 (—O—)CR 4 —, —O(R 10 CR 11 ) f O—, —(—)NC(═O)OR 5 , —OC(═O)NR 4 —,

—(—)NC(═O)SR 5 , —SC(═O)NR 4 —, —(—)NC(═S)OR 5 , —OC(═S)NR 4 —, —(—) NC(═S)SR 5 ,

—SC(═S)NR 4 —, —O—, maleate, substituted maleate, fumurate, substituted fumurate, —S—, —S—S—,

—S—S—S—, —S—S—S—S—, —S—S—S—S—S—, —S—S—S—S—S—S—, —S x —, —SC(═S)O—, —SC(═S)S—, —SC(═O)S—,

—(—)NC(═O)NR 4 R 5 , —NR 4 C(═O)NR 5 —, —(—)NC(═S)NR 4 R 5 , —NR 4 C(═S)NR 5 —, R 4 C(═O)N(—)—,

—C(═O)NR 4 —, R 4 C(═S)N(—)—, divalent melamine, divalent cyanurato; —(—)C(—O—) CR 4 —,

—(—)NC(═O)O—, —(—)NC(═O)S—, —(—)NC(═S)O—, —(—)NC(═S)S—, —(—)NC(═O)NR 4 —, —(—)NC(═S)NR 4 —, —C(═O)N(−)-, and —C(═S)N(—) 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 , and 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. The silane of claim 9 wherein the organofunctional group Y is selected from the group consisting of —NH—, —NR 4 —, —(—)N-L 3 -NR 4 R 5 , —NR 4 -L 3 -NR 5 —, ((—)NR 4 ) 2 L 1 -NR 4 R 5 —(—)C(—O—)CR 4 R 5 , —S—, —S—S—, —S—S—S—, —S—S—S—S—, —S—S—S—S—S—, —S—S—S—S—S—S—, and —S x .

11. The silane of claim 9 wherein X is a monovalent alkoxy group derived from diols.

12. 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;

(d) at least one curing agent.

13. A rubber composition of comprising

(b) at least one particulate filler;

(d) at least one curing agent wherein the silane is selected from the group consisting of:

2-(2-methyl-2,4 pentanedialkoxyethoxysilyl)-1-propyl amine;

2-(2-methyl-2,4-pentanedialkoxyisopropoxysilyl)-1-propyl mercaptan;

N-[3-(1,3-propanedialkoxyethoxysilyl)-1-propyl]phenylamine;

N-[3-(1,3-propanedialkoxyisopropoxysilyl)-1-propyl]methylamine;

3-(1,2-propanedialkoxyethoxysilyl)-1-propyl glycidyl ether; 3-(1,2-propanedialkoxyisopropoxysilyl)-1-propyl methacrylate;

3-(1,2-ethanedialkoxyethoxysilyl)-1-propyl acrylate;

3-(1,2-ethanedialkoxyisopropoxysilyl)-1-propyl acetate;

3-(neopentyl glycoxyethoxysilyl)-1-propyl amine;

3-(neopentyl glycoxyisopropoxysilyl)-1-propyl glycidyl ether;

3-(2,3-dimethyl-2,3-butanedialkoxyethoxysilyl)-1-propyl acrylate;

3-(2,3-dimethyl-2,3-butanedialkoxyisopropoxysilyl)-1-propyl methacrylate;

3-(2,2-diethyl-1,3-propanedialkoxyethoxysilyl)-1-propyl mercaptan;

S-[3-(2,2-diethyl-1,3-propanedialkoxyisopropoxysilyl)-1-propyl]ethylthioether;

bis[3-(2-methyl-1,3-propanedialkoxyethoxysilyl)-1-propyl]disulfide;

bis[3-(2-methyl-1,3-propanedialkoxyisopropoxysilyl)-1-propyl]trisulfide;

bis[3-(1,3-butanedialkoxymethylsilyl)-1-propyl]tetrasulfide;

bis[3-(1,3-propanedialkoxymethylsilyl)-1-propyl]thioether;

3-(1,3-propanedialkoxyphenylsilyl)-1-propyl glycidyl thioether;

tris-N,N′,N″-[3-(1,2-propanedialkoxymethylsilyl)-1-propyl]melamine;

tris-N,N′,N″-[3-(1,2-propanedialkoxyphenylsilyl)-1-propyl]melamine;

3-(neopentyl glycoxymethylsilyl)-1-propyl acetate;

3-(neopentyl glycoxyphenylsilyl)-1-propyl octanoate;

3-(2,3-dimethyl-2,3-butanedialkoxymethylsilyl)-1-propyl amine;

3-(2,3-dimethyl-2,3-butanedialkoxyphenylsilyl)-1-propyl amine;

3-(2,2-diethyl-1,3-propanedialkoxymethylsilyl)-1-propyl acrylate;

3-(2,2-diethyl-1,3-propanedialkoxyphenylsilyl)-1-propyl methacrylate;

3-(2-methyl-1,3-propanedialkoxyethylsilyl)-1-propyl glycidyl ether;

3-(2-methyl-1,3-propanedialkoxyphenylsilyl)-1-propyl acetate;

2-(2-methyl-2,4-pentanedialkoxyethoxysilyl)-1-ethyl acrylate;

2-(2-methyl-2,4-pentanedialkoxy methylsilyl)-1-ethyl benzenesulfonate;

2-methyl-2,4-pentanedialkoxyethoxysilylmethyl methacrylate;

neopentylglycoxypropoxysilylmethyl amine;

propyleneglycoxymethylsilylmethyl mercaptan;

neopentylglycoxyethylsilylmethyl glycidyl ether;

2-(neopentylglycoxyisopropoxysilyl)-1-ethyl butyrate; 2-(neopentylglycoxy methylsilyl)-1-ethyl propionate;

2-(1,3-butanedialkoxymethylsilyl)-1-ethyl acrylate;

3-(1,3-butanedialkoxyisopropoxysilyl)-4-butyl methacrylate;

3-(1,3-butanedialkoxyethylsilyl)-1-propyl mercaptan;

3-(1,3-butanedialkoxymethylsilyl)-1-propyl methanesulfonate;

6-(2-methyl-2,4-pentanedialkoxyethoxysilyl)-1-hexyl amine;

1-(2-methyl-2,4-pentanedialkoxyethoxysilyl)-5-hexyl acrylate;

8-(2-methyl-2,4-pentanedialkoxyethoxysilyl)-1-octyl methacrylate;

10-(2-methyl-2,4-pentanedialkoxyethoxysilyl)-1-decyl glycidyl ether;

3-(2-methyl-2,4-pentanedialkoxyethoxysilyl)-1-propyl trifluoromethanesulfonate;

3-(2-methyl-2,4-pentanedialkoxypropoxysilyl)-1-propyl amine;

N-[3-(2-methyl-2,4-pentanedialkoxyisopropoxysilyl)-1-propyl]ethylene diamine;

tris-N,N′,N″-[3-(2-methyl-2,4-pentanedialkoxybutoxysilyl)-1-propyl]diethylene triamine;

tetrakis-N,N′,N″,N′″-[3-(2-methyl-2,4-pentanedialkoxyisopropoxysilyl)-1-propyl]triethylene tetramine;

bis-(3-(2-methyl-2,4-pentanedialkoxyethoxysilyl)-1-propyl)sulfide;

6-(1,3-butanedialkoxyethoxysilyl)-1-hexyl amine;

1-(1,3-butanedialkoxyethoxysilyl)-5-hexyl glycidyl ether;

8-(1,3-butanedialkoxyethoxysilyl)-1-octyl acrylate;

10-(1,3-butanedialkoxyethoxysilyl)-1-decyl methacrylate;

bis-(3-(2-methyl-2,4-pentanedialkoxyethoxysilyl)-1-propyl)thioether and, mixtures thereof.

14. The cured rubber composition resulting from curing the curable rubber composition of claim 12 .

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 X is independently —O(R 10 CR 11 ) f OH, wherein 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 ) 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 R 7 R 8 , and —NR 4 -L 1 -N(-L 2 NR 5 R 6 ) 2 ,

—O—CH 2 —C 2 H 3 O, —C 6 H 9 O, —CR 6 (—O—)CR 4 R 5 , 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, —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 —, and R 4 C(═S)NR 4 —;

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.

16. A silane of claim 1 wherein each occurrence of Y is mercapto, acryloxy methacryloxy, —O—CH 2 —C 2 H 3 O, —C 6 H 9 O, —NH 2 , —NHR 4 , —NR 4 R 5 or

—N═C═O group and each occurrence of R 4 and R 5 is independently R 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.

17. A silane of claim 15 wherein each occurrence of Y is —O—CH 2 —C 2 H 3 O, —C 6 H 9 O or —CR 6 (—O—)CR 4 R 5 and each occurrence of R 4 , R 5 and R 6 is independently 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.

18. A silane of claim 15 wherein each occurrence of Y is maleimide, —N═C═O, —SCN, —N═C═S, —NR 4 C(═O)NR 5 R 6 and each occurrence of R 4 , R 5 and R 6 is independently 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.

19. A silane of claim 15 wherein G is —(CH 2 ) m — wherein m is 1 to 12.

20. A silane of claim 19 wherein —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.

21. A sizing for fiberglass comprising the silane of claim 1 .

22. A sizing for fiberglass comprising the silane of claim 6 .

23. A sizing for fiberglass comprising the silane of claim 9 .

24. A sizing for fiberglass comprising the silane of claim 15 .

25. A silane of claim 15 wherein the silane is selected from the group consisting of 3-(1,2-propanedialkoxyethoxysilyl)-1-propyl glycidyl ether;

3-(neopentyl glycoxyisopropoxysilyl)-1-propyl glycidyl ether;

3-(2-methyl-1,3-propanedialkoxyethylsilyl)-1-propyl glycidyl ether;

neopentylglycoxyethylsilylmethyl glycidyl ether;

10-(2-methyl-2,4-pentanedialkoxyethoxysilyl)-1-decyl glycidyl ether;

1-(1,3-butanedialkoxyethoxysilyl)-5-hexyl glycidyl ether; and, mixtures thereof.

26. A silane selected from the group consisting of:

2-(2-methyl-2,4 pentanedialkoxyethoxysilyl)-1-propyl amine;

2-(2-methyl-2,4-pentanedialkoxyisopropoxysilyl)-1-propyl mercaptan;

N-[3-(1,3-propanedialkoxyethoxysilyl)-1-propyl]phenylamine;

N-[3-(1,3-propanedialkoxyisopropoxysilyl)-1-propyl]methylamine;

3-(1,2-propanedialkoxyethoxysilyl)-1-propyl glycidyl ether;

3-(1,2-propanedialkoxyisopropoxysilyl)-1-propyl methacrylate;