Granted Patent B2

US 8,383,850 · App. 12/820,198 · Granted Feb 26, 2013

Abstract

Claims (67)

1. A rubber composition including a compound having formula 1:

[R k —Y—S(CH 2 ) n ] r -G-(CH 2 ) m —(SiX 1 X 2 X 3 )  (1)

wherein:

each occurrence of Y is selected from the group consisting of —C(═NR 1 )—; —SC(═NR 1 )—; (—NR 1 )C(═NR 1 )—; —SC(═O)—; (—NR 1 )C(═O)—; (—NR 1 )C(═S)—; —OC(═O)—; —OC(═S)—; —C(═O)—; —SC(═S)—; —C(═S)—; —S(═O)—; (—NR)S(═O) 2 —; —SS(═O)—; —OS(═O)—; (—NR 1 )S(═O)—; —SS(═O) 2 —; (—S) 2 P(═O)—; —(—S)P(═O)—; —P(═O)(−) 2 ; (—S) 2 P(═S)—; —(—S)P(═S)—; —P(═S)(−) 2 ; (—NR 1 ) 2 P(═O)—; (—NR)(—S)P(═O)—; (—O)(—NR 1 )P(═O)—; (—O) 2 P(═O)—; —(—O)P(═O)—; —(—NR 1 )P(═O)—; (—NR 1 ) 2 P(═S)—; (—NR 1 )(—S)P(═S)—; (—O)(—NR 1 )P(═S)—; (—O)(—S)P(═S)—; (—O) 2 P(═S)—; —(—O)P(═S)—; and —(—NR 1 )P(═S)—;

each occurrence of R is chosen independently from hydrogen, straight, cyclic, or branched alkyl groups, alkenyl groups, aryl groups, and aralkyl groups, with each R containing up to about 18 carbon atoms;

each occurrence of G is chosen independently from a group consisting of a trivalent or other polyvalent hydrocarbon group of 3 to 30 carbon atoms derived from an alkane, alkene or aralkane or a trivalent or other polyvalent heterocarbon group of 2 to 29 carbon atoms with the proviso that G contains a cyclic structure (ring);

each occurrence of X 1 is independently selected from the set of hydrolysable groups group consisting of —Cl, —Br, R 1 O—, R 1 C(═O)O—, R 1 2 C═NO—, R 1 2 NO— or R 2 N—, wherein each R 1 is chosen independently from hydrogen, alkyl, alkenyl, aryl or aralkyl groups with each R 1 containing up to about 18 carbon atoms;

each occurrence of X 2 and X 3 are independently chosen from the group consisting of the members listed for R 1 and X 1 ;

k is 1 to 2; m=1 to 5; n=1 to 5; and r is 2 to 4.

2. A rubber composition comprising:

(a) a compound of formula 1:

[R k —Y—S(CH 2 ) n ] r -G-(CH 2 ) m —(SiX 1 X 2 X 3 )  (1)

wherein:

each occurrence of Y is selected from the group consisting of —C(═NR 1 )—; —SC(═NR 1 )—; (—NR 1 )C(═NR 1 )—; —SC(═O)—; (—NR 1 )C(═O)—; (—NR 1 )C(═S)—; —OC(═O)—; —OC(═S)—; —C(═O)—; —SC(═S)—; —C(═S)—; —S(═O)—; (—NR)S(═O) 2 —; —SS(═O)—; —OS(═O)—; (—NR 1 )S(═O)—; —SS(═O) 2 —; (—S) 2 P(═O)—; —(—S)P(═O)—; —P(═O)(−) 2 ; (—S) 2 P(═S)—; —(—S)P(═S)—; —P(═S)(−) 2 ; (—NR 1 ) 2 P(═O)—; (—NR)(—S)P(═O)—; (—O)(—NR 1 )P(═O)—; (—O) 2 P(═O)—; —(—O)P(═O)—; —(—NR 1 )P(═O)—; (—NR 1 ) 2 P(═S)—; (—NR 1 )(—S)P(═S)—; (—O)(—NR 1 )P(═S)—; (—O)(—S)P(═S)—; (—O) 2 P(═S)—; —(—O)P(═S)—; and —(—NR 1 )P(═S)—;

each occurrence of R is chosen independently from hydrogen, straight, cyclic, or branched alkyl, alkenyl groups, aryl groups, and aralkyl groups, with each R containing up to about 18 carbon atoms;

each occurrence of G is chosen independently form a group consisting of a trivalent or other polyvalent hydrocarbon group of 3 to 30 carbon atoms derived by substitution of alkane, alkene or aralkane or a trivalent or other polyvalent heterocarbon group of 2 to 29 carbon atoms with the proviso that G contains a cyclic structure (ring);

each occurrence of X 1 is independently selected from the set of hydrolysable groups group consisting of —Cl, —Br, R 1 O—, R 1 C(═O)O—, R 1 2 C═NO—, R 1 2 NO— or R 2 N—, wherein each R 1 is chosen independently from hydrogen, alkyl, alkenyl, aryl or aralkyl groups with each R 1 containing up to about 18 carbon atoms;

each occurrence of X 2 and X 3 are independently chosen from the group consisting of the members listed for R 1 and X 1 ;

k is 1 to 2; m=1 to 5; n=1 to 5; and r is 2 to 4;

(b) an organic polymer;

(c) a filler; and optionally,

(d) other additives and curatives.

3. A process for preparing a cured rubber composition comprising:

(A) thermomechanically mixing, in at least one preparatory mixing step, to a temperature of 140° to 200° C.:

(i) 100 parts by weight of at least one sulfur vulcanizable rubber selected from conjugated diene homopolymers and copolymers, and copolymers of at least one conjugated diene and aromatic vinyl compound;

(ii) 5 to 100 phr (parts per hundred rubber);

(iii) 0.05 to 20 parts by weight filler of at least one compound having formula 1:

[R k —Y—S(CH 2 ) n ] r -G-(CH 2 ) m —(SiX 1 X 2 X 3 )  (1)

wherein:

each occurrence of Y is selected from the group consisting of —C(═NR 1 )—; —SC(═NR 1 )—; (—NR 1 )C(═NR 1 )—; —SC(═O)—; (—NR 1 )C(═O)—; (—NR 1 )C(═S)—; —OC(═O)—; —OC(═S)—; —C(═O)—; —SC(═S)—; —C(═S)—; —S(═O)—; (—NR)S(═O) 2 —; —SS(═O)—; —OS(═O)—; (—NR 1 )S(═O)—; —SS(═O) 2 —; (—S) 2 P(═O)—; —(—S)P(═O)—; —P(═O)(−) 2 ; (—S) 2 P(═S)—; —(—S)P(═S)—; —P(═S)(−) 2 ; (—NR 1 ) 2 P(═O)—; (—NR)(—S)P(═O)—; (—O)(—NR 1 )P(═O)—; (—O) 2 P(═O)—; —(—O)P(═O)—; —(—NR 1 )P(═O)—; (—NR 1 ) 2 P(═S)—; (—NR 1 )(—S)P(═S)—; (—O)(—NR 1 )P(═S)—; (—O)(—S)P(═S)—; (—O) 2 P(═S)—; —(—O)P(═S)—; and —(—NR 1 )P(═S)—;

each occurrence of R is chosen independently from hydrogen, straight, cyclic, or branched alkyl groups, alkenyl groups, aryl groups, and aralkyl groups, with each R containing up to about 18 carbon atoms;

each occurrence of G is chosen independently from a group consisting of a trivalent or other polyvalent hydrocarbon group of 3 to 30 carbon atoms derived from an alkane, alkene or aralkane or a trivalent or other polyvalent heterocarbon group of 2 to 29 carbon atoms with the proviso that G contains a cyclic structure (ring);

each occurrence of X 1 is independently selected from the set of hydrolysable groups group consisting of —Cl, —Br, R 1 O—, R 1 C(═O)O—, R 1 2 C═NO—, R 1 2 NO— or R 2 N—, wherein each R 1 is chosen independently from hydrogen, alkyl, alkenyl, aryl or aralkyl groups with each R 1 containing up to about 18 carbon atoms;

each occurrence of X 2 and X 3 are independently chosen from the group consisting of the members listed for R 1 and X 1 ;

k is 1 to 2; m=1 to 5; n=1 to 5; and r is 2 to 4;

(B) subsequently blending therewith, in a final thermomechanical mixing step at a temperature of 50° to 130° C., the rubber from step (A), at least one deblocking agent at about 0.05 to 20 parts by weight of the filler, and a curing agent at 0 to 5 phr; and optionally

(C) curing said mixture.

4. A free flowing filler composition comprising at least one silane and a particulate filler, the silane having a chemical structure in accordance with formula 1:

[R k —Y—S(CH 2 ) n ] r -G-(CH 2 ) m —(SiX 1 X 2 X 3 )  (1)

wherein:

each occurrence of Y is selected from the group consisting of —C(═NR 1 )—; —SC(═NR 1 )—; (—NR 1 )C(═NR 1 )—; —SC(═O)—; (—NR 1 )C(═O)—; (—NR 1 )C(═S)—; —OC(═O)—; —OC(═S)—; —C(═O)—; —SC(═S)—; —C(═S)—; —S(═O)—; (—NR)S(═O) 2 —; —SS(═O)—; —OS(═O)—; (—NR 1 )S(═O)—; —SS(═O) 2 —; (—S) 2 P(═O)—; —(—S)P(═O)—; —P(═O)(−) 2 ; (—S) 2 P(═S)—; —(—S)P(═S)—; —P(═S)(−) 2 ; (—NR 1 ) 2 P(═O)—; (—NR)(—S)P(═O)—; (—O)(—NR 1 )P(═O)—; (—O) 2 P(═O)—; —(—O)P(═O)—; —(—NR 1 )P(═O)—; (—NR 1 ) 2 P(═S)—; (—NR 1 )(—S)P(═S)—; (—O)(—NR 1 )P(═S)—; (—O)(—S)P(═S)—; (—O) 2 P(═S)—; —(—O)P(═S)—; and —(—NR 1 )P(═S)—;

each occurrence of R is chosen independently from hydrogen, straight, cyclic, or branched alkyl groups, alkenyl groups, aryl groups, and aralkyl groups, with each R containing up to about 18 carbon atoms;

each occurrence of G is chosen independently form a group consisting of a trivalent or other polyvalent hydrocarbon group of 3 to 30 carbon atoms derived by substitution of alkane, alkene or aralkane or a trivalent or other polyvalent heterocarbon group of 2 to 29 carbon atoms with the proviso that G contains a cyclic structure (ring);

each occurrence of X 1 is independently selected from the set of hydrolysable groups group consisting of —Cl, —Br, R 1 O—, R 1 C(═O)O—, R 1 2 C═NO—, R 1 2 NO— or R 2 N—, wherein each R 1 is chosen independently from hydrogen, alkyl, alkenyl, aryl or aralkyl groups with each R 1 containing up to about 18 carbon atoms;

each occurrence of X 2 and X 3 are independently chosen from the group consisting of the members listed for R 1 and X 1 ;

k is 1 to 2; m=1 to 5; n=1 to 5; and r is 2 to 4.

5. The rubber composition of claim 1 wherein X 1 is selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy, chloro and acetoxy, and X 2 and X 3 are each independently selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy, chloro, acetoxy, methyl, ethyl, propyl, isopropyl, sec-butyl, phenyl, vinyl, cyclohexyl, butyl, hexyl, octyl, lauryl and octadecyl.

6. The rubber composition of claim 1 wherein G is a structure derivable from vinylnorbornene, vinylcyclohexene, limonene, or trivinylcyclohexane, or any structure derivable by trisubstitution of cyclopentane, tetrahydrocyclopentadiene, cyclohexane, cyclodecane, cyclododecane, any of the cyclododecenes, any of the cyclododecadienes, cycloheptane, any of the cycloheptenes or any of the cycloheptadienes, trisubstituted cyanurate, piperazine, cyclohexanone, cyclohexenone, or any structure derivable from trisubstitued benzene, toluene, mestylene and naphthalene.

7. The rubber composition of claim 1 wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, octyl, dodecyl, octadecyl, cyclohexyl, phenyl, benzyl, phenethyl, methallyl and allyl.

8. The rubber composition of claim 1 wherein Y is selected from the group consisting of —C(═NR)—, —SC(═NR)—, —NR 1 C(═NR 1 )—, —C(═O)—, —SC(═O)—, —OC(═O)—, —NR 1 C(═O)—, —C(═S)—, —NR 1 C(═S)— and —SC(═S)—.

9. The rubber composition of claim 8 wherein Y is —C(═O)—.

10. The rubber composition of claim 1 wherein m is 2 to 4 and n is 1 to 4.

11. The rubber composition of claim 10 wherein each occurrence of m is 2 and n is 2.

12. The rubber composition of claim 1 wherein each occurrence of the G is a trivalent or other polyvalent hydrocarbon group containing at least one ring and from 3 to 18 carbon atoms.

13. The rubber composition of claim 12 wherein each occurrence of the G is selected from a group derived from cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclododecane and benzene.

14. The rubber composition of claim 1 wherein each occurrence of the R is a straight chain alkyl group from 1 to 8 carbon atoms.

15. The rubber composition of claim 14 wherein each occurrence of the R is selected from the group consisting of methyl, ethyl and propyl.

16. The rubber composition of claim 1 wherein each occurrence of G is a trivalent cyclohexane or benzene group, R is a straight chain alkyl group possessing from 1 to 8 carbon atoms, r=2, m=1 or 2, and n=1 or 2.

17. The rubber composition of claim 1 wherein said compound is selected from the group consisting of 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxopentyl)benzene, 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxohexyl)benzene, 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxoheptyl)benzene, 1-(2-tripropoxysilylethyl)-3,5-bis-(3-thia-4-oxopentyl)benzene, 4-(2-triethoxysilylethyl)-1,2-bis-(2-thia-3-oxopentyl)benzene, 1-(2-diethoxymethylsilylethyl)-3,5-bis-(3-thia-4-oxopentyl)benzene, 4-(2-dimethylethoxysilylethyl)-1,2-bis-(3-thia-4-oxopentyl)benzene, 4-(2-triethoxysilylethyl)-1,2-bis-(2-thia-3-oxopentyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(2-thia-3-oxopentyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(2-thia-3-oxopentyl)cyclohexane, 4-(2-diethoxymethylsilylethyl)-1,2-bis-(3-thia-4-oxopentyl)cyclohexane, 4-(2-dimethylethoxysilylethyl)-1,2-bis-(3-thia-4-oxopentyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxohexyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(3-thia-4-oxohexyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(3-thia-4-oxohexyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxononyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(3-thia-4-oxononyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(3-thia-4-oxononyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxoundecyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(3-thia-4-oxoundecyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(3-thia-4-oxoundecyl)cyclohexane, 4-(2-dimethylethoxysilylethyl)-1,2-bis-(3-thia-4-oxododecyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxododecyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxo-5-aza-5-methyldodecyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3,5-dithia-4-oxododecyl)cyclohexane, 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxopenyl)mesitylene and 6-(2-triethoxysilylpropyl)-2,2-bis-(3-thia-4-oxopentyl)cyclohexanone and mixtures thereof.

18. The free flowing filler composition of claim 4 wherein the particulate filler is selected from the group consisting of pyrogenic silica, precipitated silica, titanium dioxide, aluminosilicate, alumina, clay, talc and carbon black.

19. The free flowing filler of composition of claim 4 wherein the silane is selected from the group consisting of 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxopentyl)benzene, 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxohexyl)benzene, 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxoheptyl)benzene, 1-(2-tripropoxysilylethyl)-3,5-bis-(3-thia-4-oxopentyl)benzene, 4-(2-triethoxysilylethyl)-1,2-bis-(2-thia-3-oxopentyl)benzene, 1-(2-diethoxymethylsilylethyl)-3,5-bis-(3-thia-4-oxopentyl)benzene, 4-(2-dimethylethoxysilylethyl)-1,2-bis-(3-thia-4-oxopentyl)benzene, 4-(2-triethoxysilylethyl)-1,2-bis-(2-thia-3-oxopentyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(2-thia-3-oxopentyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(2-thia-3-oxopentyl)cyclohexane, 4-(2-diethoxymethylsilylethyl)-1,2-bis-(3-thia-4-oxopentyl)cyclohexane, 4-(2-dimethylethoxysilylethyl)-1,2-bis-(3-thia-4-oxopentyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxohexyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(3-thia-4-oxohexyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(3-thia-4-oxohexyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxononyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(3-thia-4-oxononyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(3-thia-4-oxononyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxoundecyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(3-thia-4-oxoundecyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(3-thia-4-oxoundecyl)cyclohexane, 4-(2-dimethylethoxysilylethyl)-1,2-bis-(3-thia-4-oxododecyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxododecyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxo-5-aza-5-methyldodecyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3,5-dithia-4-oxododecyl)cyclohexane, 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxopenyl)mesitylene and 6-(2-triethoxysilylpropyl)-2,2-bis-(3-thia-4-oxopentyl)cyclohexanone, and mixtures thereof.

20. The rubber composition of claim 2 wherein the organic polymer (b) is selected from the group consisting of solution styrene-butadiene rubber, emulsion styrene-butadiene rubber, natural rubber, polybutadiene rubber, ethylene-propylene copolymer, ethylene-propylene-diene monomer (EPDM), acrylonitrile-butadiene rubber, cis-1,4-polyisoprene rubber, 3,4-polyisoprene rubber, cis-1,4-polybutadiene rubber, medium vinyl polybutadiene rubber, high vinyl polybutadiene rubber and mixtures thereof.

21. The rubber composition of claim 20 wherein the compound (a) is selected from the group consisting of 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxopentyl)benzene, 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxohexyl)benzene, 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxoheptyl)benzene, 1-(2-tripropoxysilylethyl)-3,5-bis-(3-thia-4-oxopentyl)benzene, 4-(2-triethoxysilylethyl)-1,2-bis-(2-thia-3-oxopentyl)benzene, 1-(2-diethoxymethylsilylethyl)-3,5-bis-(3-thia-4-oxopentyl)benzene, 4-(2-dimethylethoxysilylethyl)-1,2-bis-(3-thia-4-oxopentyl)benzene, 4-(2-triethoxysilylethyl)-1,2-bis-(2-thia-3-oxopentyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(2-thia-3-oxopentyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(2-thia-3-oxopentyl)cyclohexane, 4-(2-diethoxymethylsilylethyl)-1,2-bis-(3-thia-4-oxopentyl)cyclohexane, 4-(2-dimethylethoxysilylethyl)-1,2-bis-(3-thia-4-oxopentyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxohexyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(3-thia-4-oxohexyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(3-thia-4-oxohexyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxononyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(3-thia-4-oxononyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(3-thia-4-oxononyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxoundecyl)cyclohexane, 1-(2-triethoxysilylethyl)-2,4-bis-(3-thia-4-oxoundecyl)cyclohexane, 2-(2-triethoxysilylethyl)-1,4-bis-(3-thia-4-oxoundecyl)cyclohexane, 4-(2-dimethylethoxysilylethyl)-1,2-bis-(3-thia-4-oxododecyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxododecyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3-thia-4-oxo-5-aza-5-methyldodecyl)cyclohexane, 4-(2-triethoxysilylethyl)-1,2-bis-(3,5-dithia-4-oxododecyl)cyclohexane, 1-(2-triethoxysilylethyl)-3,5-bis-(3-thia-4-oxopenyl)mesitylene and 6-(2-triethoxysilylpropyl)-2,2-bis-(3-thia-4-oxopentyl)cyclohexanone, and mixtures thereof, and the filler (c) is selected from the group consisting of pyrogenic silica, precipitated silica, titanium dioxide, aluminosilicate, alumina, clay, talc and carbon black.

22. The process of claim 3 , wherein:

in step (A), said thermomechanical mixing comprises thermomechanically mixing for a total mixing time of 2 to 20 minutes;

in step (B), said blending comprises thermomechanically mixing for a time ranging from 1 to 30 minutes, and

in optional step (C), said curing of said mixture comprises curing at a temperature of 130° C. to 200° C. for about 5 to 60 minutes.

Assignments (20)