Granted Patent B2

US 8,188,174 · App. 12/702,971 · Granted May 29, 2012

Abstract

Claims (73)

1. A silated core polysulfide of the general formula

[Y 1 R 1 S x —] m [G 1 (R 2 SiX 1 X 2 X 3 ) a ] n [G 2 ] o [R 3 Y 2 ] p

wherein:

each occurrence of G 1 is independently selected from a polyvalent hydrocarbon species having from 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:

[(CH 2 ) b —] c R 4 [—(CH 2 ) d S x —] e ;

each occurrence of G 2 is independently selected from a polyvalent hydrocarbon species of 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:

[(CH 2 ) b —] c R 5 [—(CH 2 ) d S x —] e ;

each occurrence of R 1 and R 3 is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms;

each occurrence of Y 1 and Y 2 is independently selected from the group consisting of silyl (—SiX 1 X 2 X 3 ), hydrogen, carboxylic acid and ester group (—C(═O)OR 6 ) wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;

each occurrence of R 2 is a straight chain hydrocarbon represented by —(CH 2 ) f —;

each occurrence of R 4 is independently selected from a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms;

each occurrence of R 5 is independently selected from a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms;

each occurrence of X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;

each occurrence of X 2 and X 3 is independently selected from the group consisting of hydrogen, R 6 , wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, X 1 , wherein X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, and —OSi containing groups that result from the condensation of silanols;

each occurrence of the subscripts, a, b, c, d, e, f, m, n, o, p, and x, is independently given by: a is 1 to 2; b and d are 1 to 3; c and e are 1; f is 0 to 3; m and p are 1; n is 1 to 10; o is 0 to 1; and x is 2 to 4.

2. The silated core polysulfide of claim 1 wherein each R 1 , R 3 and R 6 is independently a branched or straight chain alkyl, alkenyl, alkynyl, aryl or aralkyl group.

3. The silated core polysulfide of claim 1 wherein each R 4 and R 5 is independently a cyclic, branched or straight chain alkyl, alkenyl, alkynyl, aryl, or aralkyl group in which a+c+e−1 hydrogens have been replaced.

4. The silated core polysulfide of claim 3 wherein the alkyl, alkynyl, aryl, aralkyl and arenyl of R 4 or R 5 in which a+c+e−1 hydrogens have been replaced is derived from the group consisting of methyl, ethyl, propyl, and isobutyl, vinyl, propenyl, allyl, methallyl, ethylidenyl norbornane, ethylidene norbornyl, ethylidenyl norbornene, ethylidene norbornenyl, acetylenyl, and propargyl, methylacetylenyl, phenyl, naphthalenyl, benzyl, phenethyl, tolyl, xylyl, norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, cyclohexyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl, and cyclododecatrienyl.

5. The silated core polysulfide of claim 1 wherein each R 4 and R 5 is independently a polyvalent hydrocarbon fragment selected from the group consisting of bicyclic, tricyclic, higher cyclic structures and cyclic structures substituted with alkyl, alkenyl, and/or alkynyl groups.

6. The silated core polysulfide of claim 1 wherein X 1 is selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy, chloro, and acetoxy.

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

8. The silated core polysulfide of claim 1 wherein each R 1 and R 3 is independently a divalent hydrocarbon fragment derived from methallyl chloride, divinylbenzene, diallylether, butadiene, piperylene, isoprene, diradicals, limonene, monovinyl-containing structures derived from trivinylcyclohexane, monounsaturated structures derived from myrcene containing a trisubstituted C═C, monounsaturated structures derived from myrcene lacking a trisubstituted C═C, and mixtures thereof.

9. The silated core polysulfide of claim 1 wherein each G 1 and G 2 is independently a polyvalent hydrocarbon species containing a polysulfide group derived from nonconjugated terminal diolefins.

10. The silated core polysulfide of claim 1 wherein each G 1 and G 2 is independently a polyvalent hydrocarbon species containing a polysulfide group derived from the group consisting of —CH 2 (CH 2 ) q+1 CH(CH 2 )—, —CH(CH 3 )(CH 2 ) q CH(CH 2 —) 2 , wherein q is zero to 20.

11. The silated core polysulfide of claim 1 wherein each G 1 and G 2 is independently a polyvalent hydrocarbon species containing a polysulfide group derived from divinylbenzene, diallylether, butadiene, piperylene, isoprene, trivinylcyclohexane, myrcene, and mixture thereof.

12. The silated core polysulfide of claim 1 wherein each R 1 and R 3 is independently a divalent hydrocarbon fragment having from 1 to about 5 carbon atoms.

13. The silated core polysulfide of claim 1 wherein X 1 is independently selected from the group consisting of hydrolysable —OH, and —OR 6 , wherein R 6 is a monovalent hydrocarbon group having from 1 to 5 carbon atoms.

14. A composition comprising from about 30 to about 99 weight percent of the silated core polysulfide of claim 1 and about 70 to about 1 weight percent of a silane of the general formula:

X 1 X 2 X 3 SiR 1 S x R 3 SiX 1 X 2 X 3

wherein each occurrence of R 1 and R 3 is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms;

each occurrence of X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;

each occurrence of X 2 and X 3 is independently selected from the group consisting of hydrogen, R 6 , X 1 , and —OSi containing groups that result from the condensation of silanols;

and x is 1 to about 10.

15. The composition of claim 14 wherein the silane is selected from the group consisting of bis-(3-triethoxysilylpropyl) disulfide; bis-(3-triethoxysilylpropyl) trisulfide; bis-(3-triethoxysilylpropyl) tetrasulfide; bis-(3-triethoxysilylpropyl) pentasulfide; bis-(3-diethoxymethylsilylpropyl) disulfide; bis-(3-ethoxydimethylsilylpropyl) disulfide; bis-(triethoxysilylmethyl) disulfide; bis-(4-triethoxysilylbenzyl) disulfide, bis-(3-triethoxysilylphenyl) disulfide, and mixtures thereof.

16. A process for making a silated core polysulfide according to claim 1 which comprises:

(a) reacting a hydrosilane having the structure, HSi(X 1 X 2 X 3 ), with a hydrocarbon containing at least one reactive double bonds to produce an intermediate product;

(b) reacting the intermediate product from step (a) with a sulfuring agent, selected from the group R 6 C(═O)SH, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, in the presence of a free radical agent;

(c) deblocking the mercapto group on the product in step (b) using a proton donator;

(d) reacting the intermediate mercaptan in step (c) with a mixture of base and sulfur;

(e) reacting the intermediate in step (d) with a substituted or unsubstituted hydrocarbon containing a leaving group selected from the group consisting of chlorine, bromine or iodine and mixtures thereof.

17. A rubber composition comprising:

(a) silated core polysulfide of the general formula

[Y 1 R 1 S x —] m [G 1 (R 2 SiX 1 X 2 X 3 ) a ] n [G 2 ] o [R 3 Y 2 ] p ;

wherein each occurrence of G 1 is independently selected from a polyvalent hydrocarbon species having from 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:

[(CH 2 ) b —] c R 4 [—(CH 2 ) d S x —] e ;

each occurrence of G 2 is independently selected from a polyvalent hydrocarbon species of 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:

[(CH 2 ) b —] c R 5 [—(CH 2 ) d S x —] e ;

each occurrence of R 1 and R 3 is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms;

each occurrence of Y 1 and Y 2 is independently selected from consisting of silyl (—SiX 1 X 2 X 3 ), carboxylic acid, ester (—C(═O)OR 6 ) wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, hydroxyl, hydrogen;

each occurrence of R 2 is a straight chain hydrocarbon represented by —(CH 2 ) f —;

each occurrence of R 4 is independently a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms;

each occurrence of R 5 is independently a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms;

each occurrence of X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;

each occurrence of X 2 and X 3 is independently selected from the group consisting of hydrogen, R 6 , wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, X 1 , wherein X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, and —OSi containing groups that result from the condensation of silanols;

each occurrence of the subscripts, a, b, c, d, e, f, m, n, o, p, and x, is independently given by a is 1 to 2; b is 1 to 3; c is 1; d is 1 to 3; e is 1; f is 0 to 3; m and p are 1; n is 1 to 10; o is 0 to 1; and x is 2 to 4;

(b) inorganic filler; and,

(c) rubber.

18. The rubber composition of claim 17 , further comprising (d) curative and, optionally, at least one other additive selected from the group consisting of sulfur compounds, activators, retarders, accelerators, processing additives, oils, plasticizers, tackifying resins, silicas, fillers, pigments, fatty acids, zinc oxide, waxes, antioxidants and antiozonants, peptizing agents, reinforcing materials, and mixtures thereof.

19. The rubber composition of claim 17 , wherein the rubber component is at least one sulfur vulcanizable rubber selected from the group consisting of conjugated diene homopolymers and copolymers, copolymers of at least one conjugated diene and aromatic vinyl compound and mixtures thereof.

20. The rubber composition of claim 19 , wherein the rubber component is styrene/butadiene rubber containing from about 5 to about 50 percent vinyl content.

21. The rubber composition of claim 19 , wherein the rubber component is derived from a conjugated diene selected from the group consisting of isoprene, 1,3-butadiene, styrene, and alpha methyl styrene, and mixture thereof.

22. The rubber composition of claim 19 wherein the rubber component is styrene/butadiene having a styrene content of about 20 to about 28 weight percent.

23. The rubber composition of claim 17 , wherein the rubber component is at least one natural rubber, or emulsion polymerization derived rubber, or a solvent polymerization derived rubber.

24. The rubber composition of claim 17 , wherein the rubber is selected from the group consisting of cis-1,4-polyisoprene rubber, emulsion polymerization prepared styrene/butadiene copolymer rubber, organic solution polymerization prepared styrene/butadiene rubber, 3,4-polyisoprene rubber, isoprene/butadiene rubber, styrene/isoprene/butadiene terpolymer rubber, cis-1,4-polybutadiene, medium vinyl polybutadiene rubber, wherein the medium vinyl polybutadiene rubber has about 35 to 50 weight percent vinyl, high vinyl polybutadiene rubber wherein the high vinyl polybutadiene rubber has about 50 to 75 weight percent vinyl, styrene/isoprene copolymers, emulsion polymerization prepared styrene/butadiene/acrylonitrile terpolymer rubber and butadiene/acrylonitrile copolymer rubber.

25. The rubber composition of claim 17 wherein the silated core polysulfide is selected from the group consisting of 2-triethoxysilyl-1,3-bis-(3-triethoxysilyl-1-propyltetrathia)propane, 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(2-diethoxymethylsilyl-1-ethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(10-triethoxysilyl-3,4,5,6,7-pentathiadecyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(10-triethoxysilyl-3,4,5,6,7-pentathiadecyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1-(7-triethoxysilyl-3,4-dithiaheptyl)-2-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; -(2-triethoxysilyl-1-ethyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)benzene; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]tetrasulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]trisulfide; bis-[2-[4-(2-tiethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]disulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl]disulfide; bis-2-[4-(2-triethoxysilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl]trisulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl tetrasulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)phenyl]ethyl]tetrasulfide; bis-2-[4-(2-triethoxysilyl-1-ethyl)-3-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]trisulfide; bis-[2-[4-(2-diethoxymethylsilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl disulfide and mixtures thereof.

26. The rubber composition of claim 17 further comprising a silane of the general formula:

X 1 X 2 X 3 SiR 1 S x R 3 SiX 1 X 2 X 3

wherein each occurrence of R 1 and R 3 is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms;

each occurrence of X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;

each occurrence of X 2 and X 3 is independently selected from the group consisting of hydrogen, R 6 , X 1 , and —OSi containing groups that result from the condensation of silanols;

and x is 1 to about 10.

27. The rubber composition of claim 26 , wherein the silane is selected from the group consisting of bis-(3-triethoxysilylpropyl) disulfide; bis-(3-triethoxysilylpropyl) trisulfide; bis-(3-triethoxysilylpropyl) tetrasulfide; bis-(3-triethoxysilylpropyl) pentasulfide; bis-(3-diethoxymethylsilylpropyl) disulfide; bis-(3-ethoxydimethylsilylpropyl) disulfide; bis-(triethoxysilylmethyl) disulfide; bis-(4-triethoxysilylbenzyl) disulfide, bis-(3-triethoxysilylphenyl) disulfide, and mixtures thereof.

28. The rubber composition of claim 27 , wherein the silated core polysulfide is selected from the group consisting of 2-triethoxysilyl-1,3-bis-(3-triethoxysilyl-1-propyltetrathia)propane, 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(2-diethoxymethylsilyl-1-ethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(10-triethoxysilyl-3,4,5,6,7-pentathiadecyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(10-triethoxysilyl-3,4,5,6,7-pentathiadecyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(8-tiethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1-(7-triethoxysilyl-3,4-dithiaheptyl)-2-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane, -(2-triethoxysilyl-1-ethyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)benzene; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]tetrasulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]trisulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]disulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl]disulfide; bis-2-[4-(2-triethoxysilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl]trisulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl tetrasulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)phenyl]ethyl]tetrasulfide; bis-2-[4-(2-triethoxysilyl-1-ethyl)-3-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]trisulfide; bis-[2-[4-(2-diethoxymethylsilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl disulfide and mixtures thereof.

Assignments (21)