Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions
View Patent ↗This invention relates to novel sulfur-containing silane coupling agents, and organic polymers containing carbon-carbon double bonds. These novel silanes can be carried on organic and inorganic fillers. The invention also relates to articles of manufacture, particularly tires, made from the elastomer compositions described herein.
1. A composition comprising from about 30 to about 99 weight percent of a silated cyclic core polysulfide of the general formula I:
[Y 1 R 1 S x -] m [G 1 (SR 2 SiX 1 X 2 X 3 ) a ] n [G 2 ] o [R 3 Y 2 ] p (I)
wherein:
each occurrence of G 1 is independently selected from a polyvalent hydrocarbon species having from 5 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 in Formula I 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 ), alkoxy (—OR 6 ), hydrogen, carboxylic acid, and ester (—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 independently selected from divalent hydrocarbon fragment having from 1 to 20 carbon atoms;
each occurrence of R 4 is independently selected from a polyvalent cyclic hydrocarbon fragment of 3 to about 28 carbon atoms or a polyvalent cyclic heterocarbon fragment of 3 to about 27 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of a+c+e:
each occurrence of R 5 is independently selected from a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms or a polyvalent cyclic heterocarbon fragment of 1 to about 27 carbon atoms that was obtained by substitution of hydrogen atoms equal to the sum of c+e;
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, m, n, o, p, and x, is independently given wherein a, c and e are 1 to about 3; b is 1 to about 5; d is 1 to about 5; m and p are 1 to about 100; n is 1 to about 15; o is 0 to about 10; and x is 1 to about 10, and
about 70 to about 1 weight percent of a silane of the general formula (II):
[X 1 X 2 X 3 SiR 1 S x R 3 SiX 1 X 2 X 3 ] (II)
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 that include branched and straight chain alkyl, alkenyl, alkynyl, aryl or aralkyl groups wherein one hydrogen atom was substituted with a (—SiX 1 X 2 X 3 )group;
each occurrence of X 1 in Formula II 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.
2. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 1 and R 3 are branched or straight chain alkyl, alkenyl, alkynyl, aryl or aralkyl groups in which one hydrogen atom is substituted with a Y 1 or Y 2 group.
3. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 6 is branched or straight chain alkyl, alkenyl, aryl or aralkyl.
4. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 4 is cyclic or polycyclic alkyl, alkenyl, alkynyl, aryl, or aralkyl in which a+c+e−1 hydrogens have been replaced.
5. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 4 and R 5 are polyvalent heterocarbon fragments from 3 to 27 carbon atoms.
6. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 5 is cyclic or polycyclic alkyl, alkenyl, alkynyl, aryl, or aralkyl in which a+c+e−1 hydrogens have been replaced.
7. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I the heteroatom of R 4 and R 5 is selected from the group consisting of sulfur, oxygen, nitrogen, and mixtures thereof.
8. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I the cyclic or polycyclic alkyl, alkynyl, aryl, aralkyl and arenyl of R 4 in which a+c+e−1 hydrogens have been replaced is selected from the group consisting of ethylidenyl norbornane, ethylidene norbornyl, ethylidenyl norbornene, ethylidene norbornenyl, phenyl, naphthalenyl, benzyl, phenethyl, tolyl, xylyl, norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, cyclohexyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl, and cyclododecatrienyl.
9. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I the cyclic alkyl, alkynyl, aryl, aralkyl and arenyl of R 5 in which c+e−1 hydrogens have been replaced is selected from the group consisting of ethylidenyl norbornane, ethylidene norbornyl, ethylidenyl norbornene, ethylidene norbornenyl, phenyl, naphthalenyl, benzyl, phenethyl, tolyl, xylyl, norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, cyclohexyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl, and cyclododecatrienyl.
10. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I the cyclic structure of R 4 , R 5 , and R 6 is selected from the group consisting of bicyclic, tricyclic, higher cyclic structures, cyclic structures substituted with alkyl, alkenyl, and/or alkynyl groups.
11. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I X 1 is selected from the group of methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy, chloro, and acetoxy.
12. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I X 2 and X 3 are 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, straight-chain alkyl, butyl, hexyl, octyl, lauryl, and octadecyl.
13. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 1 and R 3 are terminal straight-chain alkyls substituted terminally at the end with —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —, beta-substituted analogs, and mixtures thereof.
14. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I the beta substituted analog is —CH 2 (CH 2 ) u CH(CH 3 )—, where u is zero to 17.
15. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 1 and R 3 are structures 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.
16. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I G 1 is selected from the group consisting of structures derivable from divinylbenzene, such as —CH 2 CH 2 (C 6 H 4 )CH(CH 2 —)—, —CH 2 CH 2 (C 6 H 3 —)CH 2 CH 2 —, and —CH 2 (CH—)(C 6 H 4 )CH(CH 2 —)—, where the notation C 6 H 4 denotes a disubstituted benzene ring and C 6 H 3 — denotes a trisubstituted ring.
17. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I G 1 is derived from trivinylcyclohexane, such as —CH 2 (CH—)(vinylC 6 H 9 )CH 2 CH 2 —, (—CH 2 CH 2 ) 3 C 6 H 9 , (—CH 2 CH 2 ) 2 C 6 H 9 CH(CH 3 )—, —CH 2 (CH—)(vinylC 6 H 9 )(CH—)CH 2 —, —CH 2 CH 2 C 6 H 9 [(CH—)CH 2 ] 2 , —CH(CH 3 )C 6 H 9 [(CH—)CH 2 —] 2 , C 6 H 9 [(CH—)CH 2 —] 3 , —CH 2 (CH—)C 6 H 9 [CH 2 CH 2 —] 2 , and —CH 2 (CH—)C 6 H 9 [CH(CH 3 )—][CH 2 CH 2 —], where the notation C 6 H 9 denotes any isomer of the trisubstituted cyclohexane ring.
18. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I G 2 is derived from divinylbenzene, such as —CH 2 CH 2 (C 6 H 4 )CH 2 CH 2 —, —CH 2 CH 2 (C 6 H 4 )CH(CH 2 —)— and —CH 2 CH 2 (C 6 H 3 —)CH 2 CH 2 —, —CH 2 (CH—)(C 6 H 4 )CH(CH 2 —)—, where the notation C 6 H 4 denotes a disubstituted benzene ring.
19. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I G 2 is selected from structures derivable from trivinylcyclohexane, such as —CH 2 CH 2 (vinylC 6 H 9 )CH 2 CH 2 —, (—CH 2 CH 2 )C 6 H 9 CH 2 CH 3 , —CH 2 (CH—)(vinylC 6 H 9 )CH 2 CH 2 —, (—CH 2 CH 2 ) 3 C 6 H 9 , (—CH 2 CH 2 ) 2 C 6 H 9 CH(CH 3 )—, —CH 2 (CH—)(vinylC 6 H 9 )(CH—)CH 2 —, —CH 2 CH 2 C 6 H 9 [(CH—)CH 2 —] 2 , —CH(CH 3 )C 6 H 9 [(CH—)CH 2 —] 2 , C 6 H 9 [(CH—)CH 2 —] 3 , —CH 2 (CH—)C 6 H 9 [CH 2 CH 2 —] 2 , and —CH 2 (CH—)C 6 H 9 [CH(CH 3 )—][CH 2 CH 2 —], where the notation C 6 H 9 denotes any isomer of the trisubstituted cyclohexane ring.
20. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I is any of the isomers of 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(13-triethoxysilyl-3,4-dithiamidecyl)cyclohexane; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(13-triethoxysilyl-3,4,5-trithiamidecyl)cyclohexane; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(12-triethoxysilyl-3,4,5-tetrathiadodecyl)cyclohexane; 1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(11-triethoxysilyl-3,4-tetrathiaunidecyl)cyclohexane 4-(3-triethoxysilyl-1-thiaethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6,7-pentathiamidecyl)cyclohexane; 4-(6-diethoxymethylsilyl-2-thia hexyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(4-triethoxysilyl-2-thiabutyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 4-(7-triethoxysilyl-3-thiaheptyl)-1,2-bis-(9-triethoxysilyl-3,4,5-trithianonyl)cyclohexane; 4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)benzene; 4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4,5-trithianonyl)benzene; 4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4-dithianonyl)benzene; bis-2-[4-(3-triethoxysilyl-2-thiapropyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl tetrasulfide; bis-2-[4-(3-triethoxysilyl-1-thiapropyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl trisulfide; bis-2-[4-(3-triethoxysilyl-1-thiapropyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl disulfide; bis-2-[4-(6-triethoxysilyl-3-thiahexyl)-3-(9-triethoxysilyl-3,4,5-trithianonyl)phenyl]ethyl tetrasulfide; bis-2-[4-(6-triethoxysilyl-3-thiahexyl)-3-(9-triethoxysilyl-3,4,5-trithianonyl)nathyl]ethyl tetrasulfide; bis-2-[4-(4-diethoxymethylsilyl-2-thiabutyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)phenyl]ethyl trisulfide; bis-2-[4-(4-triethoxysilyl-2-thiaethyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cycloheptyl]ethyl disulfide; bis-2-[4-(4-triethoxysilyl-2-thiaethyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclooctyl]ethyl disulfide; bis-2-[4-(4-triethoxysilyl-2-thiaethyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclododecyl]ethyl disulfide; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 2-(6-triethoxysilyl-3-thiahexyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 2-(6-triethoxysilyl-3-thiahexyl)-1,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane, and mixtures thereof.
21. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 1 and R 3 are independently selected from a divalent hydrocarbon fragment having from 1 to about 5 carbon atoms.
22. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 1 and R 3 are branched and/or straight chain alkyl, alkenyl or alkynyl groups in which one hydrogen atom was substituted with a Y 1 or Y 2 group.
23. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I Y 1 and Y 2 are silyl (—SiX 1 X 2 X 3 ), hydrogen, alkoxy (—OR 6 ), carboxylic acid, ester (—C(═O)OR 6 ) wherein R 6 is a monovalent hydrocarbon group having from 1 to 5 carbon atoms.
24. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 2 is a straight chain hydrocarbon represented by —(CH 2 ) f — where f is an integer from about 1 to about 5.
25. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 4 is a polyvalent hydrocarbon fragment of 5 to about 12 carbon atoms.
26. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I R 5 is a polyvalent hydrocarbon fragment of 5 to about 12 carbon atoms.
27. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I 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.
28. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I X 2 and X 3 are independently selected from the group consisting of R 6 , wherein R 6 is a monovalent hydrocarbon group having from 1 to 5 carbon atoms, X 1 , wherein X 1 is independently selected from the group consisting of hydrolysable —OH, —OR 6 , wherein R 6 is a monovalent hydrocarbon group having from 1 to 5 carbon atoms, and —OSi containing groups that result from the condensation of silanols.
29. The composition of claim 1 wherein in the silated cyclic core polysulfide of Formula I 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 about 2; b and d are 1 to about 3; c and e are 1; f is 1 to about 5; m and p are 1, n is 1 to about 10; o is 0 to about 1; and x is 1 to about 6.
30. The composition of claim 1 wherein the silane of Formula II 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.
31. A process for making a composition comprising from about 30 to about 99 weight percent of a silated cyclic core polysulfide from about 1 to about 70 weight percent of a silated according to claim 1 which comprises:
(a) reacting a thioacid with the structure, R 6 C(═O)SH with a hydrocarbon containing reactive double bonds, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
(b) deblocking the mercapto group using a proton donator;
(c) reacting the intermediate mercaptan in step (b) with a base and then a halo containing hydrocarbon silane;
(d) reacting the intermediate mercapto silane from step (c) with a base and sulfur;
(e) reacting the intermediate in step (d) with a substituted or unsubstituted hydrocarbon containing a leaving group selected from chlorine, bromine or iodine, and mixtures thereof.
32. The process of claim 31 wherein the process is carried out in an organic solvent.
33. The process of claim 32 wherein the organic solvent is selected from the group consisting of ethanol, methanol, isopropyl alcohol, tetrahydrofuran, diethyl ether, hexanes, cyclohexane, toluene, xylenes, and mixtures thereof.
34. The process of claim 31 wherein the hydrocarbon containing at least one double bond in step (a) has the general formula:
wherein R 4 is independently selected from a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms and the subscripts g, h and i are about 0 to 3.
35. The process of claim 31 wherein the free radical agent of step (b) is an oxidizing agent that converts thiocarboxylic acid to a thiocarboxylic acid radical.
36. The process of claim 35 wherein the oxidizing agent is selected from the group consisting of oxygen, peroxides, hydroperoxides, and mixtures thereof.
37. The process of claim 36 wherein the proton donator of step (c) is a hydrogen containing heterocarbon or substituted heterocarbon that is capable of reacting with the intermediate of step (b).
38. The process of claim 31 wherein the proton donor is selected from the group consisting of alcohols, amines, mercaptans, and mixtures thereof.
39. The process of claim 38 wherein the alcohol is selected from the group consisting of methanol, ethanol, isopropyl alcohol, propanol, and mixtures thereof.
40. The process of claim 38 wherein the amine is selected from the group consisting of ammonia, methyl amine, propyl amine, diethanol amine, and mixtures thereof.
41. The process of claim 38 wherein the mercaptan is selected from the group consisting of propyl mercaptans, butyl mercaptan, and mixtures thereof.
42. The process of claim 31 wherein the substituted or unsubstituted hydrocarbon of step (e) has the general formulae selected from the group consisting of:
Y 1 R 1 Z; or
Y 2 R 3 Z;
wherein each occurrence of Y 1 and Y 2 , is independently silyl (—SiX 1 X 2 X 3 ), R 1 and R 3 are independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms, and Z is selected from the group consisting of Cl, Br and I, and mixtures thereof.
43. The process of claim 31 wherein the silated cyclic core polysulfide is any of the isomers of 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(13-triethoxysilyl-3,4-dithiamidecyl)cyclohexane; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(13-triethoxysilyl-3,4,5-trithiamidecyl)cyclohexane; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(12-triethoxysilyl-3,4,5-tetrathiadodecyl)cyclohexane; 1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(11-triethoxysilyl-3,4-tetrathiaunidecyl)cyclohexane 4-(3-triethoxysilyl-1-thiaethyl)-1,2-bis-(13-triethoxysilyl -3,4,5,6,7-pentathiamidecyl)cyclohexane; 4-(6-diethoxymethylsilyl-2-thia hexyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(4-triethoxysilyl-2-thiabutyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 4-(7-triethoxysilyl-3-thiaheptyl)-1,2-bis-(9-triethoxysilyl-3,4,5-trithianonyl)cyclohexane; 4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)benzene; 4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4,5-trithianonyl)benzene; 4-(5-triethoxysilyl-2-thiapentyl)-1,2-bis-(9-triethoxysilyl-3,4-dithianonyl)benzene; bis-2-[4-(3-triethoxysilyl-2-thiapropyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl tetrasulfide; bis-2-[4-(3-triethoxysilyl-1-thiapropyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl trisulfide; bis-2-[4-(3-triethoxysilyl-1-thiapropyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl disulfide; bis-2-[4-(6-triethoxysilyl-3-thiahexyl)-3-(9-triethoxysilyl-3,4,5-trithianonyl)phenyl]ethyl tetrasulfide; bis-2-[4-(6-triethoxysilyl-3-thiahexyl)-3-(9-triethoxysilyl-3,4,5-trithianonyl)nathyl]ethyl tetrasulfide; bis-2-[4-(4-diethoxymethylsilyl-2-thiabutyl)-3-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)phenyl]ethyl trisulfide; bis-2-[4-(4-triethoxysilyl-2-thiaethyl)-3-(7-triethoxysilyl -3,4-dithiaheptyl)cycloheptyl]ethyl disulfide; bis-2-[4-(4-triethoxysilyl-2-thiaethyl)-3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclooctyl]ethyl disulfide; bis-2-[4-(4-triethoxysilyl-2-thiaethyl) -3-(7-triethoxysilyl-3,4-dithiaheptyl)cyclododecyl]ethyl disulfide; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 2-(6-triethoxysilyl-3-thiahexyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 4-(6-triethoxysilyl-3-thiahexyl)-1,2-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 2-(6-triethoxysilyl-3-thiahexyl)-1,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 1-(6-triethoxysilyl-3-thiahexyl)-2,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane, and mixtures thereof.