Granted Patent B2

US 7,081,500 · App. 09/986,512 · Granted Jul 25, 2006

Abstract

Claims (46)

1. A process of manufacturing a filled rubber comprising the steps of mixing a rubber, an inorganic filler, and a blocked mercaptosilane of the formula

[[(ROC(═O)) p -(G) j ] k -Y—S] r -G-(SiX 3 ) s   (1);

wherein

Y is a polyvalent species (Q) z A(═E) selected from the group consisting of —C(═NR)—;—SC(═NR)—; —SC(═O)—; —OC(═O)—; —S(═O)—; —S(═O) 2 —; —OS(═O) 2 —; (—NR)S(═O) 2 —; —SS(═O)—; —OS(═O)—; (—NR)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) 2 P(═O)—; (—NR)(—S)P(═O)—; (—O)(—NR)P(═O)—; (—O)(—S)P(═O)—; (—O) 2 P(═O)—; —(—O)P(═O)—; —(—NR)P(═O)—; (—NR) 2 P(═S)—; (—NR)(—S)P(═S)—; (—O)(—NR)P(═S)—; (—O)(—S)P(═S)—; (—O) 2 P(═S)—; —(—O)P(═S)—; and —(—NR)P(═S)—; wherein the atom A, attached to the unsaturated heteroatom E, is attached to the sulfur which in turn is linked via a group G to the silicon atom;

each R is chosen independently from hydrogen, straight, cyclic, or branched alkyl that may or may not contain unsaturation, alkenyl groups, aryl groups, and aralkyl groups, with each R containing from 1 to 18 carbon atoms;

each G is independently a monovalent or polyvalent group derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein G can contain from 1 to 18 carbon atoms, with the proviso that G is not such that the blocked mercaptosilane would contain an α,β-unsaturated carbonyl that can undergo polymerization reactions, and if G is univalent, G can be a hydrogen atom;

X is independently selected from the group consisting of —Cl, —Br, RO—, RC(═O)O—, R 2 C═NO—, R 2 NO—, R 2 N—, —R, and —(OSiR 2 ) t (OSiR 3 ) wherein each R is as above and at least one X is not —R;

p is 0 to 5; r is 1 to 3; z is 0 to 2; j is 0 to 1, but it may be 0 only if p is 1; t is 0 to 5; s is 1 to 3; k is 1 to 2; with the provisos that (I) if A is carbon, sulfur, or sulfonyl, then k is 1; and (II) if A is phosphorus, then k is 2; to produce a rubber mixture;

mixing into the rubber mixture (i) a deblocking agent to deblock the blocked mercaptosilane, and (ii) a curing agent; and

allowing the rubber mixture to cure.

2. The process of claim 1 wherein each R of the blocked mercaptosilane is selected from the group consisting of methyl, ethyl, propyl, isobutyl, phenyl, tolyl, phenethyl, norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, ethylcyclohexyl, ethylcyclohexenyl, and cyclohexylcyclohexyl.

3. The process of claim 1 wherein the blocked mercaptosilane has the formula:

[[(ROC(═O)) p -(G) j ] k -Y—S] r -G-(SiX 3 ) s .

4. The process of claim 1 wherein the blocked mercaptosilane is partially hydrolyzed.

5. The process of claim 1 wherein Y of the blocked mercaptosilane is selected from the group consisting of —OC(═O)—; —S(═O)—; —S(═O)—; —(—S)P(═O)—; and —P(═O)(—) 2 .

6. The process of claim 1 wherein each G of the blocked mercaptosilane is independently a monovalent or polyvalent group derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein the sum of all carbon atoms within G groups is three to eighteen carbon atoms.

7. The process of claim 1 wherein each G of the blocked mercaptosilane is independently a monovalent or polyvalent group derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein the sum of all carbon atoms within G groups is six to fourteen carbon atoms.

8. The process of claim 1 wherein X of the blocked mercaptosilane is independently selected from the group consisting of methoxy, ethoxy, isobutoxy, propoxy, isopropoxy, acetoxy, and oximato.

9. A process of manufacturing a filled rubber comprising the steps of:

mixing a rubber, an inorganic filler, and a blocked mercaptosilane of the formula

[[(ROC(═O)) p -(G) j ] k -Y—S] r -G-(SiX 3 ) s   (1);

wherein

Y is a polyvalent species (Q) z A(═E) selected from the group consisting of —C(═NR)—;—SC(═NR)—; —SC(═O)—; —OC(═O)—; —S(═O)—; —S(═O) 2 —; —OS(═O) 2 —; (—NR)S(═O) 2 —; —SS(═O)—; —OS(═O)—; (—NR)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) 2 P(═O)—; (—NR)(—S)P(═O)—; (—O)(—NR)P(═O)—; (—O)(—S)P(═O)—; (—O) 2 P(═O)—; —(—O)P(═O)—; —(—NR)P(═O)—; (—NR) 2 P(═S)—; (—NR)(—S)P(═S)—; (—O)(—NR)P(═S)—; (—O)(—S)P(═S)—; (—O) 2 P(═S)—; —(—O)P(═S)—; and —(—NR)P(═S)—; wherein the atom A, attached to the unsaturated heteroatom E, is attached to the sulfur which in turn is linked via a group G to the silicon atom;

each R is selected from the group consisting of hydrogen, phenyl, isopropyl, cyclohexyl, and isobutyl;

each G is a substituted phenyl or substituted straight chain alkyl having from 2 to 12 carbon atoms;

X is independently selected from the group consisting of RO— and RC(═O)O—, wherein each R is as above;

p is 0 to 2; r is 1 to 3; z is 0 to 2; j is 0 to 1, but it may be 0 only if p is 1; t is 0 to 5; s is 1 to 3; k is 1 to 2; with the provisos that (I) if A is carbon, sulfur or sulfonyl, then k is 1; and (II) if A is phosphorus, then k is 2; to produce a rubber mixture;

mixing into the rubber mixture (i) a deblocking agent to deblock the blocked mercaptosilane, and (ii) a curing agent; and

allowing the rubber mixture to cure.

10. A process for the manufacture of a filled rubber comprising the steps of mixing a rubber, an inorganic filler, and a blocked mercaptosilane of the formula

[[(ROC(═O)) p -(G) j ] k -Y—S] r -G-(SiX 3 ) s   (1)

wherein

Y is —C(═O)—;

R is hydrogen or an alkyl having from one to four carbon atoms;

each G is a substituted phenyl or an alkyl derivative having from 2 to 12 carbon atoms, with the proviso that G is not such that the mercaptosilane would contain an α,β-unsaturated carbonyl that can undergo polymerization reactions;

X is independently a group selected from the group consisting of —Cl, —Br, RO—, RC(═O)O—, R 2 C═NO—, R 2 NO—, R 2 N—, —R, and —(OSiR 2 ) t (OSiR 3 ) wherein each R and G is as above and at least one X is not —R; and

p is 2to 5; r is 1 to 3; j is 1; t is 0 to 5; s is 1 to 3; k is 1; to produce a rubber mixture;

mixing into the rubber mixture (i) a deblocking agent to deblock the blocked mercaptosilane, and (ii) a curing agent; and

allowing the rubber mixture to cure.

11. The process of claim 10 wherein the blocked mercaptosilane is partially hydrolyzed.

12. The process of claim 10 wherein X of the blocked mercaptosilane is selected from the group consisting of methoxy, ethoxy, isobutoxy, propoxy, isopropoxy, acetoxy, and oximato.

13. The process of claim 10 wherein X of the blocked mercaptosilane is RO— or RC(═O)O—.

14. The process of claim 10 wherein R of the blocked mercaptosilane is hydrogen.

15. The process of claim 10 wherein G of the blocked mercaptosilane is a substituted phenyl.

16. The process of claim 1 wherein G, which is directly bonded to Y, is alkyl of two to twelve carbon atoms.

17. The process of claim 1 wherein G, which is directly bonded to Y, is alkyl of six to eight carbon atoms.

Assignments (14)