Blocked mercaptosilane coupling agents for filled rubbers

1 - 3 . (canceled)

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

[(X 3 Si) q -G] a —[Y—[S-G-SiX 3 ] b ] c

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))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 ∀,∃-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;

z is 0 to 2; q is 0 to 6; a is 0 to 7; b is 1 to 3; c is 1 to 6; t is 0 to 5; with the provisos that (I) if A is carbon, sulfur, or sulfonyl, then a+b is 2; (II) if A is phosphorus, then a+b is 3 unless both (i) c is greater than 1 and (ii) b is 1, in which case a is c+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.

5 - 18 . (canceled)

19 . The process for the manufacture of a filled rubber of claim 4 comprising the steps of mixing a rubber, an inorganic filler, and a blocked mercaptosilane of the formula:

X 3 SiGSC(═O)GC(═O)SGSiX 3

wherein

each G is independently a divalent 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 ∀,∃-unsaturated carbonyl including a carbon-carbon double bond next to the thiocarbonyl group;

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 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, and at least one X is not —R; and

t is 0 to 5;

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.

20 - 22 . (canceled)

23 . A filled rubber produced by a process comprising the steps of mixing a rubber, an inorganic filler and a blocked mercaptosilane wherein the blocked mercaptosilane has the formula:

[(X 3 Si) q -G] a —[Y—[S-G-SiX 3 ] b ] c

wherein

Y is a polyvalent species (Q) z A(=E), each 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 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 if Y is —C(═O)—, G is not such that the blocked mercaptosilane would contain an ∀,∃-unsaturated carbonyl, and if G is univalent, G can be a hydrogen atom;

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 )(OSiR 3 ) wherein 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, and at least one X is not —R;

Q is oxygen, sulfur, or (—NR—);

A is carbon, sulfur, phosphorus, or sulfonyl;

E is oxygen, sulfur, or NR;

z is 0 to 2; q is 0 to 6; a is 0 to 7; b is 1 to 3; c is 1 to 6; t is 0 to 5; with the provisos that (A) if A is carbon, sulfur, or sulfonyl, then a+b is 2; (B) if A is phosphorus, then a+b is 3 unless both (i) c is greater than 1 and (ii) b is 1, in which case a is c+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.

24 - 35 . (canceled)

36 . The filled rubber of claim 23 produced by a process comprising the steps of mixing a rubber, an inorganic filler, and a blocked mercaptosilane wherein the blocked mercaptosilane has the formula:

[(X 3 Si) q -G] a —[Y—[S-G-SiX 3 ] b ] c

wherein

Y is —C(═O)—,

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

each G is a substituted phenyl with the proviso that G is not such that the mercaptosilane would contain an ∀,∃-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

q is 0 to 6; a is 0 to 7; b is 1 to 2; c is 1 to 6: t is 0 to 5; and a+b 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.

37 . (canceled)

38 . A filled rubber produced by a process comprising the steps of mixing a rubber, an inorganic filler, and a blocked mercaptosilane of the formula:

X 3 SiGSC(═O)GC(═O)SGSiX 3

wherein

each G is independently a divalent 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 ∀,∃-unsaturated carbonyl including a carbon-carbon double bond next to the thiocarbonyl group;

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 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, and at least one X is not —R; and

t is 0 to 5;

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.