Blocked mercaptosilane coupling agents for filled rubbers
View Patent ↗Disclosed herein is a blocked mercaptosilane selected from the group consisting of [[(ROC(═O)) p —(G) j ] k —Y—S] r —G—(SiX 3 ) s ; and (1) [(X 3 Si) q —G] a —[Y—[S—G—SiX 3 ] b ] c (2) 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 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; q is 0 to 6; a is 0 to 7; b is 1 to 3; j is 0 to 1, but it may be 0 only if p is 1; c is 1 to 6; 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 (i) a+b is 2 and (ii) k is 1; (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; and (III) if A is phosphorus, then k is 2.
1. A blocked mercaptosilane selected from the group consisting of:
[[(ROC(═O)) p -(G) j ] k —Y—S] r -G-(SiX 3 ) 8 (1); and
[(X 3 Si) q -G] a —[Y′—[S-G-SiX 3 ] b ] c (2)
wherein
Y is a polyvalent species (Q) z A(═E) selected from the group consisting of —C(═NR)—; —SC(═NR)—; —SC(═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)—; —P(═O)(—) 2 ; —(—S)P(═S)—; —P(═O)(—) 2 ; (—NR) 2 P(═O)—; (—O)(—NR)P(═O)—; —(—O)P(═O)—; —(—NR)P(═O)—; (—NR) 2 P(═S)—; (—NR)(—S)P(═S)—; (—O)(—NR)P(═S)—; —(—O)P(═S)—; and —(—NR)P(═S)—;
Y′ is a polyvalent species (O) z A(═E) selected from the group consisting of —C(═NR)—; —SC(═NR)—; —SC(═O)—; —S(═)—; —S(═O) 2 —; —OS(═O) 2 —; (—NR)S(═O) 2 —; —SS(═)—; —OS(═O)—; (—NR)S(═O)—; —SS(═O) 2 —;
wherein the atom A, attached to 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 carbon-carbon double bond, an alkenyl groups, an aryl groups, and/or aralkl groups, with each R contains 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 atom; wherein at least one G is polyvalent, and if G is monovalent, 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; q is 0 to 6; a is 0 to 7; b is 1 to 3; j is 0 to 1, but it may be 0 only if p is 1; c is 1 to 6; 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 (i) a+b is 2 and (ii) k is 1; (II) if A is phosphorous, 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; and (III) if A is phosphorous, then k is 2 and G is a monovalent or polyvalent group derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein G contains from 1 to 18 carbon atoms.
2. A blocked mercaptosilane according to claim 1 wherein a is selected from the group consisting of methyl, ethyl, propyl, isobutyl, phenyl, tolyl, phenethyl, norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, ethylcyclohexyl, ethylcyclohexenyl, and cyclohexylcyclohexyl.
3. A blocked mercaptosilane according to claim 1 according to formula (1).
4. A blocked mercaptosilane according to claim 1 according to formula (2).
5. A blocked mercaptosilane according to claim 1 which has been partially hydrolyzed.
6. A blocked mercaptosilane according to claim 1 wherein Y is selected from the group consisting of: —SC(═O)—; —S(O)—; —OS(═O)—; —(S))═O)—; and —P(═P═O)(—) 2 , and wherein Y′ is selected from the group consisting of: —SC(═O)—; —S(═O)—; —OS(═O)—; and —P(═O)(—) 2 .
7. The blocked mercaptosilane of claim 1 wherein Y is selected from the group consisting of —C(═NR)—and SC(═NR)—.
8. The blocked mercaptosilane of claim 1 wherein Y is selected from the group consisting of —S(═O) 2 —; (—NR)S(═O)—; (—NR)S(═O)—; SS(═O) 2 —.
9. A blocked mercaptosilane according to claim 1 wherein the sum of the carbon atoms within the G groups within the molecule is from 3 to 18.
10. A blocked mercaptosilane according to claim 1 wherein X is selected from the group consisting of methoxy, ethoxy, isobutoxy, propoxy, isopropoxy, acetoxy, and oximato.
11. A blocked mercaptosilane according to claim 1 wherein p is 0 to 2; X is RO— or RC(═O)O—; R is selected from the group consisting of hydrogen, phenyl, isopropyl, cyclohexyl, isobutyl; and G is a substituted phenyl or substituted straight chain alkyl of C 2 to C 12 .