Blocked mercaptosilane hydrolyzates as coupling agents for mineral-filled elastomer compositions

A composition comprising at least one organic polymer, at least one inorganic filler, and at least one blocked mercaptosilane condensate comprising at least one component whose chemical structure is represented by Formula 1:

• (W1)l(W2)m(W3)y(W4)u(W5)v(W6)w Formula 1
• wherein:
• m, y, u, v, and w are independently any integer from zero to 10,000;
• l is any integer from 1 to 10,000;
• W1 is a hydrolyzable blocked mercaptosilane fragment derived from a hydrolyzable blocked mercaptosilane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by either Formula 2 or Formula 3:
• {[(ROC(═O)-)p(G-)j]kY—S-}rG(-SiX3)s Formula 2:{(X3Si-)qG}a{Y(—S-G-SiX3)b}c;
• Formula 3:
• W2 is a hydrolyzable mercaptosilane fragment derived from a hydrolyzable mercaptosilane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by Formula 4:
• {[(ROC(═O)-)p(G-)j]kY—S-}r-dG(-SH)d(—SiX3)s;
• Formula 4:
• W3 is a hydrolyzable polysulfide silane fragment derived from a polysulfide silane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by Formula 5:
• X1X2X3Si-G1-Sx-G1—SiX1X2X3;
• Formula 5:
• W4 is a hydrolyzable alkyl silane fragment derived from a hydrolyzable alkyl silane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that can be represented by Formula 6:
• Y1Y2Y3Si—R2;
• Formula 6:
• W5 is a hydrolyzable bis silyl alkane fragment derived from a hydrolyzable bis silyl alkane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by Formula 7:
• Z1Z2Z3Si-J-SiZ1Z2Z3;
• Formula 7:
• W6 is a hydrolyzable tris silyl alkane fragment derived from a hydrolyzable tris silyl alkane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by either Formula 8 or Formula 9:
• (Z1Z2Z3Si—CH2CH2—)3C6H9 Formula 8:(Z1Z2Z3Si—CH2CH2CH2—)3N3C3O3;
• Formula 9:
• wherein, in the preceding Formulae 2 through 9:
• Y is a polyvalent species (Q)zA(═E);
• A is selected from the group consisting of carbon, sulfur, phosphorus, and sulfonyl;
• E is selected from the group consisting of oxygen, sulfur, and NR;
• each G is independently selected from the group consisting of monovalent and polyvalent moieties derived by substitution of alkyl, alkenyl, aryl, or aralkyl moieties, wherein G comprises from 1 to 18 carbon atoms;
• provided that G is not such that the silane would contain an α,β-unsaturated carbonyl including a carbon-carbon double bond next to the thiocarbonyl group, and provided that, if G is univalent, i.e., if p is 0, G can be hydrogen;
• in each case, 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;
• Q is selected from the group consisting of oxygen, sulfur, and (—NR—);
• each R is independently selected from the group consisting of hydrogen;
• straight, cyclic, or branched alkyl that may or may not contain unsaturation;
• alkenyl groups;
• aryl groups;
• and aralkyl groups, wherein each R, other than where R is hydrogen, comprises from 1 to 18 carbon atoms;
• each X is independently selected from the group consisting of —Cl, —Br, RO—, RC(═O)O—, R2C═NO—, R2NO—, R2N—, —R, —(OSiR2)t(OSiR3), and (—O—)0.5 wherein each R is as above and at least one X is not —R;
• R1, R2, R3, J, and G1 are independently selected from the group consisting of hydrocarbon fragments obtained by removal of one hydrogen atom from a hydrocarbon having from 1 to 20 carbon atoms including aryl groups and any branched or straight chain alkyl, alkenyl, arenyl, or aralkyl groups;
• each X1 is a hydrolyzable moiety independently selected from the group consisting of —Cl, —Br, —OH, —OR1, R1C(═O)O—, —O—N═CR12, and (—O—)0.5;
• each X2 and X3 is independently selected from the group consisting of hydrogen, the members listed above for R1, and the members listed above for X1;
• at least one occurrence of X1, X2, and X3 is (—O—)0.5;
• Y1 is a moiety selected from hydrolyzable groups consisting of —Cl, —Br, —OH, —OR, R2C(═O)O—, —O—N═CR22, and (—O—)0.5;
• Y2 and Y3 are independently selected from the group consisting of hydrogen, the members listed above for R2, and the members listed above for Y1;
• and
• at least one occurrence of Y1, Y2, and Y3 is (—O—)0.5.
• Z1 is selected from the hydrolyzable groups consisting of —Cl, —Br, —OH, —OR3, R3C(═O)O—, —O—N═CR32, and (—O—)0.5;
• Z2 and Z3 are independently selected from the group consisting of hydrogen, the members listed above for R3, and the members listed above for Z1;
• at least one occurrence of Z1, Z2, and Z3 in Formula 7 is (—O—)0.5;
• C6H9 in Formula 8 represents any cyclohexane fragment obtainable by removal of three hydrogen atoms from a cyclohexane molecule;
• N3C3O3 in Formula 9 represents N,N′,N″-trisubstituted cyanurate;
• a is 0 to 7;
• b is 1 to 3;
• c is 1 to 6;
• d is 1 to r;
• j is 0 or 1, but it may be 0 if, and only if, p is 1;
• k is 1 to 2;
• p is 0 to 5;
• q is 0 to 6;
• r is 1 to 3;
• s is 1 to 3;
• t is 0 to 5;
• x is 2 to 20;
• z is 0 to 2;
• provided that:
• (a) if A is carbon, sulfur, or sulfonyl, then
• (i) a+b is 2, and
• (ii) k is 1;
• (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;
• and
• c) if A is phosphorus, then k is 2.

A article of manufacture comprising a composition comprising at least one organic polymer, at least one inorganic filler, and at least one blocked mercaptosilane condensate comprising at least one component whose chemical structure is represented by Formula 1:

• (W1)l(W2)m(W3)y(W4)u(W5)v(W6)w Formula 1
• wherein:
• m, y, u, v, and w are independently any integer from zero to 10,000;
• l is any integer from 1 to 10,000;
• W1 is a hydrolyzable blocked mercaptosilane fragment derived from a hydrolyzable blocked mercaptosilane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by either Formula 2 or Formula 3:
• {[(ROC(═O)-)p(G-)j]kY—S-}rG(-SiX3)s Formula 2:{(X3Si-)qG}a{Y(—S-G-SiX3)b}c;
• Formula 3:
• W2 is a hydrolyzable mercaptosilane fragment derived from a hydrolyzable mercaptosilane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by Formula 4:
• {[(ROC(═O)-)p(G-)j]kY—S-}r-dG(-SH)d(—SiX3)s;
• Formula 4:
• W3 is a hydrolyzable polysulfide silane fragment derived from a polysulfide silane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by Formula 5:
• X1X2X3Si-G1-Sx-G1—SiX1X2X3;
• Formula 5:
• W4 is a hydrolyzable alkyl silane fragment derived from a hydrolyzable alkyl silane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that can be represented by Formula 6:
• Y1Y2Y3Si—R2;
• Formula 6:
• W5 is a hydrolyzable bis silyl alkane fragment derived from a hydrolyzable bis silyl alkane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by Formula 7:
• Z1Z2Z3Si-J-SiZ1Z2Z3;
• Formula 7:
• W6 is a hydrolyzable tris silyl alkane fragment derived from a hydrolyzable tris silyl alkane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by either Formula 8 or Formula 9:
• (Z1Z2Z3Si—CH2CH2—)3C6H9 Formula 8:(Z1Z2Z3Si—CH2CH2CH2—)3N3C3O3;
• Formula 9:
• wherein, in the preceding Formulae 2 through 9:
• Y is a polyvalent species (Q)zA(═E);
• A is selected from the group consisting of carbon, sulfur, phosphorus, and sulfonyl;
• E is selected from the group consisting of oxygen, sulfur, and NR;
• each G is independently selected from the group consisting of monovalent and polyvalent moieties derived by substitution of alkyl, alkenyl, aryl, or aralkyl moieties, wherein G comprises from 1 to 18 carbon atoms;
• provided that G is not such that the silane would contain an α,β-unsaturated carbonyl including a carbon-carbon double bond next to the thiocarbonyl group, and provided that, if G is univalent, i.e., if p is 0, G can be hydrogen;
• in each case, 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;
• Q is selected from the group consisting of oxygen, sulfur, and (—NR—);
• each R is independently selected from the group consisting of hydrogen;
• straight, cyclic, or branched alkyl that may or may not contain unsaturation;
• alkenyl groups;
• aryl groups;
• and aralkyl groups, wherein each R, other than where R is hydrogen, comprises from 1 to 18 carbon atoms;
• each X is independently selected from the group consisting of —Cl, —Br, RO—, RC(═O)O—, R2C═NO—, R2NO—, R2N—, —R, —(OSiR2)t(OSiR3), and (—O—)0.5 wherein each R is above and at least one X is not —R;
• R1, R2, R3, J, and G1 are independently selected from the group consisting of hydrocarbon fragments obtained by removal of one hydrogen atom from a hydrocarbon having from 1 to 20 carbon atoms including aryl groups and any branched or straight chain alkyl, alkenyl, arenyl, or aralkyl groups;
• each X1 is a hydrolyzable moiety independently selected from the group consisting of —Cl, —Br, —OH, —OR1, R1C(═O)O—, —O—N═CR12, and (—O—)0.5;
• each X2 and X3 is independently selected from the group consisting of hydrogen, the members listed above for R1, and the members listed above for X1;
• at least one occurrence of X1, X2, and X3 is (—O—)0.5;
• Y1 is a moiety selected from hydrolyzable groups consisting of —Cl, —Br, —OH, —OR, R2C(═O)O—, —O—N═CR22, and (—O—)0.5;
• Y2 and Y3 are independently selected from the group consisting of hydrogen, the members listed above for R2, and the members listed above for Y1;
• and
• at least one occurrence of Y1, Y2, and Y3 is (—O—)0.5.
• Z1 is selected from the hydrolyzable groups consisting of —Cl, —Br, —OH, —OR3, R3C(═O)O—, —O—N═CR32, and (—O—)0.5;
• Z2 and Z3 are independently selected from the group consisting of hydrogen, the members listed above for R3, and the members listed above for Z1;
• at least one occurrence of Z1, Z2, and Z3 in Formula 7 is (—O—)0.5;
• C6H9 in Formula 8 represents any cyclohexane fragment obtainable by removal of three hydrogen atoms from a cyclohexane molecule;
• N3C3O3 in Formula 9 represents N,N′,N″-trisubstituted cyanurate;
• a is 0 to 7;
• b is 1 to 3;
• c is 1 to 6;
• d is 1 to r;
• j is 0 or 1, but it may be 0 if, and only if, p is 1;
• k is 1 to 2;
• p is 0 to 5;
• q is 0 to 6;
• r is 1 to 3;
• s is 1 to 3;
• t is 0 to 5;
• x is 2 to 20;
• z is 0 to 2;
• provided that:
• (a) if A is carbon, sulfur, or sulfonyl, then
• (i) a+b is 2, and
• (ii) k is 1;
• (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;
• and
• c) if A is phosphorus, then k is 2.