Free flowing filler composition comprising mercapto-functional silane
View Patent ↗The disclosure herein relates to organofunctional silanes and mixtures of organofunctional silanes possessing mercaptan and hydrocarbyl and/or heterocarbyl functionality. These silanes reduce or eliminate the generation of volatile organic compounds (VOC's) during use, aid in the processing of filled elastomeric materials and enhance the end-use properties of the filled elastomer. The present disclosure relates to a free flowing filler composition comprising these silanes.
1. A free flowing filler composition comprising
a) at least one particulate filler; and,
b) a mercaptofunctional silane composition comprising at least one of the structures (10) and (11):
[G 1 —(SiX α u Z β v Z θ w ) s ] m [(HS) r -G 2 —(SiX α u Z β v Z θ w ) s ] n (10)
[[G 3 —(YG 2 ) k Y] j G 2 —(SiX α u Z β v Z θ w ) s ] m [(HS) r -G 2 —(SiX α u Z β v Z θ w ) s ] n (11)
wherein:
each occurrence of Y is independently selected from a polyvalent species (-Q) a [C(═E)] b (A-) c , wherein the atom (E) is attached to an unsaturated carbon atom;
each occurrence of G 1 is independently selected from the group consisting of monovalent and polyvalent groups derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein G 1 can have from 1 to about 30 carbon atoms;
each occurrence of G 2 is independently selected from the group consisting of divalent or polyvalent group derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein G 2 can have from 1 to 30 carbon atoms;
each occurrence of G 3 is independently selected from the group consisting of monovalent and polyvalent groups derived by substitution of alkyl, alkenyl, aryl, or aralkyl wherein G 3 can have from 1 to about 30 carbon atoms, with the proviso that if G 3 is monovalent, G 3 can be hydrogen;
each occurrence of is X α independently selected from the group consisting of —Cl, —Br, RO—, RC(═O)O—, R 2 C=NO—, R 2 NO—, R 2 N—, —R, (HO) d-1 G 4 O—, HO(CR 0 2 ) 1 O—, and HO(CR 0 2 CR 0 2 O) e — wherein each R is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl that can or can not contain unsaturation, alkenyl groups, aryl groups, and aralkyl groups, wherein each R, other than hydrogen, contains from 1 to 18 carbon atoms, G 4 is independently a substituted hydrocarbon group of from about 2 to about 15 carbon atoms or a substituted heterocarbon group of from about 4 to 15 carbon atoms and contains one or more etheric oxygen atoms, R 0 is independently given by one of the members listed for R, f is from about 2 to about 15, and e is from about 2 to about 7;
each occurrence of Q is independently selected from the group consisting of oxygen, sulfur, and (—NR—) and with the proviso that when Q is sulfur, b is 0;
each occurrence of A is independently selected from the group consisting of oxygen, sulfur, and (—NR—) and with the proviso that when A is sulfur, b is 0;
each occurrence of E is independently selected from the group consisting of oxygen, sulfur, and (—NR—);
each occurrence of Z β , which forms a bridging structure between two silicon atoms, is independently selected from the group consisting of, [—OG 4 (OH) d-2 O—] 0.5 , [—O(CR 0 2 CR 0 2 O) e —] 0.5 and [—O(R 0 CR 0 ) 1 O—] 0.5 , wherein each occurrence of R 0 is independently given by one of the members listed above for R; and, each occurrence of G 4 is independently selected form the group consisting of a substituted hydrocarbon group from 2 to 15 carbon atoms or a substituted hetercarbon from 4 to 15 carbon atoms and contain one or more etheric oxygen atoms;
each occurrence of Z θ , which forms a cyclic structure with a silicon atom, is independently given by —OG 4 (OH) d-2 O—, —O(CR 0 2 CR 0 2 O) e — and —O(R 0 CR 0 ) f O— wherein each occurrence of R 0 is independently given by one of the members listed above for R;
each occurrence of the subscripts, a, b, c, d, e, f, j, k, m, n, r, s, u, v, and w are integers independently given by a is 0 or 1; b is 0 or 1; c is 0 or 1; d is from about 2 to about 8; e is from about 2 to about 7; f is from about 2 to about 15; j is from 1 to about 3; k is from 0 to about 15;
m is from about 1 to about 20; n is from about 1 to about 20; r is from 1 to about 3; and s is from 1 to about 3; u is from 0 to 3; v is from 1 to 3; w is from 0 to about 1; with the proviso that u+v+2w=3; and with the proviso that the each of the above structures (10) and/or (11) contains at least one hydrolysable group, Z β or Z θ .
2. The free flowing filler composition of claim 1 wherein, the filler is reactive with the mercaptofunctional silane composition.
3. The free flowing filler composition of claim 1 wherein the filler is a metal oxide.
4. The free flowing filler composition of claim 1 wherein the filler is a siliceous material.
5. The free flowing filler composition of claim 1 wherein the :filler is a silica alone or in combination with one or more other fillers.
6. The free flowing filler composition of claim 1 wherein the filler is a precipitated silica.
7. The free flowing filler composition of claim 1 wherein the amount of mercaptofunctional silane present is from about 0.1 to about 70 weight percent based on total weight of free flowing filler composition.
8. The free flowing filler composition of claim 1 wherein the amount of filler is of from about 99.5 to about 80 weight percent based on total weight of free flowing filler composition.
9. The free-flowing filler composition of claim 1 wherein the mercaptofunctional silane is selected from the group consisting of 3-{4-methyl-2-[2(4-methyl-2-pentyl-[1,3,2]dioxasilolan-2-yloxy)-propoxy]-[1,3,2]dioxasilolan-2-yl}-propane-1-thiol; 3-{2-[2-(2-methyl-[1,3,2]dioxasilolan-2-yloxy)-ethoxy]-[1,3,2]dioxasilolan-2-yl}-propane-1-thiol; 4-{2-[3-(2-butyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-[1,3,2]dioxasilinan-2-yl}-butane-1-thiol; 4-[2-(3-{2-[3-(2-methoxy-ethoxy)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-butane-1-thiol; 4-[5-methyl-2-(2-methyl-3-{5-methyl-2-[3-(2-methylamino-ethylamino)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-butane-1-thiol; 2-acetylamino-N-[3-(2- {3-[2-(4-mercapto-butyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-acetamide; (2-{3-[3-(2-{3-[2-(4-mercapto-butyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy)}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-ureido}-ethyl)-urea; 4-acetoxy-butyric acid 3-(2-{3[2-(4-mercapto-butyl)-5,5-dimethyl-[1,3,2]dioxasilinan-2-yloxy]-2,2-dimethyl-propoxy}-5,5-dimethyl-[1,3,2]dioxasilinan-2-yl)-propyl ester; carbonic acid 2-[3-(2-{3-[2-(4-mercapto-butyl)-5,5-dimethyl-[1,3,2]dioxasilinan-2-yloxy]-2,2-dimethyl-propoxy}-5,5-dimethyl-[1,3,2]dioxasilinan-2-yl)-propoxycarbonyloxy]-ethyl ester methyl ester; 4-{[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-dimethyl-silanyl}-butane-1-thiol; 4-{[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-diethoxy-silanyl}-butane- 1-thiol; 4-[butyl-[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)- 1,1-dimethyl-butoxy]-(4-mercapto-butyl)-silanyloxy]-2-methyl-pentan-2-ol; 4- {(3-hydroxy-2-methyl-propoxy)-(4-mercapto-butyl)-[2-methyl-3-(5-methyl-2-octyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-silanyl}-2-methyl-butan-1-ol; 3-{(3-hydroxy-2-methyl-propoxy) -(4-mercapto-butyl)-[2-methyl-3-(5-methyl-2-octyl[1,3,2]dioxasilinan-2-yloxy)-propoxy]-silanyloxy }-2-methyl-propan-1-ol; 4-[(3-hydroxy-2-methyl-propoxy)- {3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(4-mercapto-butyl)-silanyl]-2-methyl-butan-1-ol ; 3-[(3-hydroxy-2-methyl-propoxy)- {3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]2-methyl-propoxy}-(4-mercapto-butyl)-silanyloxy]-2-methyl-propan-1-ol; 3-[{3-[(3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-methyl-octyl-silanyloxy]-3-methyl-butyl}-(3-mercapto- propyl) -silanyloxy]-2-methyl-propoxy}-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propan-1-ol; 4-((3-hydroxy-2-methyl-propoxy)- {4-[(3-hydroxy-2-methyl-propoxy)- {3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyloxy]-2-methyl-butoxy) -octyl-silanyloxy)-2-methyl-butan-1-ol; 3-((3-hydroxy-2-methyl-propoxy)- {4-[(3-hydroxy-2-methyl-propoxy)- {3-[(3-hydroxy-2-methyl-propoxy) -(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyloxy]-2-methyl-butoxy}-octyl-silanyloxy)-2-methyl-propan-1-ol; 4-(benzyl-(3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{(3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-phenethyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyloxy[2-methyl-butoxy) -silanyloxy)-2-methyl-butan-1-ol; 4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyloxy}-2-methyl-butoxy)-pent-4-enyl-silanyloxy]-2-methyl-butan-1-ol; 4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl[1,2]oxasilolan-2-yloxy)-propoxy]-silanyloxY}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-butan-1-ol; 4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)[2-methyl-3-(4-methyl-2-octyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyloxy}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-butan-1-ol; and combinations thereof.