Organofunctional silanes and their mixtures
View Patent ↗Organofunctional silanes, inclusive of dimers and oligomers, are provided in which individual silanes possess both free and blocked mercaptan functionality or particular mixtures of the organofunctional silanes possess both free and blocked mercaptan functionality. The organofunctional silanes and silane mixtures are useful, inter alia, as coupling agents for elastomeric compositions, e.g., rubber formulations employed in the manufacture of tires, where they exhibit a desirable balance of low scorch and good performance properties.
1. An organofunctional silane composition comprising at least one organofunctional silane having a chemical structure:
[[[(ROC(═O)) p -(G 1 ) j ] k - Y—S] r - G 2 -(SiX u Z b v Z c w ) s ] m [(HS) r -G 2 -(SiX u Z b v Z c w ) s ] n
wherein:
each occurrence of Y is independently selected from the group consisting of —C(═NR)—; —SC(═NR)—; —SC(═O)—; (—NR)C(═O)—; (—NR)C(═S)—; —OC(═O)—; —OC(═S)—; —C(═O)—; —SC(═S)—; —C(═S)—; —S(═O)—; —S(═O) 2 —; —OS(═O) 2 —; (—NR)S(═O) 2 —; —SS(═O)—; —OS(═O)—; (—NR)S(═O)—and —SS(═O) 2 —;
each occurrence of 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 hydrogen, contains from 1 to 18 carbon atoms;
each occurrence of G 1 is independently selected from the group consisting of hydrogen, monovalent alkyl, alkenyl, aryl, and aralkyl groups and polyvalent alkylene, alkenylene, arylene and aralkylene groups, wherein each G 1 , other than hydrogen, contains from 1 to 30 carbon atoms;
each occurrence of G 2 is independently selected from the group consisting of divalent and polyvalent alkylene, alkenylene, arylene, and aralkylene groups, wherein each G 2 contains from 1 to 30 carbon atoms;
each occurrence of 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, HO(R 0 CR 0 ) f O—, wherein each R is as above and each occurrence of R 0 is independently given by one of the members listed above for R;
each occurrence of Z b , which forms a bridging structure between two silicon atoms, is independently given by [—O(R 0 CR 0 ) f O—] 0.5 , wherein each occurrence of R 0 is independently given by one of the members listed above for R;
each occurrence of Z c , which forms a cyclic structure with a silicon atom, is independently given by —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 f j, k, m, n, p, r, s, u, v and w is independently given by f is 2 to 15; j is 0 to 1, but j may be 0 only if p is 1; k is 1; m is 1 to 20; n is 1 to 20; p is 0 to 5; r is 1 to 3; s is 1 to 3; u is 0 to 2; v is 1 to 3; w is 0 to 1 with the provisos that u+v+2w=3; the structure above contains at least one hydrolysable group, Z b , bound to a silicon atom of the repeat unit [[[(ROC(═O)) p —(G 1 ) j ] k —Y—S] r —G 2 —(SiX u Z b v Z c w ) s ] and at least one hydrolysable group, Z b , bound to a silicon atom of the repeat unit [(HS) r —G 2 —(SiX u Z b v Z c w ) s ], wherein the two Z b groups are combined together to form a bridging group that chemically bonds the silicon atoms of the two different repeat units together; and the structure above contains at least one hydrolysable group, Z c , that is a difunctional alkoxy group.
2. The organofunctional silane composition of claim 1 wherein Y is selected from the group consisting of —OC(═O)—; —OC(═S)—; —C(═O)—; —SC(═S)—; —C(═S)—.
3. The organofunctional silane composition of claim 2 wherein Y is —C(═O)—.
4. The organofunctional silane composition of claim 3 wherein G 1 has a primary carbon atom attached to a carbonyl and is a C 1 -C 18 alkyl.
5. The organofunctional silane composition of claim 3 wherein G 2 is a divalent or polyvalent C 1 -C 12 alkylene group.
6. The organofunctional silane composition of claim 4 wherein G 1 is a monovalent straight chain C 3 -C 10 , alkyl group.
7. The organofunctional silane composition of claim 5 wherein G 2 is a divalent or polyvalent C 3 -C 10 alkylene group, p is 0, j is 1 and k is 1 and the ratio of m to n is from about 20:1 to about 3:1.
8. The organofunctional silane composition of claim 6 wherein G 1 is a monovalent straight chain C 6 -C 8 alkyl group.
9. The organofunctional silane composition of claim 7 wherein G 2 is a divalent or polyvalent C 3 —C 6 alkylene group, p is 0, j is 1 and k is 1 and the ratio of m to n is from about 10:1 to about 4:1.
10. The organofunctional silane composition of claim 1 wherein G 1 is CH 3 (CH 2 ) g — and g is from 1 to about 29.
11. The organofunctional silane composition of claim 10 wherein G 1 is selected from the group consisting of methyl, ethyl, propyl, hexyl, heptyl, benzyl, phenyl, octyl and dodecyl.
12. The organofunctional silane composition of claim 1 wherein G 2 is —(CH 2 ) g — and g is from 1 to about 29.
13. The organofunctional silane composition of claim 12 wherein G 2 is selected from the group consisting of methylene, ethylene, propylene, butylenes and hexylene.
14. The organofunctional silane composition of claim 6 wherein the sum of the carbon atoms for G 14 and G 2 groups is from about 3 to about 18.
15. The organofunctional silane composition of claim 14 wherein the sum of the carbon atoms for G 1 and G 2 is from about 6 to about 14.
16. The organofunctional silane composition of claim 11 wherein G 1 is selected from the group consisting of —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —; —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —; —CH 2 (CH 2 ),CH(CH 3 )—, wherein i is 0 to about 16; —CH 2 CH 2 C(CH 3 ) 2 CH 2 —; —CH 2 CH(CH 3 )CH 2 —; —CH 2 CH 2 (C 6 H 4 )CH 2 CH 2 —; —CH 2 CH 2 (C 6 H 4 )CH(CH 3 )—; —CH 2 CH(CH 3 )(C 6 H 4 )CH(CH 3 )CH 2 —; —CH 2 CH 2 CH 2 CH 2 —; —CH 2 CH 2 CH(CH 3 )—; —CH 2 CH(CH 2 CH 3 )—; —CH 2 CH 2 CH 2 CH(CH 3 )—; —CH 2 CH 2 CH(CH 2 CH 3 )—; —CH 2 CH(CH 2 CH 2 CH 3 )—; —CH 2 CH(CH 3 )CH 2 CH 2 —; —CH 2 CH(CH 3 )CH(CH 3 )—; —CH 2 C(CH 3 )(CH 2 CH 3 )—; —CH 2 CH 2 CH(CH 3 )CH 2 —; —CH 2 CH 2 C(CH 3 ) 2 —; —CH 2 CH[CH(CH 3 ) 2 ]—; —CH 2 CH 2 -norbornyl-, —CH 2 CH 2 -cyclohexyl-; any of the diradicals obtainable from norbornane, cyclohexane, cyclopentane, tetrahydrodicyclopentadiene, or cyclododecene by loss of two hydrogen atoms; the structures derivable from limonene, —CH 2 CH(4—CH 3 —1—C 6 H 9 —)CH 3 ; —CH 2 CH 2 (vinylC 6 H 9 )CH 2 CH 2 —; —CH 2 CH 2 (vinylC 6 H 9 )CH(CH 3 )—, —CH 2 CH[CH 2 CH 2 CH═C(CH 3 ) 2 ]CH 2 CH 2 —; —CH 2 CH[CH 2 CH 2 CH═C(CH 3 ) 2 ]CH(CH 3 )—; —CH 2 C[CH 2 CH 2 CH═C(CH 3 ) 2 ](CH 2 CH 3 )—; —CH 2 CH 2 CH[CH 2 CH 2 CH═C(CH 3 ) 2 ]CH 2 —; —CH 2 CH 2 (C—)(CH 3 )[CH 2 CH 2 CH═C(CH 3 ) 2 ]; —CH 2 CH[CH(CH 3 )[CH 2 CH 2 CH═C(CH 3 ) 2 ]]—; —CH 2 CH(CH═CH 2 )CH 2 CH 2 CH 2 C(CH 3 ) 2 —, —CH 2 CH(CH═CH 2 )CH 2 CH 2 CH[CH(CH 3 ) 2 ]—, —CH 2 C(═CH—CH 3 )CH 2 CH 2 CH 2 C(CH 3 ) 2 —, —CH 2 C(═CH—CH 3 )CH 2 CH 2 CH[CH(CH 3 ) 2 ]—, —CH 2 CH 2 C(═CH 2 )CH 2 CH 2 CH 2 C(CH 3 ) 2 —, —CH 2 CH 2 C(═CH 2 )CH 2 CH 2 CH[CH(CH 3 ) 2 ]—, —CH 2 CH═C(CH 3 ) 2 CH 2 CH 2 CH 2 C(CH 3 ) 2 —, and —CH 2 CH═C(CH 3 ) 2 CH 2 CH 2 CH[CH(CH 3 ) 2 ].
17. The organofunctional silane composition of claim 12 wherein G 2 is selected from the group consisting of —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —; —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 (CH 2 ),CH(CH 3 )—, where i is 0 to about 16; —CH 2 CH 2 C(CH 3 ) 2 CH 2 —; —CH 2 CH(CH 3 )CH 2 —; —CH 2 CH 2 (C 6 H 4 )CH 2 CH 2 —; —CH 2 CH 2 (C 6 H 4 )CH(CH 3 )—; —CH 2 CH(CH 3 )(C 6 H 4 )CH(CH 3 )CH 2 —; —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH(CH 3 )—; —CH 2 CH(CH 2 CH 3 )—; —CH 2 CH 2 CH 2 CH(CH 3 )—; —CH 2 CH 2 CH(CH 2 CH 3 )—; —CH 2 CH(CH 2 CH 2 CH 3 )—; —CH 2 CH(CH 3 )CH 2 CH 2 —; —CH 2 CH(CH 3 )CH(CH 3 )—; —CH 2 C(CH 3 )(CH 2 CH 3 )—; —CH 2 CH 2 CH(CH 3 )CH 2 —; —CH 2 CH 2 C(CH 3 ) 2 —; —CH 2 CH[CH(CH 3 ) 2 ]—; —CH 2 CH 2 -norbornyl-, —CH 2 CH 2 -cyclohexyl-; any of the diradicals obtainable from norbornane, cyclohexane, cyclopentane, tetrahydrodicyclopentadiene, or cyclododecene by loss of two hydrogen atoms; the structures derivable from limonene, —CH 2 CH(4—CH 3 —1—C 6 H 9 —)CH 3 ; —CH 2 CH 2 (vinylC 6 H 9 )CH 2 CH 2 — and —CH 2 CH 2 (vinylC 6 H 9 )CH(CH 3 )—; —CH 2 CH[CH 2 CH 2 CH═C(CH 3 ) 2 ]CH 2 CH 2 —; —CH 2 CH[CH 2 CH 2 CH═C(CH 3 ) 2 ]CH(CH 3 )—; —CH 2 C[CH 2 CH 2 CH═C(CH 3 ) 2 ](CH 2 CH 3 )—; —CH 2 CH 2 CH[CH 2 CH 2 CH═C(CH 3 ) 2 ]CH 2 —, —CH 2 CH 2 (C—)(CH 3 )[CH 2 CH 2 CH═C(CH 3 ) 2 ]; —CH 2 CH[CH(CH 3 )[CH 2 CH 2 CH═C(CH 3 ) 2 ]]—; —CH 2 CH(CH═CH 2 )CH 2 CH 2 CH 2 C(CH 3 ) 2 —, —CH 2 CH(CH═CH 2 )CH 2 CH 2 CH[CH(CH 3 ) 2 ]—, —CH 2 C(═CH—CH 3 )CH 2 CH 2 CH 2 C(CH 3 ) 2 —; —CH 2 C(═CH—CH 3 )CH 2 CH 2 CH[CH(CH 3 ) 2 ]—, —CH 2 CH 2 C(═CH 2 )CH 2 CH 2 CH 2 C(CH 3 ) 2 —, —CH 2 CH 2 C(═CH 2 )CH 2 CH 2 CH[CH(CH 3 ) 2 ]—, —CH 2 CH═C(CH 3 ) 2 CH 2 CH 2 CH 2 C(CH 3 ) 2 —, and —CH 2 CH═C(CH 3 ) 2 CH 2 CH 2 CH[CH(CH 3 ) 2 ].
18. The organofunctional silane composition of claim 1 wherein the organofunctional silane is selected from the group consisting of thioacetic acid 2-(2-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-ethyl ester; thioacetic acid 3-(2-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl ester; thiobutyric acid 3-(2-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2—yl)-propyl ester; octanethioic acid 3-(2-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl -[1,3,2]dioxasilinan-2-yl)-propyl ester; octanethioic acid S-[3-(2-{3-[2-(3-mercapto-propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]ester; octanethioic acid S-[3-(2-{3-[2-(3-mercapto-propyl)-4-methyl-[1,3,2]dioxasilinan-2-yloxy]-butoxy}-4-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]ester; undecanethioic acid S-[3-(2-{3-[2-(3-mercapto-propyl)-4-methyl-[1,3,2]dioxasilinan-2-yloxy]-butoxy}-4-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]ester; heptanethioic acid S-[3-((3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl]ester; heptanethioic acid S-[3-(2-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilepan-2—yl)-propyl]ester; thiopropionic acid 3-{2-[3-((3-mercapto-propyl)-methyl-{2-methyl-3-[5-methyl-2-(3-propionylsulfanyl-propyl)-[1,3,2]dioxasilinan-2-yloxy]-propoxy}-silanyloxy)-2-methyl-propoxy]-5-methyl-[1,3,2]dioxasilepan-2-yl}-propyl ester; octanethioic acid 3-{2-[3-((3-mercapto-propyl)-methyl-{2-methyl-3-[5-methyl-2-(3-octanoylsulfanyl-propyl)-[1,3,2]dioxasilinan-2-yloxy]-propoxy}-silanyloxy)-2-methyl-propoxy]-5-methyl-[1,3,2]dioxasilepan-2-yl}-propyl ester; octanethioic acid S-[3-((3-hydroxy-2-methyl-propoxy)-{3-[{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl -propoxy}-methyl-(3-octanoylsulfanyl-propyl)-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl]ester; octanethioic acid S-[3-((3-hydroxy-2-methyl-propoxy)-{3-[{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl]ester; octanethioic acid S-[3-((3-hydroxy-2-methyl-propoxy)-{3-[{3-[bis-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-(3-hydroxy-2-methyl-propoxy)-silanyloxy]-2-methyl-propoxy}-(3-hydroxy-2-methyl-propoxy)-silanyl)-propyl]ester; dimethyl-thiocarbamic acid S-[3-((3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl]ester; dimethyl-dithiocarbamic acid 3-((3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; dimethyl-dithiocarbamic acid 3-((3-hydroxy-2-methyl-propoxy)-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; thiocarbonic acid O-ethyl ester S-[3-((3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl]ester; trithiocarbonic acid ethyl ester 3-((3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; trithiocarbonic acid ethyl ester 3-((3-hydroxy-2-methyl-propoxy)-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; dithiobutyric acid 3-((3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; dithiobutyric acid 3-((3-hydroxy-2-methyl-propoxy)-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; diethyl-dithiocarbamic acid 3-((3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; diethyl-dithiocarbamic acid 3-((3-hydroxy-2-methyl-propoxy)-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; N-methyl-thiobutyrimidic acid 3-((3-hydroxy-2-methyl-propoxy)-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; N-methyl-thiobutyrimidic acid 3-((3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl ester; and mixtures thereof.
19. The organofunctional silane composition of claim 1 wherein the organofunctional silane is selected from the group consisting of octanethioic acid S-[3-((3-hydroxy-2-methyl-propoxy)-{3-[{3-[bis-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-(3-hydroxy-2-methyl-propoxy)-silanyloxy]-2-methyl-propoxy}-(3-hydroxy-2-methyl-propoxy)-silanyl)propyl]ester; octanethioic acid S-[3-((3-hydroxy-2-methyl-propoxy)-{3-[{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl]ester; octanethioic acid 3-(2-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl ester; octanethioic acid S-[3-(2-{3-[2-(3-mercapto-propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propyl]ester; octanethioic acid S-[3-(2-{3-[2-(3-mercapto-propyl)-4-methyl-[1,3,2]dioxasilinan-2-yloxy]-butoxy}-4-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]ester; undecanethioic acid S-[3-(2-{3-[2-(3-mercapto-propyl)-4-methyl-[1,3,2]dioxasilinan-2-yloxy]-butoxy}-4-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]ester; heptanethioic acid S-[3-((3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-methyl-silanyl)-propyl]ester; heptanethioic acid S-[3-(2-{3-[(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-methyl-silanyloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilepan-2-yl)-propyl]ester; thiopropionic acid 3-{2-[3-((3-mercapto-propyl)-methyl-{2-methyl-3-[5-methyl-2-(3-propionylsulfanyl-propyl)-[1,3,2]dioxasilinan-2-yloxy]-propoxy}-silanyloxy)-2-methyl-propoxy]-5-methyl-[1,3,2]dioxasilepan-2-yl}-propyl ester; and octanethioic acid 3-{2-[3-((3-mercapto-propyl)-methyl-{2-methyl-3-[5-methyl-2-(3-octanoylsulfanyl-propyl)-[1,3,2]dioxasilinan-2-yloxy]-propoxy}-silanyloxy)-2-methyl-propoxy]-5-methyl-[1,3,2]dioxasilepan-2-yl}-propyl ester.