Vinylsilanes for use in functionalized elastomeric polymers
View Patent ↗The present invention relates to novel vinylsilane compounds which are useful as modifying monomers in the polymerization of conjugated diene monomers, optionally together with aromatic vinyl monomers, thus producing polymers, specifically elastomeric polymers, which can favorably be used in rubber articles such as tires.
1. A vinylsilane compound of the following Formula 1:
wherein R is independently selected from C 1 -C 18 hydrocarbyl;
R″ is selected from C 1 -C 6 hydrocarbyl;
R a , R b and R c are independently selected from hydrogen, methyl, ethyl and vinyl;
x and y are independently integers selected from 1 and 2; z is an integer selected from 0 and 1; and x+y+z=3;
R′ is independently selected from C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 6 -C 18 aryl, C 7 -C 18 alkylaryl, and tri(C 1 -C 6 alkyl, C 6 -C 12 aryl or C 7 -C 18 alkylaryl)silyl, wherein the two R′ groups may be connected to form a ring and the ring may contain, further to the Si-bonded nitrogen atom, one or more of an oxygen atom, a nitrogen atom, an >N(C 1 -C 6 alkyl) group and a sulfur atom; and one R′ may be —Si(CR c ═CR a R b )(OSiR 3 ) y (R″) z , wherein R a , R b , R c , R, R″, y and z are independently as defined above and y+z=2.
2. The vinylsilane compound according to claim 1 , which is represented by the following Formula 6:
wherein R* is independently selected from C 1 -C 6 alkyl, C 6 -C 12 aryl and C 7 -C 18 alkylaryl and the remaining parameters are as defined for Formula 1.
3. The vinylsilane compound according to claim 2 , wherein R is (methyl, methyl, t-butyl); R′ is selected from methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl and octyl; R* is selected from methyl and ethyl; R″ is methyl; R a , R b and R c are each hydrogen; and x=y=z=1.
4. The vinylsilane compound according to claim 1 , wherein R is independently selected from C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 6 -C 18 aryl and C 7 -C 18 alkylaryl.
5. The vinylsilane compound according to claim 1 , wherein R′ is independently selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, pentyl, hexyl and benzyl.
6. The vinylsilane compound according to claim 1 , wherein the two R′ groups are connected to form, together with the Si-bonded nitrogen atom, a 5- to 12-membered ring.
7. The vinylsilane compound according to claim 1 , wherein R″ is selected from C 1 -C 6 alkyl and phenyl.
8. The vinylsilane compound according to claim 1 , wherein R a , R b and R c are identical.
9. The vinylsilane compound according to claim 1 , wherein x, y and z are each 1.
10. The vinylsilane compound according to claim 1 , wherein R is (methyl, methyl, t-butyl) or (phenyl, phenyl, phenyl) or (t-butyl, phenyl, phenyl) or (hexyl, hexyl, hexyl); R′ is independently selected from methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, octyl and benzyl (bonded via methyl group), or —NR′R′ forms a morpholine group, pyrrolidine group, piperidine group or oxazolidine group; R″ is methyl; R a , R b and R c are each hydrogen; and x=y=z=1.
11. The vinylsilane compound according to claim 1 , wherein R is (methyl, methyl, t-butyl) or (hexyl, hexyl, hexyl); R′ is independently selected from methyl and ethyl, or —NR′R′ forms a morpholine group, pyrrolidine group, piperidine group or oxazolidine group; R″ is methyl; R a , R b and R c are each hydrogen; and x=2, y=1 and z=0.
12. The vinylsilane compound according to claim 1 , wherein R is (methyl, methyl, t-butyl) or (hexyl, hexyl, hexyl); R′ is independently selected from methyl and ethyl, or —NR′R′ forms a morpholine group, pyrrolidine group, piperidine group or oxazolidine group; R″ is methyl; R a and R b are each hydrogen and R c is vinyl; and x=y=z=1.
13. A process for preparing the vinylsilane compound of Formula 1 as defined in claim 1 , said process comprising reacting a dihalovinylsilane or trihalovinylsilane of the following Formula 2 with a tri(C 1 -C 18 hydrocarbyl)silanol of the following Formula 3 and a secondary aliphatic or aromatic amine of the following Formula 4 according to the following reaction scheme, in the presence of a proton scavenger:
wherein R, R′, R″, R a , R b , R c , x, y and z are as defined in claim 1 and X is halogen.
14. A process for preparing the vinylsilane compound of Formula 6 as defined in claim 2 , said process comprising reacting a dihalovinylsilane or trihalovinylsilane of the following Formula 2 with a tri(C 1 -C 18 hydrocarbyl)silanol of the following Formula 3, a primary aliphatic or aromatic amine of the following Formula 4′ and a halosilane of the following Formula 5 in the presence of a proton scavenger:
wherein R, R′, R″, R*, R a , R b , R c , x, y and z are as defined in claim 2 and X is halogen.
15. A process for preparing an elastomeric polymer, said process comprising polymerizing at least one conjugated diene monomer, a vinylsilane compound as defined in claim 1 and-optionally one or more aromatic vinyl monomers in the presence of an initiator compound.
16. The process according to claim 15 , wherein the polymerization is an anionic, radical or transition metal-catalyzed polymerization.
17. An elastomeric polymer obtainable by the process as defined in claim 15 .
18. A non-cured polymer composition comprising the elastomeric polymer as defined in claim 17 and one or more further components selected from (i) components which are added to or formed as a result of the polymerization process used for making said polymer, (ii) components which remain after solvent removal from the polymerization process and (iii) components which are added to the polymer after completion of the polymer manufacturing process.
19. The polymer composition according to claim 18 , comprising one or more components selected from extender oils, stabilizers and further polymers.
20. The polymer composition according to claim 18 , further comprising one or more fillers.
21. The polymer composition according to claim 20 , wherein the one or more fillers are selected from carbon black, carbon nanotubes, graphite, graphene, silica, carbon-silica dual-phase filler, clays, calcium carbonate, magnesium carbonate, lignin, glass particle-based fillers and starch-based fillers.
22. The polymer composition according to claim 18 , further comprising one or more vulcanizing agents.
23. A vulcanized polymer composition obtainable by vulcanizing the polymer composition as defined in claim 22 .
24. A method of making a vulcanized polymer composition, comprising the step of vulcanizing the polymer composition as defined in claim 22 .
25. An article comprising at least one component formed from the vulcanized polymer composition as defined in claim 23 .
26. The article according to claim 25 , which is a tire, a tire tread, a tire side wall, a tire carcass, a belt, a gasket, a seal, a vibration damper, a footwear component, a golf ball or a hose.