Method of producing modified conjugated diene rubber, modified conjugated diene rubber, and rubber composition
There is provided a method of producing a conjugated diene rubber capable of being used as a starting material for a crosslinked rubber that can be used in applications such as tire treads and can raise the fuel efficiency. This method of producing a conjugated diene rubber comprises (a) a step of reacting a first alkoxysilane compound having in a molecule at least one group convertible to onium by an onium generator and at least one alkoxysilyl group that has at least two alkoxy groups, with a conjugated diene polymer having an alkali metal or alkaline-earth metal active terminal and obtained by polymerizing a conjugated diene compound and an aromatic vinyl compound, thereby to obtain a modified conjugated diene polymer that has the group convertible to onium and the alkoxysilyl group, and (b) a step of mixing the resulting modified conjugated diene polymer with the onium generator and a second alkoxysilane compound having in a molecule at least one alkoxysilyl group and at least one group convertible to onium by the onium generator.
1. A method of producing a modified conjugated diene rubber, the method comprising:
(a) reacting a first alkoxysilane compound comprising a group, which is a protected group protected from an alkali metal or alkaline-earth metal active terminal of a conjugated diene polymer, and after deprotection, is convertible to onium by an onium generator, and an alkoxysilyl group comprising at least two alkoxy groups, with the conjugated diene polymer comprising the alkali metal or alkaline-earth metal active terminal and obtained by polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound, thereby obtaining a modified conjugated diene polymer comprising the group convertible to onium and the alkoxysilyl group; and
(b) mixing the modified conjugated diene polymer with an onium generator and a second alkoxysilane compound comprising an alkoxysilyl group and a group convertible to onium by the onium generator; and
(c) bringing a mixture obtained in (b) into contact with water.
2. The method of claim 1 , wherein the group convertible to onium in the first alkoxysilane compound is at least one selected from the group consisting of a nitrogenous group obtained by substituting two hydrogen atoms on a primary amine with two protective groups, a nitrogenous group obtained by substituting one hydrogen atom on a secondary amine with one protective group, a tertiary amino group, an imino group, a pyridyl group, a phosphorous-comprising group obtained by substituting two hydrogen atoms of a primary phosphine with two protective groups, a phosphorous-comprising group obtained by substituting one hydrogen atom of a secondary phosphine with one protective group, a tertiary phosphino group, and a sulfur-comprising group obtained by substituting one hydrogen atom on a thiol with one protective group.
3. The method of claim 1 , wherein the onium generator is at least one selected from the group consisting of a silicon halide compound, a tin halide compound, an aluminum halide compound, a titanium halide compound, a zirconium halide compound, a germanium halide compound, a gallium halide compound, a zinc halide compound, a sulfate ester, a phosphate ester, a carboxylic acid, and a sulfonic acid.
4. The method of claim 1 , wherein the group convertible to onium in the second alkoxysilane compound is at least one selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, an imino group, a pyridyl group, a primary phosphino group, a secondary phosphino group, a tertiary phosphino group, and a thiol group.
5. The method of claim 1 , wherein the modified conjugated diene rubber comprises the modified conjugated diene polymer, the second alkoxysilane compound, and a hydrolysis and condensation product from the modified conjugated diene polymer and the second alkoxysilane compound, and has onium structures formed by the modified conjugated diene polymer, the second alkoxysilane compound, and the hydrolysis and condensation product.
6. A modified conjugated diene rubber obtained by the method of claim 1 .
7. A rubber composition, comprising:
the modified conjugated diene rubber of claim 6 ;
at least one selected from the group consisting of a silica and a carbon black; and
a crosslinking agent.
8. A crosslinked rubber composition obtained by crosslinking the rubber composition of claim 7 .
9. A tire, comprising the crosslinked rubber composition of claim 8 .
10. The method of claim 1 , wherein the onium generator is a silicon halide compound.
11. The method of claim 1 , wherein the onium generator is a tin halide compound.
12. The method of claim 1 , wherein the onium generator is an aluminum halide compound.
13. The method of claim 1 , wherein the onium generator is a titanium halide compound.
14. The method of claim 1 , wherein the onium generator is a zirconium halide compound.
15. The method of claim 1 , wherein the onium generator is a germanium halide compound.
16. The method of claim 1 , wherein the onium generator is a gallium halide compound.
17. The method of claim 1 , wherein the onium generator is a zinc halide compound.
18. The method of claim 1 , wherein the onium generator is at least one selected from the group consisting of a sulfate ester or a phosphate ester.
19. The method of claim 1 , wherein the onium generator is at least one selected from the group consisting of a carboxylic acid and a sulfonic acid.