Modified conjugated diene rubber, method for producing same, and rubber composition
By a method comprising a process including (a) producing a modified conjugated diene polymer through reaction of a conjugated diene polymer having an alkali metal or alkaline-earth metal active terminal with a first alkoxysilane compound which has both an alkoxysilyl group and at least one group convertible into an onium, and (b) mixing the modified conjugated diene polymer, an agent for producing onium, a second alkoxysilane compound having an alkoxysilyl group and at least one group convertible into an onium and a condensation catalyst containing metal element(s) for alkoxysilane compounds, conjugated diene rubber usable as a starting material of cross-linked rubber which is used for a tire tread or the like and allows enhancement of low fuel consumption property can be obtained.
1. A method of producing a modified conjugated diene rubber, the method comprising:
mixing i) a modified conjugated diene polymer comprising a group convertible into an onium and an alkoxysilyl group, ii) an agent that produces onium, iii) a second alkoxysilane compound comprising an alkoxysilyl group and a group which is convertible into an onium with the agent per molecule, and iv) a condensation catalyst comprising a metal element for alkoxysilane compounds, to obtain a mixture.
2. The method of claim 1 , wherein the modified conjugated diene polymer is produced by reacting:
a conjugated diene polymer comprising an alkali metal or alkaline-earth metal active terminal, which is a polymer produced by polymerizing a conjugated diene compound or a conjugated diene compound with an aromatic vinyl compound; and
a first alkoxysilane compound comprising both of an alkoxysilyl group comprising two or more alkoxy groups and a group which is convertible into an onium with the agent per molecule.
3. The method of claim 2 , wherein the group convertible into an onium in the first alkoxysilane compound is at least one group selected from the group consisting of a nitrogen-comprising group formed by substituting two protective groups for two hydrogen atoms of a primary amine, a nitrogen-comprising group formed by substituting one protective group for one hydrogen atom of a secondary amine, a tertiary amino group, an imino group, a pyridyl group, a phosphorus-comprising group formed by substituting two protective groups for two hydrogen atoms of a primary phosphine, a phosphorus-comprising group formed by substituting one protective group for one hydrogen atom of a secondary phosphine, a tertiary phosphino group and a sulfur-comprising group formed by substituting one protective group for one hydrogen atom of a thiol.
4. The method of claim 1 , wherein the agent is at least one compound selected from the group consisting of a silicon halide compound, a tin halide compound, an aluminum halide compound, a titanium halide compound, zirconium halide compound, a germanium halide compound, a gallium halide compound, a zinc halide compound, a sulfuric ester, a phosphoric ester, a carboxylic acid, and a sulfonic acid.
5. The method of claim 1 , wherein the group convertible into an onium in the second alkoxysilane compound is at least one group 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.
6. The method of claim 1 , wherein the condensation catalyst is a metallic compound comprising at least one metal element selected from group 4, group 12, group 13, group 14, and group 15 of the periodic table.
7. The method of claim 6 , wherein the metallic compound is an alkoxide, carboxylate, or acetylacetonate complex salt of the metal element.
8. The method of claim 1 , further comprising:
contacting the mixture with water.
9. The method of claim 1 , wherein the modified conjugated diene rubber comprises:
(i) the modified conjugated diene polymer;
(ii) the second alkoxysilane compound;
(iii) a hydrolytic condensation product of the modified conjugated diene polymer and the second alkoxysilane compound;
(iv) a hydrolytic condensation product of the modified conjugated diene polymer and the condensation catalyst;
(v) a hydrolytic condensation product of the second alkoxysilane compound and the condensation catalyst; and
(vi) a hydrolytic condensation product of the modified conjugated diene polymer, the second alkoxysilane compound, and the condensation catalyst, and
wherein the modified conjugated diene rubber has onium structures formed from substances (i) to (vi).
10. The method of claim 2 , wherein the agent is at least one compound selected from the group consisting of a silicon halide compound, a tin halide compound, an aluminum halide compound, a titanium halide compound, zirconium halide compound, a germanium halide compound, a gallium halide compound, a zinc halide compound, a sulfuric ester, a phosphoric ester, a carboxylic acid, and a sulfonic acid.
11. The method of claim 2 , wherein the group convertible into an onium in the second alkoxysilane compound is at least one group 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.
12. The method of claim 2 , wherein the condensation catalyst is a metallic compound comprising at least one metal element selected from group 4, group 12, group 13, group 14, and group 15 of the periodic table.
13. The method of claim 12 , wherein the metallic compound is an alkoxide, carboxylate, or acetylacetonate complex salt of the metal element.
14. The method of claim 2 , further comprising:
contacting the mixture with water.
15. The method of claim 2 , wherein the modified conjugated diene rubber comprises:
(i) the modified conjugated diene polymer;
(ii) the second alkoxysilane compound;
(iii) a hydrolytic condensation product of the modified conjugated diene polymer and the second alkoxysilane compound;
(iv) a hydrolytic condensation product of the modified conjugated diene polymer and the condensation catalyst;
(v) a hydrolytic condensation product of the second alkoxysilane compound and the condensation catalyst; and
(vi) a hydrolytic condensation product of the modified conjugated diene polymer, the second alkoxysilane compound, and the condensation catalyst, and
wherein the modified conjugated diene rubber has onium structures formed from substances (i) to (vi).