Process for production of modified conjugated diene rubber, modified conjugated diene rubber, and rubber composition
To provide a producing method of conjugated diene rubber which can be used as a starting material of cross-linked rubber which is used for such as tire tread and can enhance low fuel consumption performance. The method of producing modified conjugated diene rubber, comprising: a process step (a) wherein a conjugated diene polymer with an alkali metal or alkaline-earth metal active terminal, which polymer is obtained from polymerization of a conjugated diene compound or polymerization of a conjugated diene compound with an aromatic vinyl compound, is allowed to react with a hydrocarbyloxysilane compound having in its molecule at least one or more of each of the following functional groups (I): a hydrocarbyloxysilyl group and (II): a nitrogen-containing 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 to obtain a modified conjugated diene polymer with the functional group (II), and a process step (b) wherein the modified conjugated diene polymer produced in the process step (a) is mixed with an onium-forming agent.
1. A method of producing a modified conjugated diene rubber, the method comprising:
(a) reacting a conjugated diene polymer comprising an alkali metal or alkaline-earth metal active terminal, which polymer is obtained from polymerization of a conjugated diene compound or polymerization of a conjugated diene compound with an aromatic vinyl compound, with a hydrocarbyloxysilane compound comprising at least one or more of each of the following functional groups (I) and (II) to obtain a modified conjugated diene polymer comprising the functional group (II); and
(b) mixing the modified conjugated diene polymer produced in (a) with an onium-forming agent,
wherein:
no hydrocarbyloxysilane compound is added in the process step (b), and the process step (b) does not include a situation in which the modified conjugated diene polymer produced in the process step (a), the onium-forming agent, and the hydrocarbyloxysilane compound are mixed together;
the functional group (I) is a hydrocarbyloxysilyl group; and
the functional group (II) is a nitrogen-containing 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-containing group formed by substituting two protective groups for two hydrogen atoms of a primary phosphine, a phosphorus-containing group formed by substituting one protective group for one hydrogen atom of a secondary phosphine, a tertiary phosphino group or a sulfur-containing group formed by substituting one protective group for one hydrogen atom of a thiol.
2. The method of claim 1 , wherein the onium-forming agent is one or more compound(s) selected from the group consisting of a metal halide, an ester of an inorganic acid, an organic acid and derivatives of organic acids.
3. The method of claim 1 , further comprising:
(c) contacting a mixture obtained in the process step (b) with water.
4. The method of claim 1 , wherein the modified conjugated diene rubber has an onium structure formed by the modified conjugated diene polymer.
5. A modified conjugated diene rubber obtained by the method of claim 1 .
6. A rubber composition, comprising:
the modified conjugated diene rubber of claim 5 ;
silica, carbon black, or both; and
a cross-linking agent.
7. A cross-linked rubber composition produced by cross-linking of the rubber composition of claim 6 .
8. A tire made from the cross-linked rubber composition of claim 7 .
9. The method of claim 1 , wherein the modified conjugated diene rubber has a Mooney viscosity (ML 1+4, 100° C.) ranging from 30 to 150, a cold flow value of 1.5 mg/min or less, and a temporal stability (AML 1+4, 100° C.) of 6 or less.
10. The method of claim 1 , wherein the modified conjugated diene rubber has a Mooney viscosity (ML 1+4, 100° C.) ranging from 40 to 63, a cold flow value of 0.3 mg/min or less, and a temporal stability (AML 1+4, 100° C.) of 3 or less.