Method for producing modified conjugated diene polymer, modified conjugated diene polymer, and rubber composition
A method for producing a modified conjugated diene polymer includes a step (A) carrying out a primary modification reaction that reacts a heterocumulene compound having two or more specific functional groups with a conjugated diene polymer having a vinyl content of below 10% and a cis-1,4-bond content of 75% or more and possessing an active end to obtain a primary-modified conjugated diene polymer, and a step (B) carrying out a secondary modification reaction that reacts an active hydrogen-containing compound that includes one or more functional groups selected from the group consisting of an amino group, an imino group, a mercapto group, and a hydroxyl group with the primary-modified conjugated diene polymer to obtain a secondary-modified conjugated diene polymer. The method can produce a modified conjugated diene polymer that exhibits low heat build-up (low fuel consumption) and excellent wear resistance.
1. A method for producing a modified conjugated diene polymer, comprising:
(A) carrying out a primary modification reaction that reacts a component (a) with a conjugated diene polymer having a vinyl content of below 10% and a cis-1,4-bond content of 75% or more and possessing an active end to which component (a) is introduced to obtain a primary-modified conjugated diene polymer, and
(B) carrying out a secondary modification reaction that reacts a component (b) with the primary-modified conjugated diene polymer to introduce component (b) into a functional group of the primary-modified conjugated diene polymer derived from the component (a) to obtain a secondary-modified conjugated diene polymer, wherein
the component (a) is a heterocumulene compound that includes two or more functional groups shown by the general formula (1): X═C═Y in which X represents a carbon atom or a nitrogen atom, and Y represents an oxygen atom, a nitrogen atom, or a sulfur atom in the molecular structure, and
the component (b) is an active hydrogen-containing compound that includes one or more functional groups selected from the group consisting of an amino group, an imino group, and a mercapto group,
wherein the secondary modification reaction (B) utilizes a catalyst that promotes a reaction between the component (b) and the functional group of the primary-modified conjugated diene polymer derived from the component (a).
2. The method for producing a modified conjugated diene polymer according to claim 1 , wherein two or more functional groups among the functional groups shown by the general formula (1) included in the heterocumulene compound are isocyanate groups.
3. The method for producing a modified conjugated diene polymer according to claim 1 , wherein the component (b) is an active hydrogen-containing compound that includes two or more functional groups selected from the group consisting of an amino group, an imino group, and a mercapto group.
4. The method for producing a modified conjugated diene polymer according to claim 1 , wherein the catalyst is a compound that includes a tertiary amino group or a compound that includes one or more elements selected from the elements of the groups 4A, 2B, 3B, 4B, and 5B in the periodic table.
5. The method for producing a modified conjugated diene polymer according to claim 1 , wherein the conjugated diene polymer includes a repeating unit derived from a monomer selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
6. The method for producing a modified conjugated diene polymer according to claim 1 , wherein the conjugated diene polymer has been polymerized in the presence of a catalyst that includes components (c) to (e) as main components, wherein
component (c) is a lanthanoid element-containing compound that contains at least one lanthanoid element or a reaction product obtained by reacting the lanthanoid element-containing compound with a Lewis base,
component (d) is at least one compound selected from an alumoxane and an organoaluminum compound shown by the general formula (2): AlR 1 R 2 R 3 in which R 1 and R 2 individually represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R 3 represents a hydrocarbon group having 1 to 10 carbon atoms that is the same as or differs from R 1 and R 2 , and
component (e) is a halogen-containing compound that contains at least one halogen element in the molecular structure.
7. The method for producing a modified conjugated diene polymer according to claim 1 , wherein the conjugated diene polymer has a cis-1,4-bond content of 98.5% or more and a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 3.5 or less determined by gel permeation chromatography.
8. The method for producing a modified conjugated diene polymer according to claim 1 , wherein component (b) includes an amino group.
9. The method for producing a modified conjugated diene polymer according to claim 1 , wherein component (b) includes an imino group.
10. The method for producing a modified conjugated diene polymer according to claim 1 , wherein component (b) includes a mercapto group.