Method for producing modified conjugated diene based (co)polymer, modified conjugated diene based (co)polymer, and rubber composition
The method for producing a modified conjugated diene based (co)polymer, according to the present invention comprises (a) obtaining a primarily modified polymer by carrying out a primary modification reaction wherein at least one member selected from the group consisting of an alkoxysilane compound and a silanol compound is introduced into the active alkali metal terminal of a conjugated diene based (co)polymer having an active alkali metal terminal, and (b) obtaining a secondarily modified polymer (a modified conjugated diene based (co)polymer) by subjecting the above-obtained primarily modified polymer to reactions comprising (b1) and (b2). (b1): a reaction with a condensation accelerator comprising a metal element. (b2): a reaction with at least one member selected from the group consisting of inorganic acids and metal halides.
1. A method for producing a modified conjugated diene based (co)polymer, comprising:
(a) obtaining a primarily modified polymer by carrying out a primary modification reaction wherein at least one member selected from the group consisting of an alkoxysilane compound and a silanol compound is introduced into the active alkali metal terminal of a conjugated diene based (co)polymer having an active alkali metal terminal, wherein the conjugated diene based (co)polymer is obtained by subjecting at least a diene monomer to anionic polymerization in a hydrocarbon solvent comprising an alkali metal-based initiator, and
(b) subjecting the above-obtained primarily modified polymer to reactions comprising (b1) and (b2) to obtain a secondarily modified polymer (a modified conjugated diene based (co)polymer),
(b1): a reaction with a condensation accelerator comprising a metal element, and
(b2): a reaction with at least one member selected from the group consisting of inorganic acids and metal halides.
2. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein the condensation accelerator comprising a metal element is a metal compound comprising at least one kind of metal selected from the group consisting of the groups 2 to 15 of periodic table.
3. The method for producing a modified conjugated diene based (co)polymer, according to claim 2 , wherein the condensation accelerator comprising a metal element is an alkoxide, a carboxylic acid salt, or an acetyl acetonate complex salt, of the metal.
4. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein the metal halide is a metal halide containing at least one kind of metal selected from the group consisting of the groups 2 to 15 of periodic table.
5. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein the alkoxysilane compound is a compound comprising at least one member selected from the group consisting of the compounds represented by following general formula (I), the compounds represented by following general formula (II), and partial condensation products of these compounds, wherein
[Formula 1]
R 1 a —Si—(OR 2 ) 4-a (I)
R 1 and R 2 are each independently a mono-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a mono-valent aromatic hydrocarbon group having 6 to 18 carbon atoms; a is an integer of 0 to 2; when there are a plurality of OR 2 s, the plurality of OR 2 s may be the same or different from each other; and there is no active proton in the molecule
A 1 is a mono-valent group having at least one functional group selected from the group consisting of epoxy, isocyanate, imine, carboxylic acid ester, carboxylic acid anhydride, cyclic tertiary amine, acyclic tertiary amine, pyridine, silazane and disulfide; R 3 is a single bond or a bi-valent hydrocarbon group; R 4 and R 5 are each independently a mono-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a mono-valent aromatic hydrocarbon group having 6 to 18 carbon atoms; b is an integer of 0 to 2; when there are a plurality of OR 5 s, the plurality of OR 5 s may be the same or different from each other; and there is no active proton in the molecule.
6. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein the conjugated diene based (co)polymer is obtained by subjecting the diene monomer and other monomer comprising an aromatic vinyl compound to anionic polymerization.
7. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein the conjugated diene based (co)polymer is obtained by subjecting, to anionic polymerization, at least one kind of diene monomer selected from the group consisting of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.
8. The method for producing a modified conjugated diene based (co)polymer, according to claim 6 , wherein the aromatic vinyl compound is styrene.
9. A modified conjugated diene based (co)polymer obtained by the method for producing a modified conjugated diene based (co)polymer, according to claim 1 .
10. A rubber composition comprising, as a rubber component, the modified conjugated diene based (co)polymer according to claim 9 .
11. The rubber composition according to claim 10 , which further comprises at least one selected from the group consisting of silica and carbon black.
12. The rubber composition according to claim 11 , comprising a rubber component comprising 20 mass % or more of the modified conjugated diene based (co)polymer and at least one selected from the group consisting of silica and carbon black in an amount of 20 to 120 parts by mass relative to 100 parts by mass of the rubber component.
13. The rubber composition according to claim 10 , wherein the rubber component consists of the modified conjugated diene based (co)polymer and other rubber component, and the content of the modified conjugated diene based (co)polymer is 20 to 100 mass % and the content of the other rubber component is 0 to 80 mass % (the modified conjugated diene based (co)polymer+the other rubber component=100 mass %).
14. The rubber composition according to claim 13 , wherein the other rubber component is at least one kind of rubber component selected from the group consisting of natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber and halogenated butyl rubber.
15. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein (b2) is a reaction with an inorganic acid.
16. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein (b2) is a reaction with an metal halide.
17. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein (b2) is a reaction with an metal halide, wherein the metal halide contains at least one kind of metal selected from the group consisting of the groups 2 to 15 of periodic table.
18. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein the alkoxysilane compound is introduced into the active alkali metal terminal of the conjugated diene based (co)polymer.
19. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein the silanol compound is introduced into the active alkali metal terminal of the conjugated diene based (co)polymer.
20. The method for producing a modified conjugated diene based (co)polymer, according to claim 1 , wherein the metal element of the condensation accelerator is titanium, zirconium, aluminum, bismuth or tin.