Method for producing hydrogenated conjugated diene copolymer
The present invention relates to a method for producing a hydrogenated conjugated diene copolymer including a polymerization step and a hydrogenation step, wherein in the polymerization step, a conjugated diene copolymer having a high vinyl bond amount of a conjugated diene block moiety and a narrow molecular weight distribution can be produced, and in the hydrogenation step, the rate of hydrogenation is high and productivity is excellent.
1. A method of producing a hydrogenated conjugated diene copolymer comprising:
a polymerization step of copolymerizing butadiene monomers and vinyl aromatic monomers using an initiator comprising an organolithium compound; and
a hydrogenation step of hydrogenating the conjugated diene copolymer obtained in the polymerization step,
wherein in the polymerization step, the organolithium compound, an ether compound (A) having two or more oxygen atoms, and an alkali metal alkoxide (B) are present together in the following molar ratios:
ether compound (A)/organolithium compound ((A)/organolithium compound) is 1.7 or more and 2.4 or less;
alkali metal alkoxide (B)/organolithium compound ((B)/organolithium compound) is 0.015 or more and 0.150 or less,
alkali metal alkoxide (B)/ether compound (A) ((B)/(A)) is 0.006 or more and 0.076 or less,
the ether compound (A) is selected from the group consisting of 2,2-diethoxypropane, 1,2-diethoxypropane, ethylene glycol dibutyl ether ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethyl ethylene glycol t-butyl ether, ethyl ethylene glycol butyl ether, triethylene glycol dimethyl ether, bis(2-oxolanyl)ethane, 2,2-bis(2-oxolanyl)propane, 1,1-bis(2-oxolanyl)ethane, 2,2-bis(2-oxolanyl)butane, 2,2-bis(5-methyl-2-oxolanyl)propane, and 2,2-bis(3,4,5-trimethyl-2-oxolanyl)propane,
the alkali metal alkoxide (B) is sodium, lithium or potassium alkoxide having an alkyl group having 2 to 12 carbon atoms, and
the vinyl aromatic monomers comprise styrene, α-methylstyrene, p-methylstyrene, vinylethylbenzene, and/or 2-vinylnaphthalene.
2. The method according to claim 1 , wherein the molar ratio of (B)/(A) is 0.015 or more and 0.08 or less.
3. The method according to claim 1 or 2 , wherein the ether compound (A) having two or more oxygen atoms is ethylene glycol dibutyl ether, ethyl ethylene glycol t-butyl ether, or 2,2-bis(2-oxolanyl)propane.
4. The method according to claim 1 or 2 , wherein an alkali metal of the alkali metal alkoxide (B) is sodium or potassium.
5. The method according to claim 1 or 2 , wherein in the hydrogenation step, a titanocene compound is used as a hydrogenation catalyst.
6. The method according to claim 1 or 2 , wherein the molar ratio of (A)/organolithium compound is 1.7 or more and 2.0 or less.
7. The method according to claim 1 , wherein in the molar ratio of (B)/(A) is 0.025 or more and 0.08 or less.
8. The method according to claim 1 or 2 , wherein
the ether compound (A) having two or more oxygen atoms is ethylene glycol dibutyl ether, ethyl ethylene glycol t-butyl ether, or 2,2-bis(2-oxolanyl)propane;
an alkali metal of the alkali metal alkoxide (B) is sodium or potassium; and
in the hydrogenation step, a titanocene compound is used as a hydrogenation catalyst.
9. The method according to claim 1 or 2 , wherein the ether compound (A) is selected from the group consisting of bis(2-oxolanyl)ethane, 2,2-bis(2-oxolanyl)propane, 1,1-bis(2-oxolanyl)ethane, 2,2-bis(2-oxolanyl)butane, 2,2-bis(5-methyl-2-oxolanyl)propane, and 2,2-bis(3,4,5-trimethyl-2-oxolanyl)propane.
10. The method according to claim 5 , wherein the titanocene compound comprises at least one or more ligands having an optionally substituted cyclopentadienyl skeleton, indenyl skeleton, or fluorenyl skeleton.
11. The method according to claim 5 , wherein the titanocene compound comprises bis(cyclopentadienyl)titanium dichloride, or mono-pentamethylcyclopentadienyl titanium trichloride.