Process for producing hydrogenated block copolymer, hydrogenated block copolymer obtained by the process, and composition thereof

Patent metadata

Field	Value
Publication number	US-9296853-B2
Application number	US-201013375612-A
Country	US
Kind code	B2
Filing date	Jun 3, 2010
Priority date	Jun 3, 2009
Publication date	Mar 29, 2016
Grant date	Mar 29, 2016

Abstract

The present invention relates to a method for producing a hydrogenated block copolymer, including the steps of: (a) forming a block copolymer by allowing a living polymer having a specific structure to react with a tetra- or more functional silane coupling agent; (b) hydrogenating the block copolymer to form a hydrogenated block copolymer; (c) isolating the resultant hydrogenated block copolymer; and (d) deactivating a functional group in the silane coupling agent and/or an unreacted functional group present in a coupling agent residue in the block copolymer or the hydrogenated block copolymer prior to the step (c), in which the number of functional groups derived from the coupling agent in the hydrogenated block copolymer recovered in the step (c) is 1.5 or less per block copolymer molecule; a hydrogenated block copolymer obtained by the method; and a composition containing the hydrogenated block copolymer.

First claim

The invention claimed is:

1. A method for producing a hydrogenated block copolymer, the method comprising:
(a-1) polymerizing monomers with an alkyl lithium compound as an initiator in an inert solvent, thereby obtaining a living anionic polymer of formula (I):
P—X  (I)

where P is a copolymer chain comprising, in reacted form, an aromatic vinyl compound polymer block (A) and a conjugated diene polymer block (B), and X is an active terminal of the living anionic polymer;
(a-2) reacting a silane coupling agent having a functionality of at least four, with the living anionic polymer of formula (I) after the polymerizing (a-1) monomers to obtain a block copolymer;
(b) hydrogenating the block copolymer to obtain a hydrogenated block copolymer;
(c) isolating the hydrogenated block copolymer to obtain an isolated hydrogenated block copolymer; and
(d) adding a Lewis base to the block copolymer or the hydrogenated block copolymer after said (a-2) reacting of the silane coupling agent with the living polymer such that (i) a functional group of the silane coupling agent, (ii) an unreacted functional group present in a coupling agent residue in the block copolymer or the hydrogenated block copolymer, or both (i) and (ii) is deactivated with the Lewis base,
wherein:
the Lewis base is at least one member selected from the group consisting of an alkyl lithium compound, an alkyl sodium compound, an alkyl potassium compound, an alkyl magnesium halide compound, a dialkyl copper lithium compound, and lithium amide compound;
each of (a-1) and (a-2) are carried out before said (b) hydrogenating, said (b) hydrogenating is carried out before said (d) deactivating, and said (d) deactivating is carried out before said (c) isolating; or
each of (a-1) and (a-2) are carried out before said (d) deactivating, said (d) deactivating is carried out before said (b) hydrogenating, and said (b) hydrogenating is carried out before said (c) isolating; and
a number of functional groups derived from the coupling agent in the isolated hydrogenated block copolymer is 1.5 or less per block copolymer molecule.

2. The method of claim 1 , wherein the silane coupling agent comprises a compound of formula (II):
SiY 4   (II)

wherein each Y is independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group, a carboxyl group, or a carboxylic acid ester group; or the silane coupling agent comprises a compound of formula (III):
R 1 m Y 3-m Si-A-SiY 3-m R 1 m   (III)

wherein each R 1 is independently a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 12 carbon atoms; each Y is independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group, a carboxyl group, or a carboxylic acid ester group; A is a single bond or a linear alkylene group having 1 to 20 carbon atoms; and m is 0 or 1.

3. The method of claim 2 wherein each Y in formulae (II) or (III) is an alkoxy group OR 2 , wherein each R 2 is independently a linear or branched alkyl group having 1 to 12 carbon atoms.

4. The method of claim 1 , wherein the functional groups derived from the coupling agent in the hydrogenated block copolymer comprise hydroxyl groups bonded directly to Si atoms.

5. The method of claim 1 , wherein the living polymer has a weight-average molecular weight of 8,000 to 500,000.

6. The method of claim 2 , wherein the deactivating is performed in the presence of a deactivating reagent, and a molar ratio of the deactivating reagent to the Y in the coupling agent residue is 0.5 or more.

7. The method of claim 1 , wherein the polymer block (A) comprises, in reacted form, at least one aromatic vinyl compound selected from the group consisting of styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene and 2-vinylnaphthalene.

8. The method of claim 7 , wherein the polymer block (A) comprises, in reacted form, styrene.

9. The method of claim 7 , wherein the polymer block (A) comprises, in reacted form, α-methylstyrene.

10. The method of claim 1 , wherein the polymer block (B) comprises, in reacted form, at least one conjugated diene selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene.

11. The method of claim 10 , wherein the polymer block (B) comprises, in reacted form, 1,3-butadiene and isoprene.

12. The method of claim 1 , wherein the living polymer has a weight-average molecular weight of 60,000 to 300,000.

13. The method of claim 1 , wherein the coupling agent is selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, bisdimethoxymethylsilylethane, bisdiethoxymethylsilylethane, bisdiethoxyethylsilylpentane, bisdibutoxymethylsilylethane, bistrimethoxysilylhexane, bistriethoxysilylethane, and bistripropoxysilylpentane.

14. The method of claim 1 , wherein a molar ratio of the coupling agent to the active terminal is 0.1 to 0.5.

15. The method of claim 6 , wherein the molar ratio of the deactivating reagent to the Y in the coupling agent residue is 1.0 or more.

16. The method of claim 1 , wherein the Lewis base comprises at least one member selected from the group consisting of
an alkyl sodium compound, an alkyl potassium compound, an alkyl magnesium halide compound, a dialkyl copper lithium compound, and lithium amide compound.

Assignees

• Nishikawa Takaaki
• Jogo Yosuke
• Moriguchi Nobuhiro
• Maeda Mizuho
• Kuraray Co

Inventors

• Nishikawa Takaaki
• Jogo Yosuke
• Moriguchi Nobuhiro
• Maeda Mizuho

Classifications

• C08F8/04

  Reduction, e.g. hydrogenation · CPC title

• C08K5/01

  Hydrocarbons {(C08K5/0091 takes precedence)} · CPC title

• C08L53/025

  modified · CPC title

• C08F2800/20

  as weight or mass percentages · CPC title

• C08F297/046 Primary

  polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes · CPC title