Method of producing a conjugated diene polymer, a modified conjugated diene polymer, and a vinyl cis-polybutadiene composition

Patent metadata

Field	Value
Publication number	US-10633470-B2
Application number	US-201916403880-A
Country	US
Kind code	B2
Filing date	May 6, 2019
Priority date	Mar 13, 2013
Publication date	Apr 28, 2020
Grant date	Apr 28, 2020

Abstract

A method for producing a conjugated diene polymer having a high content of cis-1,4-structures with a high activity, a conjugated diene polymer, and a modified conjugated diene polymer. The catalyst for conjugated diene polymerization in the method includes: a non-metallocene type gadolinium compound (A) represented by the general formula (1); an ionic compound (B) formed of a non-coordinating anion and a cation; and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table.

First claim

The invention claimed is:

1. A method for producing a conjugated diene polymer comprising:
polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization including a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table to obtain a conjugated diene polymer,

wherein R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.

2. The method for producing a conjugated diene polymer according to claim 1 , wherein the organic metal compound (C) is an organic aluminum compound.

3. The method for producing a conjugated diene polymer according to claim 1 , wherein the ionic compound (B) is a boron-containing compound.

4. The method for producing a conjugated diene polymer according to claim 1 , wherein the molecular weight is adjusted with a compound selected from the group consisting of (1) a hydrogen, (2) a metal hydride compound, and (3) a hydrogenated organic metal compound in the polymerization of the conjugated diene compound.

5. A method for producing a modified conjugated diene polymer comprising:
polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization including a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table to obtain a conjugated diene polymer; and
modifying the conjugated diene polymer with at least one compound selected from the group consisting of amino group-containing carbonyl compounds, halogenated benzyl compounds, and aldehyde compounds to obtain a modified conjugated diene polymer,

wherein R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.

6. The method for producing a modified conjugated diene polymer according to claim 5 , wherein the amino group-containing carbonyl compound is a 4,4′-bis-dialkylaminobenzophenone.

7. The method for producing a modified conjugated diene polymer according to claim 5 , wherein the halogenated benzyl compound is a piperonyl chloride, a dimethoxybenzyl bromide, or a methoxybenzyl chloride.

8. The method for producing a modified conjugated diene polymer according to claim 5 , wherein the aldehyde compound is a heliotropin or a veratrum aldehyde.

9. A method for producing a vinyl⋅cis-polybutadiene comprising performing a cis-1,4 polymerization of a 1,3-butadiene, and performing a subsequent syndiotactic-1,2 polymerization in the resulting polymerization system,
wherein a catalyst for a conjugated diene polymerization including a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table is used as a catalyst in the cis-1,4 polymerization, and a catalyst system containing a sulfur compound is used as a catalyst in the syndiotactic-1,2 polymerization,

wherein R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.

10. The method for producing a vinyl⋅cis-polybutadiene according to claim 9 , wherein the organic metal compound (C) is an organic aluminum compound.

11. The method for producing a vinyl⋅cis-polybutadiene according to claim 9 , wherein the ionic compound (B) is a boron-containing compound.

12. The method for producing a vinyl⋅cis-polybutadiene according to claim 9 , wherein a catalyst system including a cobalt compound, a trialkyl aluminum compound, and a sulfur compound is used as the catalyst in the syndiotactic-1,2 polymerization.

13. A method for producing a conjugated diene polymer composition comprising:
polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization including a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table to obtain a conjugated diene polyme (α);
adding a diene polymer (β) other than the (α) and a rubber-reinforcing agent to the (α) to form a mixture; and
kneading the mixture to form a conjugated diene polymer composition,

wherein R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.

14. The method for producing a conjugated diene polymer composition according to claim 13 , wherein the organic metal compound (C) is an organic aluminum compound.

15. The method for producing a conjugated diene polymer composition according to claim 13 , wherein the ionic compound (B) is a boron-containing compound.

16. A method for producing a modified conjugated diene polymer composition comprising:
polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization including a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table to obtain a conjugated diene polymer;
modifying the conjugated diene polymer with at least one compound selected from the group consisting of amino group-containing carbonyl compounds, halogenated benzyl compounds, and aldehyde compounds to obtain a modified conjugated diene polymer (α′);
adding a diene polymer (β) other than the (α′) and a rubber-reinforcing agent to the (α′) to form a mixture; and
kneading the mixture to form a modified conjugated diene polymer composition,

wherein R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.

17. The method for producing a modified conjugated diene polymer composition according to claim 16 , wherein the amino group-containing carbonyl compound is a 4,4′-bis-dialkylaminobenzophenone.

18. The method for producing a modified conjugated diene polymer composition according to claim 16 , wherein the halogenated benzyl compound is a piperonyl chloride, a dimethoxybenzyl bromide, or a methoxybenzyl chloride.

19. The metho

Assignees

• Ube Industries

Inventors

• Shiba Koji
• Murakami Masato
• Suzuki Michinori
• Okamoto Naomi
• Anbe Mitsuharu
• Tanaka Masahiro

Classifications

• C08K3/04

  Carbon · CPC title

• C08L47/00

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers (C08L45/00 takes precedence; of conjugated diene rubbers C08L9/00 - C08L21/00) · CPC title

• C08F36/06

  Butadiene · CPC title

• C08C19/22

  Incorporating nitrogen atoms into the molecule · CPC title

• C08K3/045

  Fullerenes · CPC title