Nickel-based catalyst composition

Patent metadata

Field	Value
Publication number	US-9422379-B2
Application number	US-201414319441-A
Country	US
Kind code	B2
Filing date	Jun 30, 2014
Priority date	Apr 10, 2007
Publication date	Aug 23, 2016
Grant date	Aug 23, 2016

Abstract

In general the present invention provides a process for forming conjugated diene polymer, the process comprising the step of polymerizing conjugated diene monomer in the presence of a catalytically effective amount of a catalyst composition formed by combining (a) a nickel-containing compound, (b) an alkylating agent, (c) a fluorine-containing compound, (d) a carboxylic acid, and (e) an alcohol.

First claim

What is claimed is:

1. A process for forming conjugated diene polymer, the process comprising the step of:
polymerizing conjugated diene monomer in the presence of a catalytically effective amount of a catalyst composition formed by combining:
(a) a nickel-containing compound;
(b) an alkylating agent;
(c) a fluorine-containing compound; and
(d) a carboxylic acid; and
(e) an alcohol,
where the nickel-containing compound is selected from nickel carboxylates, nickel organophosphates, nickel organophosphonates, nickel organophosphinates, nickel carbamates, nickel dithiocarbamates, nickel xanthates, nickel β-diketonates, nickel alkoxides or aryloxides, nickel halides, nickel pseudo-halides, nickel oxyhalides, and organonickel compounds, and
said step of combining includes introducing the fluorine-containing compound after the nickel-containing compound, the alkylating agent, the carboxylic acid, and the alcohol are combined.

2. The process of claim 1 , where said step of polymerizing takes place within a non-polar solvent.

3. The process of claim 2 , when the non-polar solvent is an aliphatic solvent, a cycloaliphatic solvent, or a mixture thereof.

4. The process of claim 3 , where the molar ratio of said alkylating agent to said nickel-containing compound (alkylating agent/Ni) is from about 1:1 to about 200:1, where the molar ratio of said fluorine-containing compound to said nickel-containing compound (F/Ni) is from about 7:1 to about 500:1, where the molar ratio of said carboxylic acid to said nickel-containing compound (COOH/Ni) is from about 0.1:1 to about 10:1, and where the molar ration of said alcohol to said nickel-containing compound (OH/Ni) is from about 0.4:1 to about 80:1.

5. The process of claim 4 , where the molar ratio of said alkylating agent to said nickel-containing compound (alkylating agent/Ni) is from about 3:1 to about 30:1, where the molar ratio of said fluorine-containing compound to said nickel-containing compound (F/Ni) is from about 7.5:1 to about 450:1, where the molar ratio of said carboxylic acid to said nickel-containing compound (COOH/Ni) is from about 0.5:1 to about 5:1, and where the molar ration of said alcohol to said nickel-containing compound (OH/Ni) is from about 0.5:1 to about 75:1.

6. The process of claim 2 , where the alkylating agent is an organoaluminum compound.

7. The process of claim 2 , where said organoaluminum compound includes those represented by the formula AlR n X 3-n , where each R, which may be the same or different, is a mono-valent organic group that is attached to the aluminum atom via a carbon atom, where each X, which may be the same or different, is a hydrogen atom, a carboxylate group, an alkoxide group, or an aryloxide group, and where n is an integer of 1 to 3.

8. The process of claim 2 , where said fluorine-containing compound is selected from the group consisting of elemental fluorine, halogen fluorides, hydrogen fluoride, organic fluorides, inorganic fluorides, metallic fluorides, organometallic fluorides, and mixtures thereof.

9. The process of claim 2 , where said fluorine-containing compound includes a complex with an ether, alcohol, water, aldehyde, ketone, ester, nitrile, or combinations thereof.

10. The process of claim 2 , where the conjugated diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene.

11. The process of claim 2 , where the alcohol is defined by the formula R—OH, where R is a monovalent organic group.

12. The process of claim 11 , where R includes from about 1 to about 40 carbon atoms.

13. The process of claim 11 , where the alcohol is selected from the group consisting of aliphatic alcohols, cyclic alcohols, unsaturated alcohols, aromatic alcohols, heterocyclic alcohols, and polycyclic alcohols.

14. The process of claim 2 , where the carboxylic acid is defined by the formula R—COOH, where R is a monovalent organic group.

Assignees

• Bridgestone Corp

Inventors

• Qin Zengquan
• Poulton Jason T
• Roggeman David M
• Matsuo Shigeaki

Classifications

• C08F136/04

  conjugated · CPC title

• C08F4/06

  Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen · CPC title

• C08F136/06 Primary

  Butadiene · CPC title

• C08F4/42

  Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors · CPC title

• C08F36/04 Primary

  conjugated · CPC title