Bulk polymerization of conjugated dienes using a nickel-based catalyst system

Patent metadata

Field	Value
Publication number	US-9546227-B2
Application number	US-201113976315-A
Country	US
Kind code	B2
Filing date	Dec 30, 2011
Priority date	Dec 31, 2010
Publication date	Jan 17, 2017
Grant date	Jan 17, 2017

Abstract

A process for preparing a polydiene, the process comprising the steps of (i) providing conjugated diene monomer; (ii) charging a nickel-based catalyst system to the conjugated diene monomer; and (iii) charging a modulating Lewis base to the conjugated diene monomer, to thereby polymerize the conjugated diene monomer in the presence of the modulating Lewis base, where said step of charging a modulating Lewis base is separate from said step of charging a nickel-based catalyst, and where said steps of providing conjugated diene monomer, charging a nickel-based catalyst system and charging a Lewis base form a polymerization mixture that includes less than 20% by weight of organic solvent based on the total weight of the polymerization mixture.

First claim

What is claimed is:

1. A process for preparing a polydiene, the process comprising the steps of:
(i.) providing conjugated diene monomer;
(ii.) charging a nickel-based catalyst system to the conjugated diene monomer; and
(iii.) charging a modulating Lewis base to the conjugated diene monomer, to thereby polymerize the conjugated diene monomer in the presence of the modulating Lewis base, where said step of charging a modulating Lewis base is separate from said step of charging a nickel-based catalyst, and where said steps of providing conjugated diene monomer, charging a nickel-based catalyst system and charging a Lewis base form a polymerization mixture that includes less than 20% by weight of organic solvent based on the total weight of the polymerization mixture,
where said step of charging a nickel-based catalyst system to the conjugated diene monomer takes place prior to said step of charging a modulating Lewis base to the conjugated diene monomer, and said step of charging a modulating Lewis base takes place before 5% of the conjugated diene monomer is polymerized, or
where said step of charging a modulating Lewis base to the conjugated diene monomer takes place prior to said step of charging a nickel-based catalyst system to the conjugated diene monomer, and
where the polydiene has a cis-1,4-linkage content of at least 97%, a 1,2-linkage content of less than 1.0%, a molecular weight distribution of less than 3.0, a Mooney viscosity (ML 1+4 @100° C.) of less than 60, and a gel content of less than 20% by weight, where the nickel-based catalyst system is the combination or reaction product of (a) a nickel-containing compound, (b) an alkylating agent, and (c) a fluorine source, and
where the molar ratio of the alkylating agent to the nickel-containing compound is from about 10:1 to about 50:1, and where the ratio of the moles of fluorine atoms in the fluorine source to the moles of nickel atoms in the nickel-containing compound is from about 70:1 to about 130:1.

2. The process of claim 1 , where the nickel-containing compound is selected from the group consisting of nickel carboxylates, nickel carboxylate borates, 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.

3. The process of claim 1 , where the alkylating agent is defined by the formula AlR n X 3-n , where each R independently can be a monovalent organic group that is attached to the aluminum atom via a carbon atom, where each X independently can be a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group, and where n can be an integer in the range of from 1 to 3.

4. The process of claim 1 , where the fluorine source is selected from the group consisting of elemental fluorine, halogen fluorides, hydrogen fluoride, organic fluorides, inorganic fluorides, metallic fluorides, organometallic fluorides, and mixtures thereof.

5. The process of claim 1 , where the nickel-containing compound is a nickel carboxylate borate, the alkylating agent is trihydrocarbylaluminum, and the fluorine source is an inorganic fluoride.

6. The process of claim 5 , where the inorganic fluoride source is complexed with an alcohol.

7. The process of claim 1 , where the molar ratio of the alkylating agent to the nickel-containing compound is from about 20:1 to about 40:1, and where the molar ratio of the fluorine source to the nickel-containing compound is from about 80:1 to about 120:1.

8. The process of claim 7 , where the molar ratio of the alkylating agent to the nickel-containing compound is from about 25:1 to about 35:1, and where the molar ratio of the fluorine source to the nickel-containing compound is from about 90:1 to about 108:1.

9. The process of claim 1 , where the polymerization mixture includes less than 5% by weight of organic solvent.

10. The process of claim 1 , where the temperature of the polymerization mixture is maintained within a range from about −10° C. to about 130° C.

11. The process of claim 1 , where the peak temperature of the polymerization mixture is greater than 34° C.

12. The process of claim 1 , where the polymerization mixture is devoid of a molecular weight regulator.

13. The process of claim 1 , where the polymerization of the conjugated diene monomer is maintained at less than 30% conversion.

14. The process of claim 1 , where the modulating Lewis base is a dihydrocarbyl ether or an amine.

15. The process of claim 14 , where the modulating Lewis base is a dihydrocarbyl ether selected from the group consisting of dialkyl ethers, dicycloalkyl ethers, diaryl ethers, and mixed dihydrocarbyl ethers.

16. The process of claim 15 , where the nickel-based catalyst system includes a nickel-containing compound, and where the molar ratio of the dihydrocarbyl ether to the nickel-containing compound is from about 10:1 to about 80:1.

17. The process of claim 14 , where the modulating Lewis base is a tertiary amine.

18. The process of claim 17 , where the nickel-based catalyst system includes a nickel-containing compound, where the molar ratio of the tertiary amine to the nickel-containing compound is from about 0.1:1 to about 2:1.

19. A process for preparing a polydiene, the process comprising the step of:
forming a polymerization mixture by introducing a nickel-based catalyst system and a modulating Lewis base to conjugated diene monomer, where the polymerization mixture includes less than about 20% by weight of organic solvent, and where the modulating Lewis base is introduced directly and individually to the conjugated diene monomer,
where the nickel-based catalyst system is introduced to the conjugated diene monomer prior to the modulating Lewis base and the modulating Lewis base is added to the conjugated diene monomer before 5% of the monomer is polymerized, or
where the modulating Lewis base is introduced to the conjugated diene monomer prior to the nickel-based catalyst system, and
where the polydiene has a cis-1,4-linkage content of at least 97%, a 1,2-linkage content of less than 1.0%, a molecular weight distribution of less than 3.0, a Mooney viscosity (ML 1+4 @100° C.) of less than 60, and a gel content of less than 20% by weight,
where the nickel-based catalyst system is the combination or reaction product of (a) a nickel-containing compound, (b) an alkylating agent, and (c) a fluorine source, and
where the molar ratio of the alkylating agent to the nickel-containing compound is from about 10:1 to about 50:1, and where the molar ratio of the mole of fluorine atoms in the fluorine source to the mole of nickel atoms in the nickel-containing compound is from about 70:1 to about 130:1.

20. The process of claim 19 , where the nickel-based catalyst system is introduced to the conjugated diene monomer prior to the modulating Lewis base.

21. The process of claim 19 , where the modulating Lewis base is introduced to the conjugated diene monomer prior to the nickel-based catalyst system.

22. A process for producing a polydiene, the process comprising the step of:
polymerizing conjugated diene monomer in the presence of a catalytically effective amount of an active nickel-based catalyst and a modulating Lewis base, where the modulating Lewis base is introduced directly and individually to the conjugated diene monomer, and where said step of polymerizin

Assignees

• Mccauley Kevin M
• Luo Steven
• Bridgestone Corp

Inventors

• Mccauley Kevin M
• Luo Steven

Classifications

• C08F4/70

  Iron group metals, platinum group metals or compounds thereof · CPC title

• C08F4/52 Primary

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C08F36/04 Primary

  conjugated · CPC title

• C08F4/7098

  Nickel or compounds thereof · CPC title

• C08F2/02

  Polymerisation in bulk · CPC title