Nickel-based catalyst composition

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.

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 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 3 , 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 said nickel-containing compound is selected form 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. 
     
     
         7 . The process of  claim 2 , where the alkylating agent is an organoaluminum compound. 
     
     
         8 . 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. 
     
     
         9 . 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. 
     
     
         10 . 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. 
     
     
         11 . 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. 
     
     
         12 . The process of  claim 2 , where the alcohol is defined by the formula R—OH, where R is a monovalent organic group. 
     
     
         13 . The process of  claim 12 , where R includes from about 1 to about 40 carbon atoms. 
     
     
         14 . The process of  claim 12 , where the alcohol is selected from the group consisting of aliphatic alcohols, cyclic alcohols, unsaturated alcohols, aromatic alcohols, heterocyclic alcohols, and polycyclic alcohols. 
     
     
         15 . The process of  claim 2 , where the carboxylic acid is defined by the formula R—COOH, where R is a monovalent organic group. 
     
     
         16 . The process of  claim 15 , where R includes from 1 to about 30 carbon atoms. 
     
     
         17 . The process of  claim 15 , where the carboxylic acid is selected from the group consisting of aliphatic carboxylic acids, saturated fatty acids, unsaturated fatty acids, aromatic acids, and cyclic acids. 
     
     
         19 . A process for forming polydienes, the process comprising:
 (i.) charging to a reactor, either together, partially together, or individually:
 (ia.) a nickel-containing compound; 
 (ib.) an alkylating agent; 
 (ic.) a carboxylic acid; 
 (id.) an alcohol; and 
 (ie.) optional conjugated diene monomer; 
   (ii) charging to the reactor in a step separate than (i):
 (iia.) a fluorine-containing compound; 
   (iii) charging together with step (i), together with step (ii), or separately:
 (iiia.) conjugated diene monomer; and 
   (iv) allowing the conjugated diene monomer to polymerize, 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 ratio of said alcohol to said nickel-containing compound (OH/Ni) is from about 0.4:1 to about 80:1, and where said step of charging employs from about 0.01 to about 0.1 mmole of nickel-containing compound per 100 g of conjugated diene monomer.   
     
     
         20 . The process of  claim 19 , where the molar ratio of the carboxylic acid to the nickel-containing compound is from about 0.5:1 to about 5:1.