High trans-1,4-polybutadiene and catalyst and process for preparing crystalline high trans-1,4-poly-butadiene
AssigneeBridgestone/Firestone, Inc.
InventorsJung W. Kang, Jason T. Poulton
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Abstract
Diene polymers having a high content of trans-1,4 addition and two distinct melting points in the ranges of 30.degree. C. to 50.degree. C. and 70.degree. C. to 130.degree. C. are prepared by polymerizing a 1,3-diene monomer in a hydrocarbon solvent in the presence of a catalyst composition comprising (a) a carboxylated nickel oxy borate compound; (b) an orKanoaluminum compound; (c) a triaryloxy phosphorus compound and (d) a carboxylic acid preferably a fluorinated carboxylic acid. The resultant polymers are useful as additives to tire rubbers to improve processability by reducing compound Mooney viscosity and reducing the shrinkage of various compound stocks.
Claims21
A process for the synthesis of high trans-1,4-polybutadiene comprising contacting a polymerization medium containing 1,3-butadiene monomer and an organic solvent with a catalyst system comprising components:
- (a) a carboxylated nickel oxy borate compound selected from the group consisting of compounds represented by the formulae (RCOOMO).sub.3 B and (RCOOMO).sub.2 BOR', wherein R and R' are alkyl radicals containing from 1 to 17 carbon atoms and M is nickel;
- (b) an organoaluminum compound of the formula:
- ##STR3## wherein R.sub.1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, arylalkyl, alkoxy, fluorine, and hydrogen, R.sub.2 and R.sub.3 being selected from the group of alkyl, cycloalkyl, aryl, alkaryl and arylalkyl;
- (c) an organophosphorus compound of the formula (ArO).sub.3 P wherein Ar is a substituted or unsubstituted aryl group;
- and (d) a carboxylic acid or a fluorinated carboxylic acid, and allowing the 1,3-butadiene monomer to polymerize at a temperature in a range of about 0.degree. C. to about 150.degree. C. to produce high trans-1,4-polybutadiene.
A catalyst comprising:
- (a) a carboxylated nickel oxy borate compound selected from the group consisting of compounds represented by the formulae (RCOOMO).sub.3 B and (RCOOMO).sub.2 BOR', wherein R and R' are alkyl radicals containing from 1 to 17 carbon atoms and M is nickel;
- (b) an organoaluminum compound of the formula:
- ##STR4## wherein R.sub.1 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, arylalkyl, alkoxy, fluorine, and hydrogen, R.sub.2 and R.sub.3 being selected from the group of alkyl, cycloalkyl, aryl, alkaryl and arylalkyl;
- (c) an organophosphorus compound of the formula (ArO).sub.3 P wherein Ar is a substituted or unsubstituted aryl group;
- and (d) a carboxylic acid or a fluorinated carboxylic acid.
Dependencies are inferred from the claim text.