Unsaturated hydrocarbons polymerization catalysts containing transition metal complexes and Bronsted acids
AssigneeInstitut Francais du Petrole, des Carburants et Lubrifiants
InventorsFrancois Dawans, Philippe Teyssie
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Abstract
Catalysts compositions and methods for polymerizing conjugated diolefins comprising (a) A complex of a transition metal of Groups IV through VIII of Mendeleev's Periodic Table as a nuclear atom and unsaturated hydrocarbon having at least one pair of .pi. electrons as ligand, and (b) A Bronsted acid. Preferred embodiments include a catalyst resulting from a pre-treatment of (a) with a conjugated diolefin and the polymerization process incorporating the pretreated catalyst.
Claims26
A catalyst composition consisting essentially of the reaction product of
- (a) a non-ionic coordination complex of a transition metal of Groups IV through VIII of Mendeleev's Periodic Table as the nuclear atom, and unsaturated hydrocarbon as ligand, said hydrocarbon having at least one pair of .pi. electrons;
- and
- (b) a Bronsted acid, the molar of (a) to (b) being 0.1:1 to 3:1 respectively.
A process for the polymerization of a conjugated diolefinic hydrocarbon, which process comprises polymerizing said hydrocarbon is a substantially anhydrous medium and in the presence of a catalyst composition as defined by claim 20.
A process for the polymerization of butadiene which process comprises polymerizing butadiene in the liquid phase in contact with a catalyst comprising bis-(1,5-cyclooctadiene) nickel and an acid selected from the group consisting of trifluoroacetic acid, hydrochloric acid, and hydriodic acid, the molar ratio of the bis-(1,5-cyclooctadiene) nickel to the acid being 0.01:1 to 50:1, respectively. 18. A catalyst composition as defined
- by claim 1, wherein said transition metal is nickel. 19. A catalyst composition as defined by claim 18 wherein the Bronsted acid is
- trifluoroacetic acid. 20. A catalyst composition according to claim 1, wherein said transition metal is from Groups V through VIII of Mendeleev's
- Periodic Table. 21. A process for the polymerization of an ethylenically unsaturated hydrocarbon, which process comprises polymerizing said hydrocarbon in the presence of a catalyst composition as defined by claim
- 18, in a substantially anhydrous medium. 22. A process for the polymerization of an ethylenically unsaturated hydrocarbon, which process comprises polymerizing said hydrocarbon in the presence of a catalyst composition as defined by claim 19, in a substantially anhydrous medium.
A process for producing polybutadienes, said process comprising polymerizing butadiene-1,3 in the presence of a catalyst which is a product obtained by reacting a .pi.-allylic complex of a transition metal of Groups IV through VIII of the Periodic Table with a compound of the Formula III:
- ##STR1## wherein R.sub.7, R.sub.8 and R.sub.9 are independently selected from the group consisting of hydrogen, halogen;
- and alkyl, alkenyl, and haloalkyl groups having from 1 to 6 carbon atoms;
- and
- Y is hydrogen.
A butadiene polymerization catalyst which is a product obtained by reacting a .pi.-allylic complex of a transition metal of Groups IV- VIII of the Periodic Table with a compound selected from the Formula III:
- ##STR2## wherein R.sup.7, R.sup.8 and R.sup.9 are independently selected from the group consisting of hydrogen, halogen;
- and alkyl, alkenyl, and haloalkyl groups having from 1 to 6 carbon atoms;
- and
- Y is hydrogen.
A process for producing polybutadiene, said process comprising polymerizing butadiene-1,3 in the presence of a catalyst which is a product obtained by reacting:
- (a) a non-ionic coordination complex of a transition metal of Groups IV through VIII of Mendeleev's Periodic Table as the nuclear atom, and unsaturated hydrocarbon as ligand, said hydrocarbon having at least one pair of .pi. electrons;
- and
- (b) a carboxylic acid.
Dependencies are inferred from the claim text.