Unsaturated hydrocarbons polymerization catalysts containing transition metal complexes and Bronsted acids

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 π 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.

What is claimed is: 
     
       1. 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 π electrons; and   (b) a Bronsted acid, the molar of (a) to (b) being 0.1:1 to 3:1 respectively.   
     
     
       2. A catalyst composition as defined by claim 1 wherein said unsaturated hydrocarbon is a cyclopolyolefin having about 5-1 carbon atoms per molecule, a nucleus of about 5-14 carbon atoms and about 2-6 double bonds per molecule. 
     
     
       3. A catalyst composition as defined by claim 2 wherein the coordination compound is bis-(1,5-cyclooctadiene) nickel. 
     
     
       4. A catalyst composition as defined by claim 1 wherein the Bronsted acid has a dissociation constant higher than 10 -4 . 
     
     
       5. A catalyst composition as defined by claim 1 wherein the Bronsted acid is trifluoroacetic acid. 
     
     
       6. A catalyst composition as defined by claim 1 wherein the Bronsted acid is hydrochloric acid. 
     
     
       7. A catalyst composition as defined by claim 1 wherein the Bronsted acid is hydriodic acid. 
     
     
       8. A catalyst composition as defined by claim 1, further comprising a Lewis acid. 
     
     
       9. A catalyst composition as defined by claim 1 wherein the coordination compound is subjected to a pretreatment comprising reacting said coordination compound with a polymerizable monomer, the resultant reaction product being then reacted with the Bronsted acid. 
     
     
       10. A catalyst composition as defined by claim 9 wherein said polymerizable monomer is butadiene. 
     
     
       11. A catalyst composition as defined by claim 9 wherein at least a portion of hydrocarbon ligand of the coordination compound is separated by distillation after the reaction of the coordination compound with the polymerizable monomer. 
     
     
       12. A catalyst composition as defined by claim 9 wherein at least 0.5 mol of polymerizable monomer is employed per atom of transition metal in the form of the coordination compound. 
     
     
       13. A catalyst composition as defined by claim 9 wherein the addition of said reaction product to the Bronsted acid is conducted in the absence of unreacted polymerizable monomer, and excess Bronsted acid is separated from the resultant product. 
     
     
       14. 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. 
     
     
       15. A process for the polymerization of a conjugated diolefinic hydrocarbon, which process comprises polymerizing said hydrocarbon in a substantially anhydrous medium and in the presence of a catalyst composition as defined by claim 5. 
     
     
       16. A process for the polymerization of a conjugated diolefinic hydrocarbon, which process comprises polymerizing said hydrocarbon in a substantially anhydrous medium and in the presence of a catalyst composition as defined by claim 13. 
     
     
       17. 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. .Iadd. 23. 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 π-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 7 , R 8  and R 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. .Iaddend. .Iadd. 24.  A process according to claim 23, wherein the polymerization is carried out at a temperature ranging from -40 to +80° C. in a medium of an inert organic solvent selected from the group consisting of aliphatic, cycloaliphatic, aromatic hydrocarbons and halogen derivatives thereof. .Iaddend..Iadd. 25. A process according to claim 23, wherein said product is formed in the presence of the butadiene-1,3 monomer. .Iaddend..Iadd. 26. A butadiene polymerization catalyst which is a product obtained by reacting a π-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 7 , R 8  and R 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. .Iaddend. .Iadd. 27.  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 π electrons; and   (b) a carboxylic acid. .Iaddend. .Iadd. 28. A process as defined by claim 27 wherein said carboxylic acid is selected from the group consisting of acetic acid, formic acid, isobuteric acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid and trifluoroacetic acid. .Iaddend..Iadd. 29. A process as defined by claim 27 wherein said non-ionic coordination complex is bis π-allyl nickel. .Iaddend..Iadd. 30. A process as defined by claim 28 wherein said non-ionic coordination complex is bis π-allyl nickel. .Iaddend. .Iadd. 31. A process according to claim 23, wherein the π-allylic complex is selected from the group consisting of bis-(π-allyl) nickel, π-allyl-cyclopentadienyl nickel and tris-(π-allyl) chromium.