Group Va and VII oxygen mineral acids as catalyst modifiers

Abstract

A propylene polymerization catalyst is formed by incorporation into a catalytic mixture, comprising a transition metal compound and an organoaluminum compound, effective amounts of Group Va or Group VII oxygen mineral acids whereby the amount of n-hexane-soluble polymeric product is decreased.

I claim: 
     
       1. A polymerization process comprising contacting, under polymerization conditions, propylene or a mixture of propylene and one or more copolymerizable alpha-olefins with a catalyst comprising a titanium trihalide; an organoaluminum compound; and an effective amount of a .[.Group Va.]. .Iadd.nitrogen .Iaddend.or .Iadd.a group .Iaddend.VII oxygen mineral acid .Iadd.in aqueous solution .Iaddend.in a molar ratio .Iadd.to titanium trihalide .Iaddend.from about 0.01 to 1 to about 0.7 to 1 whereby the amount of n-hexane soluble polymeric product produced is decreased. 
     
     
       2. The process of claim 1 wherein the organoaluminum compound is diethylaluminum halide, triethylaluminum, a mixture thereof or a mixture of triethylaluminum with ethylaluminum dihalide. .[.3. The process of claim 1 wherein the oxygen mineral acid is phosphoric acid, phosphorous 
     
     
        acid, or perchloric acid..]. 4. The process of claim 1 wherein the mineral acid is nitric acid. .[.5. The process of claim 1 wherein the mineral acid is phosphoric acid..]. .[.6. The process of claim 1 wherein the mineral 
     
     
        acid is phosphorous acid..]. 7. The process of claim 1 wherein the mineral 
     
     
        acid is perchloric acid. 8. The process of claim 2 wherein the organoaluminum compound is diethylaluminum chloride, triethylaluminum, a mixture thereof or a mixture of triethylaluminum with ethylaluminum dichloride. .[.9. The process of claim 3 wherein the molar ratio of oxygen mineral acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 
     
     
        1..]. 10. The process of claim 4 wherein the molar ratio of nitric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1. .[.11. The process of claim 5 wherein the molar ratio of phosphoric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1..]. .[.12. The process of claim 6 wherein the molar ratio of phosphorous acid to titanium trihalide 
     
     
        is about 0.02 to 1 to about 0.5 to 1..]. 13. The process of claim 7 wherein the molar ratio of perchloric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1. .[.14. The process of claim 3 wherein the organoaluminum compound is diethylaluminum dichloride..]. .Iadd. 15. A polymerization process comprising contacting under polymerization conditions, propylene or a mixture of propylene and one or more copolymerizable alpha-olefins with a catalyst comprising a titanium trihalide; a dialkyl aluminum halide; and a phosphorous mineral acid in aqueous solution in a molar ratio to titanium trihalide from about 0.01 to 1 to about 0.5 to 1. .Iaddend..Iadd. 16. The process of claim 15 wherein the mineral acid is phosphoric acid. .Iaddend..Iadd. 17. The process of claim 15 wherein the mineral acid is phosphorous acid. .Iaddend..Iadd. 18. The process of claim 15 wherein the titanium trihalide is titanium trichloride. .Iaddend..Iadd. 19. The process of claim 16 wherein the molar ratio of phosphoric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1. .Iaddend..Iadd. 20. The process of claim 17 wherein the molar ratio of phosphorous acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1. .Iaddend.