Catalyst system

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 catalyst composition for the polymerization of propylene or mixtures of propylene and copolymerizable alpha-olefins, which produces low amounts of n-hexane-soluble polymer, comprising a titanium trihalide; an organoaluminum compound selected from the group consisting of dialkyl aluminum halide, trialkyl aluminum, a mixture thereof, and a mixture of trialkyl aluminum with alkyl aluminum dihalide; and a .[.Group Va.]. .Iadd.nitrogen .Iaddend.or Group VII oxygen mineral acid in a molar ratio to titanium trihalide from about 0.005 to 1 to about 0.7 to 1. 
     
     
       2. The catalyst composition of claim 1 wherein the .[.transition metal compound.]. .Iadd.titanium trihalide .Iaddend.is titanium trichloride. 
     
     
       3. The catalyst composition of claim 1 wherein the mineral acid is an oxygen mineral acid of .[.nitrogen, phosphorus or.]. chlorine. 
     
     
       4. The catalyst composition of claim 1 wherein the mineral acid is nitric acid. .[.5. The catalyst composition of claim 1 wherein the mineral acid is phosphoric acid..]. .[.6. The catalyst composition of claim 1 wherein 
     
     
        the mineral acid is phosphorous acid..]. 7. The catalyst composition of 
     
     
        claim 1 wherein the mineral acid is perchloric acid. 8. The catalyst composition of claim 3 wherein the titanium trihalide is titanium trichloride and the organoaluminum compound is diethylaluminum chloride, triethylaluminum, a mixture thereof or a mixture of triethylaluminum with 
     
     
        ethylaluminum dichloride. 9. The catalyst composition of claim 3 wherein the molar ratio of oxygen mineral acid to titanium tirhalide is about 0.02 
     
     
        to 1 to about 0.5 to 1. 10. The catalyst composition of claim 4 wherein the molar ratio of nitric acid to titanium trihalide is about 0.2 to 1 to about 0.5 to 1. .[.11. The catalyst composition 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 catalyst composition 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 catalyst composition of claim 7 wherein the molar ratio of perchloric acid to titanium trihalide is about 0.02 to 1 to 
     
     
        about 0.1 to 1. 14. The catalyst composition of claim 3 wherein the titanium trihalide is titanium trichloride and the organoaluminum compound 
     
     
        is diethylaluminum chloride. 15. A process for forming a catalyst composition for the polymerization of propylene or mixtures of propylene and copolymerizable alphaolefins, which produces low amounts of n-hexanesoluble polymer, comprising mixing in a suitable medium a titanium trihalide; an organoaluminum compound selected from the group consisting of dialkyl aluminum halide, trialkyl aluminum, mixtures thereof, and mixtures of trialkyl aluminum with alkyl aluminum dihalide; and a .[.Group Va.]. .Iadd.nitrogen .Iaddend.or Group VII oxygen mineral acid in a molar 
     
     
        ratio to titanium trihalide from about 0.005 to 1 to about 0.7 to 1. 16. The process of claim 15 wherein the oxygen mineral acid is added to a solution of organoaluminum compound in an inert hydrocarbon then the resulting mixture is added to a mixture of titanium trihalide in an inert 
     
     
        hydrocarbon. 17. The process of claim 15 wherein the titanium trihalide is titanium trichloride and the organoaluminum compound is diethylaluminum 
     
     
        chloride. 18. The process of claim 16 wherein the inert hydrocarbon is 
     
     
        n-hexane. 19. The process of claim 16 wherein the mineral acid is nitric acid. .[.20. The process of claim 15 wherein the mineral acid is phosphoric acid..]. .[.21. The process of claim 15 wherein the mineral 
     
     
        acid is phosphorous acid..]. 22. The process of claim 15 wherein the mineral acid is perchloric acid. .Iadd. 23. A catalyst composition for the polymerization of propylene or mixtures of propylene and copolymerizable alpha-olefins, which produces low amounts of n-hexane-soluble polymer, comprising a titanium trihalide; a dialkyl aluminum halide; and a phosphorous oxygen mineral acid in a molar ratio to titanium trihalide from about 0.005 to 1 to about 0.5 to 1. .Iaddend..Iadd. 24. The catalyst composition of claim 23 wherein the mineral acid is phosphoric acid. .Iaddend..Iadd. 25. The catalyst composition of claim 23 wherein the mineral acid is phosphorous acid. .Iaddend..Iadd. 26. The catalyst composition of claim 23 wherein the titanium trihalide is titanium trichloride. .Iaddend..Iadd. 27. The catalyst composition of claim 24 wherein the molar ratio of phosphoric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1. .Iaddend..Iadd. 28. The catalyst composition of claim 25 wherein the molar ratio of phosphorous acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1. .Iaddend. .Iadd. 29. A process for forming a catalyst composition for the polymerization of propylene or mixtures of propylene and copolymerizable alpha-olefins, which produces low amounts of n-hexane-soluble polymer, comprising mixing in a suitable medium, a titanium trihalide; a dialkyl aluminum halide; and a phosphorus oxygen mineral acid in a molar ratio to titanium trihalide from about 0.005 to 1 to about 0.5 to 1. .Iaddend..Iadd. 30. The process of claim 29 wherein the oxygen mineral acid is added to a solution of dialkyl aluminum halide in an inert hydrocarbon, then the resulting mixture is added to a mixture of titanium trihalide in an inert hydrocarbon. .Iaddend..Iadd. 31. The process of claim 30 wherein the inert hydrocarbon is n-hexane. .Iaddend..Iadd. 32. The process of claim 29 wherein the mineral acid is phosphoric acid. .Iaddend..Iadd. 33. The process of claim 29 wherein the mineral acid is phosphorous acid. .Iaddend.