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 hexavalent sulfur mineral acid or anhydride 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.]. .Iadd.a dialkyl aluminum halide.Iaddend.; and a hexavalent sulfur mineral acid or anhydride in a molar ratio to titanium trihalide from about 0.005 to 1 to about .[.0.7.]. .Iadd.0.5 .Iaddend.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 hexavalent sulfur mineral acid or anhydride is sulfuric acid, oleum, halosulfonic acid or sulfur trioxide. 
     
     
       4. The catalyst composition of claim 1 wherein the hexavalent sulfur mineral acid is sulfuric acid. 
     
     
       5. The catalyst composition of claim 1 wherein the hexavalent mineral acid is oleum. 
     
     
       6. The catalyst composition of claim 1 wherein the hexavalent mineral acid is chlorosulfonic acid. 
     
     
       7. The catalyst composition of claim 1 wherein the hexavalent mineral anhydride is sulfur trioxide. 
     
     
       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 hexavalent mineral acid to titanium trihalide is about 0.01 to 1 to about .Badd..[.0.7.]..Baddend. .Iadd.0.5 .Iaddend.to 1. 
     
     
       10. The catalyst composition of claim 4 wherein the molar ratio of sulfuric acid to titanium trihalide is about 0.01 to 1 to about 0.5 to 1. 
     
     
       11. The catalyst composition of claim 5 wherein the molar ratio of oleum to titanium trihalide is about 0.01 to 1 to about 0.5 to 1. 
     
     
       12. The catalyst composition of claim 7 wherein the molar ratio of sulfur trioxide to titanium trihalide is about 0.01 to 1 to about 0.5 to 1. 
     
     
       13. The catalyst composition of claim 6 wherein the molar ratio of chlorosulfonic acid to titanium trihalide is about 0.01 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 alpha-olefins, which produces low amounts of n-hexane-soluble 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 a mixture of trialkyl aluminum with alkyl aluminum dihalide.]. .Iadd.a dialkyl aluminum halide.Iaddend.; and a hexavalent sulfur mineral acid or anhydride in a molar ratio to titanium trihalide from about 0.005 to 1 to about .Badd..[.0.7.]..Baddend. .Iadd.0.5 
     
     
        .Iaddend.to 1. 16. The process of claim 15 wherein the hexavalent sulfur mineral acid is added to a solution of .[.organoaluminum compound.]. .Iadd.dialkyl aluminum halide .Iaddend.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 diethyl-aluminum.]. .Iadd.dialkyl aluminum halide is diethyl aluminum 
     
     
        .Iaddend.chloride. 18. The process of claim 16 wherein the inert 
     
     
        hydrocarbon is n-hexane. 19. The process of claim 15 wherein the 
     
     
        hexavalent mineral acid is sulfuric acid. 20. The process of claim 15 
     
     
        wherein the hexavalent mineral acid is oleum. 21. The process of claim 15 
     
     
        wherein the hexavalent mineral anhydride is sulfur trioxide. 22. The process of claim 15 wherein the hexavalent mineral acid is chlorosulfonic acid.