Catalyst and method

A new catalyst and method of making polymers therewith and the process of preparing the catalyst in which the catalyst is prepared by dispersing on a finely divided carrier material, particularly a difficultly reducible inorganic support such as silica, an organic chromium complex such as a chelate derived from orthohydroxyphenyl or 2'-hydroxyphenyl carbonyl compounds, including ketone, aldehyde and amide types, and their derivatives, and activating the resulting mixture by heating at an elevated temperature in a non-oxidizing atmosphere.

I claim:

1. A catalyst prepared by dispersing on a finely divided, difficultly reducible, inorganic support of the class consisting of silica, alumina, thoria, zironia, titania, magnesia, and mixtures thereof a chromium chelate of an orthohydroxy carbonyl compound essentially of the formula of the class consisting of ##STR2## wherein R is individually selected from hydrogen, alkyl, alkenyl, aryl, cycloalkyl, cycloalkenyl, and arylalkyl radicals and combinations of these radicals with each R containing 0-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, X is a negative group relative to chromium selected from the group consisting of halide, alkyl and alkoxy, Y is selected from hydrogen, hydroxyl, alkoxy, and alkyl groups, m is a whole number of 1 to 3, n is a whole number of 0 to 2, and m plus n is 2 or 3, and activating the resulting mixture by heating to and at an elevated temperature of from about 600-2000.degree. F. in a non-oxidizing atmosphere.

2. The catalyst of claim 1 wherein said chromium compound is essentially of the formula ##STR3##

3. The catalyst of claim 1 wherein said chromium compound is essentially of the formula ##STR4##

4. The catalyst of claim 1 wherein said support prior to the addition of said chromium compound is dried by heat pretreatment by heating at a temperature of from about 300-2000.degree. F. until volatile matter is at least partially driven off.

5. The catalyst of claim 1 wherein said chromium compound is dissolved in a solvent and the resulting solution used to impregnate said support.

6. The catalyst of claim 1 wherein said dispersing of said chromium compound is accomplished by dry blending with said finely divided support followed by heating in a fluid bed maintained in suspension with a non-oxidizing gas flowing through said support during said heating.

7. The catalyst of claim 1 wherein said activating is accomplished in a fluid bed maintained in suspension with the flow of a non-oxidizing gas.

8. The catalyst of claim 1 wherein said catalyst on a dry basis contains an amount of said chromium compound to provide about 0.05-10 wt.% of chromium.

9. The catalyst of claim 1 wherein said chromium compound is a member of the class consisting of chromium (III) 2'-hydroxyacetophenone complex, chromium (III) salicylaldehyde complex, chromium (III) salicylanilide complex, chromium (III) salicylamide complex and chromium (III) 2',5'-dihydroxyacetophenone complex.

10. The method of making polymers of 1-olefins of 2 to 8 carbon atoms and copolymers of said olefins and 1-olefins of 2 to 20 carbon atoms which comprises polymerizing said olefins under polymerizing conditions with the catalyst of claim 1.

11. The method of making polymers of 1-olefins of 2 to 8 carbon atoms and copolymers of said olefins and 1-olefins of 2 to 20 carbon atoms which comprises polymerizing said olefins under polymerizing conditions with the catalyst of claim 2.

12. The method of making polymers of 1-olefins of 2 to 8 carbon atoms and copolymers of said olefins and 1-olefins of 2 to 20 carbon atoms which comprises polymerizing said olefins under polymerizing conditions with the catalyst of claim 3.

13. The method of making polymers of 1-olefins of 2 to 8 carbon atoms and copolymers of said olefins and 1-olefins of 2 to 20 carbon atoms which comprises polymerizing said olefins under polymerizing conditions with the catalyst of claim 4.

14. The method of making polymers of 1-olefins of 2 to 8 carbon atoms and copolymers of said olefins and 1-olefins of 2 to 20 carbon atoms which comprises polymerizing said olefins under polymerizing conditions with the catalyst of claim 5.

15. The method of making polymers of 1-olefins of 2 to 8 carbon atoms and copolymers of said olefins and 1-olefins of 2 to 20 carbon atoms which comprises polymerizing said olefins under polymerizing conditions with the catalyst of claim 6.

16. The method of making polymers of 1-olefins of 2 to 8 carbon atoms and copolymers of said olefins and 1-olefins of 2 to 20 carbon atoms which comprises polymerizing said olefins under polymerizing conditions with the catalyst of claim 7.

17. The method of making polymers of 1-olefins of 2 to 8 carbon atoms and copolymers of said olefins and 1-olefins of 2 to 20 carbon atoms which comprises polymerizing said olefins under polymerizing conditions with the catalyst of claim 8.

18. The method of making polymers of 1-olefins of 2 to 8 carbon atoms and copolymers of said olefins and 1-olefins of 2 to 20 carbon atoms which comprises polymerizing said olefins under polymerizing conditions with the catalyst of claim 9.

19. The process of preparing an active polymerization catalyst comprising the steps of dispersing on a finely divided, difficultly reducible, inorganic support of the class consisting of silica, alumina, thoria, zirconia, titania, magnesia, and mixtures thereof a chromium chelate of an orthohydroxy carbonyl compound essentially of the formula of the class consisting of ##STR5## wherein R is individually selected from hydrogen, alkyl, alkenyl, aryl, cycloalkyl, cycloalkenyl, and arylalkyl radicals and combinations of these radicals with each R containing 0-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, X is a negative group relative to chromium selected from the group consisting of halide, alkyl and alkoxy, Y is selected from hydrogen, hydroxyl, alkoxy, and alkyl groups, m is a whole number of 1 to 3, n is a whole number of 0 to 2, and m plus n is 2 or 3, and activating the resulting mixture by heating to and at an elevated temperature of from about 600.degree.-2000.degree. F. in a non-oxidizing atmosphere.

20. The process of claim 19 wherein said chromium compound is essentially of the formula ##STR6##

21. The process of claim 19 wherein said chromium compound is essentially of the formula ##STR7##

22. The process of claim 19 wherein said support prior to the addition of said chromium compound is dried by heat pretreatment by heating at a temperature of from about 300.degree.-2000.degree. F. until volatile matter is at least partially driven off.

23. The process of claim 19 wherein said chromium compound is dissolved in a solvent and the resulting solution used to impregnate said support.

24. The process of claim 19 wherein said dispersing of said chromium compound is accomplished by dry blending with said finely divided support followed by heating in a fluid bed maintained in suspension with a non-oxidizing gas flowing through said support during said heating.

25. The process of claim 19 wherein said activating is accomplished in a fluid bed maintained in suspension with the flow of a non-oxidizing gas.

26. The process of claim 25 wherein said non-oxidizing gas is selected from the class consisting of nitrogen, hydrogen, carbon monoxide, noble gases and mixtures of these gases.

27. The process of claim 19 wherein said catalyst on a dry basis contains an amount of said chromium compound to provide about 0.05-10 wt.% of chromium.

28. The process of claim 19 wherein said chromium compound is a member of the class consisting of chromium (III) 2'-hydroxyacetophenone complex, chromium (III) salicylaldehyde complex, chromium (III) salicylanilide complex, chromium (III) salicylamide complex and chromium 2',5'-dihydroxyacetophenone complex.

29. The process of claim 19 wherein said activating is in a stationary bed in a non-oxidizing atmosphere provided by evacuation of gas from said bed.

30. The process of claim 19 wherein said activating is in a stationary bed in a non-oxidizing atmosphere provided by a non-oxidizing gas.

31. The process of claim 30 wherein said non-oxidizing gas is selected from the class consisting of nitrogen, hydrogen, carbon monoxide, noble gases and mixtures of these gases.

32. The process of claim 19 wherein said activating is in a fluid bed using a non-oxidizing gas to maintain the mixture of support and said chromium compound in suspension while heating to a final activation temperature of from 850.degree.-2000.degree. F.

33. The process of claim 32 wherein said non-oxidizing gas is selected from the class consisting of nitrogen, hydrogen, carbon monoxide, noble gases and mixtures of these gases.

34. The process of claim 19 wherein said activating is in a fluid bed using a non-oxidizing gas to maintain the mixture of support and said chromium compound in a fluid condition while heating at activating temperatures of from about 300.degree.-350.degree. F. for from about 1 to 3 hours and then at about 550.degree.-600.degree. F. for about 1 to 3 hours to produce an interaction between the chromium compound and the support, followed by final activation at a temperature of of about 850.degree.-2000.degree. F. for a period of about 0.5-12 hours.

35. The process of claim 34 wherein said non-oxidizing gas is selected from the class consisting of nitrogen, hydrogen, carbon monoxide, noble gases and mixtures of these gases.