Claims
- 1. A method of homopolymerizing propylene or copolymerizing propylene with at least one other polymerizable 1-olefin having two to eight carbon atoms, inclusive, said method comprising the step of polymerizing said propylene and said 1-olefin, if any, under polymerizing conditions in the presence of a catalyst system comprising a dialkyl aluminum halide cocatalyst in combination with a catalyst component being prepared by reacting TiCl3 which is substantially free of extraneous halide with an electron donor compound dissolved in a liquid hydrocarbon solvent in which said TiCl3 is dispersed, said electron donor compound being selected from the group consisting of:
- (a) organic acid esters of the general formula ##STR3## wherein R.sup.1 is an alkyl group of 1 to 16 carbon atoms, inclusive; (b) hindered phenolic compounds of the general formula ##STR4## wherein R.sup.2 is an alkyl group of 1 to 6 carbon atoms, inclusive; R.sup.3 is hydrogen or an alkyl group of 1 to 6 carbon atoms, inclusive; and R.sup.4 is an alkyl group of 2 to 24 carbon atoms, inclusive; and
- (c) silyl esters of the general formula
- R.sup.5.sub.n Si(OR.sup.6).sub.4-n
- wherein R.sup.5 and R.sup.6 can be the same or different and are alkyl groups of 1 to 8 carbon atoms, inclusive, or aryl groups, and n=1 or 2.
- 2. The method of claim 1 wherein said polymerization is carried out at a temperature in the range of about 0.degree. to 120.degree. C., inclusive, and at a pressure of about 1 to 60 atmospheres, inclusive.
- 3. The method of claim 1 wherein said polymerization is carried out in the gas phase at a temperature of about 60.degree. to 100.degree. C. and a pressure of about 20 to 40 atm.
- 4. The method of claim 1 wherein said polymerization is carried out with said catalyst system and product polymer dispersed in a liquid hydrocarbon at a temperature of about 60.degree. to 90.degree. C.
- 5. The method of claim 4 wherein said polymerization is carried out at a pressure of about 1 to 20 atm.
- 6. The method of claim 4 wherein said liquid hydrocarbon comprises liquid propylene and is carried out at a pressure sufficiently high to maintain said propylene in the liquid state.
- 7. The method of claim 6 wherein said pressure is between about 20 and 40 atm.
- 8. The method of claim 1 wherein said TiCl3 is substantially pure.
- 9. The method of claim 1 wherein the reaction between said TiCl3 and said electron donor compound is carried out at a temperature of about 0.degree. to 100.degree. C.
- 10. The method of claim 9 wherein said reaction is carried out at ambient temperature.
- 11. The method of claim 1 wherein the molar ratio of said electron donor compound to said TiCl3 is in the range of about 0.05 to 5:1.
- 12. The method of claim 1 wherein said electron donor compound is an organic acid ester of (a) selected from the group consisting of ethyl benzoate, propyl benzoate and butyl benzoate.
- 13. The method of claim 1 wherein said electron donor compound is a hindered phenolic compound of (b) comprising n-octadecyl-4-hydroxy-3,5-ditertbutyl phenyl propionate.
- 14. The method of claim 1 wherein said electron donor compound is a silyl ester of (c) comprising isobutyl trimethoxy silane.
- 15. The method of claim 1 wherein said hydrocarbon solvent is an alkane or cycloalkane having 4 to 20 carbon atoms, inclusive.
- 16. The method of claim 1 wherein said TiCl3 is in the form of substantially spherical particles.
- 17. The method of claim 1 wherein said cocatalyst comprises a compound of the formula R.sup.7.sub.2 AlX where R.sup.7 is an alkyl group of 1 to 20 carbon atoms, inclusive, and X is a halogen atom.
- 18. The method of claim 17 wherein R.sup.7 is an alkyl group of 2 to 4 carbon atoms, inclusive.
- 19. The method of claim 17 wherein X is chlorine.
- 20. The method of claim 17 wherein said cocatalyst comprises diethylaluminum chloride.
- 21. The method of claim 17 wherein the molar ratio of said cocatalyst compound to said TiCl3 is in the range of about 1 to 50:1.
- 22. The method of claim 20 wherein said molar ratio is about 3.5 to 12:1.
- 23. The method of claim 17 wherein said cocatalyst compound is mixed with a trialkyl aluminum compound.
- 24. The method of claim 17 wherein said cocatalyst compound is mixed with a phenolic compound.
- 25. The method of claim 1 wherein said catalyst component is prepared by a method consisting essentially of the step of reacting reactants consisting essentially of unmilled TiCl.sub.3 which is substantially free of extraneous halide and said electron donor compound dissolved in a liquid alkane or cycloalkane solvent in which said TiCl.sub.3 is dispersed without a milling step, whereby said TiCl.sub.3 is modified.
- 26. The method of claim 25 wherein said solvent has 4 to 20 carbon atoms, inclusive.
- 27. The method of claim 26 wherein said solvent is heptane.
- 28. The method of claim 1 wherein said hydrocarbon solvent contains substantially no olefin.
- 29. A method of homopolymerizing propylene or copolymerizing propylene with at least one other polymerizable 1-olefin having two to either carbon atoms, inclusive, said method comprising the step of polymerizing said propylene and said 1-olefin, if any, under polymerizing conditions in the presence of a catalyst system comprising a dialkyl aluminum halide cocatalyst in combination with a catalyst component, said catalyst component being substantially free of extraneous halide and prepared by a method consisting essentially of the step of reacting reactants consisting essentially of unmilled TiCl.sub.3 which is substantially free of extraneous halide and an electron donor compound dissolved in a liquid alkane or cycloalkane solvent containing substantially no olefin in which said TiCl.sub.3 is dispersed without a milling step whereby said TiCl.sub.3 is modified, said electron donor compound being selected from the group consisting of:
- (a) organic acid esters of the general formula ##STR5## wherein R.sup.1 is an alkyl group of 1 to 16 carbon atoms, inclusive; (b) hindered phenolic compounds of the general ##STR6## wherein R.sup.2 is an alkyl group of 1 to 6 carbon atoms, inclusive; R.sup.3 is hydrogen or an alkyl group of 1 to 6 carbon atoms, inclusive; and R.sup.4 is an alkyl group of 2 to 24 carbon atoms, inclusive; and
- (c) silyl esters of the general formula
- R.sub.n.sup.5 Si(OR.sup.6).sub.4-n
- wherein R.sup.5 and R.sup.6 can be the same or different and are alkyl groups of 1 to 8 carbon atoms, inclusive, or aryl groups, and n=1 or 2.
- 30. The method of claim 29 wherein said polymerization is carried out at a temperature in the range of about 0.degree. to 120.degree. C., inclusive, and at a pressure of about 1 to 60 atmospheres, inclusive.
- 31. The method of claim 29 wherein said polymerization is carried out in the gas phase at a temperature of about 60.degree. to 100.degree. C., inclusive, and a pressure of about 20 to 40 atmospheres, inclusive.
- 32. The method of claim 29 wherein said polymerization is carried out with said catalyst system and product polymer dispersed in a liquid hydrocarbon at a temperature of about 60.degree. to 90.degree. C., inclusive.
- 33. The method of claim 29 ad wherein TiCl.sub.3 is substantially pure.
- 34. The method of claim 29 wherein the reaction between said TiCl.sub.3 and said electron donor compound is carried out at a temperature of about 0.degree. to 100.degree. C.
- 35. The method of claim 29 wherein the molar ratio of said electron donor compound to said TiCl.sub.3 is in the range of about 0.05 to 5:1.
- 36. The method of claim 29 wherein said solvent has 4 to 20 carbon atoms, inclusive.
- 37. The method of claim 29 wherein said electron donor compound is selected from the group consisting of ethyl benzoate, propyl benzoate, butyl benzoate, n-octadecyl-4-hydroxy-3,5-ditertbutyl phenyl propionate, and isobutyl trimethoxy silane.
- 38. The method of claim 29 wherein said TiCl.sub.3 is in the form of substantially spherical particles.
- 39. The method of claim 29 wherein said cocatalyst comprises a compound of the formal R.sub.2.sup.7 AlX where R.sup.7 is an alkyl group of 1 to 20 carbon atoms, inclusive, and X is a halogen atom.
- 40. A method of homopolymerizing propylene or copolymerizing propylene with at least one other polymerizable 1-olefin having two to either carbon atoms, inclusive, said method comprising the step of polymerizing said propylene and said 1-olefin, if any, under polymerizing conditions in the presence of a catalyst system comprising a dialkyl aluminum halide cocatalyst in combination with a catalyst component, which is substantially free of extraneous halide and prepared by reacting TiCl.sub.3 which is substantially free of extraneous halide with an electron donor compound dissolved in a liquid hydrocarbon solvent in which said TiCl.sub.3 is dispersed, said electron donor compound being selected from the group consisting of:
- (a) organic acid esters of the general formula ##STR7## wherein R.sup.1 is an alkyl group of 1 to 16 carbon atoms, inclusive; (b) hindered phenolic compounds of the general formula ##STR8## wherein R.sup.2 is an alkyl group of 1 to 6 carbon atoms, inclusive; R.sup.3 is hydrogen or an alkyl group of 1 to 6 carbon atoms, inclusive; and R.sup.4 is an alkyl group of 2 to 24 carbon atoms, inclusive; and
- (c) silyl esters of the general formula
- R.sub.n.sup.5 Si(OR.sup.6).sub.4-n
- wherein R.sup.5 and R.sup.6 can be the same or different and are alkyl groups of 1 to 8 carbon atoms, inclusive, or aryl groups, and n=1 or 2.
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a division of copending, commonly assigned application Ser. No. 07/341,242 filed Apr. 20, 1989, now U.S. Pat. No. 5,128,294 issued Jul. 7, 1992, which is a continuation of application Ser. No. 07/071,978 filed Jul. 10, 1987 and now abandoned.
US Referenced Citations (47)
Divisions (1)
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Date |
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341242 |
Apr 1989 |
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Continuations (1)
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71978 |
Jul 1987 |
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