Claims
- 1. A process for polymerizing at least one olefin comprising polymerizing at least one olefin under olefin polymerization conditions in the presence of a catalyst system comprising
- (I) a catalyst component comprising the product prepared by the steps of:
- (a) contacting silica with components
- (1) at least one hydrocarbon soluble magnesium-containing compound; and
- (2) a first modifying compound selected from the group consisting of silicon halide, boron halides, aluminum halides and mixtures thereof followed by a second modifying compound selected from the group consisting of a silane of the formula SiH.sub.r X.sup.2.sub.s, where X.sup.2 is halogen; r is an integer of 1 to 3; and s is an integer of 1 to 3, with the proviso that the sum of r and s is 4, hydrogen halides having the structural formula HX.sup.3, where X.sup.3 is halogen, and mixtures thereof, said sequence of contact of silica with said components (1) and (2) being random; and
- (b) contacting the product of step (a) with a titanium-containing compound having the structural formula TiX.sup.1.sub.p (OR.sup.1).sub.q, where X.sup.1 is halogen; R.sup.1 is hydrocarbyl; p is an integer of 1 to 4; q is 0 or an integer of 1 to 3, with the provisos that the sum of p and q is 4 and that a second titanium-containing compound having the structural formula Ti(OR).sub.m X.sub.n, where R is hydrocarbyl; X is halogen; m is an integer of 1 to 4; n is 0 or an integer of 1 to 3; and the sum of m and n is 4, is not utilized in the formation of said catalyst component;
- (II) an aluminum-containing compound first co-catalyst component; and
- (III) at least one silane second co-catalyst component.
- 2. A process in accordance with claim 1 wherein said silica is at least 90% pure silica having a surface area of between about 80 m.sup.2 /g. and about 300 m.sup.2 /g., a median particle size of between about 20 microns and about 200 microns and a pore volume of between about 0.6 cc/g. and about 3.0 cc/g.
- 3. A process in accordance with claim 1 wherein said silica is pretreated, prior to step (a), to replace surface hydroxyl groups with a surface characterized by the structural formula ##STR2##
- 4. A process in accordance with claim 3 wherein said silica pretreatment comprises calcining said silica at a temperature of at least about 150.degree. C. in inert atmosphere.
- 5. A process in accordance with claim 3 wherein said silica pretreatment comprises contacting said silica with a hexaalkyl disilazane.
- 6. A process in accordance with claim 3 wherein said silica pretreatment comprises (a) contacting said silica with a hexaalkyl disilazane and (b) calcining said silica at a temperature of at least about 100.degree. C. in an inert atmosphere, said steps (a) and (b) occurring in random order.
- 7. A process in accordance with claim 1 wherein said hydrocarbon soluble magnesium compound is selected from the group consisting of dihydrocarbyloxymagnesiums, hydrocarbyloxymagnesium halides and mixtures thereof.
- 8. A process in accordance with claim 1 wherein said first modifying compound is selected from the group consisting of silicon tetrachloride, boron trichloride and aluminum trichloride.
- 9. A process in accordance with claim 1 wherein said second modifying compound or compounds are characterized by X.sup.2 and X.sup.3 being the same or different and being chlorine or bromine; r being 1 or 2; and s being 2 or 3.
- 10. A process in accordance with claim 1 wherein said titanium-containing compound is characterized by X.sup.1 being chlorine or bromine; R.sup.1 being alkyl; p being an integer of 2 to 4; and q being 0, 1 or 2.
- 11. A process in accordance with claim 1 wherein said silica in step (a) contacts component (1) prior to contact with component (2).
- 12. A process in accordance with claim 1 wherein said first modifying compound and said second modifying compound contact said silica in an amount such that the molar ratio of said first modifying compound to said second modifying compound is in the range of between about 50:50 and about 99:1.
- 13. A process in accordance with claim 1 including the step of washing said product of step (a) with an organic solvent prior to said step (b).
- 14. A process in accordance with claim 1 including the step of washing said product of step (b) with an organic solvent.
- 15. A process in accordance with claim 1 wherein said contact between said silica and said hydrocarbon soluble magnesium compound of step (a) occurs at a temperature in the range of between about 15.degree. C. and about 120.degree. C. over a period in the range of between about 30 minutes and 4 hours.
- 16. A process in accordance with claim 1 wherein said contact between said silica and said first and second modifying compounds of step (a) occurs at a temperature of between about 10.degree. C. and about 60.degree. C. over a period of between about 10 minutes and about 2 hours.
- 17. A process in accordance with claim 1 wherein said step (b) occurs at a temperature in the range of between about 60.degree. C. and about 130.degree. C. over a period in the range of between 15 minutes and about 3 hours.
- 18. A process for polymerizing at least one olefin comprising polymerizing at least one olefin under olefin polymerization conditions in the presence of a catalyst system comprising
- (I) a catalyst component comprising the product prepared by the steps of:
- (a) contacting silica, pretreated to replace surface hydroxyl groups with a surface characterized by the structural formula ##STR3## with components: (1) a compound selected from the group consisting of a dihydrocarbyloxymagnesium, a hydrocarbyloxymagnesium halide and mixtures thereof; and
- (2) a first modifying compound selected from the group consisting of a silicon tetrahalide, a boron trihalide and an aluminum trihalide followed by a second modifying compound selected from the group consisting of halogenated silane having the structural formula SiH.sub.r X.sup.2.sub.s, where X.sup.2 is halogen; r is an integer of 1 or 2; and s is an integer of 2 or 3, with the proviso that the sum of r and s is 4, a hydrogen halide having the structural formula HX.sup.3, where X.sup.3 is chlorine or bromine, and mixtures thereof; said first and said second modifying compounds contacting said silica in an amount such that the molar ratio of said first to said second modifying compound is in the range of between about 50:50 and about 99:1, said sequence of contact of said components (1) and (2) with silica being random; and
- (b) contacting the product of step (a) with a titanium compound having the structural formula TiX.sup.1.sub.p (OR.sup.1).sub.q, where X.sup.1 is chlorine or bromine; R.sup.1 is alkyl; p is an integer of 2 to 4; and q is 0, 1 or 2, with the provisos that the sum of p and q is 4 and that a second titanium-containing compound having the structural formula Ti(OR).sub.m X.sub.n, where R is hydrocarbyl; X is halogen; m is an integer of 1 to 4; n is 0 or an integer of 1 to 3; and the sum of m and n is 4, is not utilized in the formation of said catalyst component;
- (II) an alkylaluminum-containing compound first co-catalyst component; and
- (III) at least one hydrocarbylalkoxysilane second co-catalyst component.
- 19. A process in accordance with claim 18 wherein said silica is pretreated by:
- (a) calcining said silica at a temperature of at least about 150.degree. C. in an inert atmosphere,
- (b) treating said silica with a hexaalkyl disilazane or
- (c) in random order, calcining said silica at a temperature of at least about 100.degree. C. in an inert atmosphere and treating said silica with a hexaalkyl disilazane.
- 20. A process in accordance with claim 19 wherein said calcining step (a) occurs at a temperature in the range of between about 550.degree. C. and about 650.degree. C. in a nitrogen atmosphere, and said hexaalkyl disilazane of steps (b) and (c) is hexamethyl disilazane.
- 21. A process in accordance with claim 18 wherein said component (1) is a hydrocarbyloxymagnesium halide.
- 22. A process in accordance with claim 21 wherein said hydrocarbyloxymagnesium halide is selected from the group consisting of 2-methylpentyloxymagnesium chloride and 2-ethylhexyloxymagnesium chloride.
- 23. A process in accordance with claim 22 wherein said first modifying compound of component (2) is silicon tetrachloride.
- 24. A process in accordance with claim 23 wherein said second modifying compound of component (2) is selected from the group consisting of dichlorosilane, trichlorosilane, hydrogen chloride and mixtures thereof.
- 25. A process in accordance with claim 24 wherein said second modifying compound of component (2) is trichlorosilane.
- 26. A process in accordance with claim 25 wherein said molar ratio of component (1) to component (2) is in the range of between about 60:40 and about 95:5.
- 27. A process in accordance with claim 26 wherein said sequence of contact of silica with components (1) and (2) in step (a) is component (1) followed by component (2).
- 28. A process in accordance with claim 25 wherein said titanium-containing compound is characterized by p being 4 and n being 0.
- 29. A process in accordance with claim 28 wherein said titanium-containing compound is titanium tetrachloride.
- 30. A process in accordance with claim 21 wherein said contact between said silica and said hydrocarbyloxymagnesium halide of step (a) occurs at a temperature of between about 50.degree. C. and about 110.degree. C. over a period of between about 1 hour and about 31/2 hours.
- 31. A process in accordance with claim 30 wherein said contact between said silica and said first and said second modifying compounds of step (a) occurs at a temperature in the range of between about 20.degree. C. and about 55.degree. C. over a period of between about 20 minutes and about 11/2 hours.
- 32. A process in accordance with claim 31 wherein said step (b) occurs at a temperature in the range of between about 75.degree. C. and about 120.degree. C. over a period in the range of between about 30 minutes and about 4 hours.
- 33. A process in accordance with claim 32 comprising the step of washing the product of step (a) with an alkane containing 5 to 15 carbon atoms prior to said step (b).
- 34. A process in accordance with claim 33 comprising the step of washing the product of step (b) with an alkane having 5 to 15 carbon atoms.
- 35. A process for polymerizing propylene comprising polymerizing propylene under propylene polymerization conditions in the presence of a catalyst system comprising
- (I) a catalyst component comprising the product prepared by the steps of:
- (a) contacting silica, said silica characterized by a surface area of between about 80 m.sup.2 /g. and about 300 m.sup.2 /g., a median particle size of between about 20 microns and about 200 microns and a pore volume of between about 0.6 cc/g. and about 3.0 cc/g., with 2-methyl-1-pentyloxymagnesium chloride;
- (b) contacting the product of step (a) with silicon tetrachloride;
- (c) contacting the product of step (b) with trichlorosilane, with the proviso that the concentration of said silicon tetrachloride and said trichlorosilane contacting said products of steps (a) and (b), respectively, is such that the molar ratio of said silicon tetrachloride to said trichlorosilane is in the range of between about 70:30 and about 92:8;
- (d) contacting the product of step (c) with titanium tetrachloride, with the proviso that titanium tetrachloride is the sole titanium-containing compound utilized in the formation of said catalyst component;
- (II) a compound selected from the group consisting of triethylaluminum and tri-n-propylaluminum; and
- (III) isobutylisopropyldimethoxysilane.
- 36. A process in accordance with claim 35 wherein said step (a) occurs at a temperature in the range of between about 50.degree. C. and about 110.degree. C. for a period of between about 11/2 hours and about 21/2 hours.
- 37. A process in accordance with claim 36 wherein said step (b) occurs at ambient temperature followed immediately by said step (c) conducted at a temperature in the range of between about 25.degree. C. and about 50.degree. C. over a period of between about 30 minutes and about 1 hour.
- 38. A process in accordance with claim 37 wherein said step (d) is conducted at between about 85.degree. C. and about 115.degree. C. over a period of between about 45 minutes and about 11/2 hours.
- 39. A process in accordance with claim 38 comprising the washing of the product of step (c) with hexane or heptane prior to said step (d).
- 40. A process in accordance with claim 39 comprising the washing of said product of step (d) with hexane or heptane.
REFERENCE TO RELATED APPLICATION
This is a divisional of copending application Ser. No. 717,956, filed on Jun. 20, 1991, now U.S. Pat. No. 5,145,821, which is a continuation-in-part of application Ser. No. 521,302, filed May 9, 1990, now U.S. Pat. No. 5,034,365.
US Referenced Citations (27)
Foreign Referenced Citations (8)
Number |
Date |
Country |
3614889 |
Dec 1989 |
AUX |
0115833 |
Aug 1984 |
EPX |
0193281 |
Sep 1986 |
EPX |
0206172 |
Dec 1986 |
EPX |
0244678 |
Nov 1987 |
EPX |
0292134 |
Nov 1988 |
EPX |
58-162607 |
Jul 1983 |
JPX |
WO8902446 |
Mar 1989 |
WOX |
Divisions (1)
|
Number |
Date |
Country |
Parent |
717956 |
Jun 1991 |
|
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
521302 |
May 1990 |
|