Claims
- 1. The method of making polymers from polymerizable 1-olefins which comprises polymerizing at least one of said 1-olefins under polymerizing conditions with a catalyst system comprising an alkyl or aryl aluminum compound cocatalyst and a solid catalyst prepared by:
- (1) reacting a multifunctional organic silicon compound of the formula RSiX.sub.3, with silica or alumina or a mixture thereof having surface hydroxyl groups, where R is a hydrocarbon group or hydrocarbon derivative group and X is a group chemically reactive with said surface hydroxyl groups selected from the group consisting of --OR.sup.1, --N(R.sup.1).sub.2, --N(H)SiR.sub.3.sup.1, --OCH.sub.2 CH.sub.2 OR.sup.1, --O.sub.2 CR.sup.1, or mixtures, where R.sup.1 is a hydrocarbon group or hydrocarbon derivative group;
- (2) reacting the product of step (1) with a halide or alkoxide of titanium, vanadium or zirconium or mixture of these; and
- (3) reacting the product of step (2) with an organomagnesium compound or complex; or
- (2') reacting the product of step (1) with an organomagnesium compound or complex; and
- (3') reacting the product of step (2') with a halide or alkoxide of titanium, vanadium or zirconium or mixture of these.
- 2. The method of claim 1 wherein R is an alkyl group or derivative.
- 3. The method of claim 1 wherein the molar ratio of said cocatalyst to said halide or alkoxide of step (2) or step (3') in the catalyst is about 0.1-100:1.
- 4. The method of claim 1 wherein the molar ratio of said cocatalyst to said halide or alkoxide of step (2) or step (3') in the catalyst is about 1-20:1.
- 5. The method of claim 1 wherein the organomagnesium compounds of step (3) or step (2') are alkyl derivatives of magnesium of about 1 to 18 carbon atoms and aryl derivatives of magnesium.
- 6. The method of claim 1 wherein said catalyst has a ratio of magnesium to titanium, vanadium or zirconium of between about 0.1 and 5.
- 7. The method of claim 1 wherein said catalyst has a ratio of magnesium to titanium, vanadium or zirconium of between about 0.5 to 1.5.
- 8. The method of claim 1 wherein said silica or alumina or mixture are dried to remove surface water.
- 9. The method of claim 1 wherein said halide or alkoxide of step (2) or step (3') is TiX.sup.1 or Tix.sub.3.sup.1 (OR.sup.2).sub.4-m, in which X.sup.1 is halogen, R.sup.2 is alkyl or aryl of 1 to about 12 carbon atoms and m is 0, 1, 2, 3 or 4.
- 10. The method of claim 1 wherein said organomagnesium compound is: ##STR3## in which R.sup.3 and R.sup.4 are alkyl groups, branched or straight chained, and identical or different and a is an integer of from 1-10.
- 11. The method of claim 1 wherein said cocatalyst is a trialkyl aluminum compound or an alkyl aluminum hydride compound, or a mixture.
- 12. The method of claim 11 wherein each said alkyl is a hydrocarbon chain of about 1-10 carbon atoms.
- 13. The method of claim 1 wherein said reaction of step (1) is with silica which has been predried at about 100.degree.-200.degree. C. for a time sufficient to remove surface water prior to said reaction.
- 14. The method of claim 1 wherein said organic silicon compound in step (1) is in stoichiometric excess thereby facilitating a complete reaction, and said excess is later removed.
- 15. The method of claim 1 wherein the product of (1) is separated from any unreacted organic silicon compound and reaction by-products.
- 16. The method of claim 1 wherein said separation is at a temperature between ambient and 200.degree. C.
- 17. The method of claim 1 wherein said cocatalyst is an alkyl aluminum and the alkyl groups comprise hydrocarbon chains that are straight or branched and each chain contains about 1 to 10 carbon atoms.
- 18. The method of claim 1 wherein said cocatalyst comprises an aryl aluminum compound.
- 19. The method of claim 1 wherein said 1-olefin consists essentially of ethylene.
- 20. The method of claim 1 wherein said 1-olefin consists essentially of ethylene and another 1-olefin which are copolymerized to produce medium and low density copolymers.
- 21. The method of claim 1 wherein said 1-olefin is of the formula R.sup.6 --CH.dbd.CH.sub.2 wherein R.sup.6 is hydrogen or alkyl having 1-10 carbon atoms.
- 22. The method of claim 1 wherein said polymerization is at a temperature of from about 20.degree.-150.degree. C. at a pressure of between about 100 and 1000 psi.
- 23. The method of claim 1 wherein said polymerization is at a temperature of from about 60.degree.-110.degree. C. at a pressure of between about 100 and 1000 psi.
- 24. The method of claim 1 wherein said polymerization is at a temperature of from about 60.degree.-110.degree. C. at a pressure of between about 300 and 800 psi.
- 25. The method of claim 1 wherein the halide or alkoxide of step (2) or step (3') comprises a titanium halide or alkoxide.
- 26. The method of claim 1 wherein said organic silicon compound comprises 3-aminopropyl triethoxysilane.
- 27. The method of claim 1 wherein said organic silicon compound comprises 3-chloropropyl trimethoxysilane
- 28. The method of claim 21 wherein said 1-olefin is a mixture containing about 70 wt. % ethylene.
- 29. The method of claim 1 wherein R has one to about 10 carbon atoms.
- 30. The method of claim 1 wherein R.sup.1 has one to about 10 carbon atoms.
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation of copending, commonly assigned U.S. application Ser. No. 06/414,970 filed Sept. 7, 1982, now abandoned, which is a division of copending, commonly assigned U.S. application Ser. No. 06/270,410 filed June 4, 1981, now U.S. Pat. No. 4,530,912 issued July 23, 1985.
US Referenced Citations (6)
Foreign Referenced Citations (3)
Number |
Date |
Country |
2621591 |
Nov 1976 |
DEX |
2543219 |
Apr 1977 |
DEX |
2390456 |
Dec 1978 |
FRX |