Claims
- 1. A continuous catalytic process for producing ethylene copolymer containing .gtoreq.90 mol percent of ethylene and .ltoreq.10 mol percent of one or more C.sub.3 to C.sub.8 .alpha. olefins with a Ti containing catalyst at a productivity of .gtoreq.500,000 pounds of polymer per pound of Ti under a pressure of <1000 psi in a gas phase fluid bed reaction, said polymer being produced in granular form and having a density of about 0.91 to 0.94 and a melt flow ratio of .gtoreq.26 to .ltoreq.40, which comprises copolymerizing ethylene with one or more C.sub.3 to C.sub.8 .alpha. olefin monomers at a temperature of about 30.degree. to 105.degree. C. by contacting a monomer charge containing said C.sub.3 to C.sub.8 .alpha. olefin monomers and ethylene in a mol ratio no greater than 0.6, in a gas phase reaction zone, with particles of a catalyst system comprising an activated copulverized composition, wherein said composition has the following empirical composition
- Mg.sub.m Ti(OR).sub.n X.sub.p [ED].sub.q
- wherein
- m is .gtoreq.5 to .ltoreq.200
- n is 0 or 1
- p is .gtoreq.10 to .ltoreq.400
- q is >0 to 3.0
- R is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C.sub.1 to C.sub.14 aliphatic or hydrocarbon radical,
- X is Cl, Br, I or mixtures thereof, and
- ED is a liquid organic electron donor compound selected from the group consisting of alkyl esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers, aliphatic ketones and di- or polyamino compounds, said composition prepared by copulverizing magnesium dihalide with a complex obtained by contacting a titanium compound of the formula
- Ti(OR).sub.a X.sub.b
- wherein R and X are as previously defined and a is 0 or 1, b is 2 to 4 inclusive and a+b=3 or 4, with an electron donor compound ED, as previously defined, said copulverized composition being either partially activated with >0 to .ltoreq.10 mols of activator compound per mol of titanium compound in said copulverized composition prior to feeding of the activated copulverized composition to said reaction zone and then being completely activated in said reaction zone with .gtoreq.10 to 400 mols of activator compound per mol of titanium compound in said copulverized composition, or completely activated in said reaction zone with .gtoreq.10 to 400 mols of activator compound per mol of titanium compound in said copulverized composition, said activator compound having the formula
- Al(R").sub.c X".sub.d H.sub.e
- wherein
- X' is Cl or OR'", R" and R'" are the same or different and are C.sub.1 to C.sub.14 saturated hydrocarbon radicals,
- d is 0 to 1.5
- e is 0 or 1
- c+d+e=3.
- 2. A process as in claim 1 in which the magnesium dihalide comprises MgCl.sub.2.
- 3. A process as in claim 2 in which said electron donor comprises at least one ether.
- 4. A process as in claim 3 in which said electron donor compound comprises tetrahydrofuran.
- 5. A process as in claim 2 in which said electron donor compound comprises at least one ether.
- 6. A process as in claim 5 in which said electron donor compound comprises ethyl anisate.
- 7. A process as in claim 1 in which the complex is TiCl.sub.4 .multidot.ethyl anisate.
- 8. A process as in claim 1 in which the complex is TiCl.sub.4 .multidot.THF.
- 9. A process as in claim 1 in which the complex is TiCl.sub.4 .multidot.2THF.
- 10. A process as in claim 1 in which a solid inert diluent is added during copulverization.
- 11. A process as in claim 10 in which said solid inert diluent is calcium carbonate.
- 12. A process as in claim 1 in which a carrier material is added to the catalyst.
- 13. A process as in claim 12 in which said carrier material is polyethylene.
- 14. A process as in claim 1 wherein the C.sub.3 to C.sub.8 .alpha. olefin is butene-1, the magnesium dihalide is MgCl.sub.2, and the complex is TiCl.sub.4 .multidot.2THF.
CROSS REFERENCES TO RELATED PATENT APPLICATIONS
This application is a continuation-in-part of patent application Ser. No. 085,313, filed Oct. 26, 1979, which is a continuation-in-part of patent application Ser. No. 962,112, filed Nov. 20, 1978, both now abandoned.
US Referenced Citations (8)
Foreign Referenced Citations (2)
Number |
Date |
Country |
2135884 |
Jan 1972 |
DEX |
1310547 |
Mar 1973 |
GBX |
Continuation in Parts (2)
|
Number |
Date |
Country |
Parent |
85313 |
Oct 1979 |
|
Parent |
962112 |
Nov 1978 |
|