Claims
- 1. In the process of polymerizing one or more .alpha.-olefins under slurry conditions in the presence of a cocatalyst and a Ziegler-Natta catalyst wherein the transition metal component consists of ( 1) a hydrocarbon soluble organomagnesium component in an inert hydrocarbon diluent, (2) an aliphatic alcohol, (3) a transition metal (Tm) compound and (4) a reducing halide source in an inert hydrocarbon diluent; wherein the components are employed in quantities so as to provide atomic ratios of Mg:Tm of from about 1:1 to about 40:1; halogen:Mg of from about 6:1 to about 20:1; the improvement which consists of mixing (A) the product resulting from mixing in an inert hydrocarbon diluent, components (1), (2) and (3) with (B) component (4); wherein
- (a) the aliphatic alcohol, component (2), is present in a quantity such that for every metal atom present in component (1) there remains on the average of no more than about 0.9 hydrocarbon group attached to the metal atom(s);
- (b) the concentration of magnesium in (A) is not greater than about 0.15 molar and the metal concentration in (B), component (4), is not greater than 1.0 molar;
- (c) said transition metal compound is represented by the formula T.sub.m Y.sub.n X.sub.z-n wherein Tm is Ti in its highest stable valence state; Y is oxygen or OR"; R is a hydrocarbyl group having from 1 to about 20 carbon atoms; R" is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, X is a halogen; z has a value corresponding to the valence of Ti; n has a value of from zero to 4 with the value of z-n being from zero up to a value equal to the valence state of Ti;
- (d) said hydrocarbon soluble magnesium component is represented by the formula R.sub.2 Mg.xMeR'.sub.x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen or a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, x has a value sufficient to render the magnesium compound hydrocarbon soluble and x' has a value equal to the valence of Me; and
- (e) said reducing halide source is represented by the formula Al(R.sup.3).sub.3-m X.sub.m wherein each R.sup.3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, X is a halogen atom and m has a value from 1 to 2;
- thereby producing a polymer having a relatively small average particle size of not greater than 200 microns and a relatively narrow particle size distribution having a d-ratio of not greater than 0.5.
- 2. A process of claim 1 wherein
- (i) the aliphatic alcohol, component (2), is present in a quantity such that for every metal atom present in component (1) there remains on the average no more than about 0.7 hydrocarbon group attached to the metal atom(s);
- (ii) the concentration of magnesium in the mixture of components (1), (2) and (3) is from about 0.05 to about 0.15 molar prior to mixing with (B), component (4), prior to addition to component (A), is from about 0.5 to about 0.9 molar; and
- (iii) the resultant polymer has a d-ratio of not greater than 0.35.
- 3. A method of claim 2 wherein
- (i) the atomic ratio of Mg:Tm is from about 5:1 to about 20:1;
- (ii) the atomic ratio of halogen:Mg is from about 8:1 to about 12:1; and
- (iii) the resultant polymer has a d-ratio of not greater than 0.30.
- 4. A process of claim 1 wherein
- said aliphatic alcohol has from about 1 to about 10 carbon atoms.
- 5. A process of claim 1, 2, 3 or 4 wherein
- (i) said magnesium component is butylethylmagnesium.1/2 triisobutylaluminum, dibutylmagnesium.1/2 triisobutylaluminum, dihexylmagnesium.1/2 triisobutylaluminum, butyloctylmagnesium.1/2 triisobutylaluminum or combination thereof;
- (ii) said aliphatic alcohol is n-propyl alcohol, 2-pentanol, n-octyl alcohol or a combination thereof;
- (iii) said transition metal component is tetraisopropoxytitanium, titanium tetra-chloride, tetra-n-butoxytitanium, tetra-(2-ethylhexoxy)titanium or a combination thereof; and
- (iv) said reducing halide source is ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride or a combination thereof.
- 6. A process of claim 1 wherein ethylene or a mixture of ethylene and an .alpha.-olefin having from 3 to about 10 carbon atoms is polymerized.
- 7. A process of claim 6 wherein ethylene and at least one of propylene, butene-1, hexene-1, heptene-1 or octene-1 are polymerized.
- 8. A process of claim 2 wherein ethylene or a mixture of ethylene and an .alpha.-olefin having from 3 to about 10 carbon atoms is polymerized.
- 9. A process of claim 8 wherein ethylene and at least one of propylene, butene-1, hexene-1, heptene-1 or octene-1 are polymerized.
- 10. A process of claim 3 wherein ethylene or a mixture of ethylene and an .alpha.-olefin having from 3 to about 10 carbon atoms is polymerized.
- 11. A process of claim 10 wherein ethylene and at least one of propylene, butene-1, hexene-1, heptene-1 or octene-1 are polymerized.
- 12. A process of claim 4 wherein ethylene or a mixture of ethylene and an .alpha.-olefin having from 3 to about 10 carbon atoms is polymerized.
- 13. A process of claim 12 wherein ethylene and at least one of propylene, butene-1, hexene-1, heptene-1 or octene-1 are polymerized.
- 14. A process of claim 5 wherein ethylene or a mixture of ethylene and an .alpha.-olefin having from 3 to about 10 carbon atoms is polymerized.
- 15. A process of claim 14 wherein ethylene and at least one of propylene, butene-1, hexene-1, heptene-1 or octene-1 are polymerized.
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 039,569 filed Apr. 15, 1987, now abandoned, which is a continuation-in-part of application Ser. No. 794,218 filed Oct. 31, 1985, now abandoned.
US Referenced Citations (2)
Number |
Name |
Date |
Kind |
4163831 |
Gessell |
Aug 1979 |
|
4526943 |
Fuentes et al. |
Jul 1985 |
|
Continuation in Parts (2)
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Number |
Date |
Country |
Parent |
39569 |
Apr 1987 |
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Parent |
794218 |
Oct 1985 |
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