Claims
- 1. In a method for preparing a transition metal component of a Ziegler-Natta catalyst from ( 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 0.1:1 to about 100:1; Cl:Mg of from about 3:1 to about 20:1; and the aliphatic alcohol component (2) is present in a quantity such that for every magnesium and aluminum atom present in component (1) there remains on the average no more than about 0.9 hydrocarbon groups attached to a magnesium atom and an aluminum atom combined; the improvement which comprises mixing (A), the product resulting from mixing in an inert hydrocarbon diluent components (1), (2) and (3), with (B), component (4), at conditions such that
- (a) when it is desirable for a polymer resulting from polymerizing one or more .alpha.-olefins in the presence of said transition metal component and a cocatalyst under slurry conditions to have a relatively small average particle size, the ratio of the moles of aliphatic alcohol added to the total number of hydrocarbyl groups originally attached to a metal atom in component (1) is relatively low;
- (b) when it is desirable for a polymer resulting from polymerizing one or more .alpha.-olefins in the presence of said transition metal component and a cocatalyst under slurry conditions to have a relatively large average particle size, the ratio of the moles of aliphatic alcohol added to the total number of hydrocarbyl groups originaly attached to a metal atom in component (1) is relatively high; and
- (c) when it is desirable for a polymer resulting from polymerizing one or more .alpha.-olefins in the presence of said transition metal component and a cocatalyst under slurry conditions to have a relatively narrow particle size distribution, the concentration of magnesium in component (A) and the metal concentration in component (B) are relatively low.
- 2. A method of Claim 1 wherein
- (i) the atomic ratio of Mg:Tm is from about 1:1 to about 40:1;
- (ii) the atomic ratio of Cl:Mg is from about 6:1 to about 20:1;
- (iii) 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 groups attached to a metal atom(s);
- (iv) the concentration of magnesium in component (A) is from about 0.05 to about 1 molar prior to mixing with component B and the metal concentration of component (B) prior to addition to component (A) is from about 0.5 to about 2 molar.
- 3. A method of claim 2 wherein (i) the atomic ratio of Mg:Tm is from about 5:1 to about 20:1; and
- (ii) the atomic ratio of Cl:Mg is from about 8:1 to about 12:1.
- 4. A method of claim 1 wherein
- (i) 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, Zn or B; x has a value sufficient to render the magnesium compound hydrocarbon soluble and x' has a value equal to the valence of Me;
- (ii) said transition metal compound is represented by the formula TmY.sub.n X.sub.z-n wherein Tm is a transition metal in its highest stable valence state and being selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR.sub.2 "; 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 the metal Tm; n has a value of from zero to 5 with the value of z-n being from zero up to a value equal to the valence state of the transition metal, Tm;
- (iii) said aliphatic alcohol has from about 1 to about 10 carbon atoms; and
- (iv) said reducing halide source is represented by the formulas Al(R.sup.3).sub.3-m X.sub.m or B(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 and m has a value from 1 to 2.
- 5. A method of claim 2 wherein
- (i) 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, Zn or B; x has a value sufficient to render the magnesium compound hydrocarbon soluble and x' has a value equal to the valence of Me;
- (ii) said transition metal compound is represented by the formula TmY.sub.n X.sub.z-n wherein Tm is a transition metal in its highest stable valence state and being selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR.sub.2 "; R" is hydrogen or carbyl group having from 1 to about 20 carbon atoms; X is a halogen; z has a value corresponding to the valence of the metal Tm; n has a value of from zero to 5 with the value of z-n being from zero up to a value equal to the valence state of the transition metal, Tm;
- (iii) said aliphatic alcohol has from about 1 to about 10 carbon atoms; and
- (iv) said reducing halide source is represented by the formulas Al(R.sup.3).sub.3-m X.sub.m or B(R.sup.3).sub.3-m X.sub.m wherein each R.sup.3 is independently hydrogen or a hydrocarby group having from 1 to about 20 carbon atoms, X is a halogen and m has a value from 1 to 2.
- 6. A method of claim 3 wherein
- (i) 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, Zn or B; x has a value sufficient to render the maqnesium compound hydrocarbon soluble and x' has a value equal to the valence of Me;
- (ii) said transition metal compound is represented by the formula TmY.sub.n X.sub.z-n wherein Tm is a transition metal in its highest stable valence state and being selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR.sub.2 "; 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 the metal Tm; n has a value of from zero to 5 with the value of z-n being from zero up to a value equal to the valence state of the transition metal, Tm;
- (iii) said aliphatic alcohol has from about 1 to about 10 carbon atoms; and
- (iv) said reducing halide source is represented by the formulas Al(R.sup.3).sub.3-m X.sub.m or B(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 and m has a value from 1 to 2.
- 7. A method of claim 4 wherein
- (i) Me is Al;
- (ii) Tm is Ti; and
- (iii) said reducing halide source is represented by the formula Al(R.sup.3).sub.3-m X.sub.m.
- 8. A method of claim 7 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 tetrachloride, 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.
- 9. A method of claim 5 wherein
- (i) Me is Al;
- (ii) Tm is Ti; and
- (iii) said reducing halide source is represented by the formula Al(R.sup.3).sub.3-m X.sub.m.
- 10. A method of claim 9 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 teyraohloride, tetra-n-butoxytitanium, tetra(2-ethylhexoxy)titanium or a combination thereof; and
- (iv) said reducing halide souuce is ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride or a combination thereof.
- 11. A method of claim 6 wherein
- (i) Me is Al;
- (ii) Tm is Ti; and
- (iii) said reducing halide source is represented by the formula Al(R.sup.3).sub.3-m X.sub.m.
- 12. A method of claim 11 wherein
- (i) said magnesium component is butylethylmagnesium. 1/2 triisobutylaluminum, dibutylmagnesium.1/2 triisobutylaluminum, dihexylmagnesium.1/2 triisobutylaluminum, butyloctylma-gnesium.1/2 triisobutyaluminum 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 tetrachloride, 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.
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of copending application Ser. No. 794,219 filed Oct. 31, 1985 and now abandoned.
US Referenced Citations (11)
Foreign Referenced Citations (13)
Number |
Date |
Country |
0000007 |
Dec 1978 |
EPX |
2758312 |
Jul 1978 |
DEX |
51-111281 |
Oct 1976 |
JPX |
51-148785 |
Dec 1976 |
JPX |
762246 |
Mar 1977 |
ZAX |
1235062 |
Jun 1971 |
GBX |
1275641 |
May 1972 |
GBX |
1306001 |
Feb 1973 |
GBX |
1309987 |
Mar 1973 |
GBX |
1311013 |
Mar 1973 |
GBX |
1502567 |
Mar 1978 |
GBX |
1538472 |
Jan 1979 |
GBX |
1539175 |
Jan 1979 |
GBX |
Non-Patent Literature Citations (3)
Entry |
Derwent Abstract of Japanese J56104908. |
Derwent Abstract of Japanese J56141304. |
Derwent Abstract of Japanese J56166206 |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
794219 |
Oct 1985 |
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