US5045612A
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US
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Catalyst and process for polymerizing olefins
Assignee: Dow Chemical Co
•
Filing: 1990-04-18
•
Granted: 1991-09-03
•
Expires: 2010-04-18
Abstract
Abstract Olefins are polymerized under solution polymerization conditions in the presence of the solid catalytic product resulting from removing the liquid components from the product resulting from admixing in an inert diluent and in an atmosphere which excludes moisture and oxygen (A) at least one hydrocarbon soluble organomagnesium compound; (B) at least one organic hydroxyl-containing compound; (C) at least one reducing halide source; (D) at least one transition metal (Tm) alkoxide.
Inventors
- 👤 Joseph G. Schell, Jr.
- 👤 Larry A. Meiske
- 👤 Gary R. Marchand
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 00:07
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
187 words
A process for polymerizing one or more α-olefins or one or more α-olefins and one or more polymerizable ethylenically unsaturated monomers which process comprises conducting the polymerization under solution polymerization conditions in the presence of the solid catalytic product resulting from removing the liquid components from the product resulting from admixing in an inert diluent and in an atmosphere which excludes moisture and oxygen (A) at least one hydrocarbon soluble organomagnesium compound; (B) at least one organic hydroxyl-containing compound; (C) at least one reducing halide (X) source; (D) at least one transition metal (Tm) alkoxide; and wherein (a) the components are added in the order (A), (B), (C) and (D) or (A), (B), (D) and (C); and (b) the components are employed in quantities so as to provide the following atomic ratios Mg:Tm of from about 0.1:1 to about 100:1; and X:Mg of from about 3:1 to about 20:1; and (c) the organic hydroxyl-containing compound is employed in a quantity such that for every metal atom present in component (A) there remains on the average not more than about 0.9 hydrocarbon group attached to such metal atoms.
Claim 2
Dependent Claim
187 words
A process for polymerizing one or more α-olefins or one or more α-olefins and one or more polymerizable ethylenically unsaturated monomers which process comprises conducting the polymerization under solution polymerization conditions in the presence of the solid catalytic product resulting from removing the liquid components from the product resulting from admixing in an inert diluent and in an atmosphere which excludes moisture and oxygen (A) at least one hydrocarbon soluble organomagnesium compound; (B) at least one organic hydroxyl-containing compound; (C) at least one reducing halide (X) source; (D) at least one transition metal (Tm) alkoxide; and wherein (a) the components are added in the order (A), (B), (C) and (D) or (A), (B), (D) and (C); and (b) the components are employed in quantities so as to provide the following atomic ratios Mg:Tm of from about 0.1:1 to about 100:1; and X:Mg of from about 3:1 to about 20:1; and (c) the organic hydroxyl-containing compound is employed in a quantity such that for every metal atom present in component (A) there remains on the average not more than about 0.9 hydrocarbon group attached to such metal atoms.
Claim 3
Dependent Claim
58 words
A process of claim 1 wherein the components are employed in amounts which provide atomic ratios of Mg:Tm of from about 1:1 to about 40:1; X:Mg of from about 6:1 to about 20:1; and on the average, there is from about 0.3 to about 0.9 hydrocarbyl or hydrocarbyloxy group attached to a metal atom in the organomagnesium compound.
Claim 4
Dependent Claim
58 words
A process of claim 2 wherein the components are employed in amounts which provide atomic ratios of Mg:Tm of from about 5:1 to about 20:1; X:Mg of from about 8:1 to about 12:1; and on the average, there is from about 0.5 to about 0.9 hydrocarbyl or hydrocarbyloxy group attached to a metal atom in the organomagnesium compound.
Claim 5
Dependent Claim
318 words
A process of claim 1, 2, or 3 wherein (a) component (A) is a compound or mixture of compounds represented by the formula R 2 Mg·xMeR' x' wherein each R is independently a hydrocarbyl group and, a hydrocarbyl or a hydrocarbyloxy group; each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group; Me is Al, Zn or B; x has a value from zero to about 10; and x' has a value equal to the valence of Me; (b) component (B) is a compound or mixture of compounds represented by the formulas Ra-(O-R b -) n -OH or Z((-O-R b -) n -O-R c ) n' wherein R a is a hydrocarbyl group having from 1 to about 20 carbon atoms; each R b is independently a divalent hydrocarbyl group having from 1 to about 20 carbon atoms; each R c is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, at least one of which is hydrogen; Z is a multivalent organic group containing from 2 to about 10 carbon atoms; n has a value from zero to about 10; and n' has a value from 2 to about 10; (c) component (C) is a compound or mixture of compounds represented by the formulas Al(R 1 ) 3-m X m or B(R 1 ) 3-m X m wherein each R 1 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; and m has a value from 1 to 2; and (d) component (D) is a compound or mixture of compounds represented by the formula ##STR2## wherein Tm is a transition metal in its highest valence state and is selected from groups IV-B, V-B and VI-B of the Periodic Table of the Elements; R is a hydrocarbyl group having from 1 to about 20 carbon atoms; and m' has a value from 1 to about 20.
Claim 6
Dependent Claim
156 words
A process of claim 4 wherein (a) in Component (A), each R is an alkyl group having from 1 to about 20 carbon atoms; each R' is an alkyl group having from 1 to about 20 carbon atoms; Me is Al; x has a value from about 0.2 to about 5 and x' has a value of 3; (b) component (B) is a compound represented by the formula R a -(O-R b -) n -OH wherein R a is a hydrocarbyl group having from 1 to about 10 carbon atoms and n has a value of zero; (c) component (C) is a compound represented by the formula Al(R 1 ) 3-m X m wherein R 1 is a hydrocarbyl group having from 1 to about 10 carbon atoms; and (d) in component (D), each R independently has from 1 to about 10 carbon atoms:Tm is Ti; and m' has a value from 1 to about 10.
Claim 7
Dependent Claim
62 words
A process of claim 5 wherein (a) component (A) is butylethylmagnesium·1/2triethylaluminum, di-n-butyl magnesium, ethyl-n-butylmagnesium, n-butyl-sec-butylmagnesium, di-n-hexylmagnesium, di-n-octylmagnesium, n-butyl-ethylmagnesium·1/2triisobutylaluminum, or a combination thereof; (b) component (B) is n-propyl alcohol, 2-pentanol, n-octyl alcohol or a combination thereof; (c) component (C) is ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, or a combination thereof; and (d) component (D) is tetraisopropoxy titanium, tetra-n-butoxytitanium, tetra-(2-ethylhexoxy)titanium, or a combination thereof.
Claim 8
Dependent Claim
30 words
A process of claim 6 wherein (a) component (A) is butylethylmagnesium; (b) component (B) is n-propyl alcohol; (c) component (C) is ethylaluminum dichloride; and (d) component (D) is tetraisopropoxy titanium.
Claim 9
Dependent Claim
180 words
A process for polymerizing one or more α-olefins or one or more α-olefins and one or more polymerizable ethylenically unsaturated monomers which process comprises conducting the polymerization under solution polymerization conditions in the presence of a catalyst prepared by (1) contacting (A) at least one organomagnesium compound with (B) at least one organic hydroxyl-containing compound by the slow addition of the organomagnesium compound and in a quantity such that for every metal atom present in component (A) there remains on the average not more than about 0.9 hydrocarbyl or hydrocarbyloxy group attached to such metal atoms; (2) contacting the product resulting from step (1) with either one, but not both of (C) at least one reducing halide (X) source or (D) at least one transition metal (Tm) alkoxide; and (3) contacting the product resulting from step (2) with whichever component (C) or (D) was not employed in step (2); and wherein the components are employed in quantities corresponding to the atomic ratios of Mg:Tm of from about 0.1:1 to about 100:1; and X:Mg of from about 3:1 to about 20:1.
Claim 10
Dependent Claim
180 words
A process for polymerizing one or more α-olefins or one or more α-olefins and one or more polymerizable ethylenically unsaturated monomers which process comprises conducting the polymerization under solution polymerization conditions in the presence of a catalyst prepared by (1) contacting (A) at least one organomagnesium compound with (B) at least one organic hydroxyl-containing compound by the slow addition of the organomagnesium compound and in a quantity such that for every metal atom present in component (A) there remains on the average not more than about 0.9 hydrocarbyl or hydrocarbyloxy group attached to such metal atoms; (2) contacting the product resulting from step (1) with either one, but not both of (C) at least one reducing halide (X) source or (D) at least one transition metal (Tm) alkoxide; and (3) contacting the product resulting from step (2) with whichever component (C) or (D) was not employed in step (2); and wherein the components are employed in quantities corresponding to the atomic ratios of Mg:Tm of from about 0.1:1 to about 100:1; and X:Mg of from about 3:1 to about 20:1.
Claim 11
Dependent Claim
57 words
The process of claim 8 wherein the components are employed in amounts which provide atomic ratios of Mg:Tm from about 1:1 to about 40:1; X:Mg of from about 6:1 to about 20:1; and on the average, there is from about 0.3 to about 0.9 hydrocarbyl or hydrocarbyloxy group attached to a metal atom in the organomagnesium compound.
Claim 12
Dependent Claim
61 words
A process of claim 9 wherein the components are employed in amounts which provide atomic ratios of Mg:Tm of from about 5:1 to about 20:1; X:Mg of from about 8:1 to about 12:1; and on the average, there is not more than from about 0.5 to about 0.9 hydrocarbyl or hydrocarbyloxy group attached to a metal atom in the organomagnesium compound.
Claim 13
Dependent Claim
320 words
A process of claim 8, 9, or 10 wherein (a) component (A) is a compound or mixture of compounds represented by the formula R 2 Mg·xMeR' x' wherein each R is independently a hydrocarbyl group and, a hydrocarbyl or a hydrocarbyloxy group; each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group; Me is Al, Zn or B; x has a value from zero to about 10; and x' has a value equal to the valence of Me; (b) component (B) is a compound or mixture of compounds represented by the formulas R a -(O-R b ) n -OH or Z((-O-R b -) n -O-R c ) n' wherein R a is a hydrocarbyl group having from 1 to about 20 carbon atoms; each R b is independently a divalent hydrocarbyl group having from 1 to about 20 carbon atoms; each R c is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, at least one of which is hydrogen; Z is a multivalent organic group containing from 2 to about 10 carbon atoms; n has a value from zero to about 10; and n' has a value from 2 to about 10; (c) component (C) is a compound or mixture of compounds represented by the formulas Al(R 1 ) 3-m X m or B(R 1 ) 3-m X m wherein each R 1 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; and m has a value from 1 to 2; and (d) component (D) is a compound or mixture of compounds represented by the formula ##STR3## wherein Tm is a transition metal in its highest valence state and is selected from groups IV-B, V-B and VI-B of the Periodic Table of the Elements; R is a hydrocarbyl group having from 1 to about 20 carbon atoms; and m' has a value from 1 to about 20.
Claim 14
Dependent Claim
157 words
A process of claim 11 wherein (a) in Component (A), each R is an alkyl group having from 1 to about 20 carbon atoms; each R' is an alkyl group having from 1 to about 20 carbon atoms; Me is Al; x has a value from about 0.2 to about 5; and x' has a value of 3; (b) component (B) is a compound represented by the formula R a -(O-R b -) n -OH wherein R a is a hydrocarbyl group having from 1 to about 10 carbon atoms and n has a value of zero; (c) component (C) is a compound represented by the formula Al(R 1 ) 3-m X m wherein R 1 is a hydrocarbyl group having from 1 to about 10 carbon atoms; and (d) in component (D), each R independently has from 1 to about 10 carbon atoms; Tm is Ti; and m' has a value from 1 to about 10.
Claim 15
Dependent Claim
60 words
A process of claim 12 wherein butylethylmagnesium·1/2triethylaluminum, di-n-butyl magnesium, di-n-butyl magnesium, ethyl-n-butylmagnesium, n-butyl-sec-butylmagnesium, di-n-hexylmagnesium, di-n-octylmagnesium, n-butyl-ethylmagnesium·1/2triisobutylaluminum, or a combination thereof; (b) component (B) is n-propyl alcohol, 2-pentanol, n-octyl alcohol or a combination thereof; (c) component (C) is ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, or a combination thereof; and (d) component (D) is tetraisopropoxy titanium, tetra-n-butoxytitanium, tetra-(2-ethylhexoxy)titanium, or a combination thereof.
Claim 16
Dependent Claim
30 words
A process of claim 13 wherein (a) component (A) is butylethylmagnesium; (b) component (B) is n-propyl alcohol; (c) component (C) is ethylaluminum dichloride; and (d) component (D) is tetraisopropoxy titanium.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1994-09-02 | 1995-03-04 | 1995-09-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1998-09-02 | 1999-03-04 | 1999-09-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2002-09-02 | 2003-03-04 | 2003-09-03 | $7700.00 | Window Closed / Lapsed |