US4910272A
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Polymerization of olefins in the presence of a catalyst prepared from an inorganic oxide which has not been heat or chemically treated, organomagnesium compound, organic hydroxyl-containing compound, reducing halide and transition metal compound
Assignee: Dow Chemical Co
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Filing: 1988-11-29
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Granted: 1990-03-20
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Expires: 2008-11-29
Abstract
Abstract A catalyst for polymerizing olefins is the product resulting from mixing in an inert hydrocarbon diluent, a mixture of (A) an inorganic oxide, (B) an organomagnesium material, (C) an organic hydroxyl-containing material, (D) a reducing halide source, and (E) a transistion metal compound.
Inventors
- 👤 Gary R. Marchand
- 👤 Ricardo Fuentes, Jr.
- 👤 William M. Coleman, III
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 17:19
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
293 words
A process for polymerizing one or more α-olefins or a mixture of one or more α-olefins with one or more polymerizable ethylenically unsaturated monomers by subjecting said one or more α-olefins or a mixture of one or more α-olefins with one or more polymerizable ethylenically unsaturated monomers to slurry polymerization conditions in the presence of (I) a transition metal catalyst which is the catalytic product resulting from admixing in an inert hydrocarbon diluent and in an atmosphere which excludes moisture and oxygen (A) at least one inorganic oxide support . which is an oxide of an element M and having a particle size of 1000 microns or less and which has not been heat or chemically treated prior to contact with the other catalyst components; (B) at least one hydrocarbon soluble organo-magnesium compound; (C) at least one alcoholic organic hydroxyl-containing compound; (D) at least one reducing halide (X red ) source; and (E) at least one transition metal (Tm) compound; and wherein (1) the components are added in the order (a) (A), (B), (C), (D) and (E) or (b) (A), (B), (C), (E) and (D) or (c) (B), (A), (C), (D) and (E) or (d) (B), (A), (C), (E) and (D); (2) the components are employed in quantities so as to provide the following atomic ratios (a) Mg:Tm of from about 0.1:1 to about 100:1; (b) M:Mg of from about 0.1:1 to about 1000:1; (c) X red :Mg of from about 3:1 to about 20:1; and (3) component (C) is present in a quantity such that for every metal atom present in component (B), there remains on the average no more than about 0.9 hydrocarbon groups attached to any metal atom therein; and (II) a cocatalyst or activator for the transition metal catalyst.
Claim 2
Dependent Claim
293 words
A process for polymerizing one or more α-olefins or a mixture of one or more α-olefins with one or more polymerizable ethylenically unsaturated monomers by subjecting said one or more α-olefins or a mixture of one or more α-olefins with one or more polymerizable ethylenically unsaturated monomers to slurry polymerization conditions in the presence of (I) a transition metal catalyst which is the catalytic product resulting from admixing in an inert hydrocarbon diluent and in an atmosphere which excludes moisture and oxygen (A) at least one inorganic oxide support . which is an oxide of an element M and having a particle size of 1000 microns or less and which has not been heat or chemically treated prior to contact with the other catalyst components; (B) at least one hydrocarbon soluble organo-magnesium compound; (C) at least one alcoholic organic hydroxyl-containing compound; (D) at least one reducing halide (X red ) source; and (E) at least one transition metal (Tm) compound; and wherein (1) the components are added in the order (a) (A), (B), (C), (D) and (E) or (b) (A), (B), (C), (E) and (D) or (c) (B), (A), (C), (D) and (E) or (d) (B), (A), (C), (E) and (D); (2) the components are employed in quantities so as to provide the following atomic ratios (a) Mg:Tm of from about 0.1:1 to about 100:1; (b) M:Mg of from about 0.1:1 to about 1000:1; (c) X red :Mg of from about 3:1 to about 20:1; and (3) component (C) is present in a quantity such that for every metal atom present in component (B), there remains on the average no more than about 0.9 hydrocarbon groups attached to any metal atom therein; and (II) a cocatalyst or activator for the transition metal catalyst.
Claim 3
Dependent Claim
305 words
A process of claim 1 wherein (a) component (A) is an oxide of silicon or aluminum or a combination thereof; (b) component (B) is represented by the formula R 2 Mg·xMER' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; each R' is independently hydrogen, a hydrocarbyl group having from 1 to about 20 carbon atoms; Me is Al or Zn; x has a value from zero to 10 and is sufficient to render the organomagnesium component hydrocarbon soluble; and x' has a value equal to the valence of Me; (c) component (C) is represented by the formula ROH wherein each R is a hydrocarbyl group having from 1 to about 20 carbon atoms; (d) component (D) is represented by the formula Al(R 3 ) 3-m X m including mixtures thereof wherein each R 3 is independently hydrogen or a hydrocarbyl group as above defined; X is a halogen; and m has a value from 1 to 2; (e) component (E) is represented by the formulae TmY n X z-n or ##STR2## wherein Tm is titanium in its highest stable valence state; Y is oxygen or OR"; R is 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 transition metal, Tm; m has a value from 2 to about 20; n has a value from zero to 4; the value of z-n is from zero up to a value equal to the valence state of the transition metal, Tm; (f) the atomic ratio of Mg:Tm is from about 1:1 to about 40:1; (g) the atomic ratio of M:Mg is from about 1:1 to about 500; and (h) the atomic ratio of X red :Mg is from about 6:1 to about 20:1.
Claim 4
Dependent Claim
148 words
A process of claim 2 wherein (a) in component (B), each R and R' is a hydrocarbyl group having from 1 to about 10 carbon atoms; Me is Al and x has a value from about 0.2 to about 2; (b) component (C), is an alcohol having from 1 to about 10 carbon atoms; (c) (component (D), is an aluminum alkyl halide wherein each R 3 is independently a hydrocarbyl group having from 1 to about 10 carbon atoms; (d) in component (E), each R independently has from 1 to about 10 carbon atoms, Tm is titanium; and m has a value from 2 to about 10; (e) the atomic ratio of Mg:Tm is from about 5:1 to about 20:1; (f) the atomic ratio of M:Mg is from about 1:1 to about 100:1; and (g) the X red :Mg atomic ratio is from about 8:1 to about 14:1.
Claim 5
Dependent Claim
74 words
A process of claim 3 wherein (a) component (B) is butyl ethyl magnesium·1/2triisobutylaluminum, di(n-butyl) magnesium·1/2triisobutylaluminum, di(n-hexyl) magnesium·1/2triisobutylaluminum, butyl octyl magnesium·1/2triisobutylaluminum, butyl ethyl magnesium, di-(n-hexyl) magnesium, or any combination thereof; (b) component (C) is n-propyl alcohol, 2-pentanol, n-octyl alcohol, or any combination thereof; (c) component (D) is ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, or any combination thereof; and (d) Component (E) is tetraisopropoxytitanium, titanium tetrachloride, tetra(n-butoxy) titanium, tetra(2-ethylhexoxy) titanium, isopropyltitanate decamer, or any combination thereof.
Claim 6
Dependent Claim
18 words
A process of claim 3 wherein component (E) is tetraisopropoxytitanium, tetra(n-butoxy) titanium, isopropyltitanate decamer, or any combination thereof.
Claim 7
Dependent Claim
38 words
A process of claim 1, 2, 3, 4, or 5 wherein said transition metal catalyst is separated from the soluble portion and the insoluble portion washed with an inert hydrocarbon prior to being employed in the polymerization process.
Claim 8
Dependent Claim
33 words
A process of claim 1, 2, 3, 4, or 5 wherein ethylene or a mixture of ethylene and at least one other α-olefin having from 3 to about 10 carbon atoms is polymerized.
Claim 9
Dependent Claim
26 words
A process of claim 7 wherein ethylene or a mixture of ethylene and at least one of propylene, butene-1, hexene-1, 4-methyl pentene-1, or octene-1 is polymerized.
Claim 10
Dependent Claim
28 words
A process of claim 6 wherein ethylene or a mixture of ethylene and at least one other α-olefin having from 3 to about 10 carbon atoms is polymerized.
Claim 11
Dependent Claim
26 words
A process of claim 9 wherein ethylene or a mixture of ethylene and at least one of propylene, butene-1, hexene-1, 4-methyl pentene-1, or octene-1 is polymerized.
References Cited (Backward Citations)
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