Patent EP0320169B1 successfully refreshed from Google Patents.
EP0320169B1
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Catalysts prepared from tetrakis (dialkylamide and diarylamide) derivatives of titanium and polymerization of olefins therewith
Assignee: Dow Chemical Co
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Filing: 1988-11-30
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Granted: 1994-01-05
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Expires: 2008-11-30
Abstract
No abstract record available.
Inventors
- 👤 John G. Hefner
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-09 01:49
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F10/00
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
182 words
A process for preparing a supported catalyst which comprises mixing in a suitable inert diluent or solvent the following components A, B, and C: (A) an inorganic support; (B) a metal-containing reducing agent of the formula Al(R') 3-m X m or B(R') 3-m X m wherein each R' is independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, X is halogen and m has a value from 1 to 2; and (C) a transition metal compound selected from a titanium tetrakis(dialkylamide) or titanium tetrakis(diarylamide) or a combination thereof; characterized in that the addition of said transition metal compound (C) is delayed until all of said support (A) and reducing agent (B) have been added and wherein the components are employed in quantities which provide an atomic ratio of Ms:Tm of from 2:1 to 160:1; an atomic ratio of Mr:Tm of from 1:1 to 64:1; and wherein Ms represents the metal atoms in the support material, Mr represents the metal atoms in the reducing agent and Tm represents the sum of the transition metal atoms in the transition metal component.
Claim 2
Dependent Claim
35 words
A process of Claim 1, wherein the components are employed in quantities which provide an atomic ratio of Ms:Tm of from 8:1 to 80:1 and an atomic ratio of Mr:Tm of from 2:1 to 32:1.
Claim 3
Dependent Claim
35 words
A process of Claim 2, wherein the components are employed in quantities which provide an atomic ratio of Ms:Tm of from 11:1 to 40:1 and an atomic ratio of Mr:Tm of from 4:1 to 16:1.
Claim 4
Dependent Claim
18 words
A process of any one of the preceding claims, wherein component (A) is a magnesium dichloride or dibromide.
Claim 5
Dependent Claim
11 words
A process of Claim 4, wherein component (A) is magnesium dichloride.
Claim 6
Dependent Claim
81 words
A process of any one of the preceding claims, wherein component (C) is a compound represented by the formula Ti(NR₂)₄ wherein each R is independently an alkyl group having from 1 to 4 carbon atoms, a benzyl group, an alkyl substituted benzyl group wherein each alkyl group has from 1 to 4 carbon atoms, a phenyl group, or an alkyl substituted aryl group having from 7 to 20 carbon atoms, wherein the alkyl groups have from 1 to 14 carbon atoms.
Claim 7
Dependent Claim
29 words
A process of any one of the preceding claims, wherein component (B) is ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diethylboron chloride, diethylaluminum bromide, ethylaluminum dibromide, or any combination thereof.
Claim 8
Dependent Claim
11 words
A process of Claim 7, wherein component (B) is ethylaluminum dichloride.
Claim 9
Dependent Claim
40 words
A process of any one of the preceding claims, wherein component (C) is titanium tetrakis(dimethylamide), titanium tetrakis(diethylamide), titanium tetrakis(di-i-propylamide), titanium tetrakis(di-n-propylamide), titanium tetrakis(di-i-butylamide), titanium tetrakis(di-n-butylamide), titanium tetrakis(diphenylamide), titanium tetrakis(dibenzylamide), titanium bis(diethylamide) bis(dimethylamide) or di-i-propylamide titanium tris(dimethylamide), or any combination thereof.
Claim 10
Dependent Claim
55 words
A process of any one of the preceding claims, wherein the transition metal component (C) additionally contains at least one zirconium or hafnium compound selected from a zirconium tetrakis(dialkylamide), a zirconium tetrakis(diarylamide), a hafnium tetrakis(dialkylamide), a hafnium tetrakis(diarylamide), or any combination thereof; wherein the atomic ratio of (Zr+Hf) to (Ti+Zr+Hf) is from >0:1 to 0.9:1.
Claim 11
Dependent Claim
162 words
A process of Claim 10, wherein (a) the zirconium compound is represented by the formula Zr(NR₂)₄ wherein each R is independently an alkyl group having from 1 to 4 carbon atoms, a benzyl group, an alkyl substituted benzyl group wherein each alkyl group has from 1 to 4 carbon atoms, a phenyl group, or an alkyl substituted aryl group having from 7 to 20 carbon atoms, wherein the alkyl groups have from 1 to 14 carbon atoms; (b) the hafnium compound is represented by the formula Hf(NR₂)₄ wherein each R is independently an alkyl group having from 1 to 4 carbon atoms, a benzyl group, an alkyl substituted benzyl group wherein each alkyl group has from 1 to 4 carbon atoms, a phenyl group, or an alkyl substituted aryl group having from 7 to 20 carbon atoms, wherein the alkyl groups have from 1 to 14 carbon atoms; and (c) the atomic ratio of (Zr+Hf) to (Ti+Zr+Hf) is from >0:1 to 0.8:1.
Claim 12
Dependent Claim
82 words
A process of Claim 11, wherein (a) the zirconium compound is zirconium tetrakis(dimethylamide), zirconium tetrakis(diethylamide), zirconium tetrakis(di-i-propylamide), zirconium tetrakis(di-n-propylamide), zirconium tetrakis(di-i-butylamide), zirconium tetrakis(di-n-butylamide), zirconium tetrakis(diphenylamide), zirconium bis(diethylamide) bis(dimethylamide) or di-i-propylamide zirconium tris(dimethylamide), or any combination thereof; (b) the hafnium compound is hafnium tetrakis(dimethylamide), hafnium tetrakis(diethylamide), hafnium tetrakis(di-i-propylamide), hafnium tetrakis(di-n-propylamide), hafnium tetrakis(di-i-butylamide), hafnium tetrakis(di-n-butylamide), hafnium tetrakis(diphenylamide), hafnium tetrakis(dibenzylamide), hafnium bis(diethylamide) bis(dimethylamide) or di-i-propylamide hafnium tris(dimethylamide), or any combination thereof; and (c) the atomic ratio of (Zr+Hf) to (Ti+Zr+Hf) is from >0:1 to 0.7:1.
Claim 13
Dependent Claim
33 words
A process of any one of the preceding claims, wherein the concentration of the catalyst components are such that the resultant catalyst slurry is from 0.1 to 0.2 molar with respect to Ms.
Claim 14
Dependent Claim
48 words
A process of any one of the preceding claims, wherein the inert diluent is selected from liquified ethane, propane, isobutane, n-butane, n-hexane, isomeric hexanes, isooctane, paraffinic mixtures of C₈-C₁₂ alkanes, cyclohexane, methylcyclohexane, dimethylcyclohexane, dodecane, industrial solvents composed of saturated or aromatic hydrocarbons, benzene, toluene, ethylbenzene, cumene and decalin.
Claim 15
Dependent Claim
19 words
A process of any one of the preceding claims, wherein said mixing is carried out under an inert atmosphere.
Claim 16
Dependent Claim
59 words
A process for polymerising one or more α-olefins or a mixture of one or more α-olefins and one or more polymerizable ethylenically unsaturated monomers which process comprises conducting the polymerization under solution conditions in the presence of (I) a supported catalyst prepared by a process of any one of the preceding claims; and (II) a cocatalyst or activator compound.
Claim 17
Dependent Claim
49 words
A process of Claim 16, wherein said cocatalyst or activator comprises a compound of the formula Al(R') 3-a X a , B(R') 3-a X a , Mg(R')₂ or Zn(R')₂, wherein each R' is independently hydrogen or a C₁₋₂₀ hydrocarbyl group, X is halogen, and a is 0 or 1.
Claim 18
Dependent Claim
27 words
A process of Claim 17, wherein said cocatalyst or activator comprises a compound of the formula AlR'₃ or BR'₃ wherein R' is independently a C₁-C₂₀ alkyl group.
Claim 19
Dependent Claim
29 words
A process according to Claim 17 or Claim 18, wherein said cocatalyst or activator is diethylaluminum chloride, trimethylaluminum, tri-i-propylaluminum, tri-i-butylaluminum, triethylaluminum, dibutylmagnesium, trimethylboron, triethylboron, diethylzinc or any combination thereof.
Claim 20
Dependent Claim
12 words
A process of Claim 19, wherein said cocatalyst or activator is triethylaluminum.
Claim 21
Dependent Claim
31 words
A process of any one of Claims 16 to 20, wherein ethylene or a mixture of ethylene and at least one α-olefin having from 3 to 10 carbon atoms is polymerized.
Claim 22
Dependent Claim
35 words
A process of Claim 21, wherein ethylene or a mixture of ethylene and at least one α-olefin selected from the group consisting of propylene, butene-1, pentene-1, 3-methylbutene-1, 4-methyl-pentene-1, hexene-1, 1,7-octadiene, 1,4-hexadiene, and octene-1 is polymerized.
Claim 23
Dependent Claim
44 words
A catalyst comprising a supported catalyst prepared by a process of any one of Claims 1 to 15 and a cocatalyst or activator as defined in any one of Claims 17 to 20 other than any present as component (B) of the supported catalyst.
Claim 24
Dependent Claim
27 words
The use of a supported catalyst prepared by a process of any one of Claims 1 to 15 with a cocatalyst or activator in an α-olefin polymerization.
References Cited (Backward Citations)
No citation records indexed.
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