US4311612A
Expired / Lapsed
US
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Olefin polymerization catalyst
Assignee: BP Corp North America Inc
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Filing: 1980-08-25
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Granted: 1982-01-19
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Expires: 2000-08-25
Abstract
Abstract High activity catalyst component for olefin polymerization comprises reaction product of Group IVB-VB metal-containing component with product prepared by reaction of components comprising magnesium alcoholate and halocarboxylic acid, provided that when such components contain less than an effective amount of halogen, reaction product is reacted with halogenating agent. Magnesium alcoholate-halocarboxylic acid reaction product can be obtained in hydrocarbon-soluble or -insoluble form such that catalyst component preparation involves a liquid-liquid or liquid-solid system as desired. Catalysts comprising the above-described component and organometallic promoter are sufficiently active to eliminate need for removal of catalyst residues from polyolefins produced in the presence thereof.
Inventors
- 👤 David E. Boone
- 👤 James L. Jezl
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 08:49
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 13
Claim 1
Independent Claim
309 words
An olefin polymerization catalyst component comprising the reaction product of components comprising (A) at least one Group IVB or VB metal-containing component selected from the group consisting of (1) compounds corresponding to the formula (O) P M(OR) n X m wherein M is a higher valent Group IVB or VB metal, R is hydrocarbyl, X is halogen, p is 0 or 1 and m and n are numbers equal to or greater than 0 such that m+n+2p equals the valance of M; and (2) compounds prepared by reaction of (1) with at least one nonreducing halogenating agent; and (B) at least one support material selected from the group consisting of (1) a reaction product of at least one magnesium alcoholate with at least one halocarboxylic acid, said acid being used in an amount effective to form an initially soluble reaction product with said alcoholate, said reaction being conducted in an inert solvent for the halocarboxylic acid and in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons; and (2) a reaction product of (1) with at least one halogenating agent; said components (A) and (B) being reacted at about 0° to about 200° C. in the substantial absence of oxygen, water, carbon oxides and other extraneous catalyst poisons in amounts such that the atomic ratio of Group IVB or VB metal in (A) to magnesium in (B) ranges from about 0.01:1 to about 100:1; provided that when the amount of reactive halogen in (A) and (B) is less than an amount effective to give an active catalyst component, said reaction product of (A) and (B) is reacted in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons with at least one halogenating agent (C) in an amount such that (A), (B) and (C) contain at least an effective amount of halogen.
Claim 2
Dependent Claim
309 words
An olefin polymerization catalyst component comprising the reaction product of components comprising (A) at least one Group IVB or VB metal-containing component selected from the group consisting of (1) compounds corresponding to the formula (O) P M(OR) n X m wherein M is a higher valent Group IVB or VB metal, R is hydrocarbyl, X is halogen, p is 0 or 1 and m and n are numbers equal to or greater than 0 such that m+n+2p equals the valance of M; and (2) compounds prepared by reaction of (1) with at least one nonreducing halogenating agent; and (B) at least one support material selected from the group consisting of (1) a reaction product of at least one magnesium alcoholate with at least one halocarboxylic acid, said acid being used in an amount effective to form an initially soluble reaction product with said alcoholate, said reaction being conducted in an inert solvent for the halocarboxylic acid and in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons; and (2) a reaction product of (1) with at least one halogenating agent; said components (A) and (B) being reacted at about 0° to about 200° C. in the substantial absence of oxygen, water, carbon oxides and other extraneous catalyst poisons in amounts such that the atomic ratio of Group IVB or VB metal in (A) to magnesium in (B) ranges from about 0.01:1 to about 100:1; provided that when the amount of reactive halogen in (A) and (B) is less than an amount effective to give an active catalyst component, said reaction product of (A) and (B) is reacted in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons with at least one halogenating agent (C) in an amount such that (A), (B) and (C) contain at least an effective amount of halogen.
Claim 3
Dependent Claim
46 words
The catalyst component of claim 1 wherein (A) is at least one compound of the formula (O) p M(OR) n X m wherein M is titanium(IV), zirconium(IV), or vanadium(III), (IV), or (V), R contains 1 to about 12 carbon atoms and X is chlorine or bromine.
Claim 4
Dependent Claim
23 words
The catalyst component of claim 2 wherein (B) is at least one hydrocarbon-soluble reaction product of said magnesium alcoholate and said halocarboxylic acid.
Claim 5
Dependent Claim
67 words
The catalyst component of claim 3 wherein said hydrocarbon-soluble reaction product is prepared by reaction of at least one magnesium alcoholate containing 1 to about 12 carbon atoms per alcoholate group with at least one monocarboxylic, haloalkanoic acid of 2 to about 8 carbon atoms in benzene in amounts such that the molar ratio of halocarboxylic acid to magnesium alcoholate ranges from about 0.8:1 to about 1.2:1.
Claim 6
Dependent Claim
90 words
The catalyst component of claim 4 wherein (A) is a titanium compound selected from the group consisting of titanium tetrachloride and titanium alkoxides and alkoxychlorides containing 1 to about 6 carbon atoms per alkoxy group, or a combination of said titanium compound with at least one chloride, oxychloride, alkoxide, oxyalkoxide, alkoxychloride or oxyalkoxychloride of zirconium or vanadium containing 1 to about 6 carbon atoms per alkoxy group and (C) is a dialkylaluminum chloride or alkylaluminum dichloride containing 1 to about 8 carbon atoms per alkyl group or a mixture thereof.
Claim 7
Dependent Claim
26 words
An alpha-olefin polymerization catalyst comprising the catalyst component of claim 1 and at least one organometallic promoter in an amount effective to activate said catalyst component.
Claim 8
Dependent Claim
36 words
An alpha-olefin polymerization catalyst comprising the catalyst component of claim 3 and a trihydrocarbylaluminum or dihydrocarbylaluminum hydride containing 1 to about 12 carbon atoms per hydrocarbyl group in an amount effective to activate said catalyst component.
Claim 9
Dependent Claim
22 words
An alpha-olefin polymerization catalyst comprising the catalyst component of claim 5 and triethylaluminum in an amount effective to activate said catalyst component.
Claim 10
Dependent Claim
138 words
An alpha-olefin polymerization catalyst comprising (A) a solid reaction product of (1) titanium tetrachloride or a titanium(IV) alkoxychloride containing 1 to about 6 carbon atoms per alkoxy group with (2) a benzene-soluble product prepared by reaction of magnesium ethoxide with trichloroacetic acid in a molar ratio of about 1:1 at about 50° to about 85° C. in benzene in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons; said components (1) and (2) being reacted at about 0° to about 200° C. in an inert solvent for (2) in the substantial absence of water, oxygen, carbon dioxides and other extraneous catalyst poisons in amounts such that the atomic ratio of titanium in (1) to magnesium in (2) ranges from about 0.2:1 to about 5:1; and (B) triethylaluminum in an amount effective to activate (A).
Claim 11
Dependent Claim
138 words
An alpha-olefin polymerization catalyst comprising (A) a solid reaction product of (1) titanium tetrachloride or a titanium(IV) alkoxychloride containing 1 to about 6 carbon atoms per alkoxy group with (2) a benzene-soluble product prepared by reaction of magnesium ethoxide with trichloroacetic acid in a molar ratio of about 1:1 at about 50° to about 85° C. in benzene in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons; said components (1) and (2) being reacted at about 0° to about 200° C. in an inert solvent for (2) in the substantial absence of water, oxygen, carbon dioxides and other extraneous catalyst poisons in amounts such that the atomic ratio of titanium in (1) to magnesium in (2) ranges from about 0.2:1 to about 5:1; and (B) triethylaluminum in an amount effective to activate (A).
Claim 12
Dependent Claim
221 words
An alpha-olefin polymerization catalyst comprising (A) a solid product prepared by reaction of (1) titanium tetrachloride or a titanium(IV) alkoxide or alkoxychloride containing 1 to about 6 carbon atoms per alkoxy group with (2) a benzene-soluble product prepared by reaction of magnesium ethoxide with trichloroacetic acid in a molar ratio of about 1:1 at about 50° to about 85° C. in benzene in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons; said components (1) and (2) being reacted at about 0° to about 200° C. in an inert solvent for (2) in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons in amounts such that the atomic ratio of titanium in (1) to magnesium in (2) ranges from about 0.2:1 to about 5:1, followed by reaction of the product of (1) and (2) with (3) ethylaluminum dichloride, diethylaluminum chloride or a mixture thereof of about 20° to about 100° C. in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons in amounts such that the atomic ratio of aluminum in (3) to titanium in (1) ranges from about 0.1:1 to about 20:1 and such that the preparative system contains sufficient reactive halogen to yield an active catalyst component; and (B) triethylaluminum in an amount effective to activate (A).
Claim 13
Dependent Claim
221 words
An alpha-olefin polymerization catalyst comprising (A) a solid product prepared by reaction of (1) titanium tetrachloride or a titanium(IV) alkoxide or alkoxychloride containing 1 to about 6 carbon atoms per alkoxy group with (2) a benzene-soluble product prepared by reaction of magnesium ethoxide with trichloroacetic acid in a molar ratio of about 1:1 at about 50° to about 85° C. in benzene in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons; said components (1) and (2) being reacted at about 0° to about 200° C. in an inert solvent for (2) in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons in amounts such that the atomic ratio of titanium in (1) to magnesium in (2) ranges from about 0.2:1 to about 5:1, followed by reaction of the product of (1) and (2) with (3) ethylaluminum dichloride, diethylaluminum chloride or a mixture thereof of about 20° to about 100° C. in the substantial absence of water, oxygen, carbon oxides and other extraneous catalyst poisons in amounts such that the atomic ratio of aluminum in (3) to titanium in (1) ranges from about 0.1:1 to about 20:1 and such that the preparative system contains sufficient reactive halogen to yield an active catalyst component; and (B) triethylaluminum in an amount effective to activate (A).
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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) | 1985-01-18 | 1985-07-20 | 1986-01-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-01-18 | 1989-07-20 | 1990-01-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-01-18 | 1993-07-20 | 1994-01-19 | $7700.00 | Window Closed / Lapsed |