Patent US4424139A successfully refreshed from Google Patents.
US4424139A
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Catalyst comprising a phosphate and with a bis-(cyclopentadienyl)chromium(II) compound
Assignee: Phillips Petroleum Co
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Filing: 1982-03-30
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Granted: 1984-01-03
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Expires: 2002-03-30
Abstract
Abstract In accordance with one embodiment of this invention, a bis-(cyclopentadienyl)chromium(II) compound is introduced onto an activated phosphate-containing support and utilized in conjunction with an organometal cocatalyst, such as an alkylaluminum. In accordance with another embodiment of this invention, a phosphate-containing zerogel is formed by removing water from an aluminum phosphate-containing hydrogel by means of azeotropic distillation or washing with a volatile, water miscible organic compound, activated and thereafter a bis-(cyclopentadienyl)chromium(II) compound is incorporated therewith. In other embodiments of this invention, a phosphate-containing support is formed by forming aluminum phosphate from an aluminum alkoxide or from a melt, or by phosphating silica or alumina, or by forming an aluminum phosphate/silica combination. A support thus formed is activated and a bis-(cyclopentadienyl)chromium(II) compound added. Alternatively in all embodiments, the chromium and phosphate components can be added separately. The resulting catalysts are capable of giving narrow molecular weight distribution polymer because of the inherent high molecular weight of the polymer produced, and the unusual sensitivity to hydrogen, a broad spectrum of polymers can be produced so far as molecular weight is concerned. The catalyst is ideally suited for forming olefin polymers such as ethylene and ethylene copolymers in a slurry system.
Inventors
- 👤 Max P. McDaniel
- 👤 James N. Short
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 22:02
CPC Classifications
C; C08; C08F; C08F10/00; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/639; C08F4/63904; C08F4/63912; C08F4/63916
Claims Analysis
Total Claims: 49
Claim 1
Independent Claim
60 words
A catalyst system comprising: (a) a catalyst comprising a bis-(cyclopentadienyl)chromium(II) compound and a phosphate-containing support; and (b) a cocatalyst selected from trihydrocarbyl borane compounds and aluminum compounds of the formula AlR' n X 3-n where X is a hydride or halide, R' is a 1 to 12 carbon atom hydrocarbyl radical and n is an integer of 1 to 3.
Claim 2
Dependent Claim
60 words
A catalyst system comprising: (a) a catalyst comprising a bis-(cyclopentadienyl)chromium(II) compound and a phosphate-containing support; and (b) a cocatalyst selected from trihydrocarbyl borane compounds and aluminum compounds of the formula AlR' n X 3-n where X is a hydride or halide, R' is a 1 to 12 carbon atom hydrocarbyl radical and n is an integer of 1 to 3.
Claim 3
Dependent Claim
14 words
A catalyst system according to claim 1 wherein said cocatalyst is an organoboron compound.
Claim 4
Dependent Claim
12 words
A catalyst system according to claim 2 wherein said cocatalyst is triethylborane.
Claim 5
Dependent Claim
35 words
A catalyst system according to claim 1 wherein said cocatalyst is present in an amount sufficient to give an atom ratio of metal from the cocatalyst to chromium within the range of 2:1 to 5:1.
Claim 6
Dependent Claim
36 words
A catalyst system according to claim 1 wherein the chromium of said chromium compound is present in an amount within the range of 1 to 3 weight percent based on the weight of said phosphate-containing support.
Claim 7
Dependent Claim
12 words
A catalyst according to claim 1 wherein said bis-(cyclopentadienyl)chromium(II) compound is bis-(cyclopentadienyl)chromium(II).
Claim 8
Dependent Claim
21 words
A catalyst according to claim 1 wherein said phosphate-containing support is an aluminum phosphate-containing support activated in air at 400°-750° C.
Claim 9
Independent Claim
75 words
A method of producing a catalyst comprising combining an aqueous solution of an aluminum salt with a source of phosphate ions and neutralizing with a base to give a hydrogel; converting said hydrogel to a xerogel by one of azeotropic distillation or washing with a water miscible organic compound, activating by heating in an oxygen-containing ambient at a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 10
Independent Claim
75 words
A method of producing a catalyst comprising combining an aqueous solution of an aluminum salt with a source of phosphate ions and neutralizing with a base to give a hydrogel; converting said hydrogel to a xerogel by one of azeotropic distillation or washing with a water miscible organic compound, activating by heating in an oxygen-containing ambient at a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 11
Dependent Claim
22 words
A method according to claim 8 wherein a ratio of P/Al in said xerogel is within the range of 0.2:1 to 0.9:1.
Claim 12
Independent Claim
49 words
A method of preparing a catalyst comprising combining an aluminum alkoxide with phosphoric acid to give a hydrogel; converting said hydrogel to a xerogel, activating the resulting xerogel by heating at a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 13
Independent Claim
49 words
A method of preparing a catalyst comprising combining an aluminum alkoxide with phosphoric acid to give a hydrogel; converting said hydrogel to a xerogel, activating the resulting xerogel by heating at a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 14
Independent Claim
56 words
A method of preparing a catalyst comprising combining a source of phosphate ions with a melt of an aluminum salt; neutralizing to give a hydrogel; converting said hydrogel to a xerogel, activating the resulting xerogel by heating to a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 15
Independent Claim
56 words
A method of preparing a catalyst comprising combining a source of phosphate ions with a melt of an aluminum salt; neutralizing to give a hydrogel; converting said hydrogel to a xerogel, activating the resulting xerogel by heating to a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 16
Dependent Claim
40 words
A method according to claim 11 wherein said aluminum salt is hydrated aluminum nitrate and said source of phosphate ions is monobasic ammonium phosphate and a ratio of P/Al in said xerogel is within the range of 0.2:1 to 0.9:1.
Claim 17
Dependent Claim
12 words
A method according to claim 12 wherein said bis-(cyclopentadienyl)chromium(II) compound is bis-(cyclopentadienyl)chromium.
Claim 18
Dependent Claim
12 words
A method according to claim 11 wherein said bis-(cyclopentadienyl)chromium(II) compound is bis-(cyclopentadienyl)chromium(II).
Claim 19
Dependent Claim
24 words
A method according to claim 11 wherein said xerogel is activated by heating to a temperature within the range of 400° to 750° C.
Claim 20
Independent Claim
59 words
A method of producing a catalyst comprising treating a silica-containing material with a phosphating agent selected from phosphate ions and vaporized phosphorus compounds so as to give 0.001 to 0.2 gram atoms of phosphorus per mole of silica; activating the resulting treated silica at a temperature of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 21
Independent Claim
59 words
A method of producing a catalyst comprising treating a silica-containing material with a phosphating agent selected from phosphate ions and vaporized phosphorus compounds so as to give 0.001 to 0.2 gram atoms of phosphorus per mole of silica; activating the resulting treated silica at a temperature of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 22
Independent Claim
50 words
A method of producing a catalyst comprising cogelling silica and aluminum phosphate to form a hydrogel; removing water from said hydrogel to form a xerogel, activating the resulting xerogel by heating at a temperature within the range of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 23
Independent Claim
50 words
A method of producing a catalyst comprising cogelling silica and aluminum phosphate to form a hydrogel; removing water from said hydrogel to form a xerogel, activating the resulting xerogel by heating at a temperature within the range of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 24
Independent Claim
64 words
A method of producing a catalyst comprising impregnating silica with aluminum phosphate by combining a source of aluminum ions and phosphate ions with a slurry of silica in a diluent; thereafter forming said aluminum phosphate by evaporating the diluent, activating the thus-impregnated silica by heating at a temperature within the range of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 25
Independent Claim
64 words
A method of producing a catalyst comprising impregnating silica with aluminum phosphate by combining a source of aluminum ions and phosphate ions with a slurry of silica in a diluent; thereafter forming said aluminum phosphate by evaporating the diluent, activating the thus-impregnated silica by heating at a temperature within the range of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 26
Independent Claim
62 words
A method of producing a catalyst comprising impregnating a silica xerogel with boron phosphate by adding a source of boron ions and a source of phosphate ions to a slurry of silica xerogel in a diluent; thereafter evaporating the diluent, activating the thus-impregnated silica by heating at a temperature of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 27
Independent Claim
62 words
A method of producing a catalyst comprising impregnating a silica xerogel with boron phosphate by adding a source of boron ions and a source of phosphate ions to a slurry of silica xerogel in a diluent; thereafter evaporating the diluent, activating the thus-impregnated silica by heating at a temperature of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 28
Independent Claim
44 words
A method of producing a catalyst comprising precipitating aluminum phosphate in the presence of silica-alumina; activating the resulting xerogel by heating in an oxygen-containing ambient at a temperature within the range of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 29
Independent Claim
44 words
A method of producing a catalyst comprising precipitating aluminum phosphate in the presence of silica-alumina; activating the resulting xerogel by heating in an oxygen-containing ambient at a temperature within the range of 150°-1000° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 30
Independent Claim
82 words
A method of producing a catalyst comprising activating a silica-alumina xerogel by heating in an oxygen-containing ambient at a temperature within the range of 150°-1000° C., activating an aluminum phosphate xerogel by heating in an oxygen-containing ambient at a temperature within the range of 150°-800° C.; and thereafter combining a bis-(cyclopentadienyl)chromium(II) compound with said thus activated silica and said thus activated aluminum phosphate, said silica and aluminum phosphate either being physically mixed prior to said activation or combined subsequent to said activation.
Claim 31
Independent Claim
82 words
A method of producing a catalyst comprising activating a silica-alumina xerogel by heating in an oxygen-containing ambient at a temperature within the range of 150°-1000° C., activating an aluminum phosphate xerogel by heating in an oxygen-containing ambient at a temperature within the range of 150°-800° C.; and thereafter combining a bis-(cyclopentadienyl)chromium(II) compound with said thus activated silica and said thus activated aluminum phosphate, said silica and aluminum phosphate either being physically mixed prior to said activation or combined subsequent to said activation.
Claim 32
Independent Claim
72 words
A method of producing a catalyst comprising phosphating an alumina-containing composition by treating same with a phosphating agent selected from (1) phosphate ions and (2) vaporous phosphorous compounds to give a surface composition having a 0.2:1 to 1:1 P/Al atom ratio; activating said thus phosphated alumina composition by heating in an oxygen-contaning ambient at a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 33
Independent Claim
72 words
A method of producing a catalyst comprising phosphating an alumina-containing composition by treating same with a phosphating agent selected from (1) phosphate ions and (2) vaporous phosphorous compounds to give a surface composition having a 0.2:1 to 1:1 P/Al atom ratio; activating said thus phosphated alumina composition by heating in an oxygen-contaning ambient at a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 34
Independent Claim
51 words
A method of making a catalyst comprising forming an aluminum phosphate hydrogel, contacting said hydrogel to a xerogel by azeotropic distillation or washing with a water miscible organic liquid; activating by heating at a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 35
Independent Claim
51 words
A method of making a catalyst comprising forming an aluminum phosphate hydrogel, contacting said hydrogel to a xerogel by azeotropic distillation or washing with a water miscible organic liquid; activating by heating at a temperature within the range of 150°-800° C.; and thereafter combining with a bis-(cyclopentadienyl)chromium(II) compound under anhydrous conditions.
Claim 36
Dependent Claim
9 words
A catalyst produced by the method of claim 8.
Claim 37
Dependent Claim
9 words
A catalyst produced by the method of claim 10.
Claim 38
Dependent Claim
9 words
A catalyst produced by the method of claim 11.
Claim 39
Dependent Claim
9 words
A catalyst produced by the method of claim 16.
Claim 40
Dependent Claim
9 words
A catalyst produced by the method of claim 17.
Claim 41
Dependent Claim
9 words
A catalyst produced by the method of claim 18.
Claim 42
Dependent Claim
9 words
A catalyst produced by the method of claim 19.
Claim 43
Dependent Claim
9 words
A catalyst produced by the method of claim 20.
Claim 44
Dependent Claim
9 words
A catalyst produced by the method of claim 21.
Claim 45
Dependent Claim
9 words
A catalyst produced by the method of claim 22.
Claim 46
Dependent Claim
9 words
A catalyst produced by the method of claim 23.
Claim 47
Independent Claim
37 words
A method of making a catalyst comprising forming an aluminum phosphate hydrogel, converting said hydrogel to a xerogel and combining said xerogel with a bis-(cyclopentadienyl)chromium(II) compound and with a chromium compound having a valence other than two.
Claim 48
Independent Claim
37 words
A method of making a catalyst comprising forming an aluminum phosphate hydrogel, converting said hydrogel to a xerogel and combining said xerogel with a bis-(cyclopentadienyl)chromium(II) compound and with a chromium compound having a valence other than two.
Claim 49
Dependent Claim
9 words
A catalyst produced by the method of claim 35.
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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) | 1987-01-02 | 1987-07-04 | 1988-01-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-01-02 | 1991-07-04 | 1992-01-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-01-02 | 1995-07-04 | 1996-01-03 | $7700.00 | Window Closed / Lapsed |