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US3922322A Expired / Lapsed US ⏱️ 0.0 years remaining

Process for dry polymerization of olefins

Assignee: BP Chimie SA
•
Filing: 1973-11-15
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Granted: 1975-11-25
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Expires: 1993-11-15
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Abstract

Abstract A dry process for polymerizing olefins to produce polymers having a molecular weight above 50,000 wherein the olefin or olefins to be polymerized are circulated with hydrogen upwardly through a reaction vessel for reaction in the presence of a solid catalyst which has been separately introduced into the reaction vessel with a stream of hydrogen and in which the catalyst is formed of a catalytically active solid compound of a transition metal of sub-groups IVa, Va and VIa of the periodic table of elements, and at least one co-catalyst formed of an organometallic compound of a metal of groups II or III of the periodic table.

Inventors

  • 👤 Dormenval Roger
  • 👤 Havas Laszlo
  • 👤 Mangin Pierre

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-27 16:52
CPC Classifications
C; C08; C08F; C08F10/00; B; B01; B01J; B01J8/00; B01J8/0015; Y; Y10; Y10S; Y10S526/00; Y10S526/904; Y10S526/905

Claims Analysis

Total Claims: 13
Claim 1
Independent Claim 246 words
A PROCESS OF PRODUCING POLYMERS HAVING A MOLECULAR WEIGHT GENERALLY ABOVE 50,000, BY POLYMERIZATION OF OLEFINS HAVING THE GENERAL FORMULA CH2=CHR IN WHICH R IS SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM AND AN ALKYL RADICAL HAVING UP TO 8 CARBON ATOMS, IN THE PRESENCE OF A PREPOLYMER CONTAINING A CATALYST FORMED OF A CATALYTICALLY ACTIVE SOLID COMPOUND OF A TRANSITION METAL OF SUB-GROUPS IVA, VA OR VIA OF THE PERIODIC TABLE OF ELEMENTS, AND AT LEAST ONE CO-CATALYST FORMED OF AN ORGANO-METALLIC COMPOUND OF A METAL OF GROUPS II OR III OF THE PERIODIC TABLE IN WHICH THE PREPOLYMER IS PREPARED BY POLYMERIZATION OF ONE OR MORE OLEFINS IN AN INET LIQUID AND A SOLID COMPOUND OF A TRANSITION METAL OF SUB-GROUPS IVA, VA AND VIA OF THE PERIODIC TABLE OF ELEMENTS AND A CO-CATALYST, COMPRISING PRESEVERING THE CATALYST CONTAINING PREPOLYMER SOLID IN A HYDROGEN ATMOSPHERE, SEPARATELY INTRODUCING INTO A REACTION VESSEL THE OLEFIN OR OLEFINS TO BE POLYMERIZED AND THE CATALYST CONTAINING PREPOLYMER SOLID; CIRCULATING UPWARDLY IN THE REACTION VESSEL CONTAINING POLYMER IN THE COURSE OF BEINF FORMED, A STREAM OF A GASEOUS MIXTURE CONTAINING THE OLEFIN OR THE OLEFINS TO BE POLYMERIZED, AND HYDROGEN, IN WHICH THE POLYMER IN THE REACTION VESSEL IS FLUIDIZED BY THE ASEOUS MIXTURE CONTAINING HYDROGEN AND THE OLEFIN OR OLEFINS TO BE POLYMERIZED, RECYCLING TO THE REACTION VESSEL THE GASES ISSUING THEREFROM; AND REMOVING AT LEAST A PART OF THE POLYMER CONTAINED IN THE REACTION VESSEL.
Claim 2
Dependent Claim 246 words
A PROCESS OF PRODUCING POLYMERS HAVING A MOLECULAR WEIGHT GENERALLY ABOVE 50,000, BY POLYMERIZATION OF OLEFINS HAVING THE GENERAL FORMULA CH2=CHR IN WHICH R IS SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM AND AN ALKYL RADICAL HAVING UP TO 8 CARBON ATOMS, IN THE PRESENCE OF A PREPOLYMER CONTAINING A CATALYST FORMED OF A CATALYTICALLY ACTIVE SOLID COMPOUND OF A TRANSITION METAL OF SUB-GROUPS IVA, VA OR VIA OF THE PERIODIC TABLE OF ELEMENTS, AND AT LEAST ONE CO-CATALYST FORMED OF AN ORGANO-METALLIC COMPOUND OF A METAL OF GROUPS II OR III OF THE PERIODIC TABLE IN WHICH THE PREPOLYMER IS PREPARED BY POLYMERIZATION OF ONE OR MORE OLEFINS IN AN INET LIQUID AND A SOLID COMPOUND OF A TRANSITION METAL OF SUB-GROUPS IVA, VA AND VIA OF THE PERIODIC TABLE OF ELEMENTS AND A CO-CATALYST, COMPRISING PRESEVERING THE CATALYST CONTAINING PREPOLYMER SOLID IN A HYDROGEN ATMOSPHERE, SEPARATELY INTRODUCING INTO A REACTION VESSEL THE OLEFIN OR OLEFINS TO BE POLYMERIZED AND THE CATALYST CONTAINING PREPOLYMER SOLID; CIRCULATING UPWARDLY IN THE REACTION VESSEL CONTAINING POLYMER IN THE COURSE OF BEINF FORMED, A STREAM OF A GASEOUS MIXTURE CONTAINING THE OLEFIN OR THE OLEFINS TO BE POLYMERIZED, AND HYDROGEN, IN WHICH THE POLYMER IN THE REACTION VESSEL IS FLUIDIZED BY THE ASEOUS MIXTURE CONTAINING HYDROGEN AND THE OLEFIN OR OLEFINS TO BE POLYMERIZED, RECYCLING TO THE REACTION VESSEL THE GASES ISSUING THEREFROM; AND REMOVING AT LEAST A PART OF THE POLYMER CONTAINED IN THE REACTION VESSEL.
Claim 3
Dependent Claim 25 words
A process as claimed in claim 1 in which the catalyst containing prepolymer solid is introduced into the reaction vessel in a stream of hydrogen.
Claim 4
Dependent Claim 26 words
A process as claimed in claim 1 which includes the step of cooling the gaseous effluent from the reaction vessel before recycling to the reaction vessel.
Claim 5
Dependent Claim 35 words
A process as claimed in claim 1 in which the solid compound of a transition metal is selected from solid compounds of a metal selected from the group consisting of trivalent titanium and tetravalent titanium.
Claim 6
Dependent Claim 20 words
A process as claimed in claim 1 in which the pre-polymer is subjected to one or more solvent extraction steps.
Claim 7
Dependent Claim 16 words
A process as claimed in claim 5 in which the extraction solvent is an aliphatic hydrocarbon.
Claim 8
Dependent Claim 54 words
A process as claimed in claim 1 in which the co-catalysts are used in amounts such that the atomic ratio between the metals of groups II and III of the co-catalysts and the transition metals of sub-groups IVa, Va and VIa of the catalytically active solid, is within the range of 1 to 50.
Claim 9
Dependent Claim 65 words
A process as claimed in claim 1 in which the co-catalysts comprise at least one organo-aluminum compound having the mean formula AlRnX3 n, in which R represents an alkyl group having from 1 to 12 carbon atoms, X represents an atom selected from the group consisting of hydrogen and halogen, and n represents an integer or a fraction within the range of 1 to 3.
Claim 10
Dependent Claim 14 words
A process as claimed in claim 8 in which X is a chlorine atom.
Claim 11
Dependent Claim 73 words
A process as claimed in claim 1 which includes a cyclone separator and in which the reaction vessel comprises a polymer bed which is fluidized by the gaseous mixture containing hydrogen and the olefin or olefins to be polymerized, and means for introducing the gaseous mixture issuing from the reaction vessel into the cyclone separator for vapor solid separation, and means for returning the separated vapors from the separator to the reaction vessel.
Claim 12
Dependent Claim 42 words
A process as claimed in claim 1 in which the polymerized olefin is mainly ethylene, and in which the gaseous mixture is subjected to polymerization at a pressure within the range of 10-40 bars and a temperature within the range of 60*-115*C.
Claim 13
Dependent Claim 20 words
A process as claimed in claim 11 in which the gaseous mixture contains up to 80% by volume of hydrogen.

References Cited (Backward Citations)

US3324101A Cited
US3475517A Cited
US3514501A Cited
US3790550A Cited
US3776979A Cited
US3779712A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1978-11-24 1979-05-26 1979-11-25 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1982-11-24 1983-05-26 1983-11-25 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1986-11-24 1987-05-26 1987-11-25 $7700.00 Window Closed / Lapsed

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