Patent US6128403A successfully refreshed from Google Patents.
EP0057050A2
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EP
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Process for the preparation of polymers of alpha-olefins at high temperatures
Assignee: DuPont Canada Inc
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Filing: 1982-01-06
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Granted: —
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Expires: 2002-01-06
Abstract
Abstract A solution process for the preparation of high molecular weight homopolymers of ethylene and copolymers of ethylene and C 3 - C 12 a-olefins is disclosed. The process involves feeding monomer, a particular coordination catalyst and hydrocarbon solvent to a reactor, polymerizing the monomer at a temperature of 105-320°C and recovering the polymer. The catalyst is obtained by either (i) combining solutions of titanium tetrahalide/vanadium oxytrihalide and of organo-aluminum compound at a temperature of less than 30°C, heating the resulting admixture to a temperature of 150-300°C for a period of 5 seconds to 60 minutes and combining the thus heat-treated mixture with a solution of an organoaluminum compound or (ii) combining solutions of titanium tetrahalide and of organoaluminum compound at a temperature of less than 30°C, heating the resultant admixture to a temperature of 150-300°C for a period of 5 seconds to 60 minutes, combining the thus heat-treated mixture with vanadium oxytrihalide and then combining the mixture so obtained with a solution of an organoaluminum compound. The catalyst thus obtained is fed to the process, without separation of any components of the catalyst. Each organoaluminum compound (they may be the same or different) is of the formula AIR n X 3-n where R is alkyl, cycloalkyl, aryl or alkyl-substituted aryl and has 1-20 carbon atoms, n=1, 1.5, 2 or 3 and X is halogen.
Inventors
- 👤 Vaclav George Zboril
- 👤 Michael Andrew Hamilton
- 👤 Richard Watkin Rees
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-01 06:47
CPC Classifications
C; C08; C08F; C08F10/00; C08F10/02; C08F2410/00; C08F2410/04
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
348 words
In a solution process for the preparation of high molecular weight polymers of α-olefins selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and C 3 ' - C 12 α-olefins, said process comprising feeding monomer selected from the group consisting of ethylene and mixtures of ethylene and at least one C 3 -C l2 α-olefin, a coordination catalyst and inert hydrocarbon solvent to a reactor, polymerizing said monomer at a temperature in the range of 105-320°C and recovering the polymer so obtained, the improvement wherein said coordination catalyst is obtained by combining a first component with a second component, said first component being prepared by a method selected from the group consisting of (i) admixing a solution of an organoaluminum compound in inert hydrocarbon solvent with a solution of titanium tetrahalide and vanadium oxytrihalide in inert hydrocarbon solvent at a temperature of less than 30°C and heating the resultant admixture to a temperature of 150-300'C for a period of from 5 seconds to 60 minutes and (ii) admixing a solution of an organoaluminum compound in inert hydrocarbon solvent with a solution of titanium tetrahalide in inert hydrocarbon solvent at a temperature of less than 30°C, heating the resultant admixture to a temperature of 150-300°C for a period of from 5 seconds to 60 minutes and admixing vanadium oxytrihalide with the admixture so obtained, said organoaluminum compound being of the formula AlR n X 3-n and being admixed with the titanium and vanadium compounds so that. the atomic ratio of aluminum in the first component to titanium and vanadium is in the range 0.2-2.0, said second component being a solution of organoaluminum compound in inert hydrocarbon solvent in which organoaluminum compound is, independently, also of the formula AlR n X 3-n , said first and second components being combined so that the atomic ratio of aluminum in the second component to titanium and vanadium is in the range 0.9 to 3; where R is alkyl, cycloalkyl, aryl or alkyl-substituted aryl and has 1-20 carbon atoms, n=l, 1.5, 2 or 3 and X is halogen.
Claim 2
Dependent Claim
348 words
In a solution process for the preparation of high molecular weight polymers of α-olefins selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and C 3 ' - C 12 α-olefins, said process comprising feeding monomer selected from the group consisting of ethylene and mixtures of ethylene and at least one C 3 -C l2 α-olefin, a coordination catalyst and inert hydrocarbon solvent to a reactor, polymerizing said monomer at a temperature in the range of 105-320°C and recovering the polymer so obtained, the improvement wherein said coordination catalyst is obtained by combining a first component with a second component, said first component being prepared by a method selected from the group consisting of (i) admixing a solution of an organoaluminum compound in inert hydrocarbon solvent with a solution of titanium tetrahalide and vanadium oxytrihalide in inert hydrocarbon solvent at a temperature of less than 30°C and heating the resultant admixture to a temperature of 150-300'C for a period of from 5 seconds to 60 minutes and (ii) admixing a solution of an organoaluminum compound in inert hydrocarbon solvent with a solution of titanium tetrahalide in inert hydrocarbon solvent at a temperature of less than 30°C, heating the resultant admixture to a temperature of 150-300°C for a period of from 5 seconds to 60 minutes and admixing vanadium oxytrihalide with the admixture so obtained, said organoaluminum compound being of the formula AlR n X 3-n and being admixed with the titanium and vanadium compounds so that. the atomic ratio of aluminum in the first component to titanium and vanadium is in the range 0.2-2.0, said second component being a solution of organoaluminum compound in inert hydrocarbon solvent in which organoaluminum compound is, independently, also of the formula AlR n X 3-n , said first and second components being combined so that the atomic ratio of aluminum in the second component to titanium and vanadium is in the range 0.9 to 3; where R is alkyl, cycloalkyl, aryl or alkyl-substituted aryl and has 1-20 carbon atoms, n=l, 1.5, 2 or 3 and X is halogen.
Claim 3
Dependent Claim
24 words
The process of Claim 1 in which the catalyst components are mixed in-line and fed to the reactor without separation of any fraction therefrom.
Claim 4
Dependent Claim
26 words
The process of Claim 1 or Claim 2 in which the organoaluminum compound of the first component is the same as that of the second component.
Claim 5
Dependent Claim
25 words
The process of Claim 1 or Claim 2 in which the organoaluminum compound of the first component is different from that of the second component.
Claim 6
Dependent Claim
14 words
The process of any one of Claims 1-4 in which the monomer is ethylene.
Claim 7
Dependent Claim
25 words
The process of any one of Claims 1-4 in which the monomer is a mixture of ethylene and a C 4 - C 10 α-olefin.
Claim 8
Dependent Claim
17 words
The process of any one of Claims 1-6 in which R is C l -C 4 alkyl.
Claim 9
Dependent Claim
16 words
The process of any one of Claims 1-7 in which any halogen is chlorine or bromine.
Claim 10
Dependent Claim
13 words
The process of any one of Claims 1-8 in which n = 2.
Claim 11
Dependent Claim
13 words
The process of any one of Claims 1-8 in which n = 3.
Claim 12
Dependent Claim
19 words
The process of any one of Claims 1-8 in which the organoaluminum compound is triethyl aluminum in both instances.
Claim 13
Dependent Claim
19 words
The process of any one of Claims 1-8 in which the organoaluminum compound is diethylaluminum chloride in both instances.
Claim 14
Dependent Claim
14 words
The process of any one of Claims 1-12 in which any halogen is chlorine.
Claim 15
Dependent Claim
28 words
The process of any one of Claims 1-13 in which the atomic ratio of aluminum to titanium plus vanadium in the first component is in the range 0.3-0.9.
Claim 16
Dependent Claim
24 words
The process of any one of Claims 1-14 in which the ratio of titanium to vanadium on an atomic basis is at least 0.25:1.
Claim 17
Dependent Claim
67 words
The process of any one of Claims 1-15 in which the first component is obtained by admixing a solution of an organoaluminum compound in inert hydrocarbon solvent with a solution of titanium tetrahalide and vanadium oxytrihalide in inert hydrocarbon solvent at a temperature of less than 30°C and heating the resultant admixture to a temperature of 150-300°C for a period of from 5 seconds to 60 minutes.
Claim 18
Dependent Claim
71 words
The process of any one of Claims 1-15 in which the first component is obtained by admixing a solution of an organoaluminum compound in inert solvent with a solution of titanium tetrahalide in inert hydrocarbon solvent at a temperature of less than 30°C, heating the resultant admixture to a -temperature of 150-300°C for a period of from 5 seconds to 60 minutes and admixing vanadium oxytrihalide with the admixture so obtained.
Claim 19
Dependent Claim
25 words
The process of any one of Claims 1-16 in which the first component is heated for a period of from 10 seconds to 10 minutes.
Claim 20
Dependent Claim
281 words
A coordination catalyst for a solution process for the preparation of high molecular weight polymers ofoC-olefins, said catalyst being in inert hydrocarbon solvent and being obtained by combining a first component with a second component, the first component being prepared by a method selected from the group consisting of (i) admixing a solution of an organoaluminum compound in inert hydrocarbon solvent with a solution of titanium tetrahalide and vanadium oxytrihalide in inert hydrocarbon solvent at a temperature of less than 30°C and heating the resultant admixture to a temperature of 150-300°C for a period of from 5 seconds to 60 minutes and (ii) admixing a solution of an organoaluminum compound in inert hydrocarbon solvent with a solution of titanium tetrahalide in inert hydrocarbon solvent at a temperature of less than 30°C, heating the resultant admixture to a temperature of 150-300°C for a period of from 5 seconds to 60 minutes and admixing vanadium oxytrihalide with the admixture so obtained, said organoaluminum compound being of the formula AlR n X 3-n and being admixed with the titanium and vanadium compounds so that the atomic ratio of aluminum in the first component to titanium and vanadium is in the range 0.2-2.0, said second component being a solution of organoaluminum compound in inert hydrocarbon solvent in which organoaluminum compound is, independently, also of the formula AlR n X 3 - n , said first and second components being combined so that the atomic ratio of aluminum in the second component to titanium and vanadium is in the range 0.9 to 3; where R is alkyl, cycloalkyl, aryl or alkyl-substituted aryl and has 1-20 carbon atoms, n=l, 1.5, 2 or 3 and X is halogen.
Claim 21
Dependent Claim
281 words
A coordination catalyst for a solution process for the preparation of high molecular weight polymers ofoC-olefins, said catalyst being in inert hydrocarbon solvent and being obtained by combining a first component with a second component, the first component being prepared by a method selected from the group consisting of (i) admixing a solution of an organoaluminum compound in inert hydrocarbon solvent with a solution of titanium tetrahalide and vanadium oxytrihalide in inert hydrocarbon solvent at a temperature of less than 30°C and heating the resultant admixture to a temperature of 150-300°C for a period of from 5 seconds to 60 minutes and (ii) admixing a solution of an organoaluminum compound in inert hydrocarbon solvent with a solution of titanium tetrahalide in inert hydrocarbon solvent at a temperature of less than 30°C, heating the resultant admixture to a temperature of 150-300°C for a period of from 5 seconds to 60 minutes and admixing vanadium oxytrihalide with the admixture so obtained, said organoaluminum compound being of the formula AlR n X 3-n and being admixed with the titanium and vanadium compounds so that the atomic ratio of aluminum in the first component to titanium and vanadium is in the range 0.2-2.0, said second component being a solution of organoaluminum compound in inert hydrocarbon solvent in which organoaluminum compound is, independently, also of the formula AlR n X 3 - n , said first and second components being combined so that the atomic ratio of aluminum in the second component to titanium and vanadium is in the range 0.9 to 3; where R is alkyl, cycloalkyl, aryl or alkyl-substituted aryl and has 1-20 carbon atoms, n=l, 1.5, 2 or 3 and X is halogen.
Claim 22
Dependent Claim
25 words
The catalyst of Claim 19 in which the catalyst components are mixed in-line and fed to a polymerization reactor without separation of any fraction therefrom.
Claim 23
Dependent Claim
26 words
The catalyst: of Claim 19 or Claim 20 in which the organoaluminum compound of the first component is the same as that of the second component.
Claim 24
Dependent Claim
25 words
The catalyst of Claim 19 or Claim 20 in which the organoaluminum compound of the first component is different from that of the second component.
Claim 25
Dependent Claim
21 words
The catalyst of any one of Claim 19, Claim 20 and Claim 21 in which the organoaluminum compound is triethyl aluminum.
Claim 26
Dependent Claim
14 words
The catalyst of any one of Claims 19-23 in which any halogen is chlorine.
Claim 27
Dependent Claim
27 words
The catalyst of any one of Claims 19-24 in which the ratio of titanium to vanadium on an atomic basis is in the range 1:1 to 30:1.
Claim 28
Dependent Claim
27 words
The catalyst of any one of Claims 19-24 in which the ratio of titanium to vanadium on an atomic basis is in the range 3:1 to 10:1.
Claim 29
Dependent Claim
25 words
The catalyst of any one of Claims 19-26 in which the first component is heated for a period of from 10 seconds to 10 minutes.
References Cited (Backward Citations)
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