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US4435552A
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Process for the preparation of copolymers of ethylene with at least one other 1-alkene
Assignee: DSM BV
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Filing: 1981-07-10
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Granted: 1984-03-06
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Expires: 2001-07-10
Abstract
Abstract Process for the preparation of copolymers consisting of 25-85% by wt. of ethylene, 15-75% by wt. of at least one other 1-alkene and optionally up to 20% by wt. of a polyunsaturated compound with application of a catalyst system containing a compound of a metal from sub-groups IV-VI of the periodic system and a compound of a metal from groups I-III of the periodic system, in which at least one hydrocarbon group is bound directly to the metal atom via a carbon atom, the polymerization being carried out in the presence of a halogen-containing compound of the general formula <IMAGE> where A is a phenyl group which may contain one or two substituent halogen atoms or alkyl groups, or is a thienyl, furyl, pyrollyl, N-alkylpyrollyl or pyridyl group, which group is bound to the carbon atom directly or via a carbonyl group, X is a chlorine or bromine atom, Y is a chlorine, bromine or hydrogen atom or a hydrocarbon group with 1-8 carbon atoms, and Z is a nitrile group, a carboxyl group, an ester group, a hydrocarbyloxyalkylcarboxyl group, a carboxylic acid halide group, an amide group, a benzoyl group, a carboxyphenyl group or a carboxylhydrocarbylphenyl group.
Inventors
- 👤 Georges G. Evens
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 07:22
CPC Classifications
C; C08; C08F; C08F210/00; C08F210/16
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
224 words
A process for copolymerization to form copolymers containing from 25-85 Wt. % of ethylene units, from 15-75 Wt. % of units of at least one other 1-alkene, and up to 20% of units of aliphatic or alicyclic polyunsaturated monomer of from 3 to 20 carbon atoms and having at least two non-conjugated carbon-carbon double bonds wherein the catalyst system employed contains (a) a compound of vanadium which is soluble in the polymerization medium, (b) a compound of metal from Periodic Table Groups I-III in which at least one hydrocarbon group is bound directly to the metal atom through a carbon atom in the presence of a halogen compound of the general formula: ##STR5## wherein A represents a phenyl group having at most one substituent halogen atom or up to two alkyl groups, or a thienyl, furyl, pyrollyl, N-alkylpyrollyl, or pyridyl group bonded to the carbon atom directly or through a carbonyl group X is chlorine or bromine Y is chlorine, bromine, hydrogen, or a hydrocarbon group of from 1 to 8 carbon atoms, and Z represents one of the radicals represented by the following formulae: ##STR6## wherein R and R 1 represent hydrocarbon groups of from 1 to 8 carbon atoms, and wherein A, X, Y, and Z are chosen such that said halogen compound contains a total of at most two halogen atoms.
Claim 2
Dependent Claim
224 words
A process for copolymerization to form copolymers containing from 25-85 Wt. % of ethylene units, from 15-75 Wt. % of units of at least one other 1-alkene, and up to 20% of units of aliphatic or alicyclic polyunsaturated monomer of from 3 to 20 carbon atoms and having at least two non-conjugated carbon-carbon double bonds wherein the catalyst system employed contains (a) a compound of vanadium which is soluble in the polymerization medium, (b) a compound of metal from Periodic Table Groups I-III in which at least one hydrocarbon group is bound directly to the metal atom through a carbon atom in the presence of a halogen compound of the general formula: ##STR5## wherein A represents a phenyl group having at most one substituent halogen atom or up to two alkyl groups, or a thienyl, furyl, pyrollyl, N-alkylpyrollyl, or pyridyl group bonded to the carbon atom directly or through a carbonyl group X is chlorine or bromine Y is chlorine, bromine, hydrogen, or a hydrocarbon group of from 1 to 8 carbon atoms, and Z represents one of the radicals represented by the following formulae: ##STR6## wherein R and R 1 represent hydrocarbon groups of from 1 to 8 carbon atoms, and wherein A, X, Y, and Z are chosen such that said halogen compound contains a total of at most two halogen atoms.
Claim 3
Dependent Claim
23 words
Process according to claim 1 characterized in that the halogen-containing compound is an alkyl or alkoxy alkyl ester of phenyl mono-or dichloroacetic acid.
Claim 4
Dependent Claim
22 words
Process according to claim 1 characterized in that the halogen-containing compound is an alkyl or alkoxy alkyl ester of diphenyl monochloroacetic acid.
Claim 5
Dependent Claim
33 words
Process according to any one of claims 1, 2, or 3 characterized in that the catalyst system contains a vanadium compound which is soluble in the polymerization medium and an alkyl aluminum halide.
Claim 6
Dependent Claim
24 words
Process according to any one of claims 1, 2, or 3 characterized in that the catalyst system contains vanadium oxytrichloride and ethyl aluminum sesquihalide.
Claim 7
Dependent Claim
36 words
Process according to any one of claims 1, 2, or 3 characterized in that the halogen-containing compound is used in such a quantity that the molar ration relative to the vanadium is between 0.1:1 and 300:1.
Claim 8
Dependent Claim
36 words
Process according to any one of claims 1, 2, or 3 characterized in that the halogen-containing compound is used in such a quantity that the molar ratio relative to the vanadium is between 1:1 and 50:1.
Claim 9
Dependent Claim
114 words
A process for copolymerization to form copolymers containing from 25-85 Wt. % of ethylene units, from 15-75 Wt. % of units of at least one other 1-alkene, and up to 20% of units of aliphatic or alicyclic polyunsaturated monomer of from 3 to 20 carbon atoms and having at least two carbon-carbon double bands wherein the catalyst system employed contains (a) a compound of metal from Periodic Table Groups IVb-VIb, (b) a compound of metal from Periodic Table Groups I-III in which at least one hydrocarbon group is bound directly to the metal atom through a carbon atom in the presence of an alkyl or alkyl alkoxy ester of benzoyl mono- or di-chloroacetic acid.
Claim 10
Dependent Claim
114 words
A process for copolymerization to form copolymers containing from 25-85 Wt. % of ethylene units, from 15-75 Wt. % of units of at least one other 1-alkene, and up to 20% of units of aliphatic or alicyclic polyunsaturated monomer of from 3 to 20 carbon atoms and having at least two carbon-carbon double bands wherein the catalyst system employed contains (a) a compound of metal from Periodic Table Groups IVb-VIb, (b) a compound of metal from Periodic Table Groups I-III in which at least one hydrocarbon group is bound directly to the metal atom through a carbon atom in the presence of an alkyl or alkyl alkoxy ester of benzoyl mono- or di-chloroacetic acid.
Claim 11
Dependent Claim
114 words
A process for copolymerization to form copolymers containing from 25-85 Wt. % of ethylene units, from 15-75 Wt. % of units of at least one other 1-alkene, and up to 20% of units of aliphatic or alicyclic polyunsaturated monomer of from 3 to 20 carbon atoms and having at least two carbon-carbon double bands wherein the catalyst system employed contains (a) a compound of metal from Periodic Table Groups IVb-VIb, (b) a compound of metal from Periodic Table Groups I-III in which at least one hydrocarbon group is bound directly to the metal atom through a carbon atom in the presence of an alkyl or alkyl alkoxy ester of thienyl mono- or di-chloroacetic acid.
Claim 12
Dependent Claim
114 words
A process for copolymerization to form copolymers containing from 25-85 Wt. % of ethylene units, from 15-75 Wt. % of units of at least one other 1-alkene, and up to 20% of units of aliphatic or alicyclic polyunsaturated monomer of from 3 to 20 carbon atoms and having at least two carbon-carbon double bands wherein the catalyst system employed contains (a) a compound of metal from Periodic Table Groups IVb-VIb, (b) a compound of metal from Periodic Table Groups I-III in which at least one hydrocarbon group is bound directly to the metal atom through a carbon atom in the presence of an alkyl or alkyl alkoxy ester of thienyl mono- or di-chloroacetic acid.
Claim 13
Dependent Claim
33 words
Process according to any one of the claims 8 or 9, characterized in that the catalyst system contains a vanadium compound which is soluble in the polymerization medium and an alkyl aluminium halide.
Claim 14
Dependent Claim
23 words
Process according to any one of claims 8 or 9, characterized in that the catalyst system contains vanadium oxytrichloride and ethyl aluminium sesquihalide.
Claim 15
Dependent Claim
39 words
Process according to any one of the claims 8 or 9, characterized in that the halogen-containing compound is used in such a quantity that the molar ratio relative to the metal from groups IV-VI is between 0.1:1 and 300:1.
Claim 16
Dependent Claim
38 words
Process according to any one of claim 8 or 9, characterized in that the halogen-containing compound is used in such a quantity that the molar ratio relative to the metal from groups IV--VI is between 1:1 and 50:1.
Claim 17
Dependent Claim
210 words
A process for copolymerization to form copolymers containing from 25-85 Wt. % of ethylene units, from 15-75 Wt. % of units of at least one other 1-alkene, and up to 20% of units of aliphatic or alicyclic polyunsaturated monomer of from 3 to 20 carbon atoms and having at least two non-conjugated carbon-carbon double bonds wherein the catalyst system employed contains (a) vanadium oxytrichloride (b) ethyl aluminum sesquihalide in the presence of a halogen compound of the general formula: ##STR7## wherein A represents a phenyl group having at most one substituent halogen atom or up to two alkyl groups, or a thienyl, furyl, pyrollyl, N-alkylpyrollyl, or pyridyl group bonded to the carbon atom directly or through a carbonyl group X is chlorine or bromine Y is chlorine, bromine, hydrogen, or a hydrocarbon group of from 1 to 8 carbon atoms, and Z represents one of the radicals represented by the following formulae: ##STR8## wherein R and R' represent hydrocarbon groups of from 1 to 8 carbon atoms, wherein A, X, Y, and Z are chosen such that said halogen compound contains a total of at most two halogen atoms and wherein said halogen-containing compound is present in a molar ratio relative to said vanadium compound of between 0.1:1 and 300:1.
Claim 18
Dependent Claim
210 words
A process for copolymerization to form copolymers containing from 25-85 Wt. % of ethylene units, from 15-75 Wt. % of units of at least one other 1-alkene, and up to 20% of units of aliphatic or alicyclic polyunsaturated monomer of from 3 to 20 carbon atoms and having at least two non-conjugated carbon-carbon double bonds wherein the catalyst system employed contains (a) vanadium oxytrichloride (b) ethyl aluminum sesquihalide in the presence of a halogen compound of the general formula: ##STR7## wherein A represents a phenyl group having at most one substituent halogen atom or up to two alkyl groups, or a thienyl, furyl, pyrollyl, N-alkylpyrollyl, or pyridyl group bonded to the carbon atom directly or through a carbonyl group X is chlorine or bromine Y is chlorine, bromine, hydrogen, or a hydrocarbon group of from 1 to 8 carbon atoms, and Z represents one of the radicals represented by the following formulae: ##STR8## wherein R and R' represent hydrocarbon groups of from 1 to 8 carbon atoms, wherein A, X, Y, and Z are chosen such that said halogen compound contains a total of at most two halogen atoms and wherein said halogen-containing compound is present in a molar ratio relative to said vanadium compound of between 0.1:1 and 300:1.
Claim 19
Dependent Claim
14 words
The process of claim 14 wherein said molar ratio is between 1:1 and 50:1.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-03-06 | 1987-09-05 | 1988-03-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-03-06 | 1991-09-05 | 1992-03-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-03-06 | 1995-09-05 | 1996-03-06 | $7700.00 | Window Closed / Lapsed |