[특허]Emulsifier free aqueous emulsion polymerization process for making fluoropolymers

IPC분류정보
국가/구분	United States(US) Patent 등록
국제특허분류(IPC7판)	C08F-214/16 C08F-214/00
출원번호	US-0474523 (2002-04-30)
국제출원번호	PCT/US02/013691 (2002-04-30)
§371/§102 date	20031009 (20031009)
국제공개번호	WO02/088207 (2002-11-07)
발명자 / 주소	Kaspar,Harald Hintzer,Klaus Dewitte,Greta Schwertfeger,Werner
출원인 / 주소	3M Innovative Properties Company
인용정보	피인용 횟수 : 27 인용 특허 : 31

초록 ▼

Emulsifier free fluoropolymer manufacturing method in which (a) a chain transfer agent, or a mixture of chain transfer agents are used wherein the chain transfer agents do not yield more than 0.4 weight % relative to the monomer feed of water soluble fluorinated compounds, or (b) a chain transfer ag

Emulsifier free fluoropolymer manufacturing method in which (a) a chain transfer agent, or a mixture of chain transfer agents are used wherein the chain transfer agents do not yield more than 0.4 weight % relative to the monomer feed of water soluble fluorinated compounds, or (b) a chain transfer agent or a mixture of chain transfer agents selected from alkanes, dialkyl ethers, hydrofluoroethers and/or hydrofluorocarbons.

대표청구항 ▼

The invention claimed is: 1. Method of making a fluoropolymer comprising repeating units derived from at least one first and at least one second monomer that are different from each other, said first monomer being a fluoroolefin selected from tetrafluoroethylene, vinylidene fluoride, or combination

The invention claimed is: 1. Method of making a fluoropolymer comprising repeating units derived from at least one first and at least one second monomer that are different from each other, said first monomer being a fluoroolefin selected from tetrafluoroethylene, vinylidene fluoride, or combinations thereof and said second monomer being at least one comonomer selected from the group consisting of vinylfluoride, a perfluoroalkyl vinyl monomer, ethylene, propylene, fluorinated allyl ethers, fluorinated vinyl ethers and vinylidene fluoride, said method comprising an aqueous emulsion polymerization of said first and second monomers in absence of added surfactant, said method being characterized in that said aqueous polymerization is carried out in the presence of a chain transfer agent or mixture of chain transfer agents selected from the group consisting of alkanes and dialkyl ethers. 2. Method according to claim 1 wherein a mixture of an oxidizing agent and a reducing agent is used to start the polymerization and wherein there is further added during the polymerization either the oxidizing agent or the reducing agent but not both. 3. Method according to claim 1 wherein the polymerization is initiated using a persulfate. 4. Method according to claim 1 wherein said fluoropolymer is a copolymer selected from the group consisting of a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of tetrafluoroethylene and vinylidene fluoride, a copolymer of tetrafluoroethylene and hexafluoropropylene, a copolymer of tetrafluoroethylene and ethylene, a copolymer of tetrafluoroethylene and propylene, a copolymer of tetrafluoroethylene and a perfluorovinyl ether and a copolymer of vinylidene fluoride and a perfluorovinyl ether. 5. Method according to claim 1 wherein said fluoropolymer is a copolymer selected from a copolymer of tetrafluoroethylene, hexafluoropropylene and a perfluorovinyl ether, a copolymer of tetrafluoroethylene, vinylidene fluoride and propylene and a copolymer of tetrafluoroethylene, vinylidene fluoride and hexafluoropropylene. 6. Method according to claim 1 wherein said fluoropolymer further comprises units derived from chlorotrifluoroethylene. 7. Method according to claim 1 wherein said fluoropolymer is a curable fluoroelastomer further comprising a cure site component. 8. Method according to claim 1 wherein said fluoropolymer is a fluorothermoplast that has a melting point of 60째 C. to 250째 C. 9. Method according to claim 2 wherein said reducing agent is a sulfite, a metabisulfite or a metal ion. 10. Method according to claim 1 wherein said chain transfer agent is dimethyl ether, methyl t-butyl ether or ethane. 11. Method according to claim 1 wherein the dialkyl ethers comprise partially fluorinated ethers of the general structure Rf--O--CH3, whereby Rf can be a linear or branched partially or perfluorinated compounds of C1-C10. 12. Method according to claim 1 wherein the alkane is methane, ethane, propane, or n-pentane. 13. Method according to claim 1 wherein the polymerization includes at least one fluoroolefin capable of acting as a reducing agent for an oxidizing metal ion and wherein that oxidizing metal ion is used to start the polymerization and wherein said oxidizing metal ion is further added during the polymerization. 14. Method according to claim 13 wherein said oxidizing metal ion derives from a manganate salt. 15. Method according to claim 14 wherein said manganate salt is potassium permanganate. 16. Method according to claim 13 wherein said fluoroolefin is tetrafluoroethylene or vinylidene fluoride. 17. Method according to claim 1 wherein said method is carried out by varying the amount of chain transfer agent during the polymerization so as to produce a multi-modal fluoropolymer. 18. Method according to claim 1 wherein the polymerization conditions do not yield more than 0.4% by weight of water soluble fluorinated compounds relative to the total weight of monomers fed to the polymerization. 19. Method according to claim 1 wherein the method results in an aqueous dispersion having an average polymer particle size of up to 500 nm and wherein the aqueous dispersion exhibits no coagulation or settling.

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이 특허에 인용된 특허 (31) 인용/피인용 타임라인 분석

Anolick Colin (Wilmington DE) Wheland Robert Clayton (Wilmington DE), Amorphous tetrafluoroethylene-hexafluoropropylene copolymers.
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Kuhls Jrgen (Burghausen DEX) Weiss Eduard (Burghausen DEX) Burgstaller Gottfried (Burgkirchen DEX), Continuous process for the agglomeration of PTFE powders in a liquid medium.
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Hartwimmer Robert (Burghausen DEX) Kuhls Jrgen (Burghausen DEX), Copolymers of tetrafluoroethylene and process for their manufacture.
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Kaspar, Harald; Hintzer, Klaus; Dewitte, Greet, Emulsifier free aqueous emulsion polymerization process for making fluoropolymers.
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Blong Thomas J. ; Greuel Michael P. ; Lavallee Claude,CAX, Extrudable thermoplastic hydrocarbon compositions.
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Araki, Takayuki; Hirano, Nobuhiro; Oka, Noritoshi, Flexible fluorine-containing material having heat resistance and non-tackiness.
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Coggio William D. (Woodbury MN) Arren Dirk H. C. (Borsbeek BEX) Parker Douglas S. (Afton MN) Worm Allan T. (North St. Paul MN), Fluorinated onium salts, curable compositions containing same, and method of curing using same.
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Grootaert Werner M. (Oakdale MN), Fluorine-containing polymers and preparation and use thereof.
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Grootaert Werner M. (Oakdale MN), Fluorine-containing polymers and preparation and use thereof.
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Albin Loren D. (Oakdale MN), Fluorocarbon elastomer.
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Worm Allan T. (North St. Paul MN), Fluoroelastomer composition containing sulfonium curing agents.
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Jing Naiyong ; Kolb Robert E., Fluoroelastomer composition with organo-onium and blocked-carbonate compounds.
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Kolb Robert E. (St. Paul MN) Grootaert Werner M. (Oakdale MN), Fluoroelastomer composition with organo-onium compounds.
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Guenthner Richard A. (Birchwood MN) Kolb Robert E. (St. Paul MN), Fluoroelastomer compositions containing fluoroaliphatic sulfonamides as curing agents.
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Grootaert Werner M. A. (St. Paul MN) Kolb Robert E. (St. Paul MN), Fluoroelastomer curing process with phosphonium compound.
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William Brown Farnham ; Andrew Edward Feiring ; Patrick Edward Lindner, Fluoromonomer polymerization.
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Wheland Robert C. (Wilmington DE), Fluoroolefin polymerization process using fluoroxy compound solution as initiator.
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Chapman ; Jr. George R. (Media PA) Crenshaw Lewis E. (Wilmington DE) McMinn Rita S. (Newark DE) Morgan Richard A. (Vienna WV) Priester Donnan E. (Greenville DE) Stewart Charles W. (Newark DE) Tarney , Low-melting tetrafluoroethylene copolymer and its uses.
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McCarthy Thomas F. ; Chen Yan ; Rainal Eric J., Method of manufacturing fluoropolymers.
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DeSimone Joseph M. (Chapel Hill NC) Romack Timothy (Durham NC), Multi-phase polymerization process.
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DeSimone Joseph M. ; Romack Timothy, Multi-phase polymerization process.
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Logothetis Anestis Leonidas (Wilmington DE) Schmiegel Walter Werner (Wilmington DE), Perfluoroelastomer composition having enhanced curing performance.
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Slocum Edgar W. (Wilmington DE) Sobrero Aquiles C. (Parkersburg WV) Wheland Robert C. (Wilmington DE), Polymerization of fluoroolefins.
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Felix Bernd (Burgkirchen DEX) Hintzer Klaus (Kastl DEX) Lhr Gernot (Burgkirchen DEX), Preparation of a modified polytetrafluoroethylene and use thereof.
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Chapman ; Jr. George R. (Media PA) Priester Donnan E. (Wilmington DE), Process and processing aid for extruding a hydrocarbon polymer.
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Oxenrider Bryce C. (Florham Park NJ) Mares Frank (Whippany NJ) Yang Mo-Shu (Somerset NJ), Process of polymerizing chloroetrifluoroethylene with alkyl hydroperoxide and metal metabisulfite.
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Mayo James D. (Toronto NY CAX) Lyons Christine C. (Webster NY) Croucher Melvin D. (Oakville CAX), Processes for the preparation of particles.
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Aufdermarsh ; Jr. Carl A. (Newark DE), Stabilized fluoroelastomer compositions.
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Arcella Vincenzo (Novara ITX) Brinati Giulio (Milan ITX) Albano Margherita (Milan ITX) Minutillo Anna (Milan ITX) Chiodini Graziella (Saronno ITX), Vinylidene fluoride based fluoroelastomeric copolymers modified with perfluoroalkylvinylether.
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Hintzer, Klaus; Jürgens, Michael; Kaspar, Harald; Königsmann, Herbert; Lochhaas, Kai Helmut; Maurer, Andreas R.; Zipplies, Tilman C.; Flynn, Richard M., Fluorinated surfactants for use in making a fluoropolymer.
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Dadalas, Michael C.; Hintzer, Klaus; Mayer, Ludwig; Zipplies, Tilman C.; McDonell, James A., Fluoropolymer coated articles.
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Dadalas, Michael C.; Epsch, Rebekka; Kloos, Friedrich; Harvey, Leonard W., Fluoropolymer dispersion containing no or little low molecular weight fluorinated surfactant.
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[미국특허] Emulsifier free aqueous emulsion polymerization process for making fluoropolymers 원문보기

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[미국특허] Emulsifier free aqueous emulsion polymerization process for making fluoropolymers 원문보기

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