WO1999005179A1 - Procede de production d'un polymere fluore - Google Patents

Procede de production d'un polymere fluore Download PDF

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Publication number
WO1999005179A1
WO1999005179A1 PCT/JP1998/003294 JP9803294W WO9905179A1 WO 1999005179 A1 WO1999005179 A1 WO 1999005179A1 JP 9803294 W JP9803294 W JP 9803294W WO 9905179 A1 WO9905179 A1 WO 9905179A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluoropolymer
copolymer
producing
polymerization
tetrafluoroethylene
Prior art date
Application number
PCT/JP1998/003294
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Atsushi Funaki
Teruo Takakura
Original Assignee
Asahi Glass Company Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Company Ltd. filed Critical Asahi Glass Company Ltd.
Priority to DE69805050T priority Critical patent/DE69805050T2/de
Priority to EP98933908A priority patent/EP0928796B1/en
Priority to US09/269,166 priority patent/US6258907B1/en
Publication of WO1999005179A1 publication Critical patent/WO1999005179A1/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • C08F214/188—Monomers containing fluorine with non-fluorinated comonomers with non-fluorinated vinyl ethers

Definitions

  • the present invention relates to a method for producing a fluorinated polymer, and more specifically, to efficiently produce a fluorinated polymer having good heat resistance, solvent resistance, chemical resistance, etc. using a polymerization medium that does not cause environmental destruction. On how to do it.
  • fluoropolymers are polymer materials with excellent heat resistance, solvent resistance, chemical resistance, etc., and have been used in various applications taking advantage of their characteristics.
  • Known methods for producing fluoropolymers include solution polymerization, suspension polymerization, and emulsion polymerization, and as a polymerization medium for solution polymerization and suspension polymerization, such as fluorinated carbon (CFC).
  • CFC fluorinated carbon
  • the inert solvent is generally used from the viewpoint of obtaining a high molecular weight copolymer and the polymerization rate.
  • Specific examples of CFCs include trichlorofluoromethane, dichlorodifluromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, and the like. It was mainly used.
  • the present invention has a high polymerization rate, can sufficiently increase the molecular weight of a fluorinated polymer, and has no heat resistance and solvent resistance without using a CFC having a large ozone destruction coefficient.
  • a method for efficiently producing a fluoropolymer having excellent properties and chemical resistance is provided.
  • PFAE fluoroalkyl alkyl ether
  • R is a perfluoroalkyl group having 2 to 6 carbon atoms
  • R ′ is an alkyl group having 1 or 2 carbon atoms.
  • the present invention provides a method for producing a fluoropolymer, which comprises using PFAE represented by Formula 1 as the polymerization medium when producing the fluoropolymer by polymerization in a polymerization medium.
  • the fluorinated polymer in the present invention is a polymer containing a polymerized unit based on a fluorinated monomer having a polymerizable double bond group, for example, a polymer containing a polymerized unit based on a full-blown olefin as a main constituent unit
  • a polymer containing a polymerized unit based on a fluorine-containing monomer having two or more polymerizable double bond groups as a main constituent unit, and a polymerized unit based on a fluorine-containing monomer having an aliphatic ring structure as a main structural unit are polymers and the like.
  • the fluorine-containing polymer may be a copolymer of the above-described fluorine-containing monomer having two or more polymerizable double bond groups and a fluorine-containing monomer having an aliphatic ring structure.
  • a fluorine-containing polymer containing a polymerized unit based on a full-blown olefin as a main constituent unit can be obtained by polymerizing a flu-bran refine monomer alone or two or more kinds thereof in PFAE, It is produced by copolymerizing the following monomers, which are copolymerized with the monomer and the fluoro-refin monomer.
  • the fluororefin monomer used in the present invention is an olefin having one or more fluorine atoms in the molecule, and preferably has 2 or 3 carbon atoms from the viewpoint of polymerizability and properties of the obtained polymer. Is a fluent refine monomer.
  • These full-length low-refining monomers may be used alone or in combination of two or more.
  • fluorine-containing polymers containing a polymerized unit based on fluorofluorene as a main constituent unit include tetrafluoroethyleneethylene copolymer, tetrafluroethylene copolymer, lennoperfluorene (alkyl vinyl ether) copolymer, and tetrafluoroethylene copolymer.
  • fluorine-containing polymers containing a polymerized unit based on fluorofluorene as a main constituent unit include tetrafluoroethyleneethylene copolymer, tetrafluroethylene copolymer, lennoperfluorene (alkyl vinyl ether) copolymer, and tetrafluoroethylene copolymer.
  • len / hexafluoropropylene copolymer or tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer examples include le
  • a fluorine-containing polymer containing a polymerized unit based on a fluorine-containing monomer having two or more polymerizable double bond groups as a main constituent unit can be obtained by polymerizing the fluorine-containing monomer alone in PFAE, or by fluoropolymerization. It is produced by copolymerizing monomer monomers.
  • fluorine-containing monomer having two or more polymerizable double bond groups include perfluro (buturbul ether), perfluoro (aryl vol ether), or perfluoro (bisbuloxymethane).
  • the contained fluorine-containing polymer is produced by copolymerizing a fluorinated olefin monomer or a polymer capable of polymerizing the fluorine-containing monomer alone in PFAE.
  • fluorinated monomer having an aliphatic ring structure examples include perfluoro (2,2-dimethyl-1,3-dichlorobenzene), 2,2,4-trifluoro-5-trifluoromethoxy1,3 There are dixol or perflux (2-methylen-4-methyl-1,3-dioxolan).
  • the PFAE preferably has a low hydrogen content.
  • R in the PFAE is a perfluoroalkyl group having 2 to 6 carbon atoms, and is particularly preferably a perfluoroalkyl group having 3 or 4 carbon atoms.
  • R may have a straight chain structure or a branched structure.
  • R ' is a methyl group or an ethyl group.
  • P FAE is a specific example, F (CF 2) 4 0CH 3, F (CF 2) 4 0 C 2 H 5, F (CF 2) a 0 CH 3, is (CF 3) 2 CF 0 CH 3 No.
  • PFAE has a hydrogen atom, so its global warming potential is also lower than that of Perfluent compounds.
  • the estimated lifetime values that are indicators of the global warming potential are about 100 years for C 6 F 14 and 20 to 30 years for C 6 F 13 H, but F (CF 2 ) 40 CH 3 Is 4.1 years, F (CF 2 ) 3 OCH 3 is 1.9 years, and F (CF 2 ) 40 C 2 H 5 is 1.2 years.
  • a mixed medium of PTFE and an inert solvent such as water can be used as the polymerization medium.
  • the amount of the polymerization medium to be used is 3 to 100 times, preferably 5 to 50 times the weight of the total amount of the force monomer which can be changed depending on the type of the monomer to be polymerized.
  • any of a solution polymerization method and a suspension polymerization method can be adopted as a polymerization method, and a polymerization initiator to be used is one conventionally used depending on the polymerization method. You can choose from among them.
  • a polymerization initiator to be used is one conventionally used depending on the polymerization method. You can choose from among them.
  • the amount of the polymerization initiator used can be appropriately changed depending on the type, polymerization reaction conditions, and the like, but is usually 0.005 to 5% by weight, and particularly 0.05 to 0% by weight, based on the whole monomers to be polymerized. About 5% by weight is adopted.
  • the polymerization reaction temperature is such that the optimum value can be selected depending on the type of the polymerization initiation source and the like.
  • the reaction pressure can also be appropriately selected, but it is usually preferable to employ 2 to 100 kg / cm 2 , especially 5 to 20 kg / cm 2 .
  • the polymerization can be advantageously carried out without requiring an excessive reaction pressure. However, a higher pressure can be employed and the pressure can be reduced.
  • the present invention can be carried out by a batch operation, a continuous operation, or the like as appropriate.
  • a compound having a chain transfer property for the purpose of controlling the molecular weight of the polymer, but this compound needs to be soluble in PFAE.
  • compounds with a large chain transfer constant need only be slightly dissolved in PFAE, considering the ease of molecular weight control. Further, it preferably has a small ozone depletion potential.
  • hydrocarbons such as hexa down to for example, HFC such as CF 2 H 2, CF 3 CF 2 CHC 1 Hidorokuro port Furuoroka one carbon, such as 2 (HCFC) such, such as acetone
  • HFC such as CF 2 H 2
  • HCFC one carbon
  • acetone such as ketones
  • alcohols such as methanol and ethanol
  • mercaptans such as methyl mercaptan.
  • the amount of addition may vary depending on the magnitude of the chain transfer constant of the compound used, but may be employed from about 0.01% by weight to about 50% by weight based on the polymerization medium.
  • the polymerization initiator was charged intermittently so that the polymerization rate was almost constant, and a total of 12 cc was charged.
  • 75 g of a white copolymer was obtained in a slurry state.
  • the copolymer has a Q value (297 ° C) of 5.6 as an index of molecular weight, a melting point of 272, a thermal decomposition starting point of 348 ° C, and a good compression at a molding temperature of 300 ° C.
  • a molded article was given.
  • the molded article had a tensile strength of 445 kgZcm 2 and a tensile elongation of 440%.
  • the Q value was determined by extruding the molten copolymer from a nozzle with a diameter of 2.1 mm and a length of 8 mm at a predetermined temperature with a load of 7 kg using a Koka type flow tester (manufactured by Shimadzu Corporation). (Mm 3 seconds).
  • tetrafluoroethylene was introduced into the system, and the reaction pressure was maintained at 5.1 kg / cm 2 .
  • the polymerization initiator was intermittently charged so that the polymerization rate was almost constant, and a total of 7 cc was charged. 2.
  • 80 g of a white copolymer was obtained in a slurry state.
  • the copolymer had a CH of 1.5 (380 ° C), a melting point of 305, a thermal decomposition starting point of 465, and gave a good compression molded product at a molding temperature of 34 (TC).
  • TC molding temperature
  • the molded product obtained by compression molding at 300 ° C had a low molecular weight and was brittle.
  • Example 2 Polymerization was carried out in the same manner as in Example 1, except that 1,255 g of 1,1,2-trichloro-trifluoroethane was used instead of (CF) 2 CF 0 CH 3, and after 2 hours and a half, 48 g of white copolymer was obtained.
  • the copolymer had a CI value (297 ° C) of 4.5, a melting point of 274 ° C, and a thermal decomposition onset of 352 ° C, and gave a good compression molded product at a molding temperature of 300 ° C. .
  • the molded article had a tensile strength of 431 kg / cm 2 and a tensile elongation of 450%.
  • the ozone depleting effect is much lower, and the desired fluoropolymer can be produced with an efficiency comparable to that of using conventional CFC.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
PCT/JP1998/003294 1997-07-24 1998-07-23 Procede de production d'un polymere fluore WO1999005179A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69805050T DE69805050T2 (de) 1997-07-24 1998-07-23 Verfahren zur herstellung eines fluorpolymers
EP98933908A EP0928796B1 (en) 1997-07-24 1998-07-23 Process for producing fluoropolymer
US09/269,166 US6258907B1 (en) 1997-07-24 1998-07-23 Process for producing fluoropolymer

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP19890897 1997-07-24
JP9/198908 1997-07-24
JP9/276184 1997-10-08
JP9276184A JPH1192507A (ja) 1997-07-24 1997-10-08 含フッ素重合体の製造方法

Publications (1)

Publication Number Publication Date
WO1999005179A1 true WO1999005179A1 (fr) 1999-02-04

Family

ID=26511240

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/003294 WO1999005179A1 (fr) 1997-07-24 1998-07-23 Procede de production d'un polymere fluore

Country Status (5)

Country Link
US (1) US6258907B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (1) EP0928796B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPH1192507A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE69805050T2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1999005179A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018235911A1 (ja) * 2017-06-21 2018-12-27 Ａｇｃ株式会社 含フッ素重合体、官能基含有含フッ素重合体および電解質膜の製造方法

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6416698B1 (en) * 1999-02-18 2002-07-09 E. I. Du Pont De Nemours And Company Fluoropolymer finishing process
JP2002194008A (ja) 2000-12-22 2002-07-10 Daikin Ind Ltd 含フッ素重合体の製造方法
JP4792681B2 (ja) * 2001-02-13 2011-10-12 ダイキン工業株式会社 重合開始剤組成物およびそれを用いる含フッ素ポリマーの製造法
ATE469926T1 (de) * 2001-12-04 2010-06-15 Daikin Ind Ltd Formmasse für ozonbeständige gegenstände und ozonbeständige spritzgegossene gegenstände
JP2010501673A (ja) * 2006-08-24 2010-01-21 スリーエム イノベイティブ プロパティズ カンパニー フルオロポリマーの製造方法
WO2008079937A2 (en) * 2006-12-20 2008-07-03 Honeywell International Inc. Polymer processing simplification
CN101821301B (zh) 2007-10-12 2012-06-27 3M创新有限公司 制备纯净含氟聚合物的方法
EP2239282B1 (en) * 2008-02-01 2011-09-28 Asahi Glass Company, Limited Ethylene-tetrafluoroethylene copolymer
JP5407643B2 (ja) * 2009-07-31 2014-02-05 旭硝子株式会社 含フッ素共重合体の製造方法
CN103732630B (zh) * 2011-08-24 2015-12-02 株式会社吴羽 偏氟乙烯类聚合物的制造方法
WO2014115679A1 (ja) 2013-01-23 2014-07-31 ダイキン工業株式会社 含フッ素エーテルの回収方法
EP3333229A1 (en) * 2016-12-08 2018-06-13 3M Innovative Properties Company Fluoropolymer compositions and coatings
WO2018221518A1 (ja) * 2017-06-02 2018-12-06 Ａｇｃ株式会社 変性ポリテトラフルオロエチレンおよびその製造方法
US12139453B2 (en) * 2018-12-20 2024-11-12 Solvay Specialty Polymers Italy S.P.A. Process for the preparation of perhaloacyl peroxides
CN116547316A (zh) 2020-12-24 2023-08-04 大金工业株式会社 含氟聚合物的制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06184207A (ja) * 1992-12-16 1994-07-05 Asahi Glass Co Ltd 含弗素重合体の製造方法
JPH0733807A (ja) * 1993-07-23 1995-02-03 Asahi Glass Co Ltd エチレン−テトラフルオロエチレン系共重合体の製法
JPH0790024A (ja) * 1993-09-24 1995-04-04 Daikin Ind Ltd 低分子量ポリテトラフルオロエチレンの製造方法
JPH07504224A (ja) * 1992-02-28 1995-05-11 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー フルオロモノマーの重合用ヒドロフルオロカーボン溶媒

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
US5494984A (en) 1993-03-17 1996-02-27 Asahi Glass Company Ltd. Method for producing a fluorinated polymer
JPH08333408A (ja) 1995-06-07 1996-12-17 Asahi Glass Co Ltd 含フッ素共重合体の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07504224A (ja) * 1992-02-28 1995-05-11 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー フルオロモノマーの重合用ヒドロフルオロカーボン溶媒
JPH06184207A (ja) * 1992-12-16 1994-07-05 Asahi Glass Co Ltd 含弗素重合体の製造方法
JPH0733807A (ja) * 1993-07-23 1995-02-03 Asahi Glass Co Ltd エチレン−テトラフルオロエチレン系共重合体の製法
JPH0790024A (ja) * 1993-09-24 1995-04-04 Daikin Ind Ltd 低分子量ポリテトラフルオロエチレンの製造方法

Non-Patent Citations (1)

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Title
See also references of EP0928796A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018235911A1 (ja) * 2017-06-21 2018-12-27 Ａｇｃ株式会社 含フッ素重合体、官能基含有含フッ素重合体および電解質膜の製造方法

Also Published As

Publication number Publication date
DE69805050D1 (de) 2002-05-29
EP0928796A1 (en) 1999-07-14
JPH1192507A (ja) 1999-04-06
EP0928796A4 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1999-08-11
US6258907B1 (en) 2001-07-10
DE69805050T2 (de) 2002-12-12
EP0928796B1 (en) 2002-04-24

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