WO2005121118A1 - Composé ayant une structure perfluoro(4-méthylène-1, 3-dioxolanne) et nouveau polymère - Google Patents

Composé ayant une structure perfluoro(4-méthylène-1, 3-dioxolanne) et nouveau polymère Download PDF

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Publication number
WO2005121118A1
WO2005121118A1 PCT/JP2005/010614 JP2005010614W WO2005121118A1 WO 2005121118 A1 WO2005121118 A1 WO 2005121118A1 JP 2005010614 W JP2005010614 W JP 2005010614W WO 2005121118 A1 WO2005121118 A1 WO 2005121118A1
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compound
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group
atom
represented
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PCT/JP2005/010614
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Japanese (ja)
Inventor
Eisuke Murotani
Masanori Sawaguchi
Hiromasa Yamamoto
Takashi Okazoe
Susumu Saitou
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Asahi Glass Company, Limited
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Priority to JP2006514568A priority Critical patent/JPWO2005121118A1/ja
Publication of WO2005121118A1 publication Critical patent/WO2005121118A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/16—Radicals substituted by halogen atoms or nitro radicals
    • 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

Definitions

  • the present invention relates to a novel compound having a perfluoro (4 methylene-1,1,3-dioxolane) structure, and a novel polymer.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 05-213929
  • Patent Document 2 WO 03/037885 pamphlet
  • the present invention has been made to solve the above-mentioned problems, and a novel perfluoro (4-methylene 1,3-dioxolane) having a methylene group introduced at the 4-position of the 1,3 dioxolane skeleton. ) Compounds and novel polymers are provided.
  • the present invention provides the following inventions.
  • R 1 is R F1
  • R 2 is R F2
  • R 3 is R F3
  • R 4 is R F4
  • each is a group corresponding to a chlorine atom
  • 1 ⁇ to 1 4 are chlorine atoms
  • 1 ⁇ ! ⁇ is hydrogen atom or fluorine atom corresponding to 1 to R F4 is a fluorine atom
  • a monovalent saturated organic group Perufuruoro of 1 to 20 carbon atoms 1 1 to! F corresponding to R F4 is a monovalent saturated organic group having the same carbon skeleton having 1 to 20 carbon atoms and having a hydrogen atom bonded to a carbon atom as an essential, or
  • R F ⁇ ! ⁇ 4 Represents the same group as
  • R EF represents a perfluorinated monovalent saturated organic group having 1 to 10 carbon atoms.
  • X represents a hydrogen atom or a fluorine atom.
  • a polymer containing a repeating unit represented by the following formula (A1) (however, has the same meaning as described above).
  • a polymer containing a repeating unit represented by the formula (A) is obtained by polymerizing a compound represented by the formula (a) to obtain a polymer containing a repeating unit represented by the formula (A) Production method.
  • a compound having a novel perfluoro (4-methylene-1,3-dioxolane) structure is useful as a polymerizable compound. Further, according to the present invention, a novel polymer is provided.
  • a compound represented by the formula (a) is referred to as a compound (a).
  • Other compounds are similarly described.
  • the fluorosulfonyl group is also referred to as —SO F group.
  • the compound (a) of the present invention is a novel compound having a perfluoro (4-methylene-1,3-dioxolane) structure (provided that R F1 to R 4 have the same meaning as described above).
  • Carbon number The carbon number of the perfluorinated monovalent saturated organic group having from! To 20 is preferably from! To 10, and particularly preferably from! To 4.
  • the monovalent saturated organic group may have a linear structure or a branched structure, and these structures may include a ring structure.
  • the monovalent saturated organic group is a monovalent group essentially including a carbon atom and a hydrogen atom bonded to the carbon atom, and when there is a bond between carbon atoms, all of the bonds are used.
  • Is saturated Refers to a group that is a bond (single bond).
  • the perfluorinated monovalent saturated organic group refers to a group in which all hydrogen atoms bonded to carbon atoms in the monovalent saturated organic group are substituted with fluorine atoms.
  • the fluorosulfonylated monovalent saturated organic group means a group in which a fluorosulfonyl group is bonded to a carbon atom in the monovalent saturated organic group.
  • Examples of the monovalent saturated organic group include an alkyl group and an alkyl group containing a hetero atom.
  • the alkyl group containing a hetero atom is preferably an alkyl group containing an etheric oxygen atom, a fluorosulfonylated alkyl group containing an etheric oxygen atom, or a fluorosulfonylated alkyl group.
  • the number of etheric oxygen atoms in the alkyl group containing an etheric oxygen atom and the alkyl group containing a fluorosulfonylated etheric oxygen atom may be one or two or more.
  • the etheric oxygen atom may be inserted between carbon atoms or between carbon atoms, or may be inserted at the carbon atom bond terminal.
  • Examples of the alkyl group containing an etheric oxygen atom include an alkoxy group, an alkoxyalkyl group, and an alkoxyalkoxy group.
  • the fluorosulfonyl group is the non-bonded terminal of an alkyl group or an alkyl group containing an etheric oxygen atom. It is particularly preferred that one or more is bonded to the non-bonded terminal.
  • Examples of the perfluorinated monovalent saturated organic group include a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoro (alkoxyalkyl) group, a perfluoro (alkoxyalkoxy) group, and a fluorosulfonyl group.
  • the fluorosulfonylated perfluoroalkyl group is represented by the formula — (CF 2) SO F
  • nl 2 group (where nl is an integer from:! To 20, 1 to: 10 is preferred:! To 4 is particularly preferred) or a formula — (CF) CF (SO F) (where n2 is an integer from:! to 19, preferably from! to 9
  • the fluorosulfonylated (perfluoroalkyl group containing an etheric oxygen atom) group is represented by the formula-(CF) OCFCFSOF (where n3 is an integer of:! To 18; ! ⁇ 8 is good
  • perfluoroalkyl groups include -CF-CF CF-CF CF CF
  • perfluoroalkoxy group examples include OCF-OCFCF,
  • a specific example of a perfluoro (alkoxyalkyl) group is _CF OCF -CF OC
  • perfluoro (alkoxyalkoxy) groups include OCF OCF -OC
  • fluorosulfonylated perfluoroalkyl groups include CF S
  • fluorosulfonylated (perfluoroalkyl group containing an etheric oxygen atom) group examples include -CF OCF CF SO F CF CF OCF CF SO F.
  • perfluorinated monovalent saturated organic group other than the preferred groups include a perfluoro (partially alkyl) group.
  • perfluoro (partially alkyl) group Specific examples of such a group include —CFC
  • R F3 and R F4 are each a fluorine atom
  • R F1 and R F2 are each independently a perfluorinated compound having from! To 20 carbon atoms.
  • 3 and 4 are fluorine atoms
  • R F1 is a trifluoromethyl group
  • R F2 is a perfluorinated monovalent saturated organic group having 120 carbon atoms, which is preferably a monovalent saturated organic group. It is particularly preferred.
  • the compound (a) of the present invention the following compound (a1) is preferable (provided that “has the same meaning as described above).
  • a method for producing a compound of the invention (a) is preferably by the following method (wherein, R F1 ⁇ 4, R ' -R 4, R EF, and X are as defined above M represents a sodium atom or a potassium atom.).
  • the compound (d) is perfluorinated by a liquid phase fluorination reaction to give the compound (c), and then the compound (c) is subjected to an ester decomposition reaction to give the compound (b) It is more preferable that the compound (b) is subjected to a thermal decomposition reaction to give the compound (a).
  • the liquid-phase fluorination reaction and ester decomposition reaction are preferably carried out according to the methods described in WO00 / 56694 and the like.
  • the reaction of thermally decomposing compound (b) may also be carried out by converting compound (b) to compound (bl) by heating compound (b) to obtain compound (a) directly. Then, a method of obtaining the compound (a) may be used. These methods are preferably carried out according to the methods described in WO00 / 56694 and the like.
  • the preparation 1 ⁇ to 1 4 in the method preferably a group which is converted to the respective 1 ⁇ R F4 is Perufuruoro of.
  • R ⁇ R 4 corresponding to 1 ⁇ R F4 is a fluorine atom corresponds to RF 1 to R F4 is a monovalent saturated organic group
  • Perufuruoro of preferred instrument having 1 to 20 carbon atoms is a hydrogen atom
  • 1 ⁇ to 1 4 is preferably a monovalent saturated organic radical containing, as essential hydrogen atoms bonded to carbon atoms having a monovalent saturated organic radical the same carbon skeleton and which is Perufuruoro of 1 to 20 carbon atoms.
  • X is preferably a hydrogen atom.
  • R EF is preferably a C 1-10 perfluoroalkyl group or a C 2-10 perfluoro (alkyl containing an etheric oxygen atom) group.
  • the compound (i) and the compound (h) are subjected to an esterification reaction to obtain the compound (g).
  • the compound (g) is converted to the compound (f1) by an epoxidation reaction or to the compound (f2) by a diolation reaction.
  • the obtained compound (f1) and compound (f2) can each be converted to compound (d) by a cyclization reaction with compound (e).
  • Compound (i) can be obtained from a known compound or a known compound by a known method.
  • the esterification reaction between compound (i) and compound (h) can be carried out according to a known method.
  • the epoxidation reaction or diolation reaction of compound (g) can be carried out by an oxidation reaction, and specifically, can be carried out by changing the type of oxidizing agent to be reacted with compound (g). For example, when the epoxidation reaction is carried out in compound), H 2 O
  • compound (f1) and compound (f2) are each reacted with compound (e) in the presence of an acid catalyst.
  • an acid catalyst include inorganic acids such as hydrochloric acid and sulfuric acid, Lewis acids such as tetrachloride titanium, boron trifluoride etherate, aluminum chloride and zinc chloride, and benzfluorosulfonic acid polymers.
  • the shape of the benzfluorosulfonic acid polymer include beads and a porous nanocomposite supported on amorphous silica.
  • the amount of the acid catalyst is preferably 0.05 to 0.5 times mol of the compound (fl) and the compound (f2).
  • an ortho acid ester may be used together with the acid catalyst.
  • Ortho acid esters include HC ((CH), HC (OCH), CHC (OCH), and CH
  • the amount of the ortho acid ester was determined based on the compound (fl) and the compound (f 2
  • the cyclization reaction is preferably performed in the absence of a solvent, from the viewpoint of volumetric efficiency, which may be performed in the presence or absence of a solvent.
  • the lower limit of the reaction temperature in the cyclization reaction is
  • the upper limit which is preferably 10 ° C., is preferably the boiling point of compound (e).
  • compound (h) include CF CF COF, CF CF CF (CF) COF, (CF) C
  • FC ⁇ F F (CF) OCF (CF) COF
  • F (CF) OCF (CF) CF OCF (CF) COF etc.
  • compound (e) include HC ( ⁇ ) H, CH C (O) H, CH C (O) CH, CH C (
  • the compound (d) When the compound (d) is used as a raw material for the compound (a) in which at least one of R F1 to R F4 is a fluorosulfonylated monovalent saturated organic group, the compound (d) It is preferable to prepare a compound (d) having a fluorosulfonyl group introduced into 1 ⁇ (hereinafter referred to as compound (ds)) and use the compound (ds) in the method for producing the compound (a). Masire,
  • Compound (ds) may be a SO F group or a group that can be converted to a SO F group (one SCN group, SC (S)
  • OCH group etc. can be prepared by a method using compound (d) as a starting material.
  • the compound (a) of the present invention is useful as a monomer since it has a polymerizable carbon-carbon double bond.
  • the polymer obtained by polymerizing the compound (a) is a polymer containing the following repeating unit (A) (hereinafter, also referred to as polymer (A)).
  • repeating unit (A) includes the following examples.
  • the polymer (A) may be a homopolymer obtained by homopolymerizing the compound (a), and may be a monomer other than the compound (a) and the compound (a) (hereinafter, referred to as a comonomer). And a copolymer obtained by copolymerizing the above.
  • the homopolymer is a polymer comprising a repeating unit (A), and the copolymer is a polymer containing a repeating unit (A) and a repeating unit based on a comonomer (hereinafter, referred to as a repeating unit (B)). is there.
  • the repeating unit (B) preferably contains more than 0 mol% and less than 100 mol% with respect to all the repeating units. 99.9 mol% to 10 mol 0 /. More preferably, 90 to 60 mol% is particularly preferable.
  • the comonomer may be a comonomer containing no fluorine atom or a comonomer containing a fluorine atom.
  • compound m2 perfluoro (2,2 dimethyl-1,3 dioxol) or perfluoro (2-methylene 1,3 dioxolan).
  • CF CFOCF
  • CF CFOCF CF
  • CF CFCF ⁇ CF CF
  • CF
  • CF CFCF CF SO F
  • CF CFOCF CF SO F
  • CF CFOCF CF ( CF) OCF CF SO F and the like.
  • the compound (a) is preferably polymerized in the presence of a polymerization initiator.
  • the polymerization initiator may be added from the beginning of the polymerization or from the middle of the polymerization.
  • the polymerization initiator is preferably used in an amount of 0.000 :! to 3% by mass based on the total amount of the monomers, and particularly preferably used in an amount of 0.001 to :!
  • the polymerization initiator is preferably a radical polymerization initiator.
  • the radical polymerization initiator include 2,2-azobis (2-amidinopropane) dihydrochloride, 4,4-azobis (4-cyanopentanoic acid), and 2,2-azobis (4-methoxy-1,4-dimethylvalero).
  • Azo compounds such as nitrile), 1,1-azobis (1-cyclohexanecarbonitrile), diisopropylperoxydicarbonate, benzoylperoxide, perfluorononanoylperoxide, methylethyl Ketone peroxide, diisopropylperoxide, (CF CF CF COO), (CFC
  • Organic peroxides such as (OO) and ((CH) CO), and inorganic metals such as KSO and (NH) SO.
  • the polymerization of compound (a) may be carried out in the presence of a chain transfer agent.
  • chain transfer agent include alcohols (methanol, ethanol, etc.) and carbons with a fluorinated fluoride (1,3_dichloro_1,1,2,2,3_pentanolepropronone, 1-Dichloro mouth _1-Funoleoloethane, etc.), Hyd mouth carbons (pentane, hexane, cyclohexane, etc.), eodofluorohide mouth carbons (1,4-Jodoperfluorobutane, 1_Bromo _4 _ Edo perfluorobutane etc.).
  • the pressure (gauge pressure) in the polymerization is preferably higher than OMPa and 20 MPa or less, particularly preferably 0.3 MPa or more and 5 MPa or less.
  • the temperature in the polymerization is preferably from 0 ° C to 100 ° C, particularly preferably from 10 ° C to 80 ° C.
  • Polymerization methods include solution polymerization, milk Known methods such as a chemical polymerization method, a suspension polymerization method, and a bulk polymerization method are exemplified.
  • the molecular weight of the polymer (A), 5 X 10 2 ⁇ 1 X 10 6 are preferred.
  • the melting start temperature of the polymer (A) of the present invention is preferably from 100 ° C to 400 ° C. However, the definition of the melting start temperature will be described later.
  • the polymer (A) is excellent in physical properties such as low refractive index, water / oil repellency, transparency, heat resistance, and mechanical strength.
  • the polymer (A) of the present invention can be used for optical materials (for example, optical waveguide materials, optical fiber materials, pellicle materials, light emitting element sealing materials, lens materials, etc.), electronic materials (for example, semiconductor interlayer insulating films, high frequency It is useful as an element protective film, a display surface protective film, and the like, and a water and oil repellent material (for example, an oil sealant).
  • the polymer (A) obtained by polymerizing the compound (a) containing a fluorosulfonyl group is an ion exchange membrane (such as an ion exchange membrane for salt electrolysis).
  • it is suitable as a solid polymer electrolyte for a polymer electrolyte fuel cell.
  • the polymer (A) is particularly suitable as a solid polymer electrolyte for a polymer electrolyte fuel cell operated at 120 ° C. or higher because of its high softening temperature.
  • the fluorosulfonyl group in the polymer is represented by the formula SO
  • OM (wherein M represents a hydrogen atom, a lithium atom, a potassium atom, or a sodium atom).
  • polymer (A) containing a group represented by the formula SO (OM) include any of the following:
  • Polymer (A) containing such a repeating unit Polymer (A) containing such a repeating unit.
  • CF C1CF CHC1F R_225cb CC1 FCC1F R-113, CH CC1 F R-14 lb
  • GC refers to gas chromatography. Purity was determined from the peak area ratio by GC analysis. The yield was determined by 19 F-NMR using perfluorobenzene as an internal standard.
  • the mixture was stirred while adding g) little by little. After the addition, the mixture was further stirred for 26 hours.
  • the liquid in the flask was filtered under pressure to obtain a filtrate.
  • the filtration residue was extracted with R_225cb (50 mL twice) to obtain an extract.
  • the filtrate and the extract were mixed to obtain a mixed solution.
  • the mixed solution was washed with a 10% by mass aqueous solution of sodium thiosulfate (50 mL), washed with a saturated aqueous solution of sodium hydrogencarbonate (40 mL) four times, and then dried over anhydrous sodium sulfate. .
  • the product was further concentrated by an evaporator to obtain a product (29 g).
  • the NMR data of the compound (f_1) are shown below.
  • Example 1-2 After adding H (40 mL) and boron trifluoride etherate (1.lg), the raw material obtained in Example 1-2 was added.
  • An autoclave (made of nickel, having a capacity of 500 mU) was prepared, and a cooler kept at 20 ° C, a packed bed of NaF pellets, and a cooler kept at 10 ° C were installed in series at the gas outlet of the autoclave.
  • a liquid return line was installed to return the condensed liquid from the cooler kept at 10 ° C to the autoclave.
  • R-113 (312 g) was placed in an autoclave and stirred while maintaining the temperature at 25 ° C. As it is, nitrogen gas was blown into the autoclave at 25 ° C for 1 hour, and then fluorine gas diluted to 20% volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) at 25 ° C and a flow rate of 15.89 L / h. I blew it for one hour. Next, while blowing 20% fluorine gas at the same flow rate, a solution obtained by dissolving the fraction (17.lg) obtained in Example 1-3 in R-113 (172g) was injected over 7.4 hours.
  • 20% fluorine gas fluorine gas diluted to 20% volume with nitrogen gas
  • the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow rate, and the R-113 solution having a benzene concentration of 0.1 Olg / mL was cooled to 25 ° C. 9 mL was injected while heating to a C force of 40 ° C, and the benzene solution inlet of the autoclave was closed. The total amount of benzene injected was 0.22 g.
  • Example 2-1 A flask equipped with a reflux condenser and a thermometer was charged with the contents obtained in the same manner as in Example 2-1 (including 23.6 g of the conjugated product (c_l)) and KF (0.43 g). The mixture was stirred at 100 ° C for 3 hours. The flask was cooled and then distilled under atmospheric pressure to obtain 56-62 ° ⁇ distillate 8 (4.6 g).
  • Polymer (0.16 g) (hereinafter, referred to as polymer 2) was obtained in the same manner as in Example 3, except that 37.9 mg) and compound (a-1) (18.95 g) were charged. .
  • the melting start temperature of Polymer 2 was 120 ° C.
  • the compound of the present invention is useful as a polymerizable compound.
  • the polymer obtained by polymerizing the compound of the present invention is useful as various optical materials, electronic materials, other materials, and materials for ion exchange membranes, which are particularly excellent in heat resistance and mechanical strength.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Sont dévoilés un composé ayant une structure perfluoro(4-méthylène-1, 3-dioxolanne) inconnu jusqu'à présent, et un nouveau polymère. Sont spécifiquement dévoilés un composé représenté par la formule (a) ci-dessous, ayant une structure perfluoro(4-méthylène-1, 3-dioxolanne), une méthode pour produire un tel composé, un nouveau composé utile pour produire un tel composé, et un nouveau polymère contenant une unité répétée représentée par la formule (A) ci-dessous. (Dans les formules, RF1-RF4 représentent indépendamment un atome de fluor, un atome de chlore ou un groupe organique monovalent perfluoré ayant 1-20 atomes de carbone) (a) (A)
PCT/JP2005/010614 2004-06-11 2005-06-09 Composé ayant une structure perfluoro(4-méthylène-1, 3-dioxolanne) et nouveau polymère WO2005121118A1 (fr)

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JP2006514568A JPWO2005121118A1 (ja) 2004-06-11 2005-06-09 ペルフルオロ（４−メチレン−１，３−ジオキソラン）構造を有する化合物、および新規な重合体

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1031119A (ja) * 1996-07-18 1998-02-03 Asahi Glass Co Ltd コア／クラッド型の光学樹脂材料
WO2000056694A1 (fr) * 1999-03-23 2000-09-28 Asahi Glass Company, Limited Procede de production d'un compose de fluor au moyen d'une fluoration en phase liquide
WO2003037885A1 (fr) * 2001-10-30 2003-05-08 Asahi Glass Company, Limited Composes de fluorosulfonyle et procede de production de composes en derivant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1031119A (ja) * 1996-07-18 1998-02-03 Asahi Glass Co Ltd コア／クラッド型の光学樹脂材料
WO2000056694A1 (fr) * 1999-03-23 2000-09-28 Asahi Glass Company, Limited Procede de production d'un compose de fluor au moyen d'une fluoration en phase liquide
WO2003037885A1 (fr) * 2001-10-30 2003-05-08 Asahi Glass Company, Limited Composes de fluorosulfonyle et procede de production de composes en derivant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHO I. ET AL: "Radical polymerization of 4-methylene-1,3-dioxolan-2-one and its hydrolyzed water-soluble polymer", MAKROMOLEKULARE CHEMIE, RAPID COMMUNICATIONS, vol. 10, no. 9, 1989, pages 453 - 456, XP008054824 *

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