JP2006290779A - New fluorine-containing compound and fluorine-containing polymer - Google Patents
New fluorine-containing compound and fluorine-containing polymer Download PDFInfo
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本発明は、新規な、ペルフルオロ（２−アルキリデン−１，３−ジオキソラン）構造を有する化合物およびペルフルオロ（２−アルコキシメチレン−１，３−ジオキソラン）構造を有する化合物ならびに、これらの化合物が重合したモノマー単位を含む新規な含フッ素重合体に関する。 The present invention relates to a novel compound having a perfluoro (2-alkylidene-1,3-dioxolane) structure, a compound having a perfluoro (2-alkoxymethylene-1,3-dioxolane) structure, and a monomer obtained by polymerizing these compounds. The present invention relates to a novel fluoropolymer containing units.
ペルフルオロ（１，３−ジオキソラン）構造を有する重合性の化合物としては、ペルフルオロ（２−メチレン−１，３−ジオキソラン）構造を有する化合物が知られている（特許文献１参照。）。該化合物が重合したモノマー単位を含む重合体は、非晶性、溶媒可溶性および低屈折率性等の性質を有する。 As a polymerizable compound having a perfluoro (1,3-dioxolane) structure, a compound having a perfluoro (2-methylene-1,3-dioxolane) structure is known (see Patent Document 1). A polymer containing a monomer unit obtained by polymerizing the compound has properties such as amorphousness, solvent solubility and low refractive index.
またペルフルオロ（２−メチレン−１，３−ジオキソラン）構造とフルオロスルホニル基を有する重合性の化合物としては、本出願人による下式（ｚ）で表される化合物が知られている（特許文献２参照）。該化合物を重合させて得た重合体は、食塩電解用のイオン交換膜、固体高分子型燃料電池用の固体高分子電解質等の材料として有用である。 Moreover, as a polymerizable compound having a perfluoro (2-methylene-1,3-dioxolane) structure and a fluorosulfonyl group, a compound represented by the following formula (z) by the present applicant is known (Patent Document 2). reference). A polymer obtained by polymerizing the compound is useful as a material for an ion exchange membrane for salt electrolysis, a solid polymer electrolyte for a polymer electrolyte fuel cell, or the like.
以上のように、ペルフルオロ（１，３−ジオキソラン）構造を有する重合性の化合物における重合性基としては、１，３−ジオキソラン構造の２位を構成するペルフルオロメチレン（＞Ｃ＝ＣＦ２）基が知られるだけであった。該ペルフルオロメチレン基中のフッ素原子を他の置換基に置換した化合物は、原料入手が困難であり合成できなかった。そのため該化合物の重合性等の物性も知られていない。 As described above, the polymerizable group in the polymerizable compound having a perfluoro (1,3-dioxolane) structure includes a perfluoromethylene (> C═CF 2 ) group constituting the 2-position of the 1,3-dioxolane structure. It was only known. A compound in which the fluorine atom in the perfluoromethylene group is substituted with another substituent cannot be synthesized because it is difficult to obtain raw materials. Therefore, physical properties such as polymerizability of the compound are not known.
本発明者らは、ペルフルオロ（２−アルキリデン−１，３−ジオキソラン）構造を有する新規化合物とペルフルオロ（２−アルコキシメチレン−１，３−ジオキソラン）構造を有する新規化合物とを見出した。そして、これらの化合物は重合性を有することを見出した。 The present inventors have found a novel compound having a perfluoro (2-alkylidene-1,3-dioxolane) structure and a novel compound having a perfluoro (2-alkoxymethylene-1,3-dioxolane) structure. And it discovered that these compounds have polymerizability.
すなわち、本発明は以下の発明を提供する。
［１］：下式（ａ）で表される化合物。
［２］：下式（ａ）で表される化合物が重合したモノマー単位を含む含フッ素重合体。
That is, the present invention provides the following inventions.
[1]: A compound represented by the following formula (a).
[2]: A fluorine-containing polymer containing a monomer unit obtained by polymerizing a compound represented by the following formula (a).
ただし、ＹＦは、炭素数１〜３のペルフルオロアルキル基または炭素数１〜３のペルフルオロアルコキシ基である。ＲＦ１、ＲＦ２、ＲＦ３およびＲＦ４は、それぞれ独立に、フッ素原子、フルオロスルホニル基または式−ＱＦＸで表される基である。ＱＦは、炭素数１〜６のペルフルオロアルキレン基または炭素数２〜６のペルフルオロ（アルキレンオキシアルキレン）基である。Ｘは、フッ素原子またはフルオロスルホニル基である。 However, Y F is a perfluoroalkoxy group of a perfluoroalkyl group or a 1 to 3 carbon atoms of 1 to 3 carbon atoms. R F1 , R F2 , R F3, and R F4 are each independently a fluorine atom, a fluorosulfonyl group, or a group represented by the formula -Q F X. Q F is a C 1-6 perfluoroalkylene group or a C 2-6 perfluoro (alkyleneoxyalkylene) group. X is a fluorine atom or a fluorosulfonyl group.
本発明によれば、ペルフルオロ（１，３−ジオキソラン）構造を有する重合性の新規化合物および該化合物が重合したモノマー単位を含む含フッ素重合体が提供される。該含フッ素重合体は、非晶性を有し耐熱性に優れる。 According to the present invention, there are provided a polymerizable novel compound having a perfluoro (1,3-dioxolane) structure and a fluorine-containing polymer comprising a monomer unit obtained by polymerizing the compound. The fluorine-containing polymer is amorphous and has excellent heat resistance.
本明細書において、式（ａ）で表される化合物を化合物ａと記す。他の化合物も同様に記す。またフルオロスルホニル基を単に−ＳＯ２Ｆとも記す。 In the present specification, a compound represented by the formula (a) is referred to as a compound a. Other compounds are described in the same manner. A fluorosulfonyl group is also simply referred to as —SO 2 F.
本発明は、下記化合物ａを提供する（ただし、ＲＦ１、ＲＦ４、ＲＦ３、ＲＦ４およびＹＦは前記と同じ意味である。以下同様。）。 The present invention provides the following compound a (wherein R F1 , R F4 , R F3 , R F4 and Y F have the same meanings as described above, and so on).
ＹＦは、−ＣＦ３基または−ＯＣＦ２ＣＦ２ＣＦ３基が好ましい。
ＲＦ１、ＲＦ２、ＲＦ３およびＲＦ４は、フッ素原子であるか、少なくとも１つの基が式−ＱＦＸで表される基（ただし、ＱＦおよびＸは前記と同じ意味である。以下同様。）（以下、該基を−ＱＦＸ基という。）であり残余の基がフッ素原子であるのが好ましい。
Y F is, -CF 3 group, or -OCF 2 CF 2 CF 3 group is preferred.
R F1 , R F2 , R F3 and R F4 are fluorine atoms or a group in which at least one group is represented by the formula -Q F X (where Q F and X have the same meanings as described above. Similarly.) (hereinafter, preferably the base of -Q F X group.), and the remaining radicals are fluorine atoms.
ＱＦにおける炭素数１〜６のペルフルオロアルキレン基は、式−（ＣＦ２）ｎ−で表される基（ただし、ｎは１〜６の整数を示す。以下同様。）が特に好ましい。
ＱＦにおける炭素数２〜６のペルフルオロ（アルキレンオキシアルキレン）基は、炭素数２〜６のペルフルオロ（アルキレンオキシアルキレン）基が好ましく、−ＣＦ２ＯＣＦ２−、−ＣＦ２ＯＣＦ２ＣＦ２−または−ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２−が特に好ましい。
ＱＦは、炭素数１〜６のペルフルオロアルキレン基が好ましく、式−（ＣＦ２）ｎ−で表される基が特に好ましい。この場合、より高いガラス転移点温度を有する含フッ素重合体が得られる。
Perfluoroalkylene group having 1 to 6 carbon atoms in Q F is the formula - (CF 2) n - group represented by (.. Where, n is an integer of 1 to 6 hereinafter the same) is especially preferred.
Perfluoro (alkylene oxyalkylene) group having 2 to 6 carbon atoms in Q F is preferably perfluoro (alkylene oxyalkylene) group having 2 to 6 carbon atoms, -CF 2 OCF 2 -, - CF 2 OCF 2 CF 2 - or -CF 2 OCF 2 CF 2 CF 2 - it is particularly preferred.
Q F is preferably a C 1-6 perfluoroalkylene group, particularly preferably a group represented by the formula — (CF 2 ) n —. In this case, a fluoropolymer having a higher glass transition temperature can be obtained.
化合物ａとしては、下記化合物ａ１が好ましい。 As the compound a, the following compound a1 is preferable.
化合物ａ１の具体例としては、下記の化合物が挙げられる。 Specific examples of the compound a1 include the following compounds.
化合物ａの製造方法としては、下記化合物ｄをフッ素化反応させて化合物ｃを得て、つぎに該化合物ｃとメタノールを反応させて下記化合物ｂを得て、つぎに該化合物ｂを分解反応させる方法が挙げられる。化合物ｄの入手方法は後述する。 The compound a is produced by fluorinating the following compound d to obtain a compound c, then reacting the compound c with methanol to obtain the following compound b, and then decomposing the compound b. A method is mentioned. The method for obtaining compound d will be described later.
ただし、ＹはＹＦと同一の基であるかフッ素化されてＹＦとなる基である（以下同様。）。Ｒ１はＲＦ１に、Ｒ２はＲＦ２に、Ｒ３はＲＦ３に、Ｒ４はＲＦ４に、それぞれ対応する基であり、Ｒ１〜Ｒ４はＲＦ１〜ＲＦ４と同一の基であるかフッ素化されてＲＦ１〜ＲＦ４となる基である（以下同様。）。ＲＦは炭素数１〜２０のペルフルオロアルキル基または炭素数２〜２０のエーテル性酸素原子を含有するペルフルオロアルキル基である（以下同様。）。 However, Y is a group to be a Y F is is or fluorinated same group as Y F (the same applies hereinafter.). R 1 is a group corresponding to R F1 , R 2 is a group corresponding to R F2 , R 3 is a group corresponding to R F3 , R 4 is a group corresponding to R F4 , and R 1 to R 4 are the same groups as R F1 to R F4. Or a group that is fluorinated to become R F1 to R F4 (the same applies hereinafter). R F is a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl group containing an etheric oxygen atom having 2 to 20 carbon atoms (the same applies hereinafter).
Ｙは、フッ素化されてＹＦとなる基であるのが好ましく、炭素数１〜３のアルキル基、炭素数２〜３のアルケニル基、炭素数１〜３のアルコキシ基または炭素数２〜３のアルケノキシ基であるのが好ましい。すなわち、炭素数１〜３のペルフルオロアルキル基であるＹＦに対応するＹは、炭素数１〜３のアルキル基または炭素数２〜３のアルケニル基であるのが好ましい。炭素数１〜３のペルフルオロアルコキシ基であるＹＦに対応するＹは、炭素数１〜３のアルコキシ基または炭素数２〜３のアルケノキシ基であるのが好ましい。 Y is preferably a group that is fluorinated to become Y F, and is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or 2 to 3 carbon atoms. The alkenoxy group is preferable. That, Y corresponding to Y F is a perfluoroalkyl group having 1 to 3 carbon atoms, preferably an alkyl or alkenyl group having a carbon number of 2 to 3 1 to 3 carbon atoms. Y corresponding to Y F is a perfluoroalkoxy group having 1 to 3 carbon atoms is preferably an alkoxy group or a number 2-3 alkenoxy carbons of 1 to 3 carbon atoms.
Ｒ１〜Ｒ４は、それぞれフッ素化されてＲＦ１〜ＲＦ４となる基であるのが好ましく、水素原子または式−Ｑ−Ｈで表される基（ただし、Ｑは、ＱＦと同一の基であるかフッ素化されてＱＦとなる基である。以下同様。）または式−Ｑ−ＳＯ２Ｆで表される基が好ましい。すなわち、フッ素原子であるＲＦ１〜ＲＦ４にそれぞれ対応するＲ１〜Ｒ４は、水素原子であるのが好ましい。式−ＱＦ−Ｆで表される基であるＲＦ１〜ＲＦ４にそれぞれ対応するＲ１〜Ｒ４は、式−Ｑ−Ｈで表される基であるのが好ましい。式−ＱＦ−ＳＯ２Ｆで表される基であるＲＦ１〜ＲＦ４にそれぞれ対応するＲ１〜Ｒ４は、式−Ｑ−ＳＯ２Ｆで表される基であるのが好ましい。 R 1 to R 4 are each preferably a group that is fluorinated to be R F1 to R F4, and is a hydrogen atom or a group represented by the formula -QH (where Q is the same as Q F is is one fluorinated group is a group comprising a Q F. or less similar.) or a group represented by the formula -Q-SO 2 F are preferred. That is, R 1 to R 4 corresponding to R F1 to R F4 that are fluorine atoms are preferably hydrogen atoms. R 1 to R 4 respectively corresponding to R F1 to R F4 which are groups represented by the formula -Q F -F are preferably groups represented by the formula -QH. R 1 to R 4 respectively corresponding to R F1 to R F4 that are groups represented by the formula —Q F —SO 2 F are preferably groups represented by the formula —Q—SO 2 F.
Ｑは、フッ素化されてＱＦとなる基であるのが好ましく、炭素数１〜６のアルキレン基または炭素数２〜６のアルキレンオキシアルキレン基がより好ましい。すなわち、炭素数１〜６のペルフルオロアルキレン基であるＱＦに対応するＱは、炭素数１〜６のアルキレン基であるのが好ましい。炭素数２〜６のペルフルオロ（アルキレンオキシアルキレン）基であるＱＦに対応するＱは、炭素数２〜６のアルキレンオキシアルキレン基であるのが好ましい。 Q is preferably a group as a Q F is fluorinated, more preferably an alkylene group or alkylene oxyalkylene group having 2 to 6 carbon atoms having 1 to 6 carbon atoms. That is, Q corresponding to QF which is a C 1-6 perfluoroalkylene group is preferably a C 1-6 alkylene group. Q corresponding to Q F is a perfluoro (alkyleneoxyalkylene) group having 2 to 6 carbon atoms, preferably an alkylene oxyalkylene group having 2 to 6 carbon atoms.
ＲＦは、−ＣＦ２ＣＦ３、−ＣＦ（ＣＦ３）ＣＦ２ＣＦ３、−ＣＦ（ＣＦ３）２、−ＣＦ（ＣＦ３）Ｏ（ＣＦ２）３Ｆ、−ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３が好ましい。 R F is —CF 2 CF 3 , —CF (CF 3 ) CF 2 CF 3 , —CF (CF 3 ) 2 , —CF (CF 3 ) O (CF 2 ) 3 F, —CF (CF 3 ) OCF 2 CF (CF 3) OCF 2 CF 2 CF 3 are preferred.
前記製造方法における、フッ素化反応、化合物（ｃ）とメタノールの反応および分解反応は、公知の方法を用いるのが好ましい。フッ素化反応と、化合物（ｃ）とメタノールとの反応は、国際公開第０３／０３７８８５号パンフレットに記載の方法を用いて行うのが好ましい。分解反応は、化合物ｂをアルカリ金属水酸化物水溶液中で処理してから行うのが好ましい。アルカリ金属水酸化物は、ＮａＯＨまたはＫＯＨが好ましい。 It is preferable to use a known method for the fluorination reaction, the reaction between the compound (c) and methanol, and the decomposition reaction in the production method. The fluorination reaction and the reaction between the compound (c) and methanol are preferably carried out using the methods described in WO 03/037885. The decomposition reaction is preferably carried out after treating compound b in an aqueous alkali metal hydroxide solution. The alkali metal hydroxide is preferably NaOH or KOH.
上記スキームの出発物質である化合物ｄは、公知の化合物であるか、または下記化合物ｇと下記化合物ｆをアセタール化反応させて下記化合物ｅを得て、つぎに該化合物ｅと式ＲＦ−ＣＯＦで表される化合物をエステル化反応させる方法を用いて入手できる。 Compound d which is the starting material of the above scheme is a known compound, or the following compound g and the following compound f are acetalized to obtain the following compound e, and then the compound e and the formula R F —COF It can obtain using the method of esterifying the compound represented by these.
化合物ｇの具体例としては、ＣＨ２（ＯＨ）ＣＨ２（ＯＨ）、ＣＨ２（ＯＨ）ＣＨ（ＯＨ）ＣＨ３、ＣＨ２（ＯＨ）ＣＨ（ＯＨ）ＣＨ２ＣＨ２ＳＯ２Ｆ、ＣＨ２（ＯＨ）ＣＨ（ＯＨ）（ＣＨ２）４ＳＯ２Ｆ等が挙げられる。化合物ｇは、公知の方法で合成できる原料であるか、または下記化合物ｉを酸化反応させて得るのが好ましい。
ＣＲ３Ｒ４＝ＣＲ１Ｒ２ （ｉ）。
Specific examples of compound g include CH 2 (OH) CH 2 (OH), CH 2 (OH) CH (OH) CH 3 , CH 2 (OH) CH (OH) CH 2 CH 2 SO 2 F, CH 2. (OH) CH (OH) ( CH 2) 4 SO 2 F , and the like. Compound g is preferably a raw material that can be synthesized by a known method, or obtained by subjecting the following compound i to an oxidation reaction.
CR 3 R 4 = CR 1 R 2 (i).
化合物ｉとしては、下記化合物ｉ−１が挙げられる。
ＣＨ２＝ＣＨ（ＣＨ２）ｎＳＯ２Ｆ （ｉ−１）
化合物ｉ−１の製造方法としては、式ＣＨ２＝ＣＨ（ＣＨ２）ｎＢｒで表される化合物をＮａ２ＳＯ３水溶液で処理して式ＣＨ２＝ＣＨ（ＣＨ２）ｎＳＯ３Ｎａで表される化合物を得て、つぎに該化合物を２，２−ジフルオロ−１，３−ジメチルイミダゾリジンと反応させる方法が挙げられる。
Examples of the compound i include the following compound i-1.
CH 2 = CH (CH 2) n SO 2 F (i-1)
As a production method of the compound i-1, a compound represented by the formula CH 2 ═CH (CH 2 ) n Br is treated with an aqueous Na 2 SO 3 solution, and the formula CH 2 ═CH (CH 2 ) n SO 3 Na is used. A method in which the compound represented is obtained, and then the compound is reacted with 2,2-difluoro-1,3-dimethylimidazolidine.
化合物ｆの具体例としては、ＣＨ２（ＯＨ）Ｃ（Ｏ）ＣＨ３、ＣＨ２（ＯＨ）Ｃ（Ｏ）ＣＨ２ＣＨ３、ＣＨ２（ＯＨ）Ｃ（Ｏ）ＣＨ２ＣＨ２ＣＨ３、ＣＨ２（ＯＨ）Ｃ（Ｏ）ＣＨ２ＯＣＨ３、ＣＨ２（ＯＨ）Ｃ（Ｏ）ＣＨ２ＯＣＨ２ＣＨ３、ＣＨ２（ＯＨ）Ｃ（Ｏ）ＣＨ２ＯＣＨ２ＣＨ２ＣＨ３、ＣＨ２（ＯＨ）Ｃ（Ｏ）ＣＨ２ＯＣＨ２ＣＨ＝ＣＨ２等が挙げられる。 Specific examples of the compound f include CH 2 (OH) C (O) CH 3 , CH 2 (OH) C (O) CH 2 CH 3 , CH 2 (OH) C (O) CH 2 CH 2 CH 3 , CH 2 (OH) C (O ) CH 2 OCH 3, CH 2 (OH) C (O) CH 2 OCH 2 CH 3, CH 2 (OH) C (O) CH 2 OCH 2 CH 2 CH 3, CH 2 (OH) C (O) CH 2 OCH 2 CH = CH 2 and the like.
本発明の化合物のうちＸが−ＳＯ２Ｆである化合物ａにおける−ＳＯ２Ｆは、式−ＳＯ２（Ｏ−Ｍ＋）で表される基を含む化合物ａ（ただし、Ｍは水素原子または対イオンを示す。以下同様。）に容易に変換できる。対イオンとしては、リチウム、ナトリウムまたはカリウムが好ましい。 -SO 2 F in the compound a X is a -SO 2 F of the compounds of the present invention have the formula -SO 2 - compound comprising a group represented by (O M +) a (however, M is a hydrogen atom or Counter ion is shown. The same applies hereinafter.) The counter ion is preferably lithium, sodium or potassium.
本発明の化合物ａは、ペルフルオロ（１，３−ジオキソラン）構造の２位に重合性の不飽和基を有する特徴ある構造の重合性の化合物である。よって、本発明の化合物ａを重合させることにより重合体を得ることができる。 The compound a of the present invention is a polymerizable compound having a characteristic structure having a polymerizable unsaturated group at the 2-position of the perfluoro (1,3-dioxolane) structure. Therefore, a polymer can be obtained by polymerizing the compound a of the present invention.
本発明は、化合物ａが重合したモノマー単位を含む含フッ素重合体を提供する。
本発明の含フッ素重合体は、化合物ａが単独重合したモノマー単位を含む単独重合体であってもよく化合物ａと化合物ａ以外のモノマー（以下、コモノマーという。）が共重合したモノマー単位を含む共重合体であってもよい。単独重合体は化合物ａに基づく下式（Ａ）で表されるモノマー単位（以下、単位Ａという。）からなる含フッ素重合体であり、共重合体は単位Ａとコモノマーに基づくモノマー単位（以下、単位Ｂという。）を含む含フッ素重合体である。
The present invention provides a fluoropolymer containing a monomer unit obtained by polymerizing compound a.
The fluorine-containing polymer of the present invention may be a homopolymer containing a monomer unit obtained by homopolymerizing the compound a, and may contain a monomer unit obtained by copolymerizing a monomer other than the compound a and the compound a (hereinafter referred to as comonomer). A copolymer may also be used. The homopolymer is a fluoropolymer composed of a monomer unit represented by the following formula (A) based on compound a (hereinafter referred to as unit A), and the copolymer is a monomer unit based on unit A and a comonomer (hereinafter referred to as unit A). And a unit B).
本発明の含フッ素重合体は全モノマー単位に対して単位Ａを、０モル％超１００モル％以下含むのが好ましく、０．１モル％〜９０モル％含むのがより好ましく、１０〜４０モル％含むのが特に好ましい。本発明の含フッ素重合体が単位Ｂを含む場合、含フッ素重合体は全モノマー単位に対して単位Ｂを、０モル％超１００モル％未満含むのが好ましく、９９．９モル％〜１０モル％含むのがより好ましく、９０〜６０モル％含むのが特に好ましい。 The fluoropolymer of the present invention preferably contains unit A in an amount of more than 0 mol% and not more than 100 mol%, more preferably 0.1 mol% to 90 mol%, more preferably 10 to 40 mol, based on all monomer units. % Is particularly preferable. When the fluorine-containing polymer of the present invention contains the unit B, the fluorine-containing polymer preferably contains the unit B in a proportion of more than 0 mol% and less than 100 mol%, based on all monomer units, %, More preferably 90 to 60 mol%.
コモノマーは、フッ素原子を含まないコモノマーであっても、フッ素原子を含むコモノマーであってもよい。 The comonomer may be a comonomer containing no fluorine atom or a comonomer containing a fluorine atom.
フッ素原子を含むコモノマーの具体例としては、ＣＨ２＝ＣＨＦ、ＣＨ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＦ２、式ＣＦ２＝ＣＦ−Ｗで表される化合物（ただし、Ｗは１価含フッ素有機基である。以下同様。）、式ＣＨ２＝ＣＨ−Ｗで表される化合物、ペルフルオロ（２，２−ジメチル−１，３−ジオキソール）またはペルフルオロ（２−メチレン−１，３−ジオキソラン）が挙げられる。 Examples of comonomers containing a fluorine atom, CH 2 = CHF, CH 2 = CF 2, CF 2 = CFCl, CF 2 = CF 2, the compound represented by the formula CF 2 = CF-W (however, W is Monovalent fluorine-containing organic group, the same applies hereinafter), a compound represented by the formula CH 2 ═CH—W, perfluoro (2,2-dimethyl-1,3-dioxole) or perfluoro (2-methylene-1, 3-dioxolane).
式ＣＦ２＝ＣＦ−Ｗで表される化合物の具体例としては、ＣＦ２＝ＣＦＣＦ３、ＣＦ２＝ＣＦＣＦ２Ｂｒ、ＣＦ２＝ＣＦＣＦ２Ｉ、ＣＦ２＝ＣＦＯＣＦ３、ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＣＦ３、ＣＦ２＝ＣＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ３、ＣＦ２＝ＣＦＯＣＦ２ＣＦ＝ＣＦ２、ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＣＦ＝ＣＦ２、ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＯＣＦ＝ＣＦ２、ＣＦ２＝ＣＦＣＦ２ＣＦ２ＳＯ２Ｆ、ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＳＯ２Ｆ、ＣＦ２＝ＣＦＯＣＦ２ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＳＯ２Ｆ等が挙げられる。 Specific examples of the compound represented by the formula CF 2 = CF-W, CF 2 = CFCF 3, CF 2 = CFCF 2 Br, CF 2 = CFCF 2 I, CF 2 = CFOCF 3, CF 2 = CFOCF 2 CF 2 CF 3 , CF 2 = CFCF 2 OCF 2 CF 2 CF 3 , CF 2 = CFOCF 2 CF = CF 2 , CF 2 = CFOCF 2 CF 2 CF = CF 2 , CF 2 = CFOCF 2 CF 2 OCF = CF 2 , CF 2 = CFCF 2 CF 2 SO 2 F, CF 2 = CFOCF 2 CF 2 SO 2 F, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 SO 2 F , and the like.
式ＣＨ２＝ＣＨ−Ｗで表される化合物の具体例としては、ＣＨ２＝ＣＨＣＦ２ＣＦ２ＣＦ２ＣＦ２、ＣＨ２＝ＣＨＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｈ、ＣＨ２＝ＣＨＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｂｒ、ＣＨ２＝ＣＨＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｉ等が挙げられる。 Specific examples of the compound represented by the formula CH 2 = CH-W, CH 2 = CHCF 2 CF 2 CF 2 CF 2, CH 2 = CHCF 2 CF 2 CF 2 CF 2 H, CH 2 = CHCF 2 CF 2 CF 2 CF 2 Br, CH 2 = CHCF 2 CF 2 CF 2 CF 2 I , and the like.
フッ素原子を含まないコモノマーの具体例としては、ＣＨ２＝ＣＨ２、ＣＨ２＝ＣＨＣｌ、ＣＨ２＝ＣＨＢｒ、ＣＨ２＝ＣＨＩ、ＣＨ２＝ＣＨＣＨ３、ＣＨ２＝ＣＨＣＨ２Ｃｌ、ＣＨ２＝ＣＨＣＨ２Ｂｒ、ＣＨ２＝ＣＨＣＨ２Ｉ等が挙げられる。 Specific examples of the comonomer not containing a fluorine atom include CH 2 = CH 2 , CH 2 = CHCl, CH 2 = CHBr, CH 2 = CHI, CH 2 = CHCH 3 , CH 2 = CHCH 2 Cl, CH 2 = CHCH. 2 Br, CH 2 ═CHCH 2 I and the like.
化合物ａの重合は、重合開始剤の存在下に行うのが好ましい。重合開始剤は、重合の最初から添加してもよく、重合の途中から添加してもよい。重合開始剤は、モノマーの総量に対して０.０００１〜３質量％を用いるのが好ましく、０.００１〜１質量％を用いるのが特に好ましい。 The polymerization of compound a is preferably performed in the presence of a polymerization initiator. The polymerization initiator may be added from the beginning of the polymerization or may be added during the polymerization. The polymerization initiator is preferably used in an amount of from 0.0001 to 3% by mass, particularly preferably from 0.001 to 1% by mass, based on the total amount of monomers.
重合開始剤は、ラジカル重合開始剤が好ましい。ラジカル重合開始剤としては、２，２−アゾビス（２−アミジノプロパン）２塩酸塩、４，４−アゾビス（４−シアノペンタン酸）、２，２−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、１，１−アゾビス（１−シクロヘキサンカルボニトリル）等のアゾ化合物、ジイソプロピルペルオキシジカーボネート、ベンゾイルペルオキシド、ペルフルオロノナノイルペルオキシド、メチルエチルケトンペルオキシド、ジイソプロピルペルオキシド、（ＣＦ３ＣＦ２ＣＦ２ＣＯＯ）２、（Ｃ６Ｆ５ＣＯＯ）２、（（ＣＨ３）３ＣＯ）２等の有機ペルオキシド、Ｋ２Ｓ２Ｏ８、（ＮＨ４）２Ｓ２Ｏ８等の無機ペルオキシドが挙げられる。 The polymerization initiator is preferably a radical polymerization initiator. As radical polymerization initiators, 2,2-azobis (2-amidinopropane) dihydrochloride, 4,4-azobis (4-cyanopentanoic acid), 2,2-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), azo compounds such as 1,1-azobis (1-cyclohexanecarbonitrile), diisopropyl peroxydicarbonate, benzoyl peroxide, perfluorononanoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxide, (CF 3 CF 2 CF 2 COO) 2 , (C 6 F 5 COO) 2 , organic peroxides such as ((CH 3 ) 3 CO) 2 , and inorganic peroxides such as K 2 S 2 O 8 and (NH 4 ) 2 S 2 O 8 .
また化合物ａの重合は、連鎖移動剤の存在下に行ってもよい。連鎖移動剤としては、アルコール類（メタノール、エタノール等。）、クロロフルオロハイドロカーボン類（１，３−ジクロロ−１，１，２，２，３−ペンタフルオロプロパン、１，１−ジクロロ−１−フルオロエタン等。）、ハイドロカーボン類（ペンタン、ヘキサン、シクロヘキサン等。）、ヨードフルオロハイドロカーボン類（１，４−ジヨードペルフルオロブタン、１−ブロモ−４−ヨードペルフルオロブタン等。）が挙げられる。 The polymerization of compound a may be performed in the presence of a chain transfer agent. Examples of chain transfer agents include alcohols (methanol, ethanol, etc.), chlorofluorohydrocarbons (1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1- Fluoroethane, etc.), hydrocarbons (pentane, hexane, cyclohexane, etc.), iodofluorohydrocarbons (1,4-diiodoperfluorobutane, 1-bromo-4-iodoperfluorobutane, etc.).
化合物ａの重合における圧力（ゲージ圧）は、０ＭＰａ超２０ＭＰａ以下が好ましく、０．３ＭＰａ以上５ＭＰａ以下が特に好ましい。また化合物ａの重合における温度は、０℃以上１００℃以下が好ましく、１０℃以上８０℃以下が特に好ましい。 The pressure (gauge pressure) in the polymerization of the compound a is preferably more than 0 MPa and not more than 20 MPa, particularly preferably not less than 0.3 MPa and not more than 5 MPa. The temperature in the polymerization of the compound a is preferably 0 ° C. or higher and 100 ° C. or lower, particularly preferably 10 ° C. or higher and 80 ° C. or lower.
化合物ａの重合方法としては、溶液重合法、乳化重合法、懸濁重合法、塊状重合法等の公知の重合方法が挙げられる。 Examples of the polymerization method for compound a include known polymerization methods such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method.
本発明の含フッ素重合体の分子量は、５×１０２〜１×１０６が好ましい。また本発明の含フッ素重合体のＴＱは、１００℃〜４００℃が好ましい。ＴＱとは、フローテスター（島津製作所製ＣＦＴ−５００Ｄ）を用い、ノズル（長さ１ｍｍ、内径１ｍｍ）中に３０ｋｇ／ｃｍ２の加圧下、重合体を１００ｍｍ３／秒の流量で溶融流出させた際の温度である。 The molecular weight of the fluoropolymer of the present invention is preferably 5 × 10 2 to 1 × 10 6 . The T Q of the fluorine-containing polymer of the present invention is preferably 100 ° C. to 400 ° C.. The T Q, using a flow tester (Shimadzu CFT-500D), the nozzle (length 1 mm, inner diameter 1mm) under a pressure of 30kg / cm 2 in the polymer is melted outflow at a flow rate of 100 mm 3 / sec It is the temperature at the time.
本発明の含フッ素重合体は、低屈折率性、撥水撥油性、透明性、耐熱性、機械的強度等の物性に優れる。本発明の含フッ素重合体は、光学材料（たとえば光導波路材料、光ファイバー材料、ペリクル材料、発光素子封止材料、レンズ材料等。）、電子材料（たとえば半導体層間絶縁膜、高周波素子保護膜、ディスプレイ表面保護膜等。）、撥水撥油材料（たとえばオイルシール剤等。）として有用である。 The fluoropolymer of the present invention is excellent in physical properties such as low refractive index, water / oil repellency, transparency, heat resistance and mechanical strength. The fluorine-containing polymer of the present invention includes 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 element protective films, displays). Surface protective film, etc.) and water / oil repellent materials (for example, oil sealants).
また本発明の含フッ素重合体のうち、−ＳＯ２Ｆを含む化合物ａが重合したモノマー単位を含む含フッ素重合体は、イオン交換膜（食塩電解用のイオン交換膜等。）または固体高分子型燃料電池用の固体高分子電解質として好適であり、含フッ素重合体の軟化温度が高いため１２０℃以上で運転される固体高分子型燃料電池用の固体高分子電解質として特に好適である。この場合、該含フッ素重合体は、−ＳＯ２Ｆを加水分解または対イオンを含むアルカリ性水溶液中で処理して式−ＳＯ２（ＯＭ）で表される基を含む重合体に変換し、つぎに強酸水溶液中で処理してスルホン酸基を含む重合体に変換するのが好ましい。 Of the fluorine-containing polymer of the present invention, the fluorinated polymer containing a monomer unit compounds a containing -SO 2 F are polymerized, the ion exchange membrane (ion exchange membrane for electrolysis of sodium chloride and the like.) Or a polymer It is suitable as a solid polymer electrolyte for a solid fuel cell and is particularly suitable as a solid polymer electrolyte for a solid polymer fuel cell operated at 120 ° C. or higher because the softening temperature of the fluoropolymer is high. In this case, the fluorine-containing polymer to convert the -SO 2 F into a polymer containing a group represented by the formula -SO 2 by treatment with an alkaline aqueous solution containing a hydrolysis or counterion (OM), the following It is preferable to convert it into a polymer containing a sulfonic acid group by treating in a strong acid aqueous solution.
−ＳＯ２Ｆを含む化合物ａとしては、下記化合物ａ１Ｓが好ましい。 As the compound a containing —SO 2 F, the following compound a1S is preferable.
スルホン酸基を含む重合体としては、化合物ａ１Ｓを重合させて含フッ素重合体を得て、該重合体を前記の方法により処理してＳＯ２Ｆ基をＳＯ３Ｈ基に変換する事により得た重合体が好ましい。該重合体としては、下記モノマー単位を含む重合体が挙げられる。 The polymer containing a sulfonic acid group is obtained by polymerizing the compound a1S to obtain a fluorine-containing polymer, and treating the polymer by the above-described method to convert the SO 2 F group into an SO 3 H group. Preferred polymers are. Examples of the polymer include polymers containing the following monomer units.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらに限定されない。
ジクロロペンタフルオロプロパンをＲ−２２５、ＣＦ２ＣｌＣＦ２ＣＨＣｌＦをＲ−２２５ｃｂ、ＣＣｌ２ＦＣＣｌＦ２をＲ−１１３、ガスクロマトグラフィーをＧＣ、Ｆ（ＣＦ２）３ＯＣＦ（ＣＦ３）−で表される基をＲｆ−、テトラメチルシランをＴＭＳ、テトラフルオロエチレンをＴＦＥ、と記す。純度はＧＣ分析によるピーク面積比から求めた。反応収率は、ニトロベンゼンを内部標準とした１Ｈ−ＮＭＲまたはヘキサフルオロベンゼンを内部標準とした１９Ｆ−ＮＭＲより求めた。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these.
Dichloropentafluoropropane is represented by R-225, CF 2 ClCF 2 CHClF is represented by R-225cb, CCl 2 FCClF 2 is represented by R-113, and gas chromatography is represented by GC, F (CF 2 ) 3 OCF (CF 3 )- based on the R f -, referred to tetramethyl silane TMS, tetrafluoroethylene TFE, and. The purity was determined from the peak area ratio by GC analysis. The reaction yield was determined from 1 H-NMR using nitrobenzene as an internal standard or 19 F-NMR using hexafluorobenzene as an internal standard.
［例１］化合物ａ１１の製造例 [Example 1] Production example of compound a11
［例１−１］エステル化反応による化合物ｄ１１の製造例
温度計、滴下ロート、および撹拌機を備えたフラスコを氷浴下で冷却し、化合物ｅ１１（４５ｇ）、ＮａＦ（２１．９ｇ）およびＲ−２２５（１００ｇ）を投入した。つぎにフラスコの内温を１０℃以下に保持しながら、式Ｒｆ−ＣＯＦで表される化合物（１０３．６ｇ）を滴下しながらフラスコ内を撹拌した。つづいて内温を２５℃にして、さらに１２時間撹拌した。
Example 1-1 Production Example of Compound d11 by Esterification Reaction A flask equipped with a thermometer, a dropping funnel, and a stirrer was cooled in an ice bath, and compound e11 (45 g), NaF (21.9 g) and R -225 (100 g) was charged. Next, the inside of the flask was stirred while dropping the compound (103.6 g) represented by the formula R f —COF while maintaining the internal temperature of the flask at 10 ° C. or lower. Subsequently, the internal temperature was set to 25 ° C., and the mixture was further stirred for 12 hours.
フラスコ内容液を加圧ろ過して得たろ液を濃縮して、Ｒ−２２５と未反応の化合物ｅ１１を除去した濃縮液を得た。濃縮液をＲ−２２５で希釈して、飽和炭酸水素ナトリウム水溶液で３回、イオン交換水で３回ずつ、順に洗浄した。 The filtrate obtained by pressure filtration of the flask contents was concentrated to obtain a concentrate from which R-225 and unreacted compound e11 were removed. The concentrated solution was diluted with R-225, and washed successively with a saturated aqueous sodium hydrogen carbonate solution three times and with ion-exchanged water three times.
つづいて濃縮液を硫酸マグネシウム粉末で脱水してから、エバポレーターで濃縮して粗生成物を得た。粗生成物を減圧蒸留して、１０３℃／１．５３ｋＰａ（絶対圧）の留分（１００．０ｇ）を得た。留分を分析した結果、標記化合物（純度９７．６％、収率７５．４％）の生成を確認した。化合物ｄ１１のＮＭＲデータを以下に示す。 Subsequently, the concentrated solution was dehydrated with magnesium sulfate powder and then concentrated by an evaporator to obtain a crude product. The crude product was distilled under reduced pressure to obtain a fraction (100.0 g) of 103 ° C./1.53 kPa (absolute pressure). As a result of analyzing the fraction, it was confirmed that the title compound (purity 97.6%, yield 75.4%) was produced. The NMR data of compound d11 are shown below.
１Ｈ−ＮＭＲ（３００．４ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＴＭＳ）δ（ｐｐｍ）：０．９５（６Ｈ），１．４６〜１．７９（４Ｈ），３．４７〜３．６１（１Ｈ），４．００〜４．４８（４Ｈ）。
１９Ｆ−ＮＭＲ（２８２．６ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）δ（ｐｐｍ）：−８０．０〜−８０．７（１Ｆ），−８１．８（３Ｆ），−８２．４（３Ｆ），−８６．２〜−８７．０（１Ｆ），−１３０．１（２Ｆ），−１３２．２（１Ｆ）。
1 H-NMR (300.4 MHz, solvent: CDCl 3 , standard: TMS) δ (ppm): 0.95 (6H), 1.46 to 1.79 (4H), 3.47 to 3.61 (1H ), 4.00 to 4.48 (4H).
19 F-NMR (282.6 MHz, solvent: CDCl 3 , standard: CFCl 3 ) δ (ppm): −80.0 to −80.7 (1F), −81.8 (3F), −82.4 ( 3F), -86.2 to -87.0 (1F), -130.1 (2F), -132.2 (1F).
［例１−２］化合物ｃ１１の製造例
オートクレーブ（ニッケル製、内容積３０００ｍＬ）を用意し、オートクレーブのガス出口に、２０℃に保持した冷却器、ＮａＦペレット充填層、および−１０℃に保持した冷却器を直列に設置した。また−１０℃に保持した冷却器から凝集した液をオートクレーブに戻す液体返送ラインを設置した。
[Example 1-2] Production example of compound c11 An autoclave (made of nickel, internal volume 3000 mL) was prepared, and held at a gas outlet of the autoclave at 20 ° C, a cooler maintained at 20 ° C, a NaF pellet packed layer, and -10 ° C. A cooler was installed in series. Moreover, the liquid return line which returns the liquid aggregated from the cooler hold | maintained at -10 degreeC to an autoclave was installed.
オートクレーブにＲ−１１３（１６００ｇ）を加え、２５℃に保持しながら撹拌した。そのままオートクレーブに、窒素ガスを２５℃で１時間吹き込んでから、窒素ガスで２０％体積に希釈したフッ素ガス（以下、２０％フッ素ガスと記す。）を流速１８．３Ｌ／ｈにて１時間吹き込んだ。つぎに２０％フッ素ガスを同じ流速で吹き込みながら、例１−１で得た留分（７９．９ｇ）をＲ−１１３（８００ｇ）に溶解した溶液を２３．２時間かけて注入した。 R-113 (1600 g) was added to the autoclave and stirred while maintaining at 25 ° C. Nitrogen gas was blown into the autoclave as it was at 25 ° C. for 1 hour, and then fluorine gas diluted to 20% volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was blown at a flow rate of 18.3 L / h for 1 hour. It is. Next, 20% fluorine gas was blown at the same flow rate, and a solution obtained by dissolving the fraction (79.9 g) obtained in Example 1-1 in R-113 (800 g) was injected over 23.2 hours.
つぎに、２０％フッ素ガスを同じ流速で吹き込みながらオートクレーブの内圧を０．１５ＭＰａ（ゲージ圧）まで加圧して、ベンゼン濃度が０．０１ｇ／ｍＬのＲ−１１３溶液（５０ｍＬ）を２５℃から４０℃にまで加熱しながら注入し、オートクレーブのベンゼン溶液注入口を閉めた。 Next, 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 an R-113 solution (50 mL) having a benzene concentration of 0.01 g / mL was added at 25 to 40 ° C. The autoclave was injected while heating to 0 ° C., and the autoclave benzene solution inlet was closed.
さらに２０％フッ素ガスを同じ流速で吹き込みながら１時間、撹拌を続けた。つぎに反応器内の圧力を大気圧にして、窒素ガスを１時間、吹き込んだ。オートクレーブの内容物をＮＭＲで分析した結果、化合物ｃ１１（収率９４％）の生成を確認した。化合物ｃ１１のＮＭＲデータを以下に示す。 Further, stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. Next, the pressure in the reactor was set to atmospheric pressure, and nitrogen gas was blown in for 1 hour. As a result of analyzing the contents of the autoclave by NMR, formation of compound c11 (yield 94%) was confirmed. The NMR data of compound c11 are shown below.
１９Ｆ−ＮＭＲ（２８２．６ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）δ（ｐｐｍ）：−７６．６〜−７７．１（１Ｆ），−７９．１〜−８１．３（８Ｆ），−８１．８〜−８２．１（６Ｆ），−８５．１〜−８６．９（３Ｆ），−１１９．２（１Ｆ），−１２３．５〜−１２９．４（４Ｆ），−１３０．１（２Ｆ），−１３２．１（１Ｆ）。 19 F-NMR (282.6 MHz, solvent: CDCl 3 , reference: CFCl 3 ) δ (ppm): −76.6 to −77.1 (1F), −79.1 to −81.3 (8F), -81.8 to -82.1 (6F), -85.1 to -86.9 (3F), -119.2 (1F), -123.5 to -129.4 (4F), -130. 1 (2F), -132.1 (1F).
［例１−３］化合物ａ１１の製造例
温度計および滴下漏斗を備えたフラスコに、例１−２で得た内容物（８９ｇ）およびＮａＦ（１５．１ｇ）を投入して、フラスコ内温を０℃以下に保持しながら撹拌した。内温を１０℃以下に保持して撹拌しながら、滴下漏斗からメタノール（９．７ｇ）を滴下した。滴下終了後、更に２５℃で１時間撹拌した。
[Example 1-3] Production Example of Compound a11 A flask equipped with a thermometer and a dropping funnel was charged with the contents (89 g) and NaF (15.1 g) obtained in Example 1-2, and the temperature inside the flask was adjusted. Stirring was performed while maintaining the temperature below 0 ° C. While maintaining the internal temperature at 10 ° C. or lower and stirring, methanol (9.7 g) was added dropwise from the dropping funnel. After completion of dropping, the mixture was further stirred at 25 ° C. for 1 hour.
つぎにフラスコ内溶液を加圧ろ過して得たろ液を、飽和炭酸水素ナトリウム水溶液で２回、飽和食塩水で２回、イオン交換水で１回ずつ洗浄した。さらに硫酸マグネシウム粉末で脱水してからエバポレーターで濃縮して粗生成物を得た。この粗生成物を減圧蒸留して６６．０℃／１６．０ｋＰａ（絶対圧）の留分（３５．９ｇ）を得た。 Next, the filtrate obtained by pressure filtration of the solution in the flask was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with a saturated saline solution, and once with ion-exchanged water. Furthermore, it dehydrated with magnesium sulfate powder and then concentrated with an evaporator to obtain a crude product. This crude product was distilled under reduced pressure to obtain a fraction (35.9 g) of 66.0 ° C./16.0 kPa (absolute pressure).
温度計を備えたフラスコに、この留分およびフェノールフタレインを投入した。つぎに１０質量％の水酸化ナトリウムメタノール溶液（２９ｇ）をフラスコに滴下して、赤色に呈色した溶液を得た。溶液をエバポレーターで濃縮してから、８０℃で１６時間乾燥を行い、白色固形物（３５．２ｇ）を得た。 This fraction and phenolphthalein were charged into a flask equipped with a thermometer. Next, a 10% by mass sodium hydroxide methanol solution (29 g) was dropped into the flask to obtain a red colored solution. The solution was concentrated by an evaporator and then dried at 80 ° C. for 16 hours to obtain a white solid (35.2 g).
塔頂部からドライアイストラップと液体窒素で冷却したトラップを順に備えたフラスコに、白色固形物（３４．９ｇ）を投入しフラスコ内を減圧して３５０℃まで加熱すると、それぞれのトラップに液体が留出した。 When a white solid (34.9 g) is put into a flask equipped with a dry ice strap and a trap cooled with liquid nitrogen in this order from the top of the tower, the flask is depressurized and heated to 350 ° C., and the liquid remains in each trap. I put it out.
ドライアイストラップに留出した液体（２６．０ｇ）を、スピニングバンド蒸留装置を用いて蒸留し、８８．３℃／１０１．３ｋＰａ（絶対圧）の留分（１４．０ｇ）を得た。留分を分析した結果、化合物ａ１１の生成を確認した（純度９９．１％、収率５８％）。化合物ａ１１のＮＭＲデータを以下に示す。 The liquid (26.0 g) distilled to the dry eye strap was distilled using a spinning band distillation apparatus to obtain a fraction (14.0 g) of 88.3 ° C./101.3 kPa (absolute pressure). As a result of analyzing the fraction, it was confirmed that Compound a11 was produced (purity 99.1%, yield 58%). The NMR data of compound a11 are shown below.
１９Ｆ−ＮＭＲ（２８２．６ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）δ（ｐｐｍ）：−６８．２（３Ｆ），−８１．２（３Ｆ），−８１．４〜−８２．０（１Ｆ），−８８．２〜−８８．７（１Ｆ），−１２３．７〜−１２５．３（１Ｆ），−１２６．３（１Ｆ），−１２７．８〜−１２８．９（１Ｆ），−１８７．２（１Ｆ）。 19 F-NMR (282.6 MHz, solvent: CDCl 3 , standard: CFCl 3 ) δ (ppm): −68.2 (3F), −81.2 (3F), −81.4 to −82.0 ( 1F), −88.2 to −88.7 (1F), −123.7 to −125.3 (1F), −126.3 (1F), −127.8 to −128.9 (1F), -187.2 (1F).
［例２］化合物ａ１１の重合例
［例２−１］化合物ａ１１の重合例（その１）
オートクレーブ（ハステロイ製、内容積３０ｍＬ）に、ペルフルオロ過酸化ベンゾイル（２１．９ｍｇ）、化合物（ａ１１）（４．０ｇ）およびＲ−２２５ｃｂ（２．５８ｇ）を仕込み、液体窒素による冷却下でオートクレーブ内を充分に脱気した。
[Example 2] Polymerization example of compound a11 [Example 2-1] Polymerization example of compound a11 (Part 1)
An autoclave (manufactured by Hastelloy, internal volume 30 mL) was charged with benzoyl peroxide (21.9 mg), compound (a11) (4.0 g) and R-225cb (2.58 g), and the autoclave was cooled with liquid nitrogen. Was fully degassed.
つぎに、減圧下のオートクレーブにＴＦＥ（０．５ｇ）を導入して８０℃に昇温して重合を開始した。オートクレーブの内圧は０．２５ＭＰａ（ゲージ圧）を示し、重合中はその圧力を一定に保持した。そのままオートクレーブ内を５時間、撹拌し、オートクレーブ内のガスをパージして重合反応を終了させた。 Next, TFE (0.5 g) was introduced into the autoclave under reduced pressure, and the temperature was raised to 80 ° C. to initiate polymerization. The internal pressure of the autoclave was 0.25 MPa (gauge pressure), and the pressure was kept constant during the polymerization. The autoclave was stirred as it was for 5 hours, and the gas in the autoclave was purged to complete the polymerization reaction.
Ｒ−２２５ｃｂで希釈したオートクレーブ内容物をｎ−ヘキサン中に添加し、凝集した粗重合体をろ過により回収した。粗重合体をＲ−２２５ｃｂ中で撹拌してから、再度、ｎ−ヘキサン中に添加して凝集した重合体を回収し、８０℃にて、１２時間、減圧乾燥して化合物ａ１１が重合したモノマー単位とＴＦＥが重合したモノマー単位を含む重合体Ａ１１（０．１５ｇ）を得た。 The autoclave content diluted with R-225cb was added to n-hexane, and the aggregated crude polymer was recovered by filtration. After stirring the crude polymer in R-225cb, it was added again to n-hexane to recover the aggregated polymer, and the polymer unit was polymerized by drying under reduced pressure at 80 ° C. for 12 hours. And Polymer A11 (0.15 g) containing a monomer unit obtained by polymerizing TFE.
フローテスタ（島津製作所社製、ＣＦＴ−５００Ａ）とノズル（長さ１ｍｍ、内径１ｍｍ）を用い、３０ｋｇ／ｃｍ２の押出し圧力の条件で重合体Ａ１１の溶融押出し試験を行った結果、重合体Ａ１１が溶融し始めた温度は２００℃であった。溶融１９Ｆ−ＮＭＲより求めた重合体Ａ１１中の全単位に対する化合物ａ１１に基づく単位の割合は１１．０モル％であった。 As a result of conducting a melt-extrusion test of polymer A11 using a flow tester (manufactured by Shimadzu Corporation, CFT-500A) and a nozzle (length: 1 mm, inner diameter: 1 mm) under an extrusion pressure of 30 kg / cm 2 , polymer A11 The temperature at which it started to melt was 200 ° C. The ratio of the unit based on compound a11 to the total unit in polymer A11 determined by melting 19 F-NMR was 11.0 mol%.
［例２−２］化合物ａ１１の重合例（その２）
オートクレーブ（ハステロイ製、内容積３０ｍＬ）に、ペルフルオロ過酸化ベンゾイル（３２．２ｍｇ）および化合物ａ１１（１４．４７ｇ）を仕込み、液体窒素による冷却下でオートクレーブ内を充分に脱気した。
[Example 2-2] Polymerization example of compound a11 (part 2)
Perfluorobenzoyl peroxide (32.2 mg) and compound a11 (14.47 g) were charged into an autoclave (manufactured by Hastelloy, internal volume 30 mL), and the inside of the autoclave was sufficiently deaerated under cooling with liquid nitrogen.
つぎに、減圧下のオートクレーブにＴＦＥ（０．６１ｇ）を導入して８０℃に昇温して重合を開始した。オートクレーブの内圧は０．１８ＭＰａ（ゲージ圧）を示し、重合中はその圧力を一定に保持した。そのままオートクレーブ内を６．６時間、撹拌し、オートクレーブ内のガスをパージして重合反応を終了させた。 Next, TFE (0.61 g) was introduced into the autoclave under reduced pressure, and the temperature was raised to 80 ° C. to initiate polymerization. The internal pressure of the autoclave was 0.18 MPa (gauge pressure), and the pressure was kept constant during the polymerization. The autoclave was stirred for 6.6 hours as it was, and the gas in the autoclave was purged to complete the polymerization reaction.
Ｒ−２２５ｃｂで希釈したオートクレーブ内容物をｎ−ヘキサン中に添加し、凝集した粗重合体をろ過により回収した。粗重合体をＲ−２２５ｃｂ中で撹拌してから、再度、ｎ−ヘキサン中に添加して凝集した重合体を回収し、８０℃にて、１２時間、減圧乾燥して化合物ａ１１が重合したモノマー単位とＴＦＥが重合したモノマー単位を含む重合体Ａ１２（０．１３ｇ）を得た。 The autoclave content diluted with R-225cb was added to n-hexane, and the aggregated crude polymer was recovered by filtration. After stirring the crude polymer in R-225cb, it was added again to n-hexane to recover the aggregated polymer, and the polymer unit was polymerized by drying under reduced pressure at 80 ° C. for 12 hours. And Polymer A12 (0.13 g) containing monomer units obtained by polymerizing TFE were obtained.
例２−１と同様の方法を用いて 重合体Ａ１２の溶融押出し試験を行った結果、重合体Ａ１２が溶融し始めた温度は１５０℃であった。溶融１９Ｆ−ＮＭＲより求めた重合体Ａ１２中の全単位に対する化合物ａ１１に基づく単位の割合は１７モル％であった。 As a result of conducting a melt extrusion test of the polymer A12 using the same method as in Example 2-1, the temperature at which the polymer A12 began to melt was 150 ° C. The ratio of the unit based on the compound a11 to the total unit in the polymer A12 determined by melting 19 F-NMR was 17 mol%.
［例３］化合物ａ１２の製造例 [Example 3] Production example of compound a12
［例３−１］化合物ｄ１２の製造例
温度計、滴下ロート、および撹拌機を備えたフラスコを氷浴下で冷却し、化合物ｅ２１（１０４ｇ）、ＮａＦ（７０．１ｇ）およびＲ−２２５（３００ｇ）を投入した。つぎにフラスコの内温を１０℃以下に保持しながら、式Ｒｆ−ＣＯＦで表される化合物（２４５ｇ）を滴下しながらフラスコ内を撹拌した。つづいて内温を２５℃にして、さらに１２時間撹拌した。
Example 3-1 Production Example of Compound d12 A flask equipped with a thermometer, a dropping funnel, and a stirrer was cooled in an ice bath, and compound e21 (104 g), NaF (70.1 g) and R-225 (300 g) were cooled. ). Next, the inside of the flask was stirred while dropping the compound represented by the formula R f —COF (245 g) while maintaining the internal temperature of the flask at 10 ° C. or lower. Subsequently, the internal temperature was set to 25 ° C., and the mixture was further stirred for 12 hours.
フラスコ内容液を加圧ろ過して得たろ液を濃縮して、Ｒ−２２５と未反応の化合物（ｅ２１）を除去した濃縮液を得た。濃縮液をＲ−２２５で希釈して、飽和炭酸水素ナトリウム水溶液で３回、イオン交換水で３回ずつ、順に洗浄した。 The filtrate obtained by pressure filtration of the flask contents was concentrated to obtain a concentrate from which R-225 and unreacted compound (e21) were removed. The concentrated solution was diluted with R-225, and washed successively with a saturated aqueous sodium hydrogen carbonate solution three times and with ion-exchanged water three times.
つづいて濃縮液を硫酸マグネシウム粉末で脱水してから、エバポレーターで濃縮して粗生成物を得た。粗生成物を減圧蒸留して、８６℃／０．３ｋＰａ（絶対圧）の留分（１２８．９ｇ）を得た。留分を分析した結果、標記化合物（純度９８．９％、収率５６．９％）の生成を確認した。化合物ｄ１２のＮＭＲデータを以下に示す。 Subsequently, the concentrated solution was dehydrated with magnesium sulfate powder and then concentrated by an evaporator to obtain a crude product. The crude product was distilled under reduced pressure to obtain a fraction (128.9 g) of 86 ° C./0.3 kPa (absolute pressure). As a result of analyzing the fraction, it was confirmed that the title compound (purity 98.9%, yield 56.9%) was produced. The NMR data of compound d12 are shown below.
１Ｈ−ＮＭＲ（３００．４ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＴＭＳ）δ（ｐｐｍ）：１．５８（３Ｈ），３．２５（３Ｈ），４．０４〜４．１１（３Ｈ），４．２０〜４．５６（３Ｈ），５．１７〜５．２９（２Ｈ），５．８０〜６．００（１Ｈ）。
１９Ｆ−ＮＭＲ（２８２．６ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）δ（ｐｐｍ）：−８０．０〜−８０．７（１Ｆ），−８１．８（３Ｆ），−８２．５（３Ｆ），−８６．４〜−８６．９（１Ｆ），−１３０．１（２Ｆ），−１３２．２（１Ｆ）。
1 H-NMR (300.4 MHz, solvent: CDCl 3 , standard: TMS) δ (ppm): 1.58 (3H), 3.25 (3H), 4.04 to 4.11 (3H), 4. 20-4.56 (3H), 5.17-5.29 (2H), 5.80-6.00 (1H).
19 F-NMR (282.6 MHz, solvent: CDCl 3 , standard: CFCl 3 ) δ (ppm): −80.0 to −80.7 (1F), −81.8 (3F), −82.5 ( 3F), -86.4 to -86.9 (1F), -130.1 (2F), -132.2 (1F).
［例３−２］化合物ｃ１２の製造例
オートクレーブ（ニッケル製、内容積３０００ｍＬ）を用意し、オートクレーブのガス出口に、２０℃に保持した冷却器、ＮａＦペレット充填層、および−１０℃に保持した冷却器を直列に設置した。また−１０℃に保持した冷却器から凝集した液をオートクレーブに戻す液体返送ラインを設置した。
[Example 3-2] Production example of compound c12 An autoclave (made of nickel, internal volume 3000 mL) was prepared, and held at a gas outlet of the autoclave at 20 ° C, a cooler maintained at 20 ° C, a NaF pellet packed layer, and -10 ° C. A cooler was installed in series. Moreover, the liquid return line which returns the liquid aggregated from the cooler hold | maintained at -10 degreeC to an autoclave was installed.
オートクレーブにＲ−１１３（１６００ｇ）を加え、２５℃に保持しながら撹拌した。そのままオートクレーブに、窒素ガスを２５℃で１時間吹き込んでから、２０％フッ素ガスを流速２３．０Ｌ／ｈにて１時間吹き込んだ。つぎに２０％フッ素ガスを同じ流速で吹き込みながら、例４−１で得た留分（７０．４ｇ）をＲ−１１３（５６０ｇ）に溶解した溶液を１６．６時間かけて注入した。 R-113 (1600 g) was added to the autoclave and stirred while maintaining at 25 ° C. Nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour as it was, and then 20% fluorine gas was blown at a flow rate of 23.0 L / h for 1 hour. Next, a solution obtained by dissolving the fraction (70.4 g) obtained in Example 4-1 in R-113 (560 g) was injected over 16.6 hours while blowing 20% fluorine gas at the same flow rate.
つぎに、２０％フッ素ガスを同じ流速で吹き込みながらオートクレーブの内圧を０．１５ＭＰａ（ゲージ圧）まで加圧して、ベンゼン濃度が０．０１ｇ／ｍＬのＲ−１１３溶液（３８ｍＬ）を２５℃から４０℃にまで加熱しながら注入し、オートクレーブのベンゼン溶液注入口を閉めた。 Next, 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 an R-113 solution (38 mL) having a benzene concentration of 0.01 g / mL was increased from 25 ° C. to 40 ° C. The autoclave was injected while heating to 0 ° C., and the autoclave benzene solution inlet was closed.
さらに２０％フッ素ガスを同じ流速で吹き込みながら１時間、撹拌を続けた。つぎに反応器内の圧力を大気圧にして、窒素ガスを１時間、吹き込んだ。オートクレーブの内容物をＮＭＲで分析した結果、化合物ｃ１２（収率８９％）の生成を確認した。化合物ｃ１２のＮＭＲデータを以下に示す。 Further, stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. Next, the pressure in the reactor was set to atmospheric pressure, and nitrogen gas was blown in for 1 hour. As a result of analyzing the contents of the autoclave by NMR, formation of compound c12 (yield 89%) was confirmed. The NMR data of compound c12 are shown below.
１９Ｆ−ＮＭＲ（２８２．６ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）δ（ｐｐｍ）：−７７．５〜−７８．０（１Ｆ），−７９．７〜−８１．６（５Ｆ），−８２．０〜−８２．５（１１Ｆ），−８４．５〜−８７．５（５Ｆ），−１２２．９（１Ｆ），−１３０．３（４Ｆ），−１３２．１（１Ｆ）。 19 F-NMR (282.6 MHz, solvent: CDCl 3 , reference: CFCl 3 ) δ (ppm): −77.5 to −78.0 (1F), −79.7 to −81.6 (5F), -82.0 to -82.5 (11F), -84.5 to -87.5 (5F), -122.9 (1F), -130.3 (4F), -132.1 (1F).
［例３−３］化合物ａ１２の製造例
温度計および滴下漏斗を備えたフラスコに、例３−２で得た内容物（３５．１ｇ）およびＮａＦ（４．０ｇ）を投入して、フラスコ内温を０℃以下に保持しながら撹拌した。内温を１０℃以下に保持して撹拌しながら、滴下漏斗からメタノール（５．３ｇ）を滴下した。滴下終了後、更に２５℃で１時間撹拌した。
[Example 3-3] Production example of compound a12 To a flask equipped with a thermometer and a dropping funnel, the contents (35.1 g) and NaF (4.0 g) obtained in Example 3-2 were charged, Stirring while maintaining the temperature below 0 ° C. While maintaining the internal temperature at 10 ° C. or lower and stirring, methanol (5.3 g) was added dropwise from the dropping funnel. After completion of dropping, the mixture was further stirred at 25 ° C. for 1 hour.
つぎにフラスコ内溶液を加圧ろ過して得たろ液を、飽和炭酸水素ナトリウム水溶液で２回、飽和食塩水で２回、イオン交換水で１回ずつ洗浄した。さらに硫酸マグネシウム粉末で脱水してからエバポレーターで濃縮して粗生成物を得た。この粗生成物を減圧蒸留して６１℃／２．６７ｋＰａ（絶対圧）の留分（８．７ｇ）を得た。 Next, the filtrate obtained by pressure filtration of the solution in the flask was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with a saturated saline solution, and once with ion-exchanged water. Furthermore, it dehydrated with magnesium sulfate powder and then concentrated with an evaporator to obtain a crude product. This crude product was distilled under reduced pressure to obtain a fraction (8.7 g) of 61 ° C./2.67 kPa (absolute pressure).
温度計を備えたフラスコに、この留分およびフェノールフタレインを投入した。つぎに１０質量％の水酸化ナトリウムメタノール溶液（８．３ｇ）をフラスコに滴下して、赤色に呈色した溶液を得た。溶液をエバポレーターで濃縮してから、８０℃で１６時間乾燥を行い、白色固形物（１０．４ｇ）を得た。 This fraction and phenolphthalein were charged into a flask equipped with a thermometer. Next, a 10% by mass sodium hydroxide methanol solution (8.3 g) was dropped into the flask to obtain a red colored solution. The solution was concentrated with an evaporator and then dried at 80 ° C. for 16 hours to obtain a white solid (10.4 g).
塔頂部からドライアイストラップと液体窒素で冷却したトラップを順に備えたフラスコに、白色固形物（９．５ｇ）を投入しフラスコ内を減圧して３５０℃まで加熱するとトラップに化合物ａ１２（ＧＣ純度２７．５％）とペルフルオロ（２−メチレン−４−メチル−１，３−ジオキソラン）（ＧＣ純度５５．８％）を含む粗液（３．２７ｇ）を得た。化合物ａ１２のＮＭＲデータを以下に示す。 A white solid (9.5 g) was charged into a flask equipped with a dry ice trap and a trap cooled with liquid nitrogen in this order from the top of the column, and when the pressure inside the flask was reduced to 350 ° C. and heated to 350 ° C., compound a12 (GC purity 27 0.5%) and a crude liquid (3.27 g) containing perfluoro (2-methylene-4-methyl-1,3-dioxolane) (GC purity 55.8%). The NMR data of compound a12 are shown below.
１９Ｆ−ＮＭＲ（２８２．６ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ヘキサフルオロベンゼン）δ（ｐｐｍ）：−８０．５〜−８０．６（３Ｆ），−８１．７（３Ｆ），−８６．２〜−８６．３（２Ｆ），−８７．７〜−８８．９（２Ｆ），−１２９．０（１Ｆ），−１３０．０（２Ｆ），−１３０．３〜−１３１．０（１Ｆ）。 19 F-NMR (282.6 MHz, solvent: CDCl 3 , standard: hexafluorobenzene) δ (ppm): −80.5 to −80.6 (3F), −81.7 (3F), −86.2 ~ -86.3 (2F), -87.7 to -88.9 (2F), -129.0 (1F), -130.0 (2F), -130.3 to -131.0 (1F) .
本発明の化合物ａは、重合性の化合物として有用である。本発明の化合物が重合したモノマー単位を含む含フッ素重合体は、光学材料、電子材料、撥水撥油材料、イオン交換膜用材料、固体高分子型燃料電池用電解質材料等として有用である。
The compound a of the present invention is useful as a polymerizable compound. The fluorine-containing polymer containing a monomer unit obtained by polymerizing the compound of the present invention is useful as an optical material, an electronic material, a water / oil repellent material, an ion exchange membrane material, an electrolyte material for a polymer electrolyte fuel cell, and the like.
Claims (2)
A fluorine-containing polymer containing a monomer unit obtained by polymerizing a compound represented by the following formula (a).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007136948A3 (en) * | 2006-05-19 | 2008-01-24 | 3M Innovative Properties Co | Cyclic hydrofluoroether compounds and processes for their preparation and use |
| US8193397B2 (en) | 2006-12-06 | 2012-06-05 | 3M Innovative Properties Company | Hydrofluoroether compounds and processes for their preparation and use |
| EP2436705A4 (en) * | 2009-05-29 | 2013-10-09 | Asahi Glass Co Ltd | Electrolyte material, liquid composite, and membrane electrode assembly for solid polymer fuel cells |
| WO2021141062A1 (en) * | 2020-01-08 | 2021-07-15 | ダイキン工業株式会社 | Insulating film or dielectric film |
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| JPH05213929A (en) * | 1992-01-31 | 1993-08-24 | Asahi Glass Co Ltd | Fluorine-containing compound and its production |
| WO2003037885A1 (en) * | 2001-10-30 | 2003-05-08 | Asahi Glass Company, Limited | Fluorosulfonyl compounds and process for production of compounds derived therefrom |
| WO2004097851A1 (en) * | 2003-04-28 | 2004-11-11 | Asahi Glass Company Limited | Solid polymeric electrolyte material, process for producing the same and membrane/electrode assembly for solid polymer fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05213929A (en) * | 1992-01-31 | 1993-08-24 | Asahi Glass Co Ltd | Fluorine-containing compound and its production |
| WO2003037885A1 (en) * | 2001-10-30 | 2003-05-08 | Asahi Glass Company, Limited | Fluorosulfonyl compounds and process for production of compounds derived therefrom |
| WO2004097851A1 (en) * | 2003-04-28 | 2004-11-11 | Asahi Glass Company Limited | Solid polymeric electrolyte material, process for producing the same and membrane/electrode assembly for solid polymer fuel cell |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007136948A3 (en) * | 2006-05-19 | 2008-01-24 | 3M Innovative Properties Co | Cyclic hydrofluoroether compounds and processes for their preparation and use |
| US8791254B2 (en) | 2006-05-19 | 2014-07-29 | 3M Innovative Properties Company | Cyclic hydrofluoroether compounds and processes for their preparation and use |
| US8193397B2 (en) | 2006-12-06 | 2012-06-05 | 3M Innovative Properties Company | Hydrofluoroether compounds and processes for their preparation and use |
| EP2436705A4 (en) * | 2009-05-29 | 2013-10-09 | Asahi Glass Co Ltd | Electrolyte material, liquid composite, and membrane electrode assembly for solid polymer fuel cells |
| US9508463B2 (en) | 2009-05-29 | 2016-11-29 | Asahi Glass Company, Limited | Electrolyte material, liquid composition and membrane/electrode assembly for polymer electrolyte fuel cell |
| WO2021141062A1 (en) * | 2020-01-08 | 2021-07-15 | ダイキン工業株式会社 | Insulating film or dielectric film |
| JP2021111631A (en) * | 2020-01-08 | 2021-08-02 | ダイキン工業株式会社 | Insulating film or dielectric film |
| JP7196208B2 (en) | 2020-01-08 | 2022-12-26 | ダイキン工業株式会社 | insulating film or dielectric film |
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