JP2009190970A - Method for producing acid fluoride having fluorosulfonyl group - Google Patents
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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Abstract
Description
本発明は、フルオロスルホニル基を有する酸フロリドの製造方法に関する。 The present invention relates to a method for producing an acid fluoride having a fluorosulfonyl group.
FOC−CF2−SO2Fに代表されるフルオロスルホニル基を有する酸フロリドは、種々の機能性材料、その原材料として有用である。
たとえば、FOC−CF2−SO2Fとヘキサフルオロプロピレンオキシドを反応させて得られた下式(pm)で表される化合物を適切に熱分解反応させることにより、機能性重合体(イオン交換膜、固体高分子電解質、分離膜、酸触媒等。)を製造するための単量体として有用な下式(m)で表される化合物を製造できる(ただし、nは0〜2の整数を示す。)。
FOCCF(CF3)(OCF2CF(CF3))nOCF2CF2SO2F (pm)、
CF2=CF(OCF2CF(CF3))nOCF2CF2SO2F (m)。
An acid fluoride having a fluorosulfonyl group typified by FOC—CF 2 —SO 2 F is useful as various functional materials and raw materials thereof.
For example, a functional polymer (ion exchange membrane) is obtained by appropriately thermally decomposing a compound represented by the following formula (pm) obtained by reacting FOC-CF 2 —SO 2 F with hexafluoropropylene oxide. , A solid polymer electrolyte, a separation membrane, an acid catalyst, etc.) can be produced as a monomer for producing a compound represented by the following formula (m) (where n represents an integer of 0 to 2). .)
FOCCF (CF 3 ) (OCF 2 CF (CF 3 )) n OCF 2 CF 2 SO 2 F (pm),
CF 2 = CF (OCF 2 CF (CF 3)) n OCF 2 CF 2 SO 2 F (m).
FOC−CF2−SO2Fの製造方法としては、下式(1F)で表される化合物の液体をNaFに接触させる方法(非特許文献1参照。)、および下式(11)で表される化合物の液体を極性溶媒中のKFに接触させる方法(特許文献1参照。)が知られている。 As a method for producing FOC-CF 2 -SO 2 F, a method (see Non-Patent Document 1.) Contacting a liquid compound represented by the following formula (1 F) to NaF, and the following equation (1 1) A method of contacting a liquid of a compound represented with KF in a polar solvent (see Patent Document 1) is known.
しかし、特許文献1および非特許文献1いずれの方法も、高純度のFOC−CF2−SO2Fを製造するためには、蒸留精製等の後処理工程が必要がある。そのため、FOC−CF2−SO2Fに代表されるフルオロスルホニル基を有する酸フロリドを高純度、高収率かつ簡便に製造する方法が求められている。 However, both methods of Patent Document 1 and Non-Patent Document 1 require post-treatment steps such as distillation purification in order to produce high-purity FOC—CF 2 —SO 2 F. Therefore, a method for easily producing an acid fluoride having a fluorosulfonyl group typified by FOC—CF 2 —SO 2 F with high purity and high yield is demanded.
本発明者らは、鋭意検討の結果、含フッ素環状スルホン酸エステルの気体をアルカリ金属フッ化物に接触させた場合には、フルオロスルホニル基を有する酸フロリドを高純度、高収率かつ簡便に製造できるという知見を得た。 As a result of intensive studies, the inventors of the present invention can easily produce an acid fluoride having a fluorosulfonyl group with high purity and high yield when the fluorine-containing cyclic sulfonate gas is brought into contact with an alkali metal fluoride. I got the knowledge that I can do it.
すなわち、本発明は下記の発明を提供する。
[1] 下式(1)で表される化合物の気体を金属フッ化物に接触させることを特徴とする下式(2)で表される化合物の製造方法。
That is, the present invention provides the following inventions.
[1] A process for producing a compound represented by the following formula (2), wherein a gas of the compound represented by the following formula (1) is brought into contact with a metal fluoride.
ただし、式中の記号は下記の意味を示す。
それぞれ独立に、ポリフルオロアルキル基、ポリフルオロ(アルコキシアルキル)基、ポリフルオロアルコキシ基、ポリフルオロ(アルコキシアルコキシ)基、ポリフルオロ(フルオロスルホニルアルキル)基、ポリフルオロ(フルオロスルホニルアルコキシアルキル)基、ポリフルオロ(フルオロスルホニルアルコキシ)基およびポリフルオロ(フルオロスルホニルアルコキシアルコキシ)基からなる群から選ばれる基であって炭素数1〜10の基(A)、フルオロスルホニル基、水素原子、またはハロゲン原子。
Q:単結合または炭素数1〜6のポリフルオロアルキレン基。
However, the symbol in a formula shows the following meaning.
Each independently a polyfluoroalkyl group, a polyfluoro (alkoxyalkyl) group, a polyfluoroalkoxy group, a polyfluoro (alkoxyalkoxy) group, a polyfluoro (fluorosulfonylalkyl) group, a polyfluoro (fluorosulfonylalkoxyalkyl) group, a poly A group selected from the group consisting of a fluoro (fluorosulfonylalkoxy) group and a polyfluoro (fluorosulfonylalkoxyalkoxy) group, a group (A) having 1 to 10 carbon atoms, a fluorosulfonyl group, a hydrogen atom, or a halogen atom;
Q: A single bond or a polyfluoroalkylene group having 1 to 6 carbon atoms.
[2] 式(1)で表される化合物の気体を、金属フッ化物が充填された反応器に流通させることにより、金属フッ化物に接触させる[1]に記載の製造方法。
[3] 式(1)で表される化合物の気体を金属フッ化物に接触させる温度が、式(1)で表される化合物の沸点以上である[1]または[2]に記載の製造方法。
[2] The production method according to [1], wherein the gas of the compound represented by the formula (1) is brought into contact with the metal fluoride by flowing through the reactor filled with the metal fluoride.
[3] The production method according to [1] or [2], wherein the temperature at which the gas of the compound represented by formula (1) is brought into contact with the metal fluoride is equal to or higher than the boiling point of the compound represented by formula (1). .
[4] 式(1)で表される化合物が下式(11)で表される化合物であり式(2)で表される化合物が式(21)で表される化合物である[1]〜[3]のいずれかに記載の製造方法。 [4] The compound represented by the formula (1) is a compound represented by the following formula (11), and the compound represented by the formula (2) is a compound represented by the formula (21) [1] to [1] [3] The production method according to any one of [3].
ただし、式中の記号は下記の意味を示す。
Y1:それぞれ独立に、ペルフルオロアルキル基、ペルフルオロアルコキシ基、ペルフルオロ(フルオロスルホニルアルキル)基、ペルフルオロ(フルオロスルホニルアルコキシアルキル)基、ペルフルオロ(フルオロスルホニルアルコキシ)基およびペルフルオロ(フルオロスルホニルアルコキシアルコキシ)基からなる群から選ばれる基であって炭素数1〜5の基(A1)、またはハロゲン原子。
However, the symbol in a formula shows the following meaning.
Y 1 : each independently comprises a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoro (fluorosulfonylalkyl) group, a perfluoro (fluorosulfonylalkoxyalkyl) group, a perfluoro (fluorosulfonylalkoxy) group, and a perfluoro (fluorosulfonylalkoxyalkoxy) group A group selected from the group, a group having 1 to 5 carbon atoms (A1), or a halogen atom;
[5] 金属フッ化物が、アルカリ金属フッ化物である[1]〜[4]のいずれかに記載の製造方法。 [5] The production method according to any one of [1] to [4], wherein the metal fluoride is an alkali metal fluoride.
本発明によれば、含フッ素環状スルホン酸エステルからフルオロスルホニル基を有する酸フロリドを高純度、高収率かつ簡便に製造する方法が提供される。 According to the present invention, there is provided a method for easily producing an acid fluoride having a fluorosulfonyl group from a fluorine-containing cyclic sulfonic acid ester with high purity and high yield.
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。他の式で表される化合物も同様に記す。また、基中の記号は特に記載しない限り前記と同義である。 In the present specification, a compound represented by the formula (a) is referred to as a compound (a). The same applies to compounds represented by other formulas. Further, symbols in the group are as defined above unless otherwise specified.
本発明は、下記化合物(1)の気体を金属フッ化物に接触させる下記化合物(2)の製造方法を提供する。 This invention provides the manufacturing method of the following compound (2) which makes the gas of the following compound (1) contact metal fluoride.
XおよびYは、それぞれ独立に、ポリフルオロアルキル基、ポリフルオロ(アルコキシアルキル)基、ポリフルオロアルコキシ基、ポリフルオロ(アルコキシアルコキシ)基、ポリフルオロ(フルオロスルホニルアルキル)基、ポリフルオロ(フルオロスルホニルアルコキシアルキル)基、ポリフルオロ(フルオロスルホニルアルコキシ)基およびポリフルオロ(フルオロスルホニルアルコキシアルコキシ)基からなる群から選ばれる基であって炭素数1〜10の基(A)、フルオロスルホニル基、またはハロゲン原子が好ましく、調製のしやすさの観点から、ペルフルオロアルキル基、ペルフルオロアルコキシ基、ペルフルオロ(フルオロスルホニルアルキル)基、ペルフルオロ(フルオロスルホニルアルコキシアルキル)基、ペルフルオロ(フルオロスルホニルアルコキシ)基およびペルフルオロ(フルオロスルホニルアルコキシアルコキシ)基からなる群から選ばれる基であって炭素数1〜5の基(A1)、またはハロゲン原子がより好ましい。ハロゲン原子は、フッ素原子、塩素原子、または臭素原子が好ましく、フッ素原子または塩素原子がより好ましく、フッ素原子が特に好ましい。 X and Y are each independently a polyfluoroalkyl group, polyfluoro (alkoxyalkyl) group, polyfluoroalkoxy group, polyfluoro (alkoxyalkoxy) group, polyfluoro (fluorosulfonylalkyl) group, polyfluoro (fluorosulfonylalkoxy) Alkyl) group, polyfluoro (fluorosulfonylalkoxy) group and polyfluoro (fluorosulfonylalkoxyalkoxy) group, which is a group selected from the group consisting of 1 to 10 carbon atoms (A), fluorosulfonyl group, or halogen atom From the viewpoint of ease of preparation, perfluoroalkyl group, perfluoroalkoxy group, perfluoro (fluorosulfonylalkyl) group, perfluoro (fluorosulfonylalkoxyalkyl) group, perfluoro (Fluorosulfonyl alkoxy) group and perfluoro (fluorosulfonyl alkoxyalkoxy) a group selected from group consisting of group group of 1 to 5 carbon atoms (A1), or halogen atom is more preferable. The halogen atom is preferably a fluorine atom, a chlorine atom, or a bromine atom, more preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.
さらにXおよびYは、それぞれ独立に、ペルフルオロアルキル基、ペルフルオロアルコキシ基、ペルフルオロ(フルオロスルホニルアルキル)基およびペルフルオロ(フルオロスルホニルアルコキシアルキル)基からなる群から選ばれる基であって炭素数1〜5の基(A2)、フッ素原子または塩素原子が特に好ましい。 X and Y are each independently a group selected from the group consisting of a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoro (fluorosulfonylalkyl) group, and a perfluoro (fluorosulfonylalkoxyalkyl) group, and having 1 to 5 carbon atoms The group (A2), fluorine atom or chlorine atom is particularly preferred.
XおよびYは、Xがフッ素原子であり、かつYが基(A)、フルオロスルホニル基、フッ素原子または塩素原子であるのが好ましく、Xがフッ素原子であり、かつYが基(A1)、フッ素原子または塩素原子であるのがより好ましく、Xがフッ素原子であり、かつYが基(A2)またはフッ素原子であるのが特に好ましい。 X and Y are preferably such that X is a fluorine atom and Y is a group (A), a fluorosulfonyl group, a fluorine atom or a chlorine atom, X is a fluorine atom, and Y is a group (A1), More preferably, they are a fluorine atom or a chlorine atom, It is especially preferable that X is a fluorine atom and Y is a group (A2) or a fluorine atom.
炭素数1〜10のポリフルオロアルキル基の具体例としては、式−(CF2)aFで表される基(ただし、aは1〜5の整数を示す。以下同様。)が挙げられ、より具体的には−CF3が挙げられる。
炭素数1〜10のポリフルオロアルコキシ基の具体例としては、式−O(CF2)aFで表される基が挙げられ、より具体的には−OCF2CF2CF3が挙げられる。
Specific examples of the polyfluoroalkyl group having 1 to 10 carbon atoms include a group represented by the formula-(CF 2 ) a F (where a represents an integer of 1 to 5, and the same shall apply hereinafter). More specifically, —CF 3 may be mentioned.
Specific examples of the polyfluoroalkoxy group having 1 to 10 carbon atoms include a group represented by the formula —O (CF 2 ) a F, and more specifically —OCF 2 CF 2 CF 3 .
炭素数1〜10のポリフルオロ(フルオロスルホニルアルキル)基の具体例としては、式−(CF2)aSO2Fで表される基が挙げられ、より具体的には−CF2SO2F、−CF2CF2SO2F、−CF2CF2CF2SO2F、−CF2CF2CF2SO2Fが挙げられる。
炭素数1〜10のポリフルオロ(フルオロスルホニルアルコキシアルキル)基の具体例としては、式−CF2O(CF2)bSO2Fで表される基(ただし、bは1〜4の整数を示す。)が挙げられ、より具体的には−CF2OCF2CF2SO2Fが挙げられる。
炭素数1〜10のポリフルオロ(フルオロスルホニルアルコキシ)基の具体例としては、式−O(CF2)aSO2Fで表される基が挙げられ、より具体的には−OCF2CF2SO2Fが挙げられる。
炭素数1〜10のポリフルオロ(フルオロスルホニルアルコキシ)基の具体例としては、−OCF2CF(CF3)OCF2CF2SO2Fが挙げられる。
Specific examples of the polyfluoro (fluorosulfonylalkyl) group having 1 to 10 carbon atoms include a group represented by the formula — (CF 2 ) a SO 2 F, and more specifically —CF 2 SO 2 F. , -CF 2 CF 2 SO 2 F , -CF 2 CF 2 CF 2 SO 2 F, are -CF 2 CF 2 CF 2 SO 2 F and the like.
Specific examples of the polyfluoro (fluorosulfonylalkoxyalkyl) group having 1 to 10 carbon atoms include groups represented by the formula —CF 2 O (CF 2 ) b SO 2 F (where b is an integer of 1 to 4). More specifically, —CF 2 OCF 2 CF 2 SO 2 F may be mentioned.
Specific examples of the polyfluoro (fluorosulfonyl alkoxy) group having 1 to 10 carbon atoms, the formula -O (CF 2) a SO 2 include groups represented by F, more specifically -OCF 2 CF 2 SO 2 F is mentioned.
Specific examples of the polyfluoro (fluorosulfonylalkoxy) group having 1 to 10 carbon atoms include —OCF 2 CF (CF 3 ) OCF 2 CF 2 SO 2 F.
Qは、単結合または炭素数1〜6のペルフルオロアルキレン基が好ましく、単結合が特に好ましい。Qが単結合である場合、化合物(1)における−CXY−部分と−CF2−部分は直接結合しており、化合物(2)における−COF部分と−CXY−SO2F部分は直接結合している。 Q is preferably a single bond or a C 1-6 perfluoroalkylene group, particularly preferably a single bond. When Q is a single bond, -CXY- moiety and -CF 2 in compound (1) - moiety is bonded directly, -COF moieties and -CXY-SO 2 F moiety in the compound (2) is directly attached ing.
本発明において、化合物(1)は下記化合物(11)であり化合物(2)は下記化合物(21)であるのが好ましい。ハロゲン原子は、フッ素原子または塩素原子が好ましい。 In the present invention, the compound (1) is preferably the following compound (11), and the compound (2) is preferably the following compound (21). The halogen atom is preferably a fluorine atom or a chlorine atom.
化合物(1)の具体例としては、下記化合物が挙げられる。 Specific examples of the compound (1) include the following compounds.
化合物(2)の具体例としては、下記化合物が挙げられる。
FOC−CF2−SO2F、
FOC−CFCl−SO2F、
FOC−(CF2)2−SO2F、
FOC−(CF2)3−SO2F、
FOC−(CF2)4−SO2F、
FOC−CF(CF3)−SO2F、
FOC−CF(OCF2CF2CF3)−SO2F、
FOC−CF(CF2SO2F)−SO2F、
FOC−CF(CF2CF2SO2F)−SO2F、
FOC−CF(CF2CF2CF2SO2F)−SO2F、
FOC−CF(CF2CF2CF2CF2SO2F)−SO2F、
FOC−CF(CF2OCF2CF2SO2F)−SO2F、
FOC−CF(OCF2CF2SO2F)−SO2F、
FOC−CF(OCF2CF(CF3)OCF2CF2SO2F)−SO2F。
Specific examples of the compound (2) include the following compounds.
FOC-CF 2 -SO 2 F,
FOC-CFCl-SO 2 F,
FOC- (CF 2 ) 2 —SO 2 F,
FOC- (CF 2 ) 3 —SO 2 F,
FOC- (CF 2 ) 4 —SO 2 F,
FOC-CF (CF 3) -SO 2 F,
FOC-CF (OCF 2 CF 2 CF 3) -SO 2 F,
FOC-CF (CF 2 SO 2 F) -SO 2 F,
FOC-CF (CF 2 CF 2 SO 2 F) -SO 2 F,
FOC-CF (CF 2 CF 2 CF 2 SO 2 F) -SO 2 F,
FOC-CF (CF 2 CF 2 CF 2 CF 2 SO 2 F) -SO 2 F,
FOC-CF (CF 2 OCF 2 CF 2 SO 2 F) -SO 2 F,
FOC-CF (OCF 2 CF 2 SO 2 F) -SO 2 F,
FOC-CF (OCF 2 CF ( CF 3) OCF 2 CF 2 SO 2 F) -SO 2 F.
本発明における金属フッ化物は、アルカリ金属フッ化物が好ましく、フッ化リチウム、フッ化ナトリウム、フッ化カリウムまたはフッ化セシウムがより好ましく、フッ化ナトリウムまたはフッ化カリウムが特に好ましい。 The metal fluoride in the present invention is preferably an alkali metal fluoride, more preferably lithium fluoride, sodium fluoride, potassium fluoride or cesium fluoride, and particularly preferably sodium fluoride or potassium fluoride.
金属フッ化物の形状は、特に限定されず、ペレット状であってもよく、微粉末状であってもよい。
金属フッ化物の形状は、化合物(1)の気体と均一接触し、かつ固結しにくい観点からは、ペレット状が好ましい。ペレットの形状は、特に限定されず、球状、紡錘状、棒状、筒状のいずれの形状であってもよい。ペレットの径は、1〜20mmが好ましく、2〜5mmが特に好ましい。また金属フッ化物の形状が微粉末状である場合、化合物(1)の気体の接触に伴う金属フッ化物の自発流動による温度分布を抑制する観点から、中心粒度が10〜500μmに分級された微粉末状の金属フッ化物を用いるのが好ましく、中心粒度が50〜200μmに分級された微粉末状の金属フッ化物を用いるのが特に好ましい。
また金属フッ化物は、担体に保持されていてもよい。
The shape of the metal fluoride is not particularly limited, and may be a pellet or a fine powder.
The shape of the metal fluoride is preferably in the form of pellets from the viewpoint of being in uniform contact with the gas of the compound (1) and being hard to consolidate. The shape of the pellet is not particularly limited, and may be any of a spherical shape, a spindle shape, a rod shape, and a cylindrical shape. The diameter of the pellet is preferably 1 to 20 mm, particularly preferably 2 to 5 mm. Further, when the shape of the metal fluoride is fine powder, the fine particle whose particle size is classified to 10 to 500 μm from the viewpoint of suppressing the temperature distribution due to the spontaneous flow of the metal fluoride accompanying the gas contact of the compound (1). It is preferable to use a powdered metal fluoride, and it is particularly preferable to use a fine powdered metal fluoride having a central particle size classified into 50 to 200 μm.
The metal fluoride may be held on a carrier.
本発明において、化合物(1)の気体を調製する方法は、特に限定されず、化合物(1)を化合物(1)の沸点以上の温度に保持して調製する方法が好ましく、化合物(1)の化合物(2)への転化率と反応収率との観点から、化合物(1)を前記温度〜(前記温度+100)℃に保持して調製する方法が特に好ましい。通常、化合物(1)の気体の調製する方法は、化合物(1)を80〜200℃に保持して調製する方法が好ましい。 In the present invention, the method for preparing the gas of the compound (1) is not particularly limited, and a method of preparing the compound (1) by holding it at a temperature equal to or higher than the boiling point of the compound (1) is preferable. From the viewpoint of the conversion rate to the compound (2) and the reaction yield, a method of preparing the compound (1) while maintaining it at the temperature to (the temperature + 100) ° C. is particularly preferable. Usually, the method for preparing the gas of the compound (1) is preferably a method for preparing the compound (1) while maintaining it at 80 to 200 ° C.
化合物(1)の気体を金属フッ化物に接触させるに際しては、化合物(1)の気体を不活性ガスで希釈してから金属フッ化物に接触させるのが好ましい。化合物(1)の気体を不活性ガスで希釈する場合、不活性ガスの量は、化合物(1)と不活性ガスとの総量に対して、40モル%〜95モル%が好ましく、50モル%〜90モル%が特に好ましい。不活性ガスの具体例としては、窒素ガス、ヘリウムガス、アルゴンガスが挙げられる。 When the compound (1) gas is brought into contact with the metal fluoride, the compound (1) gas is preferably diluted with an inert gas and then brought into contact with the metal fluoride. When diluting the gas of the compound (1) with an inert gas, the amount of the inert gas is preferably 40 mol% to 95 mol%, and preferably 50 mol% with respect to the total amount of the compound (1) and the inert gas. -90 mol% is particularly preferred. Specific examples of the inert gas include nitrogen gas, helium gas, and argon gas.
化合物(1)の気体を金属フッ化物に接触させる方法は、特に限定されず、化合物(1)の気体を金属フッ化物が充填された反応器に流通させる方法が好ましく、化合物(1)の気体を金属フッ化物が充填された反応器の下部から流通させて、反応器の上部から化合物(2)を含む生成物を抜き出す方法が特に好ましい。
反応器の形状は、特に限定されず、筒状が好ましい。
化合物(1)の気体の反応器中における金属フッ化物との接触時間は、2〜120秒間が好ましく、10〜60秒間が特に好ましい。
The method of bringing the gas of the compound (1) into contact with the metal fluoride is not particularly limited, and a method of circulating the gas of the compound (1) through the reactor filled with the metal fluoride is preferable, and the gas of the compound (1) Is particularly preferred in that the product containing the compound (2) is withdrawn from the upper part of the reactor by circulating the gas from the lower part of the reactor filled with metal fluoride.
The shape of the reactor is not particularly limited, and a cylindrical shape is preferable.
The contact time of the compound (1) with the metal fluoride in the gas reactor is preferably 2 to 120 seconds, particularly preferably 10 to 60 seconds.
化合物(2)は、反応器から抜き出した、化合物(2)を含む生成物からなるガスを冷却凝集させて回収できる。本発明の製造方法によれば、化合物(2)を高収率、高純度かつ簡便に得られる。 The compound (2) can be recovered by cooling and agglomerating the gas comprising the product containing the compound (2) extracted from the reactor. According to the production method of the present invention, the compound (2) can be easily obtained in high yield, high purity.
本発明の製造方法で得られた化合物(2)は、種々の機能性材料の原材料として有用である。たとえば、本発明の製造方法で得られた化合物(2)と、ヘキサフルオロプロピレンオキシドとを反応させて下記化合物(3)を得て、つぎに化合物(3)を熱分解反応させることにより下記化合物(4)を製造できる。
FOCCF(CF3)−OCF2−Q−CX1Y1−SO2F (3)、
CF2=CF−OCF2−Q−CX1Y1−SO2F (4)。
The compound (2) obtained by the production method of the present invention is useful as a raw material for various functional materials. For example, the following compound (3) is obtained by reacting the compound (2) obtained by the production method of the present invention with hexafluoropropylene oxide, and then the following compound (3) is subjected to a thermal decomposition reaction. (4) can be manufactured.
FOCCF (CF 3) -OCF 2 -Q -CX 1 Y 1 -SO 2 F (3),
CF 2 = CF-OCF 2 -Q -CX 1 Y 1 -SO 2 F (4).
化合物(3)の熱分解反応は、公知の方法(たとえば、Methods of Organic Chemistry(Houben−Weyl),4th ed.,Baasner,B.、Hagemann H.,Tatlow,J.C.,Eds.,Georg Thieme,Stuttgart,1999,Vol.E 10b(Organo−Fluorine Compounds),Pt.1,p.703.および国際公開第02/44138号パンフレットに記載の方法等。)にしたがって実施できる。 The thermal decomposition reaction of the compound (3) can be carried out by a known method (for example, Methods of Organic Chemistry (Houben-Weyl), 4th ed., Baasner, B., Hagemann H., Tatlow, JC, Eds., Georg). Thiem, Stuttgart, 1999, Vol. E 10b (Organo-Fluorine Compounds), Pt. 1, p. 703. and the method described in International Publication No. 02/44138, etc.).
化合物(4)と、たとえば、テトラフルオロエチレンまたはフッ化ビニリデンとを共重合させて得られた重合体は、機能性材料(イオン交換膜、固体高分子電解質、分離膜、酸触媒等。)として有用な材料である。 A polymer obtained by copolymerizing compound (4) with, for example, tetrafluoroethylene or vinylidene fluoride is used as a functional material (ion exchange membrane, solid polymer electrolyte, separation membrane, acid catalyst, etc.). It is a useful material.
以下、本発明を実施例を挙げて具体的に説明するが、これらによって本発明は限定されない。
化合物(1)として下記化合物(11)または下記化合物(12)を、金属フッ化物として径2〜3mmの円筒形に粒状成型されたペレット状のNaFを、用いた。純度は、ガスクロマトグラフィー分析におけるピーク面積比で求めた値を示す。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited by these.
The following compound (1 1 ) or the following compound (1 2 ) was used as the compound (1), and pellet-shaped NaF that was granulated into a cylindrical shape with a diameter of 2 to 3 mm was used as the metal fluoride. Purity shows the value calculated | required by the peak area ratio in a gas chromatography analysis.
[例1]FOC−CF2−SO2Fの製造例
筒状の反応器(内径2.6cm、高さ50cm)にNaF(容積210mL)を充填し、反応器の高さ40cmまでNaFを充填した。反応器を200℃に加熱して反応器内のNaFを乾燥させた。さらに、反応器を200℃に加熱しながら、乾燥窒素ガスを0.68mol/hの流速にて反応器底部から反応器内に1時間導入して、NaFを充分に乾燥させた。
[Example 1] Production example of FOC-CF 2 -SO 2 F A cylindrical reactor (inner diameter 2.6 cm, height 50 cm) was filled with NaF (volume 210 mL), and the reactor height 40 cm was filled with NaF. did. The reactor was heated to 200 ° C. to dry NaF in the reactor. Furthermore, while heating the reactor to 200 ° C., dry nitrogen gas was introduced into the reactor from the bottom of the reactor at a flow rate of 0.68 mol / h for 1 hour to sufficiently dry NaF.
反応器の頂部に−78℃に保持したトラップを連結し、反応器を200℃に加熱しながら、100℃に加熱して調製した化合物(11)の気体(流量0.29mol/h)と乾燥窒素ガス(流量0.68mol/h)との混合ガスを、反応器の底部から反応器内に4時間導入した。該混合ガスの反応器内における線速は2.0cm/sであり、混合ガスとNaFの接触時間は20秒であった。また、反応器に導入された化合物(11)の総量は210gであった。 A trap maintained at −78 ° C. was connected to the top of the reactor, and the gas of compound (1 1 ) prepared by heating to 100 ° C. while heating the reactor to 200 ° C. (flow rate 0.29 mol / h) and A mixed gas with dry nitrogen gas (flow rate 0.68 mol / h) was introduced into the reactor from the bottom of the reactor for 4 hours. The linear velocity of the mixed gas in the reactor was 2.0 cm / s, and the contact time between the mixed gas and NaF was 20 seconds. The total amount of compound (1 1 ) introduced into the reactor was 210 g.
該混合ガスの導入終了後、さらに乾燥窒素ガスのみを反応器に30分間導入した後にトラップ中の凝縮液を回収した。該凝集液を分析した結果、FOC−CF2−SO2Fの生成が確認された(純度98.8%、収率94%。)。 After the introduction of the mixed gas, only dry nitrogen gas was further introduced into the reactor for 30 minutes, and then the condensate in the trap was recovered. As a result of analyzing the agglomerated liquid, it was confirmed that FOC-CF 2 —SO 2 F was formed (purity 98.8%, yield 94%).
[例2]FOC−CF(CF3)−SO2Fの合成
化合物(11)のかわりに化合物(12)(267g)を用いる以外は同様にして、化合物(12)の気体と乾燥窒素ガスとの混合ガスを反応器に導入した結果、FOC−CF(CF3)−SO2Fの生成が確認された(純度99.4%、収率95%。)。
[Example 2] FOC-CF (CF 3 ) except for using Compound of -SO 2 F (1 1) compound in place of the (1 2) (267 g) in the same manner, and drying gas of the compound (1 2) As a result of introducing a mixed gas with nitrogen gas into the reactor, it was confirmed that FOC-CF (CF 3 ) —SO 2 F was produced (purity 99.4%, yield 95%).
本発明によれば、機能性重合体(イオン交換膜、固体高分子電解質、分離膜、酸触媒等。)を製造するための単量体の原材料等として有用なフルオロスルホニル基を有する酸フロリドを、高純度、高収率かつ簡便に製造する方法が提供される。
According to the present invention, an acid fluoride having a fluorosulfonyl group useful as a raw material for a monomer for producing a functional polymer (ion exchange membrane, solid polymer electrolyte, separation membrane, acid catalyst, etc.) is obtained. Provided is a method for simple, high-purity, high-yield production.
Claims (5)
X、Y:それぞれ独立に、ポリフルオロアルキル基、ポリフルオロ(アルコキシアルキル)基、ポリフルオロアルコキシ基、ポリフルオロ(アルコキシアルコキシ)基、ポリフルオロ(フルオロスルホニルアルキル)基、ポリフルオロ(フルオロスルホニルアルコキシアルキル)基、ポリフルオロ(フルオロスルホニルアルコキシ)基およびポリフルオロ(フルオロスルホニルアルコキシアルコキシ)基からなる群から選ばれる基であって炭素数1〜10の基(A)、フルオロスルホニル基、水素原子、またはハロゲン原子。
Q:単結合または炭素数1〜6のポリフルオロアルキレン基。 A method for producing a compound represented by the following formula (2), wherein a gas of the compound represented by the following formula (1) is brought into contact with a metal fluoride.
X, Y: each independently a polyfluoroalkyl group, polyfluoro (alkoxyalkyl) group, polyfluoroalkoxy group, polyfluoro (alkoxyalkoxy) group, polyfluoro (fluorosulfonylalkyl) group, polyfluoro (fluorosulfonylalkoxyalkyl) ) Group, a polyfluoro (fluorosulfonylalkoxy) group and a polyfluoro (fluorosulfonylalkoxyalkoxy) group selected from the group consisting of a group having 1 to 10 carbon atoms (A), a fluorosulfonyl group, a hydrogen atom, or Halogen atom.
Q: A single bond or a polyfluoroalkylene group having 1 to 6 carbon atoms.
Y1:それぞれ独立に、ペルフルオロアルキル基、ペルフルオロアルコキシ基、ペルフルオロ(フルオロスルホニルアルキル)基、ペルフルオロ(フルオロスルホニルアルコキシアルキル)基、ペルフルオロ(フルオロスルホニルアルコキシ)基およびペルフルオロ(フルオロスルホニルアルコキシアルコキシ)基からなる群から選ばれる基であって炭素数1〜5の基(A1)、またはハロゲン原子。 The compound represented by the formula (1) is a compound represented by the following formula (11), and the compound represented by the formula (2) is a compound represented by the formula (21): The manufacturing method of crab.
Y 1 : each independently comprises a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoro (fluorosulfonylalkyl) group, a perfluoro (fluorosulfonylalkoxyalkyl) group, a perfluoro (fluorosulfonylalkoxy) group, and a perfluoro (fluorosulfonylalkoxyalkoxy) group A group selected from the group, a group having 1 to 5 carbon atoms (A1), or a halogen atom;
The manufacturing method according to claim 1, wherein the metal fluoride is an alkali metal fluoride.
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