JP2004256462A - N-hydroxyalykyl saturated heterocyclic ammonium salt and method for producing the same - Google Patents
N-hydroxyalykyl saturated heterocyclic ammonium salt and method for producing the same Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は新規なＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩及びその製造法に関する。
【０００２】
【従来の技術】
本発明のＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩は、文献未記載の新規な化合物である。
【０００３】
近年、常温（常温は２５℃を意味する。以下同じ。）において液状を示す第四級アンモニウム塩（以下、常温溶融塩という。）が、固体高分子型燃料電池の電解質膜、有機合成反応溶媒等において使用されることから注目を浴び、新しい常温溶融塩が種々提案されている（例えば、非特許文献１参照）。
【０００４】
【非特許文献１】
Ｍ．Ｗａｔａｎａｂｅ，Ｅｌｅｃｔｒｏｃｈｉｍ．Ａｃｔａ，４５，１２６５−１２７０（２０００）
【０００５】
【発明が解決しようとする課題】
本発明は、固体高分子型燃料電池の電解質膜への利用が期待できる、プロトン伝導能を付与した新規な常温溶融塩及びその製造法を提供することを課題とする。
【０００６】
【課題を解決するための手段】
本発明者らは上記課題を解決するために鋭意検討を行ったところ、上記課題を解決し得る新規な常温溶融塩である、カチオン成分を構成する窒素原子に結合した置換基としてヒドロキシアルキル基を有する含窒素飽和複素環式アンモニウム塩を見出し、本発明を完成するに至った。
【０００７】
即ち、本発明は、一般式（１）：
【０００８】
【化５】
｛式中、Ｒ１はアルキル基又はアラルキル基を、Ｙは酸素原子又はメチレン基を及びＡ−はビストリフルオロメタンスルホニルイミダートイオン〔（ＣＦ３ＳＯ２）２Ｎ−〕、テトラフルオロボレートイオン（Ｆ４Ｂ−）またはヘキサフルオロホスファートイオン（ＰＦ６ −）を表す。ｍは１〜４の整数及びｎは０又は１である。
｝で示されるＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩〔以下、Ｎ−ヒドロキシアルキル飽和複素環式アンモニウム塩（１）という。〕、並びに一般式（２）：
【００１０】
【化６】
（式中、Ｒ１、Ｙ、ｍ、ｎ及びＸ−は前記に同じ。）で示されるＮ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド〔以下、Ｎ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）という。〕を一般式（３）：
【００１２】
ＡＭ （３）
｛式中、Ａはビストリフルオロメタンスルホニルイミダート〔（ＣＦ３ＳＯ２）２Ｎ〕、テトラフルオロボレート（Ｆ４Ｂ）またはヘキサフルオロホスファート（ＰＦ６）を及びＭは水素原子又はアルカリ金属を表す。｝で示される化合物（以下、化合物（３）という。）と反応させることを特徴とするＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩（１）の製造方法に関する。
【００１３】
【発明の実施の形態】
以下、本発明を詳細に説明する。
【００１４】
本発明のＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩（１）は、上記一般式（１）で表される化合物であり、一般式（１）中のＲ１はアルキル基又はアラルキル基を、Ｙは酸素原子又はメチレン基を及びＡ−はビストリフルオロメタンスルホニルイミダートイオン〔（ＣＦ３ＳＯ２）２Ｎ−〕、テトラフルオロボレートイオン（Ｆ４Ｂ−）またはヘキサフルオロホスファートイオン（ＰＦ６ −）を表し、並びにｍは１〜４の整数及びｎは０又は１である。Ｒ１で表されるアルキル基としては、炭素数１〜１８の直鎖状又は分岐鎖状のアルキル基が挙げられ、好ましくは炭素数１〜６の直鎖状又は分岐鎖状のアルキル基であり、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基等が挙げられ、好ましくはメチル基である。またアラルキル基としてはそれぞれベンゼン環にメチル基、エチル基等の低級アルキル基を１個以上有していてもよいベンジル基、１−フェネチル基、２−フェネチル基などが挙げられ、好ましくはベンジル基である。
【００１５】
好ましいＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩（１）は、一般式（６）：
【００１６】
【化７】
（式中、Ｒ１はアルキル基を表す。Ｙ、Ａ−およびｎは前記に同じ。）で示されるＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩である。
【００１８】
好ましいＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩（１）の具体例としては、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルピロリジニウム＝ビストリフルオロメタンスルホニルイミダート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルピペリジニウムイオン＝ビストリフルオロメタンスルホニルイミダート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルモルフォリニウム＝ビストリフルオロメタンスルホニルイミダート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルピロリジニウム＝テトラフルオロボレート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルピペリジニウムイオン＝テトラフルオロボレート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルモルフォリニウム＝テトラフルオロボレート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルピロリジニウム＝ヘキサフルオロホスファート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルピペリジニウムイオン＝ヘキサフルオロホスファート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルモルフォリニウム＝ヘキサフルオロホスファート等が挙げられる。
【００１９】
特に好ましくはＮ−（２−ヒドロキシエチル）−Ｎ−メチルピロリジニウム＝ビストリフルオロメタンスルホニルイミダート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルピペリジニウムイオン＝ビストリフルオロメタンスルホニルイミダート、Ｎ−（２−ヒドロキシエチル）−Ｎ−メチルモルフォリニウム＝ビストリフルオロメタンスルホニルイミダートであり、これらは室温で低粘度のため常温溶融塩として特に有用である。
【００２０】
本発明のＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩（１）は、種々の方法で製造することができる。好ましい製造法としては、Ｎ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）を化合物（３）と反応させてＮ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）のハロゲンイオンをビストリフルオロメタンスルホニルイミダートイオン［（ＣＦ３ＳＯ２）２Ｎ− ］、テトラフルオロボラートイオン（Ｆ４Ｂ−）又はヘキサフルオロホスファートイオン（ＰＦ６ −）にイオン交換することによって製造する方法が挙げられる。
【００２１】
Ｎ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）のハロゲンイオンとしては、塩素イオン、臭素イオン、ヨウ素イオン等が挙げられる。
【００２２】
化合物（３）としては、ビストリフルオロメチルスルホニルイミド酸［（ＣＦ３ＳＯ２）２ＮＨ］、テトラフルオロ硼酸（ＨＢＦ４）、ヘキサフルオロリン酸（ＨＰＦ６）、およびそれらのアルカリ金属塩（例えば、リチウム塩、ナトリウム塩、カリウム塩等）が挙げられる。化合物（３）の使用量は、Ｎ−ヒドロキシアルキル飽和複素環式アンモニウム（２）１モルに対して１．０モル〜１．２モル好ましくは １．０１モル〜１．０５モルである。
【００２３】
イオン交換は、次のようにして行う。Ｎ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）と化合物（３）とをＮ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）１重量部に対して１重量部〜１０重量部好ましくは１重量部〜４重量部の水中で１０℃〜６０℃好ましくは１０℃〜３０℃で１時間〜２４時間好ましくは１時間〜４時間混合し、得られた水溶液に水との溶解性が低い有機溶媒（例えば、酢酸エチル、塩化メチレン等）をＮ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）１重量部に対して１重量部〜１０重量部、好ましくは１重量部〜４重量部加えて混合する。その後、水層と有機層を分液すれば、有機層としてＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩（１）の溶液が得られる。得られた有機層を所望により水洗し、次いで有機溶媒を留出除去すれば残渣としてＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩（１）が得られる。
【００２４】
Ｎ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）は、一般式（４）：
【００２５】
【化８】
（Ｒ１、Ｙ及びｎは前記に同じ。）で示される飽和複素環式アミン類（以下、飽和複素環式アミン類（４）という）を一般式（５）：
【００２７】
【化９】
（式中、Ｘ及びｍは前記に同じ。）で示されるハロゲノアルキルアルコール（以下、ハロゲノアルキルアルコール（５）という。）と反応させれば製造することができる。
【００２９】
飽和複素環式アミン類（４）としては、例えば、Ｎ−メチルピペリジン、Ｎ−エチルピペリジン等のＮ−アルキルピペリジン、Ｎ−メチルピロリジン、Ｎ−エチルピロリジン等のＮ−アルキルピロリジン、Ｎ−メチルモルフォリン、Ｎ−エチルモルフォリン等のＮ−アルキルモルフォリン等を挙げることができ、好ましくはＮ−アルキルピロリジンである。
【００３０】
またハロゲノアルキルアルコール（５）としては、例えば、２−ブロモエタノール、２−クロロエタノール、４−ブロモブタノール等が挙げられ、好ましくは２−ブロモエタノールである。ハロゲノアルキルアルコール（５）の使用量は、飽和複素環式アミン類（４）１モルに対して１モル以上であればよく、好ましくは１．１−２．０モルである。
【００３１】
飽和複素環式アミン類（４）とハロゲノアルキルアルコール（５）の反応は、通常溶媒中で行われる。溶媒としては、メタノール、エタノール、イソプロパノール等のアルコール類、アセトニトリル、酢酸エチル、テトラヒドロフラン、ジメチルホルムアミド等が挙げられる。溶媒の使用量は特に制限はないが、飽和複素環式アミン類（４）１重量部に対して通常１〜１０重量部、好ましくは２〜５重量部である。
【００３２】
飽和複素環式アミン類（４）とハロゲノアルキルアルコール（５）の反応を実施するには、例えば、飽和複素環式アミン類（４）、ハロゲノアルキルアルコール（５）及び溶媒の混合物を、反応に使用する溶媒の種類にもよるが、通常２０℃以上、好ましくは６０℃〜１２０℃にて攪拌するだけでよい。反応時間は通常４〜１２時間である。
【００３３】
このようにしてＮ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）を含む反応混合物を得た後、得られた反応混合物を濃縮乾固してＮ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）を主成分とする残渣を得る。次いで残渣を有機溶媒（例えば、エチルエーテル、酢酸エチル、メチルエチルケトン、メチルイソブチルケトン等）と混合し、残渣に含まれる未反応原料等を有機溶媒に溶解した後、濾過する。このようにすると濾滓として高純度のＮ−ヒドロキシアルキル飽和複素環式アンモニウム＝ハライド（２）が得られる。
【００３４】
【実施例】
以下に実施例を示し、本発明を更に具体的に説明するが、本発明は以下の実施例に限定されるものではない。
【００３５】
実施例１
Ｎ−メチルピペリジン２０ｇ（０．２０モル）、２−ブロモエタノール３０ｇ（０．２４モル）及びアセトニトリル４０ｇの混合物を、８０℃で２４時間攪拌して反応させた。反応終了後、得られた反応混合物を濃縮し、残渣にメチルエチルケトン５０ｇを加えて固形物を洗浄し、濾過した。濾滓を減圧下に乾燥してＮ−（２−ヒドロキシエチル）−Ｎ−メチルピペリジニウム＝ブロミド３５．４ｇ（０．１５８モル）を得た。
【００３６】
このようにして得たＮ−（２−ヒドロキシエチル）−Ｎ−メチルピペリジニウム＝ブロミド３５．４ｇ（０．１５８モル）を水１００ｇに溶解させ、トリフルオロメチルスルホニルイミド酸リチウム〔（Ｆ３ＣＳＯ２）２ＮＬｉ〕４５．８ｇ（０．１６０モル）を混合して１時間室温で攪拌し、得られた混合物に塩化メチレン１００ｇを加えて混合した後、分液して得られた有機層を水５０ｇで２回洗浄した。その後有機層から塩化メチレンを留去して油状のＮ−（２−ヒドロキシエチル）−Ｎ−メチルピペリジニウム＝ビストリフルオロメチルスルホンイミダート４７ｇ（０．１１１モル、収率５５．３％）を得た。得られたＮ−（２−ヒドロキシエチル）−Ｎ−メチルピペリジニウム＝ビストリフルオロメチルスルホンイミダートのＮＭＲの分析結果を次に示す。
【００３７】
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ ｐｐｍ：３．９９（ｂｓ、２Ｈ）、３．４３−３．２８（ｍ、７Ｈ）、３．０８（ｓ、３Ｈ）、１．８７−１．８４（ｂｍ、４Ｈ）、１．６６−１．６４（ｂｍ、２Ｈ）
【００３８】
このアンモニウム塩の粘度、電位窓およびイオン伝導度を表１に示す。なお、粘度はＥ型粘度計、電位窓はＣＶ−５０（ビー・エー・エス株式会社製）を使用したＣＶ測定〔ＲＥ：ＳＣＥ、ＷＥ：ＧＣ（直径３ｍｍ）、ＣＥ：Ｐｔ、Ｓｃａｎ ｒａｔｅ：１０ｍＶ／ｓ〕にて、イオン伝導度は卓上電導度計ＣＭ−３０Ｓ（東亜ディーケーケー株式会社製）を使用してそれぞれ測定した。
【００３９】
実施例２
実施例１においてＮ−メチルピペリジンに代えてＮ−メチルピロリジン１７ｇ（０．２０モル）を使用した以外は実施例１と同様に行い、油状のＮ−（２−ヒドロキシエチル）−Ｎ−メチルピロリジニウム＝ビストリフルオロメチルスルホンイミダート４３ｇ（０．１０４モル、収率５２．０％）を得た。得られたＮ−エトキシエチル−Ｎ−メチルピロリジニウム＝ビストリフルオロメチルスルホンイミダートのＮＭＲの測定結果を次に示す。
【００４０】
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ ｐｐｍ：３．９６（ｂｓ、２Ｈ）、３．４９（ｍ、４Ｈ）、３．４２−３．３８（ｍ、３Ｈ）、３．０３（ｓ、３Ｈ）、２．１７（ｂｍ、４Ｈ）
【００４１】
このアンモニウム塩の粘度、電位窓およびイオン伝導度を実施例１と同様にして測定しその結果を表１に示す。
【００４２】
【表１】
【発明の効果】
本発明によれば、固体高分子型燃料電池の電解質膜への利用が期待され得る、プロトン伝導能を有する新規な常温溶融塩及びその製造方法を提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel N-hydroxyalkyl saturated heterocyclic ammonium salt and a method for producing the same.
[0002]
[Prior art]
The N-hydroxyalkyl saturated heterocyclic ammonium salt of the present invention is a novel compound not described in any literature.
[0003]
In recent years, quaternary ammonium salts (hereinafter, referred to as room temperature molten salts) which are liquid at room temperature (room temperature means 25 ° C .; the same applies hereinafter) have been used as electrolyte membranes for polymer electrolyte fuel cells, organic synthesis reaction solvents. Attention has been paid to its use in, for example, non-patent document 1 (see, for example, Non-Patent Document 1).
[0004]
[Non-patent document 1]
M. Watanabe, Electrochim. Acta, 45 , 1265-1270 (2000).
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel room-temperature molten salt having proton conductivity, which can be expected to be used for an electrolyte membrane of a polymer electrolyte fuel cell, and a method for producing the same.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, a novel room temperature molten salt that can solve the above-mentioned problems, a hydroxyalkyl group as a substituent bonded to the nitrogen atom constituting the cation component. The present inventors have found a nitrogen-containing saturated heterocyclic ammonium salt having the same and have completed the present invention.
[0007]
That is, the present invention provides a compound represented by the general formula (1):
[0008]
Embedded image
In the formula, R 1 represents an alkyl group or an aralkyl group, Y represents an oxygen atom or a methylene group, and A − represents bistrifluoromethanesulfonylimidate ion [(CF 3 SO 2 ) 2 N − ], tetrafluoroborate ion ( F 4 B − ) or hexafluorophosphate ion (PF 6 − ). m is an integer of 1 to 4 and n is 0 or 1.
N-hydroxyalkyl saturated heterocyclic ammonium salt [hereinafter referred to as N-hydroxyalkyl saturated heterocyclic ammonium salt (1)]. And general formula (2):
[0010]
Embedded image
(Wherein, R 1 , Y, m, n and X − are the same as above.) [N-hydroxyalkyl saturated heterocyclic ammonium = halide (hereinafter referred to as N-hydroxyalkyl saturated heterocyclic ammonium = halide) 2). ] To the general formula (3):
[0012]
AM (3)
In the formula, A represents bistrifluoromethanesulfonylimidate [(CF 3 SO 2 ) 2 N], tetrafluoroborate (F 4 B) or hexafluorophosphate (PF 6 ), and M represents a hydrogen atom or an alkali metal. Represent. The present invention relates to a method for producing an N-hydroxyalkyl saturated heterocyclic ammonium salt (1), which is characterized by reacting with a compound represented by｝ (hereinafter, referred to as compound (3)).
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0014]
The N-hydroxyalkyl saturated heterocyclic ammonium salt (1) of the present invention is a compound represented by the above general formula (1), wherein R 1 in the general formula (1) represents an alkyl group or an aralkyl group, Represents an oxygen atom or a methylene group, and A − represents bistrifluoromethanesulfonylimidate ion [(CF 3 SO 2 ) 2 N − ], tetrafluoroborate ion (F 4 B − ) or hexafluorophosphate ion (PF 6 − And m is an integer from 1 to 4 and n is 0 or 1. Examples of the alkyl group represented by R 1 include a linear or branched alkyl group having 1 to 18 carbon atoms, and preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like, and a methyl group is preferable. Examples of the aralkyl group include a benzyl group, which may have one or more lower alkyl groups such as a methyl group and an ethyl group on a benzene ring, a 1-phenethyl group, a 2-phenethyl group, and the like. It is.
[0015]
Preferred N-hydroxyalkyl saturated heterocyclic ammonium salt (1) is represented by the general formula (6):
[0016]
Embedded image
(In the formula, R 1 represents .Y, A alkyl group - and n are as defined above.) Is N- hydroxyalkyl saturated heterocyclic ammonium salt represented by.
[0018]
Specific examples of preferable N-hydroxyalkyl saturated heterocyclic ammonium salt (1) include N- (2-hydroxyethyl) -N-methylpyrrolidinium = bistrifluoromethanesulfonylimidate, N- (2-hydroxyethyl ) -N-methylpiperidinium ion = bistrifluoromethanesulfonylimidate, N- (2-hydroxyethyl) -N-methylmorpholinium = bistrifluoromethanesulfonylimidate, N- (2-hydroxyethyl) -N- Methylpyrrolidinium = tetrafluoroborate, N- (2-hydroxyethyl) -N-methylpiperidinium ion = tetrafluoroborate, N- (2-hydroxyethyl) -N-methylmorpholinium = tetrafluoroborate, N -(2-hydroxyethyl)- -Methylpyrrolidinium = hexafluorophosphate, N- (2-hydroxyethyl) -N-methylpiperidinium ion = hexafluorophosphate, N- (2-hydroxyethyl) -N-methylmorpholinium = hexafluoro Phosphate and the like.
[0019]
Particularly preferably, N- (2-hydroxyethyl) -N-methylpyrrolidinium = bistrifluoromethanesulfonylimidate, N- (2-hydroxyethyl) -N-methylpiperidinium ion = bistrifluoromethanesulfonylimidate, N -(2-hydroxyethyl) -N-methylmorpholinium = bistrifluoromethanesulfonylimidate, which is particularly useful as a room temperature molten salt because of its low viscosity at room temperature.
[0020]
The N-hydroxyalkyl saturated heterocyclic ammonium salt (1) of the present invention can be produced by various methods. A preferred production method is to react the N-hydroxyalkyl saturated heterocyclic ammonium halide (2) with the compound (3) to convert the halogen ion of the N-hydroxyalkyl saturated heterocyclic ammonium halide (2) into bistrifluoromethane. A method of performing ion exchange with a sulfonylimate ion [(CF 3 SO 2 ) 2 N − ], a tetrafluoroborate ion (F 4 B − ), or a hexafluorophosphate ion (PF 6 − ) may be mentioned. .
[0021]
Examples of the halogen ion of the N-hydroxyalkyl saturated heterocyclic ammonium halide (2) include a chloride ion, a bromine ion, and an iodine ion.
[0022]
As the compound (3), bis (trifluoromethylsulfonylimidic acid [(CF 3 SO 2 ) 2 NH], tetrafluoroboric acid (HBF 4 ), hexafluorophosphoric acid (HPF 6 ), and an alkali metal salt thereof (for example, Lithium salt, sodium salt, potassium salt and the like). The amount of the compound (3) to be used is 1.0 mol to 1.2 mol, preferably 1.01 mol to 1.05 mol, per 1 mol of the N-hydroxyalkyl saturated heterocyclic ammonium (2).
[0023]
The ion exchange is performed as follows. The N-hydroxyalkyl saturated heterocyclic ammonium halide (2) and the compound (3) are used in an amount of 1 to 10 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the N-hydroxyalkyl saturated heterocyclic ammonium = halide (2). Mix in 1 to 4 parts by weight of water at 10 ° C. to 60 ° C., preferably 10 ° C. to 30 ° C. for 1 hour to 24 hours, preferably 1 hour to 4 hours, and have low solubility in water in the resulting aqueous solution An organic solvent (eg, ethyl acetate, methylene chloride, etc.) is used in an amount of 1 to 10 parts by weight, preferably 1 to 4 parts by weight based on 1 part by weight of N-hydroxyalkyl saturated heterocyclic ammonium halide (2). Add and mix. Thereafter, if the aqueous layer and the organic layer are separated, a solution of the N-hydroxyalkyl saturated heterocyclic ammonium salt (1) is obtained as the organic layer. The obtained organic layer is optionally washed with water, and then the organic solvent is distilled off to obtain an N-hydroxyalkyl saturated heterocyclic ammonium salt (1) as a residue.
[0024]
An N-hydroxyalkyl saturated heterocyclic ammonium halide (2) is represented by the general formula (4):
[0025]
Embedded image
(Wherein R 1 , Y and n are the same as above) (hereinafter referred to as saturated heterocyclic amines (4)) represented by the general formula (5):
[0027]
Embedded image
(Wherein, X and m are the same as described above) (hereinafter, referred to as halogenoalkyl alcohol (5)).
[0029]
Examples of the saturated heterocyclic amines (4) include N-alkylpiperidines such as N-methylpiperidine and N-ethylpiperidine, N-alkylpyrrolidines such as N-methylpyrrolidine and N-ethylpyrrolidine, and N-methylmorpholine. Examples thereof include N-alkylmorpholine such as phosphorus and N-ethylmorpholine, and preferred is N-alkylpyrrolidine.
[0030]
Examples of the halogenoalkyl alcohol (5) include, for example, 2-bromoethanol, 2-chloroethanol, 4-bromobutanol and the like, preferably 2-bromoethanol. The amount of the halogenoalkyl alcohol (5) to be used may be 1 mol or more, preferably 1.1 to 2.0 mol, per 1 mol of the saturated heterocyclic amine (4).
[0031]
The reaction between the saturated heterocyclic amines (4) and the halogenoalkyl alcohol (5) is usually performed in a solvent. Examples of the solvent include alcohols such as methanol, ethanol and isopropanol, acetonitrile, ethyl acetate, tetrahydrofuran, dimethylformamide and the like. The amount of the solvent to be used is not particularly limited, but is usually 1 to 10 parts by weight, preferably 2 to 5 parts by weight, per 1 part by weight of the saturated heterocyclic amine (4).
[0032]
In order to carry out the reaction between the saturated heterocyclic amines (4) and the halogenoalkyl alcohol (5), for example, a mixture of the saturated heterocyclic amines (4), the halogenoalkyl alcohol (5) and a solvent is used in the reaction. Although it depends on the type of the solvent used, it is only necessary to stir usually at 20 ° C. or higher, preferably at 60 ° C. to 120 ° C. The reaction time is usually 4 to 12 hours.
[0033]
After obtaining a reaction mixture containing the N-hydroxyalkyl saturated heterocyclic ammonium halide (2) in this way, the obtained reaction mixture is concentrated to dryness and the N-hydroxyalkyl saturated heterocyclic ammonium halide (halide) is obtained. A residue mainly composed of 2) is obtained. Next, the residue is mixed with an organic solvent (eg, ethyl ether, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc.), and unreacted raw materials and the like contained in the residue are dissolved in the organic solvent, followed by filtration. In this manner, high-purity N-hydroxyalkyl saturated heterocyclic ammonium halide (2) is obtained as a filter cake.
[0034]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
[0035]
Example 1
A mixture of 20 g (0.20 mol) of N-methylpiperidine, 30 g (0.24 mol) of 2-bromoethanol and 40 g of acetonitrile was stirred and reacted at 80 ° C. for 24 hours. After completion of the reaction, the obtained reaction mixture was concentrated, 50 g of methyl ethyl ketone was added to the residue, and the solid matter was washed and filtered. The cake was dried under reduced pressure to obtain 35.4 g (0.158 mol) of N- (2-hydroxyethyl) -N-methylpiperidinium bromide.
[0036]
35.4 g (0.158 mol) of N- (2-hydroxyethyl) -N-methylpiperidinium bromide thus obtained was dissolved in 100 g of water, and lithium trifluoromethylsulfonylimidoate [(F 3 [CSO 2 ) 2 NLi] 45.8 g (0.160 mol) was mixed and stirred at room temperature for 1 hour, 100 g of methylene chloride was added to the resulting mixture, and the mixture was separated. Was washed twice with 50 g of water. Thereafter, methylene chloride was distilled off from the organic layer to obtain 47 g (0.111 mol, 55.3% yield) of oily N- (2-hydroxyethyl) -N-methylpiperidinium bistrifluoromethylsulfonimidate. Obtained. The NMR analysis results of the obtained N- (2-hydroxyethyl) -N-methylpiperidinium bistrifluoromethylsulfonimidate are shown below.
[0037]
1 H-NMR (CDCl 3) δ ppm: 3.99 (bs, 2H), 3.43-3.28 (m, 7H), 3.08 (s, 3H), 1.87-1.84 ( bm, 4H), 1.66-1.64 (bm, 2H)
[0038]
Table 1 shows the viscosity, potential window and ionic conductivity of this ammonium salt. The viscosity was measured using an E-type viscometer, and the potential window was measured using a CV-50 (manufactured by BAS Co., Ltd.) [RE: SCE, WE: GC (diameter 3 mm), CE: Pt, Scan rate: At 10 mV / s], the ionic conductivity was measured using a desktop conductivity meter CM-30S (manufactured by Toa DKK Corporation).
[0039]
Example 2
The procedure of Example 1 was repeated, except that 17 g (0.20 mol) of N-methylpyrrolidine was used instead of N-methylpiperidine, to give oily N- (2-hydroxyethyl) -N-methylpyrrolidine. 43 g (0.104 mol, 52.0% yield) of dinium bistrifluoromethylsulfonimidate were obtained. The NMR measurement results of the obtained N-ethoxyethyl-N-methylpyrrolidinium = bistrifluoromethylsulfonimidate are shown below.
[0040]
1 H-NMR (CDCl 3 ) δ ppm: 3.96 (bs, 2H), 3.49 (m, 4H), 3.42-3.38 (m, 3H), 3.03 (s, 3H) , 2.17 (bm, 4H)
[0041]
The viscosity, potential window and ionic conductivity of this ammonium salt were measured in the same manner as in Example 1, and the results are shown in Table 1.
[0042]
[Table 1]
【The invention's effect】
According to the present invention, it is possible to provide a novel room-temperature molten salt having proton conductivity, which can be expected to be used for an electrolyte membrane of a polymer electrolyte fuel cell, and a method for producing the same.
Claims (3)
｝で示されるＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩。General formula (1):
N-hydroxyalkyl saturated heterocyclic ammonium salt represented by｝.
ＡＭ （３）
｛式中、Ａはビストリフルオロメタンスルホニルイミダート［（ＣＦ３ＳＯ２）２Ｎ］、テトラフルオロボレート（Ｆ４Ｂ）またはヘキサフルオロホスファート（ＰＦ６）を及びＭは水素原子又はアルカリ金属を表す。｝で示される化合物と反応させることを特徴とする請求項１記載のＮ−ヒドロキシアルキル飽和複素環式アンモニウム塩の製造方法。General formula (2):
AM (3)
In the formula, A represents bistrifluoromethanesulfonylimidate [(CF 3 SO 2 ) 2 N], tetrafluoroborate (F 4 B) or hexafluorophosphate (PF 6 ), and M represents a hydrogen atom or an alkali metal. Represent. The method for producing an N-hydroxyalkyl saturated heterocyclic ammonium salt according to claim 1, wherein the compound is reacted with a compound represented by｝.
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| JPH11297573A (en) * | 1998-04-13 | 1999-10-29 | Sanyo Chem Ind Ltd | Electrolyte and electrochemical element using the electrolyte |
| WO2002076924A1 (en) * | 2001-03-26 | 2002-10-03 | Nisshinbo Industries, Inc., | Ionic liquid, electrolyte salt for storage device, electrolytic solution for storage device, electric double layer capacitor, and secondary battery |
| JP2002334815A (en) * | 2001-05-10 | 2002-11-22 | Sanyo Chem Ind Ltd | Electric double-layer capacitor |
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| JPH11297573A (en) * | 1998-04-13 | 1999-10-29 | Sanyo Chem Ind Ltd | Electrolyte and electrochemical element using the electrolyte |
| WO2002076924A1 (en) * | 2001-03-26 | 2002-10-03 | Nisshinbo Industries, Inc., | Ionic liquid, electrolyte salt for storage device, electrolytic solution for storage device, electric double layer capacitor, and secondary battery |
| JP2002334815A (en) * | 2001-05-10 | 2002-11-22 | Sanyo Chem Ind Ltd | Electric double-layer capacitor |
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| CN106831651A (en) * | 2016-12-28 | 2017-06-13 | 中国科学院广州能源研究所 | A kind of hydroxylating ionic liquid type hydrate inhibitor and preparation method thereof |
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