JP4082266B2 - Method for producing organic onium salt of tetrafluoroaluminate - Google Patents

Description

（式中、Ｒ¹〜Ｒ⁴はそれぞれ独立して水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアリール基または置換基を有していてもよいアラルキル基を表すが、Ｒ¹〜Ｒ⁴の２以上が水素原子を表すことはない。またＲ¹〜Ｒ⁴は、一部または全てが互いに結合し、窒素原子を有していてもよい環を形成してもよく、また環は不飽和結合を有していてもよく、さらにかかる環は置換基を有していてもよい。Ａは窒素原子またはリン原子を表す。）
Ｒ¹〜Ｒ⁴で定義されるアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等の炭素数１〜２０の、より好ましくは炭素数１〜６のアルキル基が挙げられ、シクロアルキル基としてはシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の炭素数３〜２０の、より好ましくは炭素数３〜６のシクロアルキル基が挙げられ、アリール基としてはフェニル基、トリル基、ナフチル基等の炭素数６〜２０の、より好ましくは炭素数６〜１０のアリール基が挙げられ、アラルキル基としてはベンジル基、フェネチル基、ナフチルメチル基等の炭素数７〜２０の、より好ましくは炭素数７〜１１のアラルキル基が挙げられる。
【００１１】
これらのアルキル基、シクロアルキル基、アリール基、アラルキル基は置換基を有していてもよく、かかる置換基としては、ヒドロキシル基、アミノ基、ニトロ基、シアノ基、カルボキシル基、ホルミル基等が挙げられる。
前記（Ｉ）式で表される有機オニウムの代表例としては、四級化アンモニウム、四級化ホスホニウム、四級化イミダゾリウム、四級化環状アミジニウム、アンモニウム等を挙げることができる。また有機オニウム塩としては、有機オニウム塩に水やメタノール等の配位性化合物が配位したものも包含する。
【００１２】
四級化アンモニウムの具体例としては、例えばテトラメチルアンモニウム、エチルトリメチルアンモニウム、ジエチルジメチルアンモニウム、トリエチルメチルアンモニウム、テトラエチルアンモニウム、トリメチル−ｎ−プロピルアンモニウム、トリメチルイソプロピルアンモニウム、トリメチル−ｎ−ブチルアンモニウム、トリメチルイソブチルアンモニウム、トリメチル−ｔ−ブチルアンモニウム、トリメチル−ｎ−ヘキシルアンモニウム、ジメチルジ−ｎ−プロピルアンモニウム、ジメチルジイソプロピルアンモニウム、ジメチル−ｎ−プロピルイソプロピルアンモニウム、メチルトリ−ｎ−プロピルアンモニウム、メチルトリイソプロピルアンモニウム、メチルジ−ｎ−プロピルイソプロピルアンモニウム、メチル−ｎ−プロピルジイソプロピルアンモニウム、トリエチル−ｎ−プロピルアンモニウム、トリエチルイソプロピルアンモニウム、トリエチル−ｎ−ブチルアンモニウム、トリエチルイソブチルアンモニウム、トリエチル−ｔ−ブチルアンモニウム、ジメチルジ−ｎ−ブチルアンモニウム、ジメチルジイソブチルアンモニウム、ジメチルジ−ｔ−ブチルアンモニウム、ジメチル−ｎ−ブチルエチルアンモニウム、ジメチルイソブチルエチルアンモニウム、ジメチル−ｔ−ブチルエチルアンモニウム、ジメチル−ｎ−ブチルイソブチルアンモニウム、ジメチル−ｎ−ブチル−ｔ−ブチルアンモニウム、ジメチルイソブチル−ｔ−ブチルアンモニウム、ジエチルジ−ｎ−プロピルアンモニウム、ジエチルジイソプロピルアンモニウム、ジエチル−ｎ−プロピルイソプロピルアンモニウム、エチルトリ−ｎ−プロピルアンモニウム、エチルトリイソプロピルアンモニウム、エチルジ−ｎ−プロピルイソプロピルアンモニウム、エチル−ｎ−プロピルジイソプロピルアンモニウム、ジエチルメチル−ｎ−プロピルアンモニウム、エチルジメチル−ｎ−プロピルアンモニウム、エチルメチルジ−ｎ−プロピルアンモニウム、ジエチルメチルイソプロピルアンモニウム、エチルジメチルイソプロピルアンモニウム、エチルメチルジイソプロピルアンモニウム、エチルメチル−ｎ−プロピルイソプロピルアンモニウム、テトラ−ｎ−プロピルアンモニウム、テトライソプロピルアンモニウム、ｎ−プロピルトリイソプロピルアンモニウム、ジ−ｎ−プロピルジイソプロピルアンモニウム、トリ−ｎ−プロピルイソプロピルアンモニウム、トリメチルブチルアンモニウム、トリメチルペンチルアンモニウム、トリメチルヘキシルアンモニウム、トリメチルヘプチルアンモニウム、トリメチルオクチルアンモニウム、トリメチルノニルアンモニウム、トリメチルデシルアンモニウム、トリメチルウンデシルアンモニウム、トリメチルドデシルアンモニウム等のテトラアルキルアンモニウム；トリメチルフェニルアンモニウム、テトラフェニルアンモニウム等の芳香族置換アンモニウム；Ｎ，Ｎ−ジメチルピロリジニウム、Ｎ−エチル−Ｎ−メチルピロリジニウム、Ｎ，Ｎ−ジエチルピロリジニウム、Ｎ，Ｎ−テトラメチレンピロリジニウム等ピロリジニウム化合物、Ｎ，Ｎ−ジメチルピペリジニウム、Ｎ−エチル−Ｎ−メチルピペリジニウム、Ｎ，Ｎ−ジエチルピペリジニウム、Ｎ，Ｎ−テトラメチレンピペリジニウム、Ｎ，Ｎ−ペンタメチレンピペリジニウム等のピペリジニウム化合物、Ｎ，Ｎ−ジメチルモルホリニウム、Ｎ−エチル−Ｎ−メチルモルホリニウム、Ｎ，Ｎ−ジエチルモルホリニウム等のモルホリニウム化合物等の脂肪族環状アンモニウム；Ｎ−メチルピリジニウム、Ｎ−エチルピリジニウム、Ｎ−ｎ−プロピルピリジニウム、Ｎ−イソプロピルピリジニウム、Ｎ−ｎ−ブチルピリジニウム等の含窒素ヘテロ環芳香族化合物等を挙げることができる。
【００１３】
四級化ホスホニウムの具体例としては、テトラメチルホスホニウム、トリエチルメチルホスホニウム、テトラエチルホスホニウム等を挙げることができる。
四級化イミダゾリウムの具体例としては、１，３−ジメチルイミダゾリウム、１，２，３−トリメチルイミダゾリウム、１−エチル−３−メチルイミダゾリウム、１−エチル−２，３−ジメチルイミダゾリウム、１，３−ジエチルイミダゾリウム、１，２−ジエチル−３−メチルイミダゾリウム、１，３−ジエチル−２−メチルイミダゾリウム、１，２−ジメチル−３−ｎ−プロピルイミダゾリウム、１−ｎ−ブチル−３−メチルイミダゾリウム、１−メチル−３−ｎ−プロピル−２，４−ジメチルイミダゾリウム、１，２，３，４−テトラメチルイミダゾリウム、１，２，３，４，５−ペンタメチルイミダゾリウム、２−エチル−１，３−ジメチルイミダゾリウム、１，３−ジメチル−２−ｎ−プロピルイミダゾリウム、１，３−ジメチル−２−ｎ−ペンチルイミダゾリウム、１，３−ジメチル−２−ｎ−ヘプチルイミダゾリウム、１，３，４−トリメチルイミダゾリウム、２−エチル−１，３，４−トリメチルイミダゾリウム、１，３−ジメチルベンゾイミダゾリウム、１−フェニル−３−メチルイミダゾリウム、１−ベンジル−３−メチルイミダゾリウム、１−フェニル−２，３−ジメチルイミダゾリウム、１−ベンジル−２，３−ジメチルイミダゾリウム、２−フェニル−１，３−ジメチルイミダゾリウム、２−ベンジル−１，３−ジメチルイミダゾリウム、１，３−ジメチル−２−ｎ−ウンデシルイミダゾリウム、１，３−ジメチル−２−ｎ−ヘプタデシルイミダゾリウム等、さらには２−（２′−ヒドロキシ）エチル−１，３−ジメチルイミダゾリウム、１−（２′−ヒドロキシ）エチル−２，３−ジメチルイミダゾリウム、２−エトキシメチル−１，３−ジメチルイミダゾリウム、１−エトキシメチル−２，３−ジメチルイミダゾリウム等のヒドロキシル基やエーテル結合を有する基等を挙げることができる。
【００１４】
四級化環状アミジニウムの具体例としては、１，３−ジメチルイミダゾリニウム、１，２，３−トリメチルイミダゾリニウム、１−エチル−３−メチルイミダゾリニウム、１−エチル−２，３−ジメチルイミダゾリニウム、１，３−ジエチルイミダゾリニウム、１，２−ジエチル−３−メチルイミダゾリニウム、１，３−ジエチル−２−メチルイミダゾリニウム、１，２−ジメチル−３−ｎ−プロピルイミダゾリニウム、１−ｎ−ブチル−３−メチルイミダゾリニウム、１−メチル−３−ｎ−プロピル−２，４−ジメチルイミダゾリニウム、１，２，３，４−テトラメチルイミダゾリニウム、２−エチル−１，３−ジメチルイミダゾリニウム、１，３−ジメチル−２−ｎ−プロピルイミダゾリニウム、１，３−ジメチル−２−ｎ−ペンチルイミダゾリニウム、１，３−ジメチル−２−ｎ−ヘプチルイミダゾリニウム、１，３，４−トリメチルイミダゾリニウム、２−エチル−１，３，４−トリメチルイミダゾリニウム、１−フェニル−３−メチルイミダゾリニウム、１−ベンジル−３−メチルイミダゾリニウム、１−フェニル−２，３−ジメチルイミダゾリニウム、１−ベンジル−２，３−ジメチルイミダゾリニウム、２−フェニル−１，３−ジメチルイミダゾリニウム、２−ベンジル−１，３−ジメチルイミダゾリニウム等のイミダゾリニウム化合物；１，３−ジメチルテトラヒドロピリミジニウム、１，３−ジエチルテトラヒドロピリミジニウム、１−エチル−３−メチルテトラヒドロピリミジニウム、１，２，３−トリメチルテトラヒドロピリミジニウム、１，２，３−トリエチルテトラヒドロピリミジニウム、１−エチル−２，３−ジメチルテトラヒドロピリミジニウム、２−エチル−１，３−ジメチルテトラヒドロピリミジニウム、１，２−ジエチル−３−メチルテトラヒドロピリミジニウム、１，３−ジエチル−２−メチルテトラヒドロピリミジニウム等のテトラヒドロピリミジニウム化合物；５−メチル−１，５−ジアザビシクロ〔４．３．０〕ノネン−５、８−メチル−１，８−ジアザビシクロ〔５．４．０〕ウンデセン−７、１，３−ジメチル−２−ｎ−ウンデシルイミダゾリニウム、１，３−ジメチル−２−ｎ−ヘプタデシルイミダゾリニウム、さらには２−（２′−ヒドロキシ）エチル−１，３−ジメチルイミダゾリニウム、１−（２′−ヒドロキシ）エチル−２，３−ジメチルイミダゾリニウム、２−エトキシメチル−１，３−ジメチルイミダゾリニウム、１−エトキシメチル−２，３−ジメチルイミダゾリニウム等のヒドロキシル基やエーテル結合を有する基を挙げることができる。
【００１５】
アンモニウムの具体例としては、トリメチルアンモニウム、エチルジメチルアンモニウム、ジエチルメチルアンモニウム、トリエチルアンモニウム、ピリジニウム、Ｎ−メチルイミダゾリニウム、１，５−ジアザビシクロ〔４．３．０〕ノネニウム−５、１，８−ジアザビシクロ〔５．４．０〕ウンデセニウム−７等を挙げることができる。
【００１６】
これらのうち、総炭素数が４〜１２である有機オニウムが好ましく、なかでもテトラエチルアンモニウム、トリエチルメチルアンモニウム、ジエチルジメチルアンモニウム、エチルトリメチルアンモニウム、テトラメチルアンモニウム、Ｎ，Ｎ−ジメチルピロリジニウム、Ｎ−エチル−Ｎ−メチルピロリジニウム、１，３−ジメチルイミダゾリウム、１，２，３−トリメチルイミダゾリウム、１−エチル−３−メチルイミダゾリウム、１−エチル−２，３−ジメチルイミダゾリウム、１，２，３，４−テトラメチルイミダゾリウム、１，３−ジエチルイミダゾリウム、２−エチル−１，３−ジメチルイミダゾリウム、１，３−ジメチル−２−ｎ−プロピルイミダゾリウム、１，３−ジメチル−２−ｎ−ペンチルイミダゾリウム、１，３−ジメチル−２−ｎ−ヘプチルイミダゾリウム、１，３，４−トリメチルイミダゾリウム、２−エチル−１，３，４−トリメチルイミダゾリウム、１，３−ジメチルベンゾイミダゾリウム、１−フェニル−３−メチルイミダゾリウム、１−ベンジル−３−メチルイミダゾリウム、１−フェニル−２，３−ジメチルイミダゾリウム、１−ベンジル−２，３−ジメチルイミダゾリウム、２−フェニル−１，３−ジメチルイミダゾリウム、２−ベンジル−１，３−ジメチルイミダゾリウム、１，３−ジメチルイミダゾリニウム、１，２，３−トリメチルイミダゾリニウム、１−エチル−３−メチルイミダゾリニウム、１−エチル−２，３−ジメチルイミダゾリニウム、１，２，３，４−テトラメチルイミダゾリニウム、１，３−ジエチルイミダゾリニウム、２−エチル−１，３−ジメチルイミダゾリニウム、１，３−ジメチル−２−ｎ−プロピルイミダゾリニウム、１，３−ジメチル−２−ｎ−ペンチルイミダゾリニウム、１，３−ジメチル−２−ｎ−ヘプチルイミダゾリニウム、１，３，４−トリメチルイミダゾリニウム、２−エチル−１，３，４−トリメチルイミダゾリニウム、１−フェニル−３−メチルイミダゾリニウム、１−ベンジル−３−メチルイミダゾリニウム、１−フェニル−２，３−ジメチルイミダゾリニウム、１−ベンジル−２，３−ジメチルイミダゾリニウム、２−フェニル−１，３−ジメチルイミダゾリニウム、２−ベンジル−１，３−ジメチルイミダゾリニウムからなる群から選択される一種以上の化合物であることが好ましく、更に好ましくは、１−エチル−２，３−ジメチルイミダゾリニウム、１，２，３，４−テトラメチルイミダゾリニウムであることが好ましい。
【００１７】
これらの有機オニウム塩はそのまま使用することも出来るし、溶媒に溶解したものも使用できる。また、四級化反応液をそのまま使用することも出来る。例えば１−エチル−２−メチルイミダゾールをジメチルカーボネートで四級化した反応液をそのまま使用することも出来る。
本発明の製法における原料の他の一つは、フッ化水素である。フッ化水素はフッ化水素をそのまま使用することも出来るし、溶媒に溶解したものも使用できる。溶媒としては反応不活性であればよい。これらの使用形態のうち好ましくは無水フッ化水素、フッ化水素メタノール溶液、フッ化水素水溶液が使用できる。有機オニウムが加水分解性を示す場合はフッ化水素溶液に水を含まないことが好ましい。
【００１８】
本発明の製法における原料のさらに他の一つは、三フッ化アルミニウムである。好ましくは三フッ化アルミニウムの水和物が使用でき、特に好ましくは三フッ化アルミニウムの３水和物が使用できる。
本発明の製法において使用可能な溶媒としては、例えば水；メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール等のアルコール類；アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン等のケトン類；ジエチルエーテル、エチル−ｎ−プロピルエーテル、エチル−イソプロピルエーテル、ジ−ｎ−プロピルエーテル、ジイソプロピルエーテル、ｎ−プロピルイソプロピルエーテル、ジメトキシエタン、メトキシエトキシエタン、ジエトキシエタン、テトラヒドロフラン等のエーテル類；アセトニトリル、プロピオニトリル等のニトリル類；ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、メチルシクロヘキサン、ベンゼン、トルエン、キシレン等の炭化水素系；酢酸エチル、酢酸ブチル、炭酸ジメチル、炭酸ジエチル、炭酸エチルメチル、炭酸エチレン、炭酸プロピレン等のエステル類等が挙げられる。この中で更に好ましくは、水、メタノール、エタノールが挙げられるが、有機オニウムが加水分解性を示す場合は溶媒に水を含まないことが好ましい。これらの溶媒は、単独でも混合して用いても良い。
【００１９】
反応方法は、例えばフッ化水素又はその溶液に有機オニウム塩又はその溶液を添加し、次いで三フッ化アルミニウムを添加する方法；有機オニウム塩又はその溶液にフッ化水素又はその溶液を添加し、次いで三フッ化アルミニウムを添加する方法；溶媒の存在下又は無溶媒でフッ化水素又はその溶液と有機オニウム塩又はその溶液を同時又は交互に添加し、次いで三フッ化アルミニウムを添加する方法；フッ化水素又はその溶液に三フッ化アルミニウムを添加し、次いで有機オニウム塩又はその溶液を添加する方法；溶媒の存在下又は無溶媒で三フッ化アルミニウムにフッ化水素又はその溶液を添加し、次いで有機オニウム塩又はその溶液を添加する方法；溶媒の存在下又は無溶媒でフッ化水素又はその溶液と三フッ化アルミニウムを同時又は交互に添加し、次いで有機オニウム塩又はその溶液を添加する方法；有機オニウム塩又はその溶液に三フッ化アルミニウムを添加し、次いでフッ化水素又はその溶液を添加する方法；溶媒の存在下又は無溶媒で三フッ化アルミニウムに有機オニウム塩又はその溶液を添加し、次いでフッ化水素又はその溶液を添加する方法；溶媒の存在下又は無溶媒で有機オニウム塩又はその溶液と三フッ化アルミニウムを同時又は交互に添加し、次いでフッ化水素又はその溶液を添加する方法；溶媒の存在下又は無溶媒で有機オニウム塩又はその溶液とフッ化水素又はその溶液と三フッ化アルミニウムを同時又は交互に添加する方法；及びそれらの方法の組み合わせが挙げられる。これらのうち、好ましくはフッ化水素又はその溶液に有機オニウム塩又はその溶液を添加し、次いで三フッ化アルミニウムを添加する方法；有機オニウム塩又はその溶液にフッ化水素又はその溶液を添加し、次いで三フッ化アルミニウムを添加する方法；溶媒の存在下又は無溶媒でフッ化水素又はその溶液と有機オニウム塩又はその溶液を同時又は交互に添加し、次いで三フッ化アルミニウムを添加する方法が使用できる。このとき三フッ化アルミニウムを添加する前に有機オニウム塩を晶析や溶媒抽出などの方法で単離してもよい。
【００２０】
フッ化水素の使用量は有機オニウム塩に対して好ましくは０．５〜１．５モル倍、より好ましくは０．８〜１．２モル倍、特に好ましくは０．９〜１．０モル倍である。１．５モル倍以上、好ましくは１．０モル倍以上のフッ化水素を使用した場合は、三フッ化アルミニウムと有機オニウム塩が接触する前に、例えば蒸発、中和などの方法により、過剰のフッ化水素を一部又は全部除去することが好ましい。
【００２１】
三フッ化アルミニウムの使用量は、有機オニウム塩に対してモル比で好ましくは０．５〜１０倍、より好ましくは０．８〜２倍、特に好ましくは０．９〜１．２倍使用できる。
反応温度は制限がないが、まず−２０〜１５０℃、好ましくは−１０〜５０℃、さらに好ましくは０〜２５℃で反応させた後に、−２０〜１５０℃、好ましくは０〜１００℃で反応させることができる。
【００２２】
本発明により得られるテトラフルオロアルミネートの有機オニウム塩は、蒸留、抽出、クロマトグラフィー、再結晶等の常法を用いて、分離、精製することができる。
また本発明により得られるテトラフルオロアルミネートの有機オニウム塩を電解コンデンサに用いる場合には、高純度であることが望まれるため、塩は必要により晶析や溶媒抽出等により所望の純度にまで精製して使用される。
【００２３】
【実施例】
以下に実施例を挙げて本発明を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、操作等は、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。
〔実施例１〕
ＰＦＡ製丸底フラスコに１−エチル−２，３−ジメチルイミダゾリニウムのメチル炭酸塩のメタノール−炭酸ジメチル溶液（１．７７ｍｏｌ／ｋｇ）を２８．３ｇ（５０ｍｍｏｌ）を仕込み、１５℃で無水フッ化水素１．０ｇ（５０ｍｍｏｌ）を滴下した。そのまま３０分攪拌し、さらに三フッ化アルミニウム３水和物を６．９０（５０ｍｍｏｌ）を添加し５０℃で３時間攪拌した。反応液を濾過し、固形分を濾別後、溶媒を留去し、ｎ−ブタノール２３ｇから晶析してテトラフルオロアルミネートの１−エチル−２，３−ジメチルイミダゾリニウム塩の白色結晶を得た。収量は１０．４g、仕込みからのトータル収率は９０%であった。
（電解液の調製）
このテトラフルオロアルミネートの１−エチル−２，３−ジメチルイミダゾリニウム塩をγ−ブチロラクトンに溶解し２５％濃度の電解液を調製した。電気伝導率は２４．３ｍＳ／ｃｍであった。
〔実施例２〕
ＰＦＡ製丸底フラスコに１−エチル−２，３−ジメチルイミダゾリニウムのメチル炭酸塩のメタノール−炭酸ジメチル溶液（１．７７ｍｏｌ／ｋｇ）を２８．３ｇ（５０ｍｍｏｌ）を仕込み、１５℃で２０％フッ化水素メタノール溶液５．０ｇ（５０ｍｍｏｌ）を滴下した。そのまま３０分攪拌し、さらに三フッ化アルミニウム３水和物を６．９０（５０ｍｍｏｌ）を添加し５０℃で３時間攪拌した。反応液を濾過し、固形分を濾別後、溶媒を留去し、ｎ−ブタノール２３ｇから晶析してテトラフルオロアルミネートの１−エチル−２，３−ジメチルイミダゾリニウム塩の白色結晶を得た。収量は１０．２g、仕込みからのトータル収率は８９%であった。
〔実施例３〕
ＰＦＡ製丸底フラスコに１−エチル−２，３−ジメチルイミダゾリニウムのメチル炭酸塩のメタノール−炭酸ジメチル溶液（１．７７ｍｏｌ／ｋｇ）を２８．３ｇ（５０ｍｍｏｌ）を仕込み、１５℃で５０％フッ化水素水溶液２．０ｇ（５０ｍｍｏｌ）を滴下した。そのまま３０分攪拌し、さらに三フッ化アルミニウム３水和物を６．９０（５０ｍｍｏｌ）を添加し５０℃で３時間攪拌した。反応液を濾過し、固形分を濾別後、溶媒を留去し、ｎ−ブタノール２３ｇから晶析してテトラフルオロアルミネートの１−エチル−２，３−ジメチルイミダゾリニウム塩の白色結晶を得た。収量は５．８g、仕込みからのトータル収率は５０%であった。
〔比較例１〕
ガラス製丸底フラスコに１−エチル−２，３−ジメチルイミダゾリニウムのメチル炭酸塩のメタノール−ジメチルカーボネート溶液（１．７７ｍｏｌ／ｋｇ）を５６．５ｇ（１００ｍｍｏｌ）とフッ化アンモニウム３．７０ｇ（１００ｍｍｏｌ）を仕込み、５０℃で５時間攪拌した。反応液を濾過し、濾液に三フッ化アルミニウム３水和物を１３．８０（１００ｍｍｏｌ）を添加し５０℃で３時間攪拌したところ反応液がゲル化してしまった。
〔比較例２〕
ＰＦＡ製丸底フラスコにフッ化水素３０ｇ（１５００ｍｍｏｌ）を仕込み、１−エチル−２，３−ジメチルイミダゾリニウムのメチル炭酸塩のメタノール−炭酸ジメチル溶液（１．７７ｍｏｌ／ｋｇ）を２８．３ｇ（５０ｍｍｏｌ）を滴下した。そのまま３０分攪拌し、さらに三フッ化アルミニウム３水和物を６．９０（５０ｍｍｏｌ）を添加し３時間攪拌した。反応液は一旦完溶した後、固体が析出し、反応液及び固体を分析したが、テトラフルオロアルミネートの１−エチル−２，３−ジメチルイミダゾリニウム塩は存在していなかった。
【００２４】
【発明の効果】
本発明によれば、電池、電解コンデンサ等の電気化学的素子に使用される電解質をはじめとする各種化学品として有用なテトラフルオロアルミネートの有機オニウム塩を収率よく合成することができる。[0001]
[Technical field to which the invention belongs]
The present invention relates to a method for producing an organic onium salt of tetrafluoroaluminate. Tetrafluoroaluminate organic onium salts are surfactants, phase transfer catalysts, softeners, antistatic agents such as detergents, dispersants such as asphalt and cement, disinfectants, preservatives, fertilizers and particulate antiblocking agents It is a useful chemical substance used in a wide range of fields as an anti-aggregating agent and the like, and particularly useful as an electrolyte for electrochemical devices such as batteries and electrolytic capacitors.
[0002]
[Prior art]
As a method for producing an organic onium salt of tetrafluoroaluminate, a method of reacting an organoaluminum compound and a pyridine-hydrogen fluoride complex, a method of reacting an organic onium salt of tetrafluoroaluminate and an amine compound (Journal of the American) Chemical Society, 1993, 115, 3028), a method of reacting an organic onium carbonate or hydrogen carbonate with ammonium tetrafluoroaluminate (JP-A-11-322760), an organic onium hydroxide salt and A method of reacting ammonium tetrafluoroaluminate (Japanese Patent Laid-Open No. 11-322759) is known.
[0003]
Furthermore, the synthesis method of organic onium polyfluorometalate salt includes hydrofluoric acid of polyfluorometalate and halogen salt of organic onium (Journal of Organic Chemistry, 1971, 36, 2371) and organic onium hydroxide salt. (Journal of the Chemical Society, Perkin Transactions 2, 1978, Vol. 3, page 254) and organic onium alkyl carbonates (JP-A-62-1117380), quaternary ammonium salts and hydrogen fluoride A method of synthesizing a hydrogen fluoride salt of quaternary ammonium fluoride from boron and then reacting with boron trifluoride (Japanese Patent Laid-Open No. 11-310555) is known.
[0004]
[Problems to be solved by the invention]
However, in the method using organoaluminum, a pyrophoric material must be handled, and the number of steps increases because it passes through a pyridinium salt of tetrafluoroaluminate. Further, the method of reacting ammonium tetrafluoroaluminate is not suitable for the reaction because of the low solubility of ammonium tetrafluoroaluminate. Furthermore, although the presence of tetrafluoroaluminate hydroacid (tetrafluoroaluminate) has been suggested, it has not been fully demonstrated, and even industrially available is almost impossible.
[0005]
On the other hand, boron and aluminum are elements of the same genus, but the reaction of organic fluoride hydrogen fluoride salt and aluminum trifluoride, similar to boron trifluoride, shows that hydrogen fluoride is present in a large excess in the case of aluminum. In addition to tetrafluoroaluminate, 6-coordinate hexafluoroaluminate is formed, so that it cannot be applied.
Accordingly, there has been a strong demand for development of a production method suitable for industrial production of tetrafluoroaluminate organic onium salts.
[0006]
[Means for Solving the Problems]
As a result of diligent studies to solve these problems, the present inventors have found that an organic onium salt of tetrafluoroaluminate can be produced by reacting hydrogen fluoride, an organic onium salt and aluminum trifluoride. The headline and the present invention have been completed.
[0007]
That is, the gist of the present invention resides in a method for producing an organic onium salt of tetrafluoroaluminate characterized by reacting hydrogen fluoride, an organic onium salt and aluminum trifluoride.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
One of the raw materials in the production method of the present invention is an organic onium salt, preferably QOH, QRCO _Three Or an organic onium salt represented by QX (wherein Q represents an organic onium, R represents a hydrogen atom or an alkyl group having 10 or less carbon atoms, and X represents a halogen atom). Examples of the alkyl group having 10 or less carbon atoms defined by R include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-octyl group. , N-decyl group and the like. Examples of the halogen atom defined by X include a chlorine atom and a bromine atom. In the present invention, among these organic onium salts, hydroxide salts, methyl carbonates, and hydrogen carbonates are more preferable.
[0009]
The organic onium in the present invention is a general term for compounds produced by coordination bonding of protons and other cations to these lone electron pairs in a compound containing an element having a lone electron pair (nitrogen, phosphorus, etc.), Although not particularly limited, those represented by the following formula (I) are preferably used.
[0010]
[Chemical 2]

(Wherein R ¹ ~ R ^Four Each independently has a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or substituent. Represents an aralkyl group which may be ¹ ~ R ^Four Two or more of these do not represent a hydrogen atom. Also R ¹ ~ R ^Four May be bonded to each other partially or entirely to form a ring which may have a nitrogen atom, the ring may have an unsaturated bond, and the ring may have a substituent. You may do it. A represents a nitrogen atom or a phosphorus atom. )
R ¹ ~ R ^Four The alkyl group defined by is more preferably a C1-C20 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, n-hexyl group, etc. Is an alkyl group having 1 to 6 carbon atoms, and the cycloalkyl group is a cycloalkyl group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, more preferably a cycloalkyl group having 3 to 6 carbon atoms. The aryl group includes an aryl group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. The aralkyl group includes a benzyl group and a phenethyl group. And an aralkyl group having 7 to 20 carbon atoms, more preferably 7 to 11 carbon atoms, such as a naphthylmethyl group.
[0011]
These alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups may have a substituent, such as a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, and a formyl group. Can be mentioned.
Typical examples of the organic onium represented by the formula (I) include quaternized ammonium, quaternized phosphonium, quaternized imidazolium, quaternized cyclic amidinium, ammonium and the like. Moreover, as organic onium salt, what coordinated compounds, such as water and methanol, coordinated with organic onium salt is also included.
[0012]
Specific examples of quaternized ammonium include, for example, tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl-n-propylammonium, trimethylisopropylammonium, trimethyl-n-butylammonium, trimethylisobutyl. Ammonium, trimethyl-t-butylammonium, trimethyl-n-hexylammonium, dimethyldi-n-propylammonium, dimethyldiisopropylammonium, dimethyl-n-propylisopropylammonium, methyltri-n-propylammonium, methyltriisopropylammonium, methyldi-n -Propylisopropylammonium, methyl-n-propyl Isopropylammonium, triethyl-n-propylammonium, triethylisopropylammonium, triethyl-n-butylammonium, triethylisobutylammonium, triethyl-t-butylammonium, dimethyldi-n-butylammonium, dimethyldiisobutylammonium, dimethyldi-t-butylammonium, Dimethyl-n-butylethylammonium, dimethylisobutylethylammonium, dimethyl-t-butylethylammonium, dimethyl-n-butylisobutylammonium, dimethyl-n-butyl-t-butylammonium, dimethylisobutyl-t-butylammonium, diethyldi- n-propylammonium, diethyldiisopropylammonium, diethyl-n-propyliso Propylammonium, ethyltri-n-propylammonium, ethyltriisopropylammonium, ethyldi-n-propylisopropylammonium, ethyl-n-propyldiisopropylammonium, diethylmethyl-n-propylammonium, ethyldimethyl-n-propylammonium, ethylmethyldi- n-propylammonium, diethylmethylisopropylammonium, ethyldimethylisopropylammonium, ethylmethyldiisopropylammonium, ethylmethyl-n-propylisopropylammonium, tetra-n-propylammonium, tetraisopropylammonium, n-propyltriisopropylammonium, di-n -Propyl diisopropylammonium, tri-n-propyl isopropyl Tetraalkylammonium such as pyrammonium, trimethylbutylammonium, trimethylpentylammonium, trimethylhexylammonium, trimethylheptylammonium, trimethyloctylammonium, trimethylnonylammonium, trimethyldecylammonium, trimethylundecylammonium, trimethyldodecylammonium; trimethylphenylammonium, tetra Aromatic substituted ammonium such as phenylammonium; pyrrolidinium compounds such as N, N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N, N-diethylpyrrolidinium, N, N-tetramethylenepyrrolidinium N, N-dimethylpiperidinium, N-ethyl-N-methylpiperidinium, N, N-diethyl Piperidinium compounds such as peridinium, N, N-tetramethylenepiperidinium, N, N-pentamethylenepiperidinium, N, N-dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N, N- Aliphatic cyclic ammoniums such as morpholinium compounds such as diethylmorpholinium; nitrogen-containing heterocyclic aromatics such as N-methylpyridinium, N-ethylpyridinium, Nn-propylpyridinium, N-isopropylpyridinium, Nn-butylpyridinium Group compounds and the like.
[0013]
Specific examples of the quaternized phosphonium include tetramethylphosphonium, triethylmethylphosphonium, tetraethylphosphonium and the like.
Specific examples of quaternized imidazolium include 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium. 1,3-diethylimidazolium, 1,2-diethyl-3-methylimidazolium, 1,3-diethyl-2-methylimidazolium, 1,2-dimethyl-3-n-propylimidazolium, 1-n -Butyl-3-methylimidazolium, 1-methyl-3-n-propyl-2,4-dimethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1,2,3,4,5- Pentamethylimidazolium, 2-ethyl-1,3-dimethylimidazolium, 1,3-dimethyl-2-n-propylimidazolium, 1,3-dimethyl 2-n-pentylimidazolium, 1,3-dimethyl-2-n-heptylimidazolium, 1,3,4-trimethylimidazolium, 2-ethyl-1,3,4-trimethylimidazolium, 1,3- Dimethylbenzimidazolium, 1-phenyl-3-methylimidazolium, 1-benzyl-3-methylimidazolium, 1-phenyl-2,3-dimethylimidazolium, 1-benzyl-2,3-dimethylimidazolium, 2 -Phenyl-1,3-dimethylimidazolium, 2-benzyl-1,3-dimethylimidazolium, 1,3-dimethyl-2-n-undecylimidazolium, 1,3-dimethyl-2-n-heptadecyl Imidazolium and the like, further 2- (2'-hydroxy) ethyl-1,3-dimethylimidazolium, 1- (2'- Examples of groups having a hydroxyl group or an ether bond such as droxy) ethyl-2,3-dimethylimidazolium, 2-ethoxymethyl-1,3-dimethylimidazolium, 1-ethoxymethyl-2,3-dimethylimidazolium be able to.
[0014]
Specific examples of the quaternized cyclic amidinium include 1,3-dimethylimidazolinium, 1,2,3-trimethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1-ethyl-2,3- Dimethylimidazolinium, 1,3-diethylimidazolinium, 1,2-diethyl-3-methylimidazolinium, 1,3-diethyl-2-methylimidazolinium, 1,2-dimethyl-3-n- Propylimidazolinium, 1-n-butyl-3-methylimidazolinium, 1-methyl-3-n-propyl-2,4-dimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium 2-ethyl-1,3-dimethylimidazolinium, 1,3-dimethyl-2-n-propylimidazolinium, 1,3-dimethyl-2-n-pentyl Dazolinium, 1,3-dimethyl-2-n-heptylimidazolinium, 1,3,4-trimethylimidazolinium, 2-ethyl-1,3,4-trimethylimidazolinium, 1-phenyl-3-methyl Imidazolinium, 1-benzyl-3-methylimidazolinium, 1-phenyl-2,3-dimethylimidazolinium, 1-benzyl-2,3-dimethylimidazolinium, 2-phenyl-1,3-dimethyl Imidazolinium compounds such as imidazolinium and 2-benzyl-1,3-dimethylimidazolinium; 1,3-dimethyltetrahydropyrimidinium, 1,3-diethyltetrahydropyrimidinium, 1-ethyl-3-methyl Tetrahydropyrimidinium, 1,2,3-trimethyltetrahydropyrimidinium, 1,2,3-tri Tiltetrahydropyrimidinium, 1-ethyl-2,3-dimethyltetrahydropyrimidinium, 2-ethyl-1,3-dimethyltetrahydropyrimidinium, 1,2-diethyl-3-methyltetrahydropyrimidinium, 1, Tetrahydropyrimidinium compounds such as 3-diethyl-2-methyltetrahydropyrimidinium; 5-methyl-1,5-diazabicyclo [4.3.0] nonene-5, 8-methyl-1,8-diazabicyclo [5 4.0] undecene-7, 1,3-dimethyl-2-n-undecylimidazolinium, 1,3-dimethyl-2-n-heptadecylimidazolinium, and further 2- (2'-hydroxy ) Ethyl-1,3-dimethylimidazolinium, 1- (2′-hydroxy) ethyl-2,3-dimethylimidazolinium, Examples include 2-hydroxymethyl-1,3-dimethylimidazolinium, 1-ethoxymethyl-2,3-dimethylimidazolinium and other groups having a hydroxyl group and an ether bond.
[0015]
Specific examples of ammonium include trimethylammonium, ethyldimethylammonium, diethylmethylammonium, triethylammonium, pyridinium, N-methylimidazolinium, 1,5-diazabicyclo [4.3.0] nonenium-5, 1,8- And diazabicyclo [5.4.0] undecenium-7.
[0016]
Of these, organic oniums having a total carbon number of 4 to 12 are preferable, and tetraethylammonium, triethylmethylammonium, diethyldimethylammonium, ethyltrimethylammonium, tetramethylammonium, N, N-dimethylpyrrolidinium, N- Ethyl-N-methylpyrrolidinium, 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1 , 2,3,4-tetramethylimidazolium, 1,3-diethylimidazolium, 2-ethyl-1,3-dimethylimidazolium, 1,3-dimethyl-2-n-propylimidazolium, 1,3- Dimethyl-2-n-pentylimidazolium, 1,3-dimethyl Ru-2-n-heptylimidazolium, 1,3,4-trimethylimidazolium, 2-ethyl-1,3,4-trimethylimidazolium, 1,3-dimethylbenzimidazolium, 1-phenyl-3-methyl Imidazolium, 1-benzyl-3-methylimidazolium, 1-phenyl-2,3-dimethylimidazolium, 1-benzyl-2,3-dimethylimidazolium, 2-phenyl-1,3-dimethylimidazolium, 2 -Benzyl-1,3-dimethylimidazolium, 1,3-dimethylimidazolinium, 1,2,3-trimethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1-ethyl-2,3- Dimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,3-diethylimidazolinium 2-ethyl-1,3-dimethylimidazolinium, 1,3-dimethyl-2-n-propylimidazolinium, 1,3-dimethyl-2-n-pentylimidazolinium, 1,3-dimethyl-2 N-heptylimidazolinium, 1,3,4-trimethylimidazolinium, 2-ethyl-1,3,4-trimethylimidazolinium, 1-phenyl-3-methylimidazolinium, 1-benzyl-3 -Methylimidazolinium, 1-phenyl-2,3-dimethylimidazolinium, 1-benzyl-2,3-dimethylimidazolinium, 2-phenyl-1,3-dimethylimidazolinium, 2-benzyl-1 , 3-Dimethylimidazolinium is preferably one or more compounds selected from the group consisting of 1-ethyl-2,3- Preferred are dimethylimidazolinium and 1,2,3,4-tetramethylimidazolinium.
[0017]
These organic onium salts can be used as they are, or those dissolved in a solvent can be used. Further, the quaternization reaction solution can be used as it is. For example, a reaction solution obtained by quaternizing 1-ethyl-2-methylimidazole with dimethyl carbonate can be used as it is.
Another raw material in the production method of the present invention is hydrogen fluoride. As hydrogen fluoride, hydrogen fluoride can be used as it is, or one dissolved in a solvent can be used. The solvent may be any reaction inert. Of these use forms, anhydrous hydrogen fluoride, hydrogen fluoride methanol solution, and hydrogen fluoride aqueous solution can be preferably used. When the organic onium is hydrolyzable, it is preferable that the hydrogen fluoride solution does not contain water.
[0018]
Still another raw material in the production method of the present invention is aluminum trifluoride. Preferably, aluminum trifluoride hydrate can be used, and aluminum trifluoride trihydrate can be used particularly preferably.
Examples of the solvent that can be used in the production method of the present invention include water; alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; , Ethers such as ethyl-n-propyl ether, ethyl-isopropyl ether, di-n-propyl ether, diisopropyl ether, n-propyl isopropyl ether, dimethoxyethane, methoxyethoxyethane, diethoxyethane, tetrahydrofuran; acetonitrile, propio Nitriles such as nitriles; hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene; ethyl acetate, Butyl, dimethyl carbonate, diethyl carbonate, methyl carbonate, ethyl, ethylene carbonate, esters such as propylene carbonate and the like. Among these, water, methanol, and ethanol are more preferable. When the organic onium is hydrolyzable, it is preferable that the solvent does not contain water. These solvents may be used alone or in combination.
[0019]
The reaction method is, for example, a method in which an organic onium salt or a solution thereof is added to hydrogen fluoride or a solution thereof, and then aluminum trifluoride is added; a hydrogen fluoride or a solution thereof is added to an organic onium salt or a solution thereof, and then Method of adding aluminum trifluoride; Method of adding hydrogen fluoride or a solution thereof and organic onium salt or a solution thereof in the presence or absence of a solvent simultaneously or alternately, and then adding aluminum trifluoride; Method of adding aluminum trifluoride to hydrogen or a solution thereof, and then adding an organic onium salt or solution thereof; adding hydrogen fluoride or a solution thereof to aluminum trifluoride in the presence or absence of a solvent, and then organically A method of adding an onium salt or a solution thereof; hydrogen fluoride or a solution thereof and aluminum trifluoride in the presence or absence of a solvent simultaneously Alternating addition, then adding organic onium salt or solution thereof; adding aluminum trifluoride to organic onium salt or solution thereof, then adding hydrogen fluoride or solution thereof; in the presence or absence of solvent A method in which an organic onium salt or a solution thereof is added to aluminum trifluoride with a solvent, and then hydrogen fluoride or a solution thereof is added; the organic onium salt or a solution thereof and aluminum trifluoride are simultaneously added in the presence or absence of a solvent. Or a method in which hydrogen fluoride or a solution thereof is added alternately, and then an organic onium salt or a solution thereof and hydrogen fluoride or a solution thereof and aluminum trifluoride are added simultaneously or alternately in the presence or absence of a solvent. And a combination of those methods. Among these, preferably, a method of adding an organic onium salt or a solution thereof to hydrogen fluoride or a solution thereof, and then adding aluminum trifluoride; a method of adding hydrogen fluoride or a solution thereof to an organic onium salt or a solution thereof; Next, a method of adding aluminum trifluoride; a method of adding hydrogen fluoride or a solution thereof and an organic onium salt or a solution thereof in the presence or absence of a solvent simultaneously or alternately, and then adding aluminum trifluoride is used. it can. At this time, the organic onium salt may be isolated by a method such as crystallization or solvent extraction before adding aluminum trifluoride.
[0020]
The amount of hydrogen fluoride used is preferably 0.5 to 1.5 mol times, more preferably 0.8 to 1.2 mol times, particularly preferably 0.9 to 1.0 mol times with respect to the organic onium salt. It is. When 1.5 mol times or more, preferably 1.0 mol times or more of hydrogen fluoride is used, before the aluminum trifluoride and the organic onium salt come into contact with each other, for example, evaporation, neutralization, etc. It is preferable to remove part or all of the hydrogen fluoride.
[0021]
The amount of aluminum trifluoride used is preferably 0.5 to 10 times, more preferably 0.8 to 2 times, particularly preferably 0.9 to 1.2 times in terms of molar ratio to the organic onium salt. .
The reaction temperature is not limited, but it is first reacted at -20 to 150 ° C, preferably -10 to 50 ° C, more preferably 0 to 25 ° C, and then reacted at -20 to 150 ° C, preferably 0 to 100 ° C. Can be made.
[0022]
The organic onium salt of tetrafluoroaluminate obtained by the present invention can be separated and purified using conventional methods such as distillation, extraction, chromatography, and recrystallization.
In addition, when an organic onium salt of tetrafluoroaluminate obtained according to the present invention is used for an electrolytic capacitor, it is desired to have a high purity. Therefore, the salt is purified to a desired purity by crystallization or solvent extraction, if necessary. Used.
[0023]
【Example】
The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
[Example 1]
28.3 g (50 mmol) of methanol-dimethyl carbonate solution of methyl carbonate of 1-ethyl-2,3-dimethylimidazolinium (1.77 mol / kg) was charged into a round bottom flask made of PFA, and anhydrous fluorine was added at 15 ° C. 1.0 g (50 mmol) of hydrogen halide was added dropwise. The mixture was stirred as it was for 30 minutes, and 6.90 (50 mmol) of aluminum trifluoride trihydrate was further added, followed by stirring at 50 ° C. for 3 hours. The reaction solution was filtered, the solid content was filtered off, the solvent was distilled off, and crystallization from 23 g of n-butanol gave white crystals of 1-ethyl-2,3-dimethylimidazolinium salt of tetrafluoroaluminate. Obtained. The yield was 10.4 g, and the total yield from the charge was 90%.
(Preparation of electrolyte)
This 1-ethyl-2,3-dimethylimidazolinium salt of tetrafluoroaluminate was dissolved in γ-butyrolactone to prepare an electrolyte solution having a concentration of 25%. The electric conductivity was 24.3 mS / cm.
[Example 2]
28.3 g (50 mmol) of methanol-dimethyl carbonate solution of methyl carbonate of 1-ethyl-2,3-dimethylimidazolinium (1.77 mol / kg) was charged into a round bottom flask made of PFA, and 20% at 15 ° C. Hydrogen fluoride methanol solution 5.0g (50mmol) was dripped. The mixture was stirred as it was for 30 minutes, and 6.90 (50 mmol) of aluminum trifluoride trihydrate was further added, followed by stirring at 50 ° C. for 3 hours. The reaction solution was filtered, the solid content was filtered off, the solvent was distilled off, and crystallization from 23 g of n-butanol gave white crystals of 1-ethyl-2,3-dimethylimidazolinium salt of tetrafluoroaluminate. Obtained. The yield was 10.2 g, and the total yield from the charge was 89%.
Example 3
28.3 g (50 mmol) of a methanol-dimethyl carbonate solution of methyl carbonate of 1-ethyl-2,3-dimethylimidazolinium (1.77 mol / kg) was charged in a round bottom flask made of PFA and 50% at 15 ° C. An aqueous hydrogen fluoride solution (2.0 g, 50 mmol) was added dropwise. The mixture was stirred as it was for 30 minutes, and 6.90 (50 mmol) of aluminum trifluoride trihydrate was further added, followed by stirring at 50 ° C. for 3 hours. The reaction solution was filtered, the solid content was filtered off, the solvent was distilled off, and crystallization from 23 g of n-butanol gave white crystals of 1-ethyl-2,3-dimethylimidazolinium salt of tetrafluoroaluminate. Obtained. The yield was 5.8 g, and the total yield from the preparation was 50%.
[Comparative Example 1]
In a glass round bottom flask, 56.5 g (100 mmol) of methyl carbonate solution (1.77 mol / kg) of methyl carbonate of 1-ethyl-2,3-dimethylimidazolinium and 3.70 g of ammonium fluoride ( 100 mmol) and stirred at 50 ° C. for 5 hours. The reaction solution was filtered, and 13.80 (100 mmol) of aluminum trifluoride trihydrate was added to the filtrate and stirred at 50 ° C. for 3 hours. The reaction solution gelled.
[Comparative Example 2]
A PFA round bottom flask was charged with 30 g (1500 mmol) of hydrogen fluoride, and 28.3 g of a methanol-dimethyl carbonate solution (1.77 mol / kg) of methyl carbonate of 1-ethyl-2,3-dimethylimidazolinium ( 50 mmol) was added dropwise. The mixture was stirred as it was for 30 minutes, and 6.90 (50 mmol) of aluminum trifluoride trihydrate was further added, followed by stirring for 3 hours. After the reaction solution was completely dissolved, a solid was precipitated and the reaction solution and the solid were analyzed. However, 1-ethyl-2,3-dimethylimidazolinium salt of tetrafluoroaluminate was not present.
[0024]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the organic onium salt of tetrafluoroaluminate useful as various chemicals including the electrolyte used for electrochemical elements, such as a battery and an electrolytic capacitor, can be synthesize | combined with a sufficient yield.

Claims (13)

  A method for producing an organic onium salt of tetrafluoroaluminate, comprising reacting hydrogen fluoride, an organic onium salt and aluminum trifluoride.   The manufacturing method according to claim 1, wherein hydrogen fluoride and an organic onium salt are reacted, and then reacted with aluminum trifluoride. The production method according to claim 1 or 2, wherein 0.5 to 1.5 moles of hydrogen fluoride is used with respect to the organic onium salt. A compound in which the organic onium salt is represented by the general formula QOH, QRCO ₃ or QX (wherein Q represents an organic onium, R represents a hydrogen atom or an alkyl group having 10 or less carbon atoms, and X represents a halogen atom). The manufacturing method according to any one of claims 1 to 3, wherein:   The method according to any one of claims 1 to 4, wherein the organic onium salt is selected from an organic onium hydroxide salt, methyl carbonate, and hydrogen carbonate. Organic onium is represented by the following (I) formula, The manufacturing method of any one of Claims 1-5 characterized by the above-mentioned.

(In the formula, R ^{1 to} R ⁴ may each independently have a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. It represents an aryl group or an optionally substituted aralkyl group, two or more R ¹ to R ⁴ never represent a hydrogen atom. the R ¹ to R ^4, a part or all of each other It may be bonded to form a ring which may have a nitrogen atom, the ring may have an unsaturated bond, and the ring may have a substituent. Represents a nitrogen atom or a phosphorus atom.)   The organic onium is a compound selected from the group consisting of quaternized ammonium, quaternized phosphonium, quaternized imidazolium, quaternized cyclic amidinium, and ammonium. The production method according to item.   The total carbon number of organic onium is 4-12, The manufacturing method of any one of Claims 1-7 characterized by the above-mentioned.   The organic onium is selected from 1-ethyl-2,3-dimethylimidazolinium and 1,2,3,4-tetramethylimidazolinium, according to any one of claims 1-8. Production method.   The method according to any one of claims 1 to 9, wherein the aluminum trifluoride is a trihydrate of aluminum trifluoride. The method according to any one of claims 1 to 10, wherein hydrogen fluoride and an organic onium salt are reacted, and then reacted with aluminum trifluoride in the absence of excess hydrogen fluoride. Claim 1-11 tetrafluoroaluminate electrolyte for electrolytic capacitor using an organic onium salt of the sulphonate produced by the production method according to any one of. The electrolytic capacitor using the electrolyte solution for electrolytic capacitors of Claim 12 .