JP3908382B2 - Method for producing fluorine-containing ether compound - Google Patents

Description

【００１４】
〔式中、R₂，R₃は水素原子、炭素数１〜20の直鎖又は分岐鎖のアルキル基あるいはアルケニル基、もしくはこれらの基の水素原子の少なくとも１つがフッ素原子で置換されたフッ素置換基を示し、R₂，R₃は同一であっても異なっていてもよい。また、R₂，R₃が結合した環状構造であってもよい。〕
で表される化合物又はこれらの重合体が挙げられる。
なお、一般式（２）で表される化合物の重合体としては、パラホルムアルデヒド、パラアルデヒド（アセトアルデヒドの３量体）等が挙げられる。
【００１５】
一般式（２）で表される化合物又はこれらの重合体のうち、フッ素置換基を有さないものとしては、炭素数３〜19の鎖状ケトン、炭素数１〜19のアルデヒド、炭素数５〜８の環状ケトン、パラホルムアルデヒド、パラアルデヒドが好ましく、アセトン、メチルエチルケトン、メチルイソブチルケトン（４−メチル−２−ペンタノン）等の炭素数３〜６の鎖状ケトンや、ホルムアルデヒド、アセトアルデヒド、ブチルアルデヒド、イソブチルアルデヒド、オクチルアルデヒド、イソノニルアルデヒド（３, ５, ５−トリメチルヘキサナール）、ドデシルアルデヒド等の炭素数１〜12の脂肪族アルデヒド類、シクロヘキサノン等の炭素数５〜６の環状ケトン、パラホルムアルデヒド、パラアルデヒドが特に好ましく、更にはアセトン、メチルエチルケトン、メチルイソブチルケトン（４−メチル−２−ペンタノン）、ブチルアルデヒド、イソブチルアルデヒド、オクチルアルデヒド、イソノニルアルデヒド（３, ５, ５−トリメチルヘキサナール）、パラアルデヒドが特に好ましい。これらのカルボニル化合物は１種以上を用いることができる。
【００１６】
また、フッ素置換基を有する一般式（２）で表されるカルボニル化合物としては、上記で示したフッ素置換基を有さないカルボニル化合物の水素原子の少なくとも１つがフッ素原子で置換されたフッ素置換基を有する含フッ素カルボニル化合物が挙げられ、これらの具体例としては、フルオロアセトン、１，１，１−トリフルオロアセトン、１，１，１−トリフルオロ−２−ブタノン、１，１，１−トリフルオロ−２−ペンタノン、１，１，１−トリフルオロ−２−ヘキサノン、ビス（トリフルオロメチル）ケトン、ビス（ペンタフルオロエチル）ケトン、ビス（ヘプタフルオロプロピル）ケトン、トリフルオロメチルペンタフルオロエチルケトン、トリフルオロメチルヘプタフルオロプロピルケトン等の含フッ素ケトン類、３，３，３−トリフルオロプロピルアルデヒド、４，４，４−トリフルオロブチルアルデヒド、５，５，５−トリフルオロペンチルアルデヒド、６，６，６−トリフルオロヘキシルアルデヒド等の含フッ素アルデヒド類などが挙げられる。これらの含フッ素カルボニル化合物の中では、炭素数１〜12の含フッ素鎖状ケトン、炭素数１〜12の含フッ素鎖状アルデヒドが好ましく、特に一般式（５）で表される含フッ素ケトン又は一般式（６）で表される含フッ素アルデヒドが好ましい。
【００１７】
【化３】

【００１８】
（式中、Rf₂ は炭素数１〜10の含フッ素アルキル基を示し、R₄は炭素数１〜10のアルキル基を示す。）
Rf₃(CH₂)_qCHO （６）
（式中、Rf₃ は炭素数１〜10の含フッ素アルキル基を示し、q は１〜10の数を示す。）
これらの含フッ素カルボニル化合物は１種以上を用いることができる。
【００１９】
本発明においては、ヒドロキシ化合物として、精製処理によりアルカリ成分及び／又は含窒素成分を除去したヒドロキシ化合物を用いる。
即ち、例えばヒドロキシ化合物として、フッ素置換基を有する含フッ素ヒドロキシ化合物を用いる場合、この含フッ素ヒドロキシ化合物は、ハロゲン化フルオロアルキルを酸、Ｎ−メチルピロリドン又はＮ，Ｎ−ジメチルホルムアミドの存在下で加水分解することにより製造されるが、その際に残余の酸をアルカリ成分を用いて中和するためにヒドロキシ化合物中にアルカリ成分が混入したり、又は除去しきれない含窒素成分が混入する。また、ヒドロキシ化合物として、アルコールのアルキレンオキサイド付加物を用いる場合には、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム等のアルカリ金属を含有する触媒が用いられ、反応後にこの触媒が残存している。
【００２０】
本発明においては、ヒドロキシ化合物として、上記のような製造時に混入するアルカリ成分及び／又は含窒素成分を精製処理により除去したものを用いる。精製処理は、ヒドロキシ化合物中の窒素含量あるいはアルカリ金属イオン含量を200 ppm 以下とすることが好ましく、吸着剤処理、蒸留処理又は無機強酸による中和処理等の方法が挙げられる。これらの中ではヒドロキシ化合物が蒸留可能な低沸点物の場合は蒸留処理が、ヒドロキシ化合物が蒸留不可能な高沸点物の場合は吸着剤処理が好ましい。
【００２１】
本発明における吸着剤処理に用いられる吸着剤としては、シリカ、マグネシア及びアルミナから選択される少なくとも１種を主成分とするものが挙げられ、具体的にはケイ酸マグネシウム、酸化アルミニウム、酸化マグネシウム、水酸化アルミニウム、炭酸アルミニウム、炭酸マグネシウム、あるいはこれらの混合物等が挙げられ、ゼオライト、シリカ／アルミナ、活性アルミナ、キョーワード（協和化学工業（株）製）、活性白土等として市販されているものを用いればよい。吸着剤の添加量はヒドロキシル化合物に対して、 0.1〜20重量％が好ましい。また吸着剤処理は減圧下、50〜 200℃の温度で攪拌処理するのが好ましい。
【００２２】
また、本発明における蒸留処理は、13.3Pa〜常圧下、50〜 250℃の温度範囲で行うのが好ましい。
【００２３】
本発明においては、上記の吸着剤処理、蒸留処理に中和処理を組み合わせて行ってもよく、精製処理することにより、ヒドロキシ化合物中の窒素含量、あるいはＫ、Ｎａ等のアルカリ金属イオン含量を200ppm 以下、更には100ppm 以下、特に50ppm 以下とすることが好ましい。
【００２４】
本発明における無機強酸による中和処理に用いられる無機強酸としては、pKa ３以下のもの、好ましくは塩酸（pKa −８）、硫酸（pKa 1.99）、リン酸（pKa 2.15）が挙げられ、これらの酸によりpH５〜７となるように中和するのが好ましい。中和処理はアルコールの溶解条件下で酸を添加し、５〜60分攪拌すればよい。なお、このpHは１％水溶液での測定値である。
【００２５】
本発明の製造法において、ヒドロキシ化合物とカルボニル化合物の仕込み比は、特に限定されないが、通常、ヒドロキシ化合物／カルボニル化合物（モル比）＝50／１〜１／50が好ましく、30／１〜１／30がより好ましく、20／１〜１／20が更に好ましく、特に10／１〜１／10が好ましい。ヒドロキシ化合物が低分子量で、蒸留等で容易に除去できるものであれば、ヒドロキシ化合物を過剰に用いて反応させるのが好ましい。また、カルボニル化合物が低分子量で、蒸留等で容易に除去できるものであれば、カルボニル化合物を過剰に用いて反応させるのが好ましい。ヒドロキシ化合物／カルボニル化合物のモル比が上記範囲以外でも収率にはそれほど影響を与えないが、経済的ではない。
【００２６】
本発明において、ヒドロキシ化合物とカルボニル化合物を反応させる際に用いられる触媒としては、水素化能を有するものであれば特に限定されないが、パラジウム触媒；水酸化パラジウム、酸化パラジウム等のパラジウム化合物；ルテニウム、ロジウムあるいは白金触媒；酸化ルテニウム、酸化ロジウム、酸化白金等が挙げられる。また、イリジウム、オスミウム、レニウム等の触媒も用いることができる。これらの触媒は、カーボン、アルミナ、シリカアルミナ、シリカ、ゼオライト等の担体に適度に担持されていてもよい。これらの触媒の中で、好ましくはパラジウム系触媒、更に好ましくはカーボン、アルミナ、シリカアルミナもしくはシリカに担持されたパラジウム触媒、水酸化パラジウム又は酸化パラジウムであり、特にカーボンに担持されたパラジウム触媒が好ましい。
【００２７】
本発明において触媒は、通常カーボン、アルミナ等の担体に対して１〜10重量％の割合で担持して使用するが、担体に担持せずにそのまま使用しても構わない。また、20〜60重量％程度の含水品であっても構わない。
触媒は、例えば担体に対して５重量％担持されたものであれば、使用するヒドロキシ化合物に対して0.1〜10重量％使用するのが好ましい。0.1重量％より少なくても反応は進行するが、反応は遅く好ましくない。また、10重量％より多く用いても反応は速いが、逆に副反応も進行し好ましくない。さらに好ましくは0.5 〜５重量％である。
触媒はすべてのｐＨ領域で使用できるが、好ましくはｐＨ８〜２、更に好ましくはｐＨ 7.5〜３の触媒がよい。ここでいう触媒のｐＨとは、イオン交換水30ｇに触媒粉末２ｇを分散させた時の水溶液のｐＨをいう。
【００２８】
本発明においては、ヒドロキシ化合物とカルボニル化合物を水素雰囲気中で反応させるが、水素圧は特に限定されず、加圧下又は大気圧下のいずれでもよく、0.098MPa（大気圧）〜29.4MPa が好ましく、0.098MPa（大気圧）〜19.6MPa が特に好ましい。
また、本発明において、ヒドロキシ化合物とカルボニル化合物を反応させる際の反応温度は特に限定されないが、10〜 200℃が好ましく、30〜 180℃が特に好ましい。反応時間は、反応温度、水素圧、触媒量などによって適宜選べばよいが、通常１〜24時間、好ましくは１〜12時間である。
【００２９】
尚、カルボニル化合物がアルデヒド類の時は、アルデヒド類を反応系に滴下しながら反応させることが望ましい。アルデヒド類の滴下速度は反応のスケールに応じて適宜選べばよいが、例えば0.5 リットルのスケールでは、 0.1〜180 ｇ／hrが好ましく、 0.6〜60ｇ／hrが更に好ましい。
【００３０】
また、本発明の反応においては、場合によっては反応に全く悪影響を及ぼさない溶媒を用いて反応を行ってもよい。反応に全く悪影響を及ぼさない溶媒としては、ヘキサン、ヘプタン、オクタン等の炭化水素系溶媒が挙げられる。
反応に全く悪影響を及ぼさない溶媒を用いる場合の溶媒の使用量は、特に限定されないが、反応液に対して0.5 〜２倍容量が好ましい。
【００３１】
また、本発明においては、反応系中に副生する水を除去する目的で、無水硫酸マグネシウム、無水硫酸ナトリウム等の脱水剤を添加したり、水素等の気体を流通させたり、共沸脱水等を行っても良い。
【００３２】
【実施例】
例中の％は特記しない限り重量基準である。
なお、実施例７及び８は参考例である。
【００３３】
製造例１
100 mlのガラス容器に CF₃(CF₂)₅CH₂CH₂I 4.74ｇと、このCF₃(CF₂)₅CH₂CH₂Iに対して22.0モル倍のN,N −ジメチルホルムアミド、８モル倍の水を入れ、150 ℃で６時間反応させ、50mlの水で洗浄した。アルカリ洗浄を行った後、蒸留して窒素含量420ppmの粗２−（パーフルオロヘキシル）エタノールを得た。
0.5 Ｌの３つ口フラスコに上記で得られた粗２−（パーフルオロヘキシル）エタノール100 ｇ、珪酸マグネシウム（キョーワード 600S 、協和化学工業（株）製）を2.6ｇ入れ、減圧下(9.31kPa) 、100℃で１時間撹拌した。その後、珪酸マグネシウムを濾別し、精製２−（パーフルオロヘキシル）エタノールを95ｇ得た。得られた精製２−（パーフルオロヘキシル）エタノール中の窒素含量は20ppm であった。
【００３４】
製造例２〜３
CF₃(CF₂)₅CH₂CH₂I の代わりに、 CF₃(CF₂)₇CH₂CH₂I 又は CF₃(CF₂)₉CH₂CH₂I を用いる以外は、製造例１と同様にして窒素含量500ppmの粗２−（パーフルオロオクチル）エタノール、窒素含量370ppmの粗２−（パーフルオロデシル）エタノールを得た。
得られた粗２−（パーフルオロオクチル）エタノール、粗２−（パーフルオロデシル）エタノールについても製造例１と同様の精製処理を行い、それぞれ窒素含量が34ppm 、25ppm の精製２−（パーフルオロオクチル）エタノール、２−（パーフルオロデシル）エタノールを得た。
【００３５】
実施例１
１，３−ジメチルブチル｛２−（パーフルオロヘキシル）エチル｝エーテルの製造
【００３６】
【化４】

【００３７】
水素ガス導入管及び撹拌装置を備えた70mlのオートクレーブに、製造例１で得られた精製２−（パーフルオロヘキシル）エタノール（窒素含量20ppm)18.2ｇ (0.05モル）、４−メチル−２−ペンタノン30.0ｇ(0.3モル）、触媒として５％Ｐｄ−Ｃ（ｐＨ 7.2)1.5ｇを仕込み、大気圧下、 105℃、水素を18ml／min 吹き込みながら10時間反応を行った。反応終了後、濾過により触媒を除去し、減圧にて過剰の４−メチル−２−ペンタノンを除去することにより、目的の１，３−ジメチルブチル｛２−（パーフルオロヘキシル）エチル｝エーテル21.5ｇ(0.048モル）を得た。単離収率は96％であった。
【００３８】
実施例２〜６
表１に示すヒドロキシ化合物とカルボニル化合物とを、表１に示す触媒を用い、表１に示す反応条件以外は、実施例１と同様な操作で反応を行った。
得られた生成物及びその単離収率を表１に示す。
【００３９】
【表１】

【００４０】
比較例１〜６
ヒドロキシ化合物として精製前の２−（パーフルオロヘキシル）エタノール（窒素含量420ppm）、２−（パーフルオロオクチル）エタノール（窒素含量500ppm) 、２−（パーフルオロデシル）エタノール（窒素含量370ppm) を用い、表２に示す触媒及び反応条件以外は実施例１〜６と同様にして反応を行なった。
得られた生成物及びその単離収率を表２に示す。
【００４１】
【表２】

【００４２】
製造例４
オートクレーブにドデシルアルコール 185ｇ、水酸化カリウム0.81ｇを入れ、窒素置換後、 100〜 110℃でエチレンオキサイド 400ｇを４時間かけて送入し、揮発分 0.5％以下となるまで反応を続け、反応終了後、酢酸0.84ｇを加えて中和し、粗ポリオキシエチレンドデシルエーテルを得た。得られた粗ポリオキシエチレンドデシルエーテルの平均エチレンオキサイド付加モル数は 9.1モル、Ｋイオン量は970ppmであった。
【００４３】
３つ口フラスコに上記のＫイオン量970ppmの粗ポリオキシエチレン(p＝9.1)モノドデシルエーテル 100ｇ、珪酸マグネシウム（キョーワード 600S 、協和化学工業（株）製）を2.6g入れ、減圧下 (3.99〜5.32kPa)、 140℃で１時間撹拌した。その後、珪酸マグネシウムを濾別し、精製ポリオキシエチレン(p＝9.1)モノドデシルエーテルを90ｇ得た。得られた精製ポリオキシエチレン(p＝9.1)モノドデシルエーテル中のＫイオン量は33ppm であった。
製造例５
オートクレーブにブチルアルコール74ｇ、水酸化カリウム0.32ｇを入れ、窒素置換後、 100〜 110℃でエチレンオキサイド 132ｇを２時間かけて送入し、揮発分 0.5％以下となるまで反応を続け、粗ポリオキシエチレンブチルエーテルを得た。得られた粗ポリオキシエチレンブチルエーテルの平均エチレンオキサイド付加モル数は３モル、Ｋイオン量は1080ppm であった。
得られたＫイオン量1080ppm のポリオキシエチレン(p＝3)モノブチルエーテルについても、製造例４と同様に精製処理し、Ｋイオン量１ppm の精製ポリオキシエチレン(p＝3)モノブチルエーテルを得た。
【００４４】
実施例７
500ml 容オートクレーブに、製造例４で得られたＫイオン量33ppm の精製ポリオキシエチレン(p＝9.1)モノドデシルエーテル80ｇ、１，１，１−トリフルオロ−２−ブタノン105g(0.68 モル）、触媒として５％Ｐｄ−Ｃ 1.6ｇ（ｐＨ7.1)を仕込み、水素雰囲気下、反応温度 150℃、反応圧力6.86MPa 、回転数800rpmで７時間反応を行った。
反応終了後、濾過により触媒を除去し、未反応１，１，１−トリフルオロ−２−ブタノンを減圧留去することより、エーテル化度77％のポリオキシエチレングリコール(p＝9.1)｛１−（パーフルオロメチル）プロピル｝ドデシルエーテルを94ｇ得た。
【００４５】
実施例８
製造例５で得られたＫイオン量１ppm の精製ポリオキシエチレン(p＝3)モノブチルエーテル41ｇ(0.2モル）、１，１，１−トリフルオロ−２−ブタノン154g(1モル）、触媒として５％Ｐｄ−Ｃ 1.0ｇ（ｐＨ7.1)を用いる以外は実施例７と同様な条件で反応を行い、同様に処理してエーテル化度80％のポリオキシエチレングリコール(p＝3)｛１−（パーフルオロメチル）プロピル｝ブチルエーテルを63ｇ得た。
【００４６】
比較例７，８
ヒドロキシ化合物として、精製前のＫイオン量970ppmのポリオキシエチレン(p＝9.1)モノドデシルエーテル、Ｋイオン量1080ppm のポリオキシエチレン(p＝3)モノブチルエーテルを用いた以外はすべて実施例７, ８と同様の操作で反応を行った。その結果、全く反応は進行しなかった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a fluorinated ether compound capable of supplying a fluorinated ether compound that can be used in a wide range of solvents, cosmetics, cleaning compositions, emulsifiers, surface treatment agents, etc. in a simple and high yield.
[0002]
[Prior art]
Conventionally, as a method for producing a fluorinated ether compound, for example, the following formula (3)
R-CH ₂ OH (3)
(In the formula, R represents an alkyl group or a fluorine-containing alkyl group.)
A hydrocarbon-based or fluorine-containing alcohol represented by the formula (1) is converted to an alcoholate such as Na or K and then reacted with an alkyl halide or a halogenated fluorine-containing alkyl (Williamson synthesis method) to synthesize a fluorine-containing ether compound The method is known.
[0003]
Japanese Patent Publication No. 8-30021 discloses the use of a fluoroolefin by reacting a fluoroolefin with a fluorinated carbonyl compound in the presence of AgF in an aprotic polar solvent having a hydrogen atom. A method is disclosed.
[0004]
However, the former method requires alkali equivalent to the alcohol used, such as Na, K 2, and a large amount of salt is generated after the reaction, which is not industrially preferable.
In the latter method, since the catalyst AgF to be used becomes a fluorine atom constituting the fluorinated ether compound, it must be equimolar or more with respect to the fluorinated carbonyl compound as a raw material. There is a problem that cannot be reused.
[0005]
A fluorine-containing ether compound can also be synthesized from a fluorine-containing alcohol and an ester compound, but the ester compound is limited to dimethyl sulfate, diethyl sulfate, etc., and is preferred for the synthesis of methyl ether and ethyl ether. It is difficult to synthesize a fluorine-containing ether compound having a large number of carbon atoms.
[0006]
[Problems to be solved by the invention]
As described above, a fluorine-containing ether compound is expected to be used, but is difficult to produce, and therefore cannot be used for general purposes, and a method for producing a fluorine-containing ether compound that can be supplied simply and inexpensively has been desired. .
Accordingly, an object of the present invention is to provide a production method capable of supplying a fluorine-containing ether compound usable for a solvent, a cosmetic, a cleaning composition, an emulsifier, a surface treatment agent, etc. in a simple and high yield.
[0007]
[Means for Solving the Problems]
In the present invention, when an ether compound is produced by reacting a hydroxy compound and a carbonyl compound in a hydrogen atmosphere using a catalyst, a fluorine compound having a fluorine substituent is used as at least one of the hydroxy compound or the carbonyl compound, and This is a method for producing a fluorinated ether compound using a hydroxy compound from which an alkali component and / or a nitrogen-containing component has been removed by a purification treatment as the hydroxy compound.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
As the hydroxy compound used in the present invention, the general formula (1)
R ₁ O- (AO) _n -H (1)
[Wherein, R ₁ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or at least one hydrogen atom of these groups is fluorine. A fluorine substituent substituted with an atom is shown. A 1 represents a linear or branched alkylene group having 2 to 12 carbon atoms which may have a hydroxy group as a substituent, and n 1 A may be the same or different. n represents a number from 0 to 500. ]
The compound represented by these is mentioned.
[0009]
Among the compounds represented by the general formula (1), those having no fluorine substituent include aliphatic alcohols having 1 to 22 carbon atoms, particularly 6 to 22 carbon atoms, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, Methyl carbitol, ethyl carbitol, isopropyl carbitol, butyl carbitol, or ethylene oxide or / and propylene oxide adduct of aliphatic alcohol having 1 to 22 carbon atoms, especially 6 to 22 carbon atoms (average added mole number 0.1 to 200) C5-C8 cycloalkanols and C2-C10 diols are preferred, C6-C22 aliphatic alcohols; cyclohexanol; ethylene glycol, 1,4-butanediol, 1,6-hexane Diols such as diol and 1,9-nonanediol are preferred. One or more of these hydroxy compounds can be used.
[0010]
In addition, as the hydroxy compound represented by the general formula (1) having a fluorine substituent, a fluorine substituent in which at least one hydrogen atom of the hydroxy compound having no fluorine substituent described above is substituted with a fluorine atom Specific examples of these compounds include 2,2,3,3,3-pentafluoropropanol, 2- (perfluorohexyl) ethanol, 2- (perfluorooctyl) ethanol, and 2 -(Perfluorodecyl) ethanol, 6- (perfluoroethyl) hexanol, 6- (perfluorobutyl) hexanol, 6- (perfluorohexyl) hexanol, 6- (perfluorooctyl) hexanol, 2,2,3, 4,4,4-hexafluorobutanol, 2,2,3,3-tetrafluoro Linear fluorinated alcohols such as panol, 1H, 1H, 5H-octafluoropentanol, 1H, 1H, 7H-dodecafluoroheptanol, 1H, 1H, 9H-hexadecafluorononanol, 2- (perfluoro- 3-methylbutyl) ethanol, 2- (perfluoro-5-methylhexyl) ethanol, 2- (perfluoro-7-methyloctyl) ethanol, 2- (perfluoro-9-methyldodecyl) ethanol, 6- (perfluoro -1-methylethyl) hexanol, 6- (perfluoro-3-methylbutyl) hexanol, 6- (perfluoro-5-methylhexyl) hexanol, 6- (perfluoro-7-methyloctyl) hexanol, etc. Fluoroalcohols, 3- (perfluoro-3-methylbutyl) Fluorine-containing diols such as 1,2-propanediol, 3- (perfluoro-5-methylhexyl) -1,2-propanediol, 3- (perfluoro-7-methyloctyl) -1,2-propanediol And ethylene oxide, propylene oxide or butylene oxide adducts of these fluorinated alcohols or diols.
[0011]
Among these fluorine-containing hydroxy compounds, a fluorine-containing alcohol having 1 to 22 carbon atoms having a fluorine substituent is preferred, and in particular, the general formula (4)
Rf ₁ (CH ₂ ) _p OH (4)
(In the formula, Rf ₁ represents a linear or branched fluorinated alkyl group having 1 to 12 carbon atoms, and p represents a number of 1 to 10.)
The fluorine-containing alcohol represented by these is preferable.
One or more of these fluorine-containing hydroxy compounds can be used.
[0012]
In the present invention, the carbonyl compound includes a compound having a carbonyl group as well as a compound having a carbonyl group easily by acid or heating.
The carbonyl compound used in the present invention is represented by the general formula (2)
[0013]
[Chemical 2]

[0014]
[Wherein R ₂ and R ₃ are hydrogen atoms, linear or branched alkyl groups or alkenyl groups having 1 to 20 carbon atoms, or fluorine substitution in which at least one of the hydrogen atoms in these groups is substituted with a fluorine atom. Represents a group, and R ₂ and R ₃ may be the same or different. Further, it may be a cyclic structure R _2, R ₃ are bonded. ]
The compound represented by these, or these polymers are mentioned.
Examples of the polymer of the compound represented by the general formula (2) include paraformaldehyde, paraaldehyde (acetaldehyde trimer), and the like.
[0015]
Among the compounds represented by the general formula (2) or polymers thereof, those having no fluorine substituent include chain ketones having 3 to 19 carbon atoms, aldehydes having 1 to 19 carbon atoms, and carbon atoms 5 -8 cyclic ketones, paraformaldehyde, and paraaldehyde are preferable, chain ketones having 3 to 6 carbon atoms such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (4-methyl-2-pentanone), formaldehyde, acetaldehyde, butyraldehyde, C1-C12 aliphatic aldehydes such as isobutyraldehyde, octylaldehyde, isononylaldehyde (3,5,5-trimethylhexanal), dodecylaldehyde, C5-C6 cyclic ketones such as cyclohexanone, paraformaldehyde, Paraaldehyde is particularly preferred, and acetone, methyl ethyl ketone And methyl isobutyl ketone (4-methyl-2-pentanone), butyraldehyde, isobutyraldehyde, octyl aldehyde, isononyl aldehyde (3,5,5-trimethylhexanal) and paraaldehyde are particularly preferred. One or more of these carbonyl compounds can be used.
[0016]
In addition, as the carbonyl compound represented by the general formula (2) having a fluorine substituent, a fluorine substituent in which at least one hydrogen atom of the carbonyl compound not having the fluorine substituent is substituted with a fluorine atom. Specific examples of these compounds include fluoroacetone, 1,1,1-trifluoroacetone, 1,1,1-trifluoro-2-butanone, 1,1,1-trimethyl, and the like. Fluoro-2-pentanone, 1,1,1-trifluoro-2-hexanone, bis (trifluoromethyl) ketone, bis (pentafluoroethyl) ketone, bis (heptafluoropropyl) ketone, trifluoromethylpentafluoroethylketone , Fluorinated ketones such as trifluoromethylheptafluoropropyl ketone, 3,3,3-to Fluoropropyl aldehyde, 4,4,4-trifluoro-butyraldehyde, 5,5,5-trifluoro-pentyl aldehyde, and the like fluorine-containing aldehydes such as 6,6,6-trifluoro-hexyl aldehyde. Among these fluorine-containing carbonyl compounds, a fluorine-containing chain ketone having 1 to 12 carbon atoms and a fluorine-containing chain aldehyde having 1 to 12 carbon atoms are preferable, and in particular, a fluorine-containing ketone represented by the general formula (5) or The fluorine-containing aldehyde represented by the general formula (6) is preferable.
[0017]
[Chemical 3]

[0018]
(In the formula, Rf ₂ represents a fluorine-containing alkyl group having 1 to 10 carbon atoms, and R ₄ represents an alkyl group having 1 to 10 carbon atoms.)
Rf ₃ (CH ₂ ) _q CHO (6)
(In the formula, Rf ₃ represents a fluorine-containing alkyl group having 1 to 10 carbon atoms, and q represents a number of 1 to 10).
One or more of these fluorine-containing carbonyl compounds can be used.
[0019]
In the present invention, a hydroxy compound from which alkali components and / or nitrogen-containing components have been removed by purification treatment is used as the hydroxy compound.
That is, for example, when a fluorine-containing hydroxy compound having a fluorine substituent is used as the hydroxy compound, the fluorine-containing hydroxy compound hydrolyzes a halogenated fluoroalkyl in the presence of an acid, N-methylpyrrolidone or N, N-dimethylformamide. Although it is manufactured by decomposing, in order to neutralize the remaining acid using an alkali component, an alkali component is mixed in the hydroxy compound, or a nitrogen-containing component that cannot be removed is mixed. Moreover, when using the alkylene oxide adduct of alcohol as a hydroxy compound, the catalyst containing alkali metals, such as sodium hydroxide, potassium hydroxide, sodium carbonate, is used, and this catalyst remains after reaction.
[0020]
In the present invention, a hydroxy compound obtained by removing the alkali component and / or nitrogen-containing component mixed during production as described above by purification treatment is used. In the purification treatment, the nitrogen content or alkali metal ion content in the hydroxy compound is preferably 200 ppm or less, and examples thereof include adsorbent treatment, distillation treatment, and neutralization treatment with a strong inorganic acid. Among these, the distillation treatment is preferable when the hydroxy compound is a low-boiling substance that can be distilled, and the adsorbent treatment is preferable when the hydroxy compound is a high-boiling substance that cannot be distilled.
[0021]
Examples of the adsorbent used in the adsorbent treatment in the present invention include those containing as a main component at least one selected from silica, magnesia and alumina. Specifically, magnesium silicate, aluminum oxide, magnesium oxide, Examples include aluminum hydroxide, aluminum carbonate, magnesium carbonate, or a mixture thereof, such as zeolite, silica / alumina, activated alumina, Kyoward (manufactured by Kyowa Chemical Industry Co., Ltd.), activated clay, etc. Use it. The amount of adsorbent added is preferably 0.1 to 20% by weight based on the hydroxyl compound. Further, the adsorbent treatment is preferably carried out with stirring at a temperature of 50 to 200 ° C. under reduced pressure.
[0022]
Further, the distillation treatment in the present invention is preferably performed in a temperature range of 13.3 Pa to normal pressure and 50 to 250 ° C.
[0023]
In the present invention, the adsorbent treatment and the distillation treatment may be combined with a neutralization treatment, and by purifying, the nitrogen content in the hydroxy compound or the content of alkali metal ions such as K and Na is 200 ppm. In the following, it is further preferable that the content is 100 ppm or less, particularly 50 ppm or less.
[0024]
Examples of the strong inorganic acid used in the neutralization treatment with the strong inorganic acid in the present invention include those having a pKa of 3 or less, preferably hydrochloric acid (pKa-8), sulfuric acid (pKa 1.99), and phosphoric acid (pKa 2.15). It is preferable to neutralize with an acid so that the pH is 5 to 7. The neutralization treatment may be performed by adding an acid under the alcohol dissolution condition and stirring for 5 to 60 minutes. This pH is a value measured with a 1% aqueous solution.
[0025]
In the production method of the present invention, the charging ratio of the hydroxy compound and the carbonyl compound is not particularly limited, but usually the hydroxy compound / carbonyl compound (molar ratio) = 50/1 to 1/50 is preferable, and 30/1 to 1 / 30 is more preferable, 20/1 to 1/20 is still more preferable, and 10/1 to 1/10 is particularly preferable. If the hydroxy compound has a low molecular weight and can be easily removed by distillation or the like, it is preferable to carry out the reaction using an excess of the hydroxy compound. If the carbonyl compound has a low molecular weight and can be easily removed by distillation or the like, the reaction is preferably carried out using an excess of the carbonyl compound. Even if the molar ratio of the hydroxy compound / carbonyl compound is outside the above range, the yield is not greatly affected, but it is not economical.
[0026]
In the present invention, the catalyst used in the reaction of the hydroxy compound and the carbonyl compound is not particularly limited as long as it has hydrogenation ability, but palladium catalyst; palladium compounds such as palladium hydroxide and palladium oxide; ruthenium, Rhodium or platinum catalyst; ruthenium oxide, rhodium oxide, platinum oxide and the like. A catalyst such as iridium, osmium, rhenium, etc. can also be used. These catalysts may be appropriately supported on a carrier such as carbon, alumina, silica alumina, silica, zeolite or the like. Among these catalysts, a palladium-based catalyst is preferable, more preferably a palladium catalyst supported on carbon, alumina, silica alumina or silica, palladium hydroxide or palladium oxide, and a palladium catalyst supported on carbon is particularly preferable. .
[0027]
In the present invention, the catalyst is usually used in a proportion of 1 to 10% by weight based on a carrier such as carbon or alumina, but it may be used as it is without being supported on the carrier. Further, it may be a water-containing product of about 20 to 60% by weight.
The catalyst is preferably used in an amount of 0.1 to 10% by weight based on the hydroxy compound used, for example, if it is supported on the carrier by 5% by weight. The reaction proceeds even if it is less than 0.1% by weight, but the reaction is slow and not preferred. Moreover, even if it is used in an amount of more than 10% by weight, the reaction is fast, but on the contrary, side reactions also proceed, which is not preferable. More preferably, it is 0.5 to 5% by weight.
Although the catalyst can be used in all pH ranges, a catalyst having a pH of 8 to 2, more preferably pH 7.5 to 3 is preferable. Here, the pH of the catalyst refers to the pH of the aqueous solution when 2 g of the catalyst powder is dispersed in 30 g of ion-exchanged water.
[0028]
In the present invention, the hydroxy compound and the carbonyl compound are reacted in a hydrogen atmosphere, but the hydrogen pressure is not particularly limited, and may be either under pressure or atmospheric pressure, preferably 0.098 MPa (atmospheric pressure) to 29.4 MPa, 0.098 MPa (atmospheric pressure) to 19.6 MPa is particularly preferable.
In the present invention, the reaction temperature for reacting the hydroxy compound and the carbonyl compound is not particularly limited, but is preferably 10 to 200 ° C, particularly preferably 30 to 180 ° C. The reaction time may be appropriately selected depending on the reaction temperature, hydrogen pressure, catalyst amount, etc., but is usually 1 to 24 hours, preferably 1 to 12 hours.
[0029]
In addition, when the carbonyl compound is an aldehyde, it is desirable that the aldehyde is reacted while being dropped into the reaction system. The dropping rate of the aldehydes may be appropriately selected according to the scale of the reaction. For example, in the scale of 0.5 liter, 0.1 to 180 g / hr is preferable, and 0.6 to 60 g / hr is more preferable.
[0030]
In the reaction of the present invention, in some cases, the reaction may be performed using a solvent that does not adversely affect the reaction. Examples of the solvent that does not adversely influence the reaction include hydrocarbon solvents such as hexane, heptane, and octane.
The amount of solvent used in the case of using a solvent that does not adversely affect the reaction is not particularly limited, but is preferably 0.5 to 2 times the volume of the reaction solution.
[0031]
In the present invention, for the purpose of removing water by-produced in the reaction system, a dehydrating agent such as anhydrous magnesium sulfate and anhydrous sodium sulfate is added, a gas such as hydrogen is circulated, azeotropic dehydration, etc. May be performed.
[0032]
【Example】
Unless otherwise specified,% in the examples is based on weight.
Examples 7 and 8 are reference examples.
[0033]
Production Example 1
And _{CF 3 (CF 2) 5 CH} 2 CH 2 I 4.74g glass container 100 ml, the _{CF 3 (CF 2) 5 CH} 2 CH 2 I with respect to 22.0 mol per mol of N, N - dimethylformamide, 8 Molar water was added, reacted at 150 ° C. for 6 hours, and washed with 50 ml of water. After alkali washing, distillation was performed to obtain crude 2- (perfluorohexyl) ethanol having a nitrogen content of 420 ppm.
In a 0.5 L three-necked flask, 100 g of the crude 2- (perfluorohexyl) ethanol obtained above and 2.6 g of magnesium silicate (KYOWARD 600S, manufactured by Kyowa Chemical Industry Co., Ltd.) were placed under reduced pressure (9.31 kPa). ) And stirred at 100 ° C. for 1 hour. Thereafter, the magnesium silicate was filtered off to obtain 95 g of purified 2- (perfluorohexyl) ethanol. The nitrogen content in the obtained purified 2- (perfluorohexyl) ethanol was 20 ppm.
[0034]
Production Examples 2-3
Instead of CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ I, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ I or CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ I is used, except that Production Example 1 is used. Similarly, crude 2- (perfluorooctyl) ethanol having a nitrogen content of 500 ppm and crude 2- (perfluorodecyl) ethanol having a nitrogen content of 370 ppm were obtained.
The obtained crude 2- (perfluorooctyl) ethanol and crude 2- (perfluorodecyl) ethanol were subjected to the same purification treatment as in Production Example 1, and purified 2- (perfluorooctyl) having a nitrogen content of 34 ppm and 25 ppm, respectively. ) Ethanol and 2- (perfluorodecyl) ethanol were obtained.
[0035]
Example 1
Production of 1,3-dimethylbutyl {2- (perfluorohexyl) ethyl} ether
[Formula 4]

[0037]
To a 70 ml autoclave equipped with a hydrogen gas introduction tube and a stirrer, 18.2 g (0.05 mol) of purified 2- (perfluorohexyl) ethanol (nitrogen content 20 ppm) obtained in Production Example 1 and 4-methyl-2-pentanone 30.0 g (0.3 mol) and 1.5 g of 5% Pd—C (pH 7.2) were charged as a catalyst, and the reaction was carried out at atmospheric pressure at 105 ° C. for 10 hours while blowing hydrogen at 18 ml / min. After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure to obtain 21.5 g of the desired 1,3-dimethylbutyl {2- (perfluorohexyl) ethyl} ether. (0.048 mol) was obtained. The isolation yield was 96%.
[0038]
Examples 2-6
The hydroxy compound and carbonyl compound shown in Table 1 were reacted in the same manner as in Example 1 except for the reaction conditions shown in Table 1 using the catalyst shown in Table 1.
The obtained products and their isolated yields are shown in Table 1.
[0039]
[Table 1]

[0040]
Comparative Examples 1-6
2- (perfluorohexyl) ethanol (nitrogen content 420 ppm), 2- (perfluorooctyl) ethanol (nitrogen content 500 ppm), 2- (perfluorodecyl) ethanol (nitrogen content 370 ppm) before purification as hydroxy compounds, The reaction was performed in the same manner as in Examples 1 to 6 except for the catalysts and reaction conditions shown in Table 2.
The products obtained and their isolated yields are shown in Table 2.
[0041]
[Table 2]

[0042]
Production Example 4
Add 185g of dodecyl alcohol and 0.81g of potassium hydroxide to the autoclave, and after replacing with nitrogen, send 400g of ethylene oxide over 4 hours at 100-110 ° C. Continue the reaction until the volatile content is 0.5% or less. Then, 0.84 g of acetic acid was added for neutralization to obtain crude polyoxyethylene dodecyl ether. The resulting crude polyoxyethylene dodecyl ether had an average ethylene oxide addition mole number of 9.1 moles and a K ion content of 970 ppm.
[0043]
In a three-necked flask, 100 g of the above-mentioned crude polyoxyethylene (p = 9.1) monododecyl ether having a K ion content of 970 ppm and 2.6 g of magnesium silicate (KYOWARD 600S, manufactured by Kyowa Chemical Industry Co., Ltd.) were placed under reduced pressure (3.99 And stirred at 140 ° C. for 1 hour. Thereafter, magnesium silicate was separated by filtration to obtain 90 g of purified polyoxyethylene (p = 9.1) monododecyl ether. The amount of K ion in the obtained purified polyoxyethylene (p = 9.1) monododecyl ether was 33 ppm.
Production Example 5
Into an autoclave, 74g of butyl alcohol and 0.32g of potassium hydroxide were added. After purging with nitrogen, 132g of ethylene oxide was fed over 2 hours at 100-110 ° C, and the reaction was continued until the volatile content was 0.5% or less. Ethylene butyl ether was obtained. The crude polyoxyethylene butyl ether thus obtained had an average ethylene oxide addition mole number of 3 moles and a K ion content of 1080 ppm.
The obtained polyoxyethylene (p = 3) monobutyl ether with a K ion content of 1080 ppm was also purified in the same manner as in Production Example 4 to obtain purified polyoxyethylene (p = 3) monobutyl ether with a K ion content of 1 ppm. .
[0044]
Example 7
In a 500 ml autoclave, 80 g of purified polyoxyethylene (p = 9.1) monododecyl ether obtained in Production Example 4 with 33 ppm K ion, 105 g (0.68 mol) of 1,1,1-trifluoro-2-butanone, catalyst As a result, 1.6 g (pH 7.1) of 5% Pd—C was charged, and the reaction was performed in a hydrogen atmosphere at a reaction temperature of 150 ° C., a reaction pressure of 6.86 MPa, and a rotation speed of 800 rpm for 7 hours.
After completion of the reaction, the catalyst was removed by filtration, and unreacted 1,1,1-trifluoro-2-butanone was distilled off under reduced pressure to obtain polyoxyethylene glycol (p = 9.1) {1 94 g of-(perfluoromethyl) propyl} dodecyl ether was obtained.
[0045]
Example 8
41 g (0.2 mol) of purified polyoxyethylene (p = 3) monobutyl ether obtained in Production Example 5 with 1 ppm K ion, 154 g (1 mol) of 1,1,1-trifluoro-2-butanone, 5 as catalyst % Pd—C 1.0 g (pH 7.1) is used except that the reaction is carried out under the same conditions as in Example 7 and the same treatment is performed to obtain polyoxyethylene glycol (p = 3) {1- 63 g of (perfluoromethyl) propyl} butyl ether was obtained.
[0046]
Comparative Examples 7 and 8
Examples 7 and 8 except that polyoxyethylene (p = 9.1) monododecyl ether having a K ion content of 970 ppm and polyoxyethylene (p = 3) monobutyl ether having a K ion content of 1080 ppm were used as hydroxy compounds. The reaction was carried out in the same manner as in. As a result, the reaction did not proceed at all.

Claims (3)

When an ether compound is produced by reacting a hydroxy compound and a carbonyl compound in a hydrogen atmosphere using a catalyst, the hydroxy compound is a fluorine compound having a fluorine substituent , and the nitrogen content in the hydroxy compound by adsorbent treatment A process for producing a fluorinated ether compound using a hydroxy compound from which a nitrogen-containing component has been removed so that the nitrogen content is 50 ppm or less . The hydroxy compound is represented by the general formula (1)
R ₁ O- (AO) _n -H (1)
Wherein, R ₁ represents at least one fluorinated substituted with fluorine atoms of the hydrogen atoms of the straight-chain or branched-chain alkyl group or alkenyl group, or a cycloalkyl group having 3 to 12 carbon atoms having a carbon number of 1 to 40 Indicates a group. A 1 represents a linear or branched alkylene group having 2 to 12 carbon atoms which may have a hydroxy group as a substituent, and n 1 A may be the same or different. n represents a number from 0 to 500. ]
A process according to claim 1, wherein a in compounds represented. The carbonyl compound is represented by the general formula (2)

[Wherein R ₂ and R ₃ are hydrogen atoms, linear or branched alkyl groups or alkenyl groups having 1 to 20 carbon atoms, or fluorine substitution in which at least one of the hydrogen atoms in these groups is substituted with a fluorine atom. Represents a group, and R ₂ and R ₃ may be the same or different. Further, it may be a cyclic structure R _2, R ₃ are bonded. ]
The production method according to claim 1 or 2, which is a compound represented by the formula: or a polymer thereof.