JP2000212132A - Production of quaternary tetraethylammonium chloride - Google Patents
Production of quaternary tetraethylammonium chlorideInfo
- Publication number
- JP2000212132A JP2000212132A JP11009215A JP921599A JP2000212132A JP 2000212132 A JP2000212132 A JP 2000212132A JP 11009215 A JP11009215 A JP 11009215A JP 921599 A JP921599 A JP 921599A JP 2000212132 A JP2000212132 A JP 2000212132A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- triethylamine
- ethyl chloride
- chloride
- aprotic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、第４級塩化テトラ
エチルアンモニウムの製造方法に関する。さらに詳しく
は、電気２重層キャパシター、電解コンデンサー等の電
解液の電解質として有用な第４級テトラエチルアンモニ
ウムテトラフルオロホウ酸塩の合成原料である第４級塩
化テトラエチルアンモニウムの製造方法に関する。ここ
で、第４級塩化テトラエチルアンモニウムを以下に化学
式で示す。 （Ｃ2Ｈ5）4Ｎ+Ｃｌ- TECHNICAL FIELD The present invention relates to a method for producing quaternary tetraethylammonium chloride. More specifically, the present invention relates to a method for producing quaternary tetraethylammonium chloride, which is a raw material for synthesizing quaternary tetraethylammonium tetrafluoroborate, which is useful as an electrolyte for electrolytic solutions such as electric double-layer capacitors and electrolytic capacitors. Here, the quaternary tetraethylammonium chloride is represented by the following chemical formula. (C 2 H 5) 4 N + Cl -
【０００２】[0002]
【従来の技術】従来、第４級塩化テトラエチルアンモニ
ウムの製造方法としては、例えば、アンモニアと塩化エ
チルとを水酸化カルシウムの存在下に反応させる方法
（Hung.Telijes HU 54,341 1991、C.A.Vol115:70907t
）などが知られている。2. Description of the Related Art Conventionally, as a method for producing quaternary tetraethylammonium chloride, for example, a method in which ammonia and ethyl chloride are reacted in the presence of calcium hydroxide (Hung.Telijes HU 54,341 1991, CAVol 115: 70907t)
) Are known.
【０００３】しかしながら、前記の方法は、高価な塩化
エチルを多量に必要とし、また副生する塩化水素を除去
するために多量の水酸化カルシウムが必要となる。さら
に、副生した塩化カルシウムと第４級塩化テトラエチル
アンモニウムとを分離する事が困難であるといった問題
がある。However, the above-mentioned method requires a large amount of expensive ethyl chloride and a large amount of calcium hydroxide to remove by-produced hydrogen chloride. Further, there is a problem that it is difficult to separate by-produced calcium chloride and quaternary tetraethylammonium chloride.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、多量の塩化
エチルを用いる必要がなく、かつ多量の無機塩を副生し
ない、工業的に有利な第４級塩化テトラエチルアンモニ
ウムの製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention provides an industrially advantageous process for producing quaternary tetraethylammonium chloride which does not require the use of a large amount of ethyl chloride and does not produce a large amount of inorganic salts. The purpose is to:
【０００５】[0005]
【課題を解決するための手段】本発明者らは、トリエチ
ルアミンと塩化エチルを加圧下、非プロトン性溶媒中で
反応させることにより、工業的に、簡便かつ経済的に第
４級塩化テトラエチルアンモニウムが製造できることを
見出し本発明を完成した。DISCLOSURE OF THE INVENTION The present inventors industrially, easily and economically produce quaternary tetraethylammonium chloride by reacting triethylamine and ethyl chloride in an aprotic solvent under pressure. The present inventors have found that they can be manufactured and completed the present invention.
【０００６】すなわち、本発明の要旨は、（１）トリエ
チルアミンと塩化エチルを０．０１〜２ＭＰａの加圧
下、反応温度５０〜２００℃で非プロトン性溶媒中にて
反応させることを特徴とする第４級塩化テトラエチルア
ンモニウムの製造方法、（２）非プロトン性溶媒が、テ
トラヒドロフラン、ジオキサン、１，２−ジメトキシエ
タンまたはアセトニトリルである（１）記載の製造方
法、に関する。That is, the gist of the present invention is that (1) triethylamine and ethyl chloride are reacted in an aprotic solvent at a reaction temperature of 50 to 200 ° C. under a pressure of 0.01 to 2 MPa. The present invention relates to the method for producing quaternary tetraethylammonium chloride, and (2) the method for producing (1), wherein the aprotic solvent is tetrahydrofuran, dioxane, 1,2-dimethoxyethane or acetonitrile.
【０００７】[0007]
【発明の実施の形態】本発明の製造方法においては、ト
リエチルアミンと非プロトン性溶媒を耐圧容器に仕込
み、次いで塩化エチルを添加し、加圧下に反応させて第
４級塩化テトラエチルアンモニウムを得る。BEST MODE FOR CARRYING OUT THE INVENTION In the production method of the present invention, quaternary tetraethylammonium chloride is obtained by charging triethylamine and an aprotic solvent into a pressure vessel, adding ethyl chloride and reacting under pressure.
【０００８】トリエチルアミンと塩化エチルとの反応を
以下に化学式で示す。 （Ｃ2Ｈ5）3Ｎ ＋ Ｃ2Ｈ5Ｃｌ → （Ｃ2Ｈ5）4Ｎ+
Ｃｌ- The reaction between triethylamine and ethyl chloride is represented by the following chemical formula. (C 2 H 5 ) 3 N + C 2 H 5 Cl → (C 2 H 5 ) 4 N +
Cl -
【０００９】前記トリエチルアミンと塩化エチルとの反
応は、反応が速やかに進行する点と収率が向上する点か
ら、非プロトン性溶媒中で行うことが好ましい。前記反
応は、無溶媒または水溶媒では殆ど進行しない。The reaction of the above-mentioned triethylamine with ethyl chloride is preferably carried out in an aprotic solvent from the viewpoint that the reaction proceeds rapidly and the yield is improved. The reaction hardly proceeds without a solvent or an aqueous solvent.
【００１０】該非プロトン性溶媒としては、例えば、テ
トラヒドロフラン、ジオキサン、１，２−ジメトキシエ
タン、アセトニトリル、ジメチルホルムアミドおよびジ
メチルスルホキシド等が挙げられる。これらのうち、反
応後の溶媒除去が容易であるという観点からテトラヒド
ロフラン、ジオキサン、１，２−ジメトキシエタンある
いはアセトニトリルが好適に用いられる。前記非プロト
ン性溶媒の使用量は、特に限定されるものではないが、
トリエチルアミンに対して、通常０．５〜５倍重量程度
であり、好ましくは１〜３倍重量程度である。The aprotic solvent includes, for example, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, acetonitrile, dimethylformamide, dimethylsulfoxide and the like. Of these, tetrahydrofuran, dioxane, 1,2-dimethoxyethane or acetonitrile are preferably used from the viewpoint that the solvent can be easily removed after the reaction. The amount of the aprotic solvent used is not particularly limited,
It is usually about 0.5 to 5 times the weight, preferably about 1 to 3 times the weight of triethylamine.
【００１１】前記反応に用いる塩化エチルの使用量は、
特に限定されず、トリエチルアミンに対して１．０〜
１．５倍モル、好ましくは１．０〜１．２倍モル程度で
ある。塩化エチルの使用量が１．０倍モル未満ではトリ
エチルアミンが未反応で残るため反応が完結せず、１．
５倍モルを超えて用いてもそれに見合う効果が得られな
い。The amount of ethyl chloride used in the above reaction is as follows:
Not particularly limited, 1.0 to
It is about 1.5 times mol, preferably about 1.0 to 1.2 times mol. If the amount of ethyl chloride used is less than 1.0 mole, triethylamine remains unreacted and the reaction is not completed.
Even if it is used in an amount of more than 5 moles, the effect corresponding to the use cannot be obtained.
【００１２】前記トリエチルアミンと塩化エチルとの反
応は、耐圧容器中で加圧下に行う。反応の圧力としては
０．０１〜２ＭＰａ、好ましくは０．０３〜１．５ＭＰ
ａである。反応圧力が０．０１ＭＰａより小さいと、常
圧での反応と変わらず、反応が進行しにくい。また、２
ＭＰａより大きいと、その圧力に耐える特殊な反応容器
が必要となる。The reaction between the above triethylamine and ethyl chloride is carried out under pressure in a pressure vessel. The reaction pressure is 0.01 to 2 MPa, preferably 0.03 to 1.5 MPa.
a. When the reaction pressure is lower than 0.01 MPa, the reaction does not progress as in the case of the reaction under normal pressure. Also, 2
If it is higher than MPa, a special reaction vessel that can withstand the pressure is required.
【００１３】前記反応の反応温度は、溶媒の種類により
異なるが、通常、５０〜２００℃、好ましくは、５０〜
１５０℃の範囲である。反応温度が５０℃未満では反応
が完結せず、未反応のトリエチルアミンおよび塩化エチ
ルが増加する。また、２００℃を超えると未反応原料お
よび非プロトン性溶媒の蒸気圧が高くなり内圧が上昇す
る。The reaction temperature of the above reaction varies depending on the type of the solvent, but is usually 50 to 200 ° C., preferably 50 to 200 ° C.
It is in the range of 150 ° C. If the reaction temperature is lower than 50 ° C., the reaction is not completed, and unreacted triethylamine and ethyl chloride increase. On the other hand, when the temperature exceeds 200 ° C., the vapor pressure of the unreacted raw material and the aprotic solvent increases, and the internal pressure increases.
【００１４】反応時間は、通常、１〜８時間程度の範囲
であることが望ましい。The reaction time is usually desirably in the range of about 1 to 8 hours.
【００１５】このようにして生成した第４級塩化テトラ
エチルアンモニウムは、冷却することで反応液中に析出
するため、濾過等により容易に単離することができる。
得られた第４級塩化テトラエチルアンモニウムは、ホウ
フッ化水素酸と反応させることにより、容易に第４級テ
トラエチルアンモニウムテトラフルオロホウ酸塩を製造
することができる。The quaternary tetraethylammonium chloride thus formed precipitates in the reaction solution upon cooling, and can be easily isolated by filtration or the like.
The resulting quaternary tetraethylammonium chloride can be easily produced as a quaternary tetraethylammonium tetrafluoroborate by reacting with borofluoric acid.
【００１６】[0016]
【実施例】次に、本発明を実施例に基づいてさらに詳細
に説明するが、本発明はかかる実施例によってのみ限定
されるものではない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited only to such examples.
【００１７】実施例１ 攪拌機、温度計および圧力計を備え付けた１０００ｍｌ
容のステンレス製オートクレーブに、アセトニトリル２
０２ｇおよびトリエチルアミン２０２ｇ（２．０モル）
を仕込み、約１０℃に冷却した。次いで、塩化エチル１
２９ｇ（２．０モル）を添加し、反応容器を密封して１
３０℃まで昇温し６時間反応させた。この時の圧力は、
０．７５ＭＰａであった。反応終了後、７℃まで冷却
し、析出した白色の生成物を濾別した後、アセトン１０
０ｇにて洗浄し、６０℃で真空乾燥して第４級塩化テト
ラエチルアンモニウム３０３ｇを得た。収率はトリエチ
ルアミンに対して９１．５％であった。Example 1 1000 ml equipped with a stirrer, thermometer and pressure gauge
Acetonitrile 2 in a stainless steel autoclave
02 g and triethylamine 202 g (2.0 mol)
And cooled to about 10 ° C. Then, ethyl chloride 1
29 g (2.0 mol) were added, the reaction vessel was sealed and 1 g
The temperature was raised to 30 ° C., and the reaction was performed for 6 hours. The pressure at this time is
It was 0.75 MPa. After completion of the reaction, the reaction mixture was cooled to 7 ° C., and the precipitated white product was separated by filtration.
After washing with 0 g, vacuum drying was performed at 60 ° C. to obtain 303 g of quaternary tetraethylammonium chloride. The yield was 91.5% based on triethylamine.
【００１８】実施例２ 攪拌機、温度計および圧力計を備え付けた１０００ｍｌ
容のステンレス製オートクレーブに、１，２−ジメトキ
シエタン２０２ｇおよびトリエチルアミン２０２ｇ
（２．０モル）を仕込み、約１０℃に冷却した。次い
で、塩化エチル１２９ｇ（２．０モル）を添加し、反応
容器を密封して１３０℃まで昇温し６時間反応させた。
この時の圧力は、０．７５ＭＰａであった。反応終了
後、７℃まで冷却し、析出した白色の生成物を濾別した
後、アセトン１００ｇにて洗浄し、６０℃で真空乾燥し
て第４級塩化テトラエチルアンモニウム２７１ｇを得
た。収率はトリエチルアミンに対して８２．０％であっ
た。Example 2 1000 ml equipped with stirrer, thermometer and pressure gauge
In a stainless steel autoclave, 202 g of 1,2-dimethoxyethane and 202 g of triethylamine were placed.
(2.0 mol) and cooled to about 10 ° C. Next, 129 g (2.0 mol) of ethyl chloride was added, the reaction vessel was sealed, the temperature was raised to 130 ° C., and the reaction was performed for 6 hours.
The pressure at this time was 0.75 MPa. After completion of the reaction, the reaction mixture was cooled to 7 ° C., and the precipitated white product was separated by filtration, washed with 100 g of acetone, and dried in vacuo at 60 ° C. to obtain 271 g of quaternary tetraethylammonium chloride. The yield was 82.0% based on triethylamine.
【００１９】比較例１ 実施例１において、アセトニトリル２０２ｇに代えて、
メタノール２０２ｇを用いた以外は実施例１と同様にし
て、トリエチルアミンと塩化エチルを反応させ、第４級
塩化テトラエチルアンモニウム９９ｇを得た。収率はト
リエチルアミンに対して３０％であった。Comparative Example 1 In Example 1, instead of 202 g of acetonitrile,
Triethylamine and ethyl chloride were reacted in the same manner as in Example 1 except that 202 g of methanol was used to obtain 99 g of quaternary tetraethylammonium chloride. The yield was 30% based on triethylamine.
【００２０】比較例２ 実施例１において、アセトニトリル２０２ｇに代えて、
水２０２ｇを用いた以外は実施例１と同様にして、トリ
エチルアミンと塩化エチルを反応させたが、第４級塩化
テトラエチルアンモニウムはほとんど得られなかった。Comparative Example 2 In Example 1, instead of acetonitrile 202 g,
Triethylamine and ethyl chloride were reacted in the same manner as in Example 1 except that 202 g of water was used, but quaternary tetraethylammonium chloride was hardly obtained.
【００２１】[0021]
【発明の効果】本発明によれば、塩化エチルを多量に用
いる事なく、除去が困難な塩化水素が発生しない工業的
に有利な第４級塩化テトラエチルアンモニウムの製造方
法を提供することができる。According to the present invention, it is possible to provide an industrially advantageous method for producing quaternary tetraethylammonium chloride which does not generate hydrogen chloride which is difficult to remove without using a large amount of ethyl chloride.
Claims (2)
１〜２ＭＰａの加圧下、反応温度５０〜２００℃で非プ
ロトン性溶媒中にて反応させることを特徴とする第４級
塩化テトラエチルアンモニウムの製造方法。(1) triethylamine and ethyl chloride are mixed in 0.0
A method for producing a quaternary tetraethylammonium chloride, characterized in that the reaction is carried out in an aprotic solvent at a reaction temperature of 50 to 200 ° C. under a pressure of 1 to 2 MPa.
ン、ジオキサン、１，２−ジメトキシエタンまたはアセ
トニトリルである請求項１記載の製造方法。2. The method according to claim 1, wherein the aprotic solvent is tetrahydrofuran, dioxane, 1,2-dimethoxyethane or acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11009215A JP2000212132A (en) | 1999-01-18 | 1999-01-18 | Production of quaternary tetraethylammonium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11009215A JP2000212132A (en) | 1999-01-18 | 1999-01-18 | Production of quaternary tetraethylammonium chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000212132A true JP2000212132A (en) | 2000-08-02 |
Family
ID=11714243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11009215A Pending JP2000212132A (en) | 1999-01-18 | 1999-01-18 | Production of quaternary tetraethylammonium chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000212132A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002284747A (en) * | 2001-03-28 | 2002-10-03 | Kao Corp | Method for producing quaternary ammonium salt |
| JP2006143647A (en) * | 2004-11-19 | 2006-06-08 | Koei Chem Co Ltd | Method for producing quaternary ammonium salt |
| WO2011052604A1 (en) * | 2009-10-26 | 2011-05-05 | 独立行政法人産業技術総合研究所 | Photoresponsive ionic organic compound, production method therefor, and photoresponsive carbon nanotube dispersant comprising said ionic organic compound |
| CN106518687A (en) * | 2016-09-09 | 2017-03-22 | 华东理工大学 | Efficient preparation method of high-purity tetraethyl ammonium chloride |
| WO2020217001A1 (en) | 2019-04-25 | 2020-10-29 | Arkema France | Process for obtaining tetraethylammonium bromide and tetraethylammonium tetrafluoroborate, and corresponding products and uses thereof |
-
1999
- 1999-01-18 JP JP11009215A patent/JP2000212132A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002284747A (en) * | 2001-03-28 | 2002-10-03 | Kao Corp | Method for producing quaternary ammonium salt |
| JP4672164B2 (en) * | 2001-03-28 | 2011-04-20 | 花王株式会社 | Production of quaternary ammonium salts |
| JP2006143647A (en) * | 2004-11-19 | 2006-06-08 | Koei Chem Co Ltd | Method for producing quaternary ammonium salt |
| WO2011052604A1 (en) * | 2009-10-26 | 2011-05-05 | 独立行政法人産業技術総合研究所 | Photoresponsive ionic organic compound, production method therefor, and photoresponsive carbon nanotube dispersant comprising said ionic organic compound |
| US8729307B2 (en) | 2009-10-26 | 2014-05-20 | National Institute Of Advanced Industrial Science And Technology | Photoresponsive ionic organic compound, method of producing the same, and photoresponsive carbon nanotube dispersant comprising said ionic organic compound |
| JP5552641B2 (en) * | 2009-10-26 | 2014-07-16 | 独立行政法人産業技術総合研究所 | Photoresponsive ionic organic compound, process for producing the same, and photoresponsive carbon nanotube dispersant comprising the ionic organic compound |
| CN106518687A (en) * | 2016-09-09 | 2017-03-22 | 华东理工大学 | Efficient preparation method of high-purity tetraethyl ammonium chloride |
| WO2020217001A1 (en) | 2019-04-25 | 2020-10-29 | Arkema France | Process for obtaining tetraethylammonium bromide and tetraethylammonium tetrafluoroborate, and corresponding products and uses thereof |
| FR3095437A1 (en) | 2019-04-25 | 2020-10-30 | Arkema France | Process for obtaining tetraethylammonium bromide and tetraethylammonium tetrafluoroborate, corresponding products and uses |
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