JP2009269917A - Method for producing tetrafluoroboric acid quaternary ammonium salt - Google Patents

Method for producing tetrafluoroboric acid quaternary ammonium salt Download PDF

Info

Publication number
JP2009269917A
JP2009269917A JP2009111188A JP2009111188A JP2009269917A JP 2009269917 A JP2009269917 A JP 2009269917A JP 2009111188 A JP2009111188 A JP 2009111188A JP 2009111188 A JP2009111188 A JP 2009111188A JP 2009269917 A JP2009269917 A JP 2009269917A
Authority
JP
Japan
Prior art keywords
water
quaternary ammonium
solubility
ammonium salt
mol
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.)
Granted
Application number
JP2009111188A
Other languages
Japanese (ja)
Other versions
JP5075870B2 (en
Inventor
Chuten Tei
仲天 鄭
Shiken Ko
志堅 胡
Hei Ri
兵 李
Kakoku Go
科国 呉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Capchem Technology Co Ltd
Original Assignee
Shenzhen Capchem Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenzhen Capchem Technology Co Ltd filed Critical Shenzhen Capchem Technology Co Ltd
Publication of JP2009269917A publication Critical patent/JP2009269917A/en
Application granted granted Critical
Publication of JP5075870B2 publication Critical patent/JP5075870B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an organic quaternary ammonium salt, especially a tetrafluoroboric acid quaternary ammonium salt excellent in production safety, environmental aspect and production cost. <P>SOLUTION: The quaternary ammonium salt is produced by using a tetrafluoroboric acid salt and a quaternary ammonium salt as raw materials, wherein the solubility ratio of these raw materials to a tetrafluoroboric acid quaternary ammonium salt in water is ≥1.0 and the solubility of these raw materials in water is ≥0.15 mol/100 g water, reacting these raw materials in an aqueous solvent, cooling the product and subjecting the cooled product to centrifugal separation to recover the objective compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は有機第四級アンモニウム塩の製造方法、特に、テトラフルオロホウ酸第四級アンモニウム塩の製造方法に関する。   The present invention relates to a method for producing an organic quaternary ammonium salt, and more particularly to a method for producing a quaternary ammonium tetrafluoroborate salt.

テトラフルオロホウ酸第四級アンモニウム塩は、新規な材料として各分野に使用されつつあり、特に、テトラフルオロホウ酸テトラエチルアンモニウム及びテトラフルオロホウ酸メチルトリエチルアンモニウムはアルミ電解コンデンサ及びスーパーキャパシタとして多く使用されている。   Tetrafluoroboric acid quaternary ammonium salt is being used in various fields as a novel material. In particular, tetrafluoroammonium tetrafluoroborate and methyltriethylammonium tetrafluoroborate are often used as aluminum electrolytic capacitors and supercapacitors. ing.

伝統的な製造方法として、テトラフルオロホウ酸第四級アンモニウム塩は、有機溶媒に合成されたものであって、例えば、テトラフルオロホウ酸アンモニウム塩或いはアルカリ金属塩とハロゲン化第四級アンモニウム塩をジメチルホルムアミド（ＤＭＦ）或いはメタノールに溶解して反応させ、有機溶媒中に溶解しにくいハロゲン化合物を濾除し、溶媒を蒸発除去して得るものである（例えば、特許文献１、特許文献２参照）。製造過程において、溶媒として、多量の有機溶媒を使用し、ＤＭＦ及びメタノールは毒性と汚染性があるため、その伝統的な製造過程では、環境に汚染をもたらすことが避けられない、その上、有機溶媒、例えばＤＭＦ及びメタノールは燃焼性と毒性の特徴があるので、危険を有効的に防止するために、企業は必要な費用を投入しなければならない、また、操作者は操作過程で常にこれら危険な有機溶媒に接触するため、操作者に厳重な損害を与える。
特開平５−２８６９８１号公報 特開２００１−３４８３８８号公報 As a traditional production method, tetrafluoroboric acid quaternary ammonium salt is synthesized in an organic solvent, for example, tetrafluoroboric acid ammonium salt or alkali metal salt and halogenated quaternary ammonium salt. It is obtained by dissolving in dimethylformamide (DMF) or methanol for reaction, filtering off a halogen compound that is difficult to dissolve in an organic solvent, and evaporating off the solvent (see, for example, Patent Document 1 and Patent Document 2). . In the manufacturing process, a large amount of organic solvent is used as a solvent, and DMF and methanol are toxic and polluting. Therefore, in the traditional manufacturing process, it is unavoidable to cause environmental pollution. Solvents such as DMF and methanol are flammable and toxic in nature, so companies must invest the necessary costs to effectively prevent the hazards and the operator is constantly in the process of operating these hazards. In contact with various organic solvents, causing severe damage to the operator.
Japanese Patent Laid-Open No. 5-286811 JP 2001-348388 A

本発明は、上記のような問題を生じることなく、生産操作の難しさを低下するために、生産過程における有機溶媒を使わない合成方法を提供し、汚染と製造操作の複雑性を低下すると共に、安全的、低汚染的、簡単なテトラフルオロホウ酸第四級アンモニウム塩の製造方法を提供する。   The present invention provides a synthesis method that does not use an organic solvent in the production process in order to reduce the difficulty of production operations without causing the above problems, and reduces the complexity of contamination and production operations. A safe, low-pollution, and simple method for producing a quaternary ammonium tetrafluoroborate salt is provided.

本発明は上記目的を達成するために、下記のような解決手段を提供する。   In order to achieve the above object, the present invention provides the following solutions.

前記テトラフルオロホウ酸第四級アンモニウム塩は、下記の一般式による得られ、

Figure 2009269917
（ここで、反応物Ｍ１におけるＭはアルカリ金属イオンまたはＮＨ４ ＋を示し、
反応物Ｍ２におけるＲ１、Ｒ２、Ｒ３、Ｒ４はそれぞれ独立に炭素数１〜５の炭化水素基を示し、
Ｘは、Ｃｌ−、Ｂｒ−、Ｉ−若しくは硫酸モノアルキルエステル酸基を示す。）
前記物質は、水中に溶解度Ｓが以下の関係を満たしており：
ＳＭ１／ＳＭ４及びＳＭ２／ＳＭ４は１．０以上で、且つＳＭ１とＳＭ２は０．１５ｍｏｌ／１００ｇ水以上であり、
具体的に、以下の
（１）適量の反応物Ｍ１とＭ２を秤量し、適量の水に入れ、
（２）ステップ（１）における前記反応物を混合し、撹拌で加熱反応を行い、
（３）反応システムは所定の温度まで加熱し、３０℃まで自然冷却し、
（４）遠心分離して、テトラフルオロホウ酸第四級アンモニウム塩の粗製品である固体を回収する、ステップで得られたものである。 The tetrafluoroboric acid quaternary ammonium salt is obtained by the following general formula:
Figure 2009269917
 (Here, M in the reactant M 1 represents an alkali metal ion or NH 4 + ,
R 1 , R 2 , R 3 and R 4 in the reactant M 2 each independently represent a hydrocarbon group having 1 to 5 carbon atoms,
X represents a Cl − , Br − , I − or sulfuric acid monoalkyl ester acid group. )
The substance has a solubility S in water satisfying the following relationship:
S M1 / S M4 and S M2 / S M4 are 1.0 or more, and S M1 and S M2 are 0.15 mol / 100 g water or more,
Specifically, the following (1) appropriate amounts of the reactants M 1 and M 2 are weighed and put into an appropriate amount of water,
(2) The reactants in step (1) are mixed and subjected to a heating reaction with stirring,
(3) The reaction system is heated to a predetermined temperature, naturally cooled to 30 ° C,
(4) The solid obtained as a crude product of tetrafluoroboric acid quaternary ammonium salt is collected by centrifugation and obtained in the step.

反応物Ｍ１において、Ｍはアルカリ金属イオンまたはＮＨ４ ＋を示し、
反応物Ｍ２において、Ｒ１、Ｒ２、Ｒ３、Ｒ４は炭素数１〜５の炭化水素基を示し、ここで、これらＲ１、Ｒ２、Ｒ３、Ｒ４の二つが互いに連結されていてもよく、連結されなくてもよい。分岐を含んでもよく、分岐を含まなくてもよい。ヒドロキシ基、エーテル基若しくはエステル基などの官能基を有することができる。Ｘは、Ｃｌ−、Ｂｒ−、Ｉ−若しくは硫酸モノアルキルエステル酸基である。 In reactant M 1 , M represents an alkali metal ion or NH 4 + ,
In the reactant M 2 , R 1 , R 2 , R 3 , and R 4 represent a hydrocarbon group having 1 to 5 carbon atoms, where two of these R 1 , R 2 , R 3 , and R 4 are connected to each other. It may or may not be connected. A branch may be included, and a branch may not be included. It can have a functional group such as a hydroxy group, an ether group or an ester group. X is, Cl -, Br -, I - is or sulfuric monoalkyl ester groups.

ＭＢＦ４の水に対する溶解度をＳＭ１（単位ｍｏｌ／１００ｇ水）とし、

Figure 2009269917
の水に対する溶解度をＳＭ２（単位ｍｏｌ／１００ｇ水）とし、
ＭＸの水に対する溶解度をＳＭ３（単位ｍｏｌ／１００ｇ水）とし、
Figure 2009269917
 の水に対する溶解度をＳＭ４（単位ｍｏｌ／１００ｇ水）とし、
同一温度におけるＳＭ１／ＳＭ４及びＳＭ２／ＳＭ４のいずれかが１以上である場合には、この温度で水の量及び反応物の量を適宜選択すれば、目的産物Ｍ４が水から析出する。ここで、ＳＭ１／ＳＭ４及びＳＭ２／ＳＭ４が大きいほど、Ｍ４の析出量は多くなり、また、目的産物Ｍ４は、水に対する溶解度より、塩溶液に対する溶解度の方が低い。 The solubility of MBF 4 in water is S M1 (unit mol / 100 g water),
Figure 2009269917
 S M2 (unit mol / 100 g water)
The solubility of MX in water is S M3 (unit mol / 100 g water),
Figure 2009269917
 The solubility in water is S M4 (unit mol / 100 g water),
When any of S M1 / S M4 and S M2 / S M4 at the same temperature is 1 or more, if the amount of water and the amount of reactants are appropriately selected at this temperature, the target product M 4 is removed from water. Precipitate. Here, the larger the amount of S M1 / S M4 and S M2 / S M4 , the larger the amount of M 4 precipitated, and the target product M 4 has a lower solubility in salt solution than in water.

前記化合物Ｍ１とＭ２のモル比は１：１である。
同一温度におけるＳＭ１／ＳＭ４及びＳＭ２／ＳＭ４のいずれかが１．１以上で、この温度におけるＳ１、Ｓ２が０．１５ｍｏｌ／１００ｇ水以上であることが好ましい。
ＳＭ３／ＳＭ４は１以上であることが好ましく、１以上でないと、水からＭ３が析出するおそれがあり、目的産物Ｍ４の不純物が多くなる。 The molar ratio of the compound M 1 and M 2 is 1: 1.
Any of S M1 / S M4 and S M2 / S M4 at the same temperature is 1.1 or more, and S1 and S2 at this temperature are preferably 0.15 mol / 100 g water or more.
S M3 / S M4 is preferably 1 or more, and if it is not 1 or more, M 3 may be precipitated from water, and the impurity of the target product M 4 increases.

前記Ｍ１はテトラフルオロホウ酸アンモニウム或いはテトラフルオロホウ酸ナトリウムであることが好ましい。前記Ｍ２はハロゲン化テトラエチルアンモニウム、ハロゲン化メチルトリｎ−ブチルアンモニウム、ハロゲン化エチルトリｎ−ブチルアンモニウム、及びハロゲン化プロピルトリｎ−ブチルアンモニウムのいずれか一つであることが好ましい。 The M 1 is preferably ammonium tetrafluoroborate or sodium tetrafluoroborate. M 2 is preferably any one of halogenated tetraethylammonium halide, halogenated methyltri-n-butylammonium halide, halogenated ethyltri-n-butylammonium halide, and halogenated propyltri-n-butylammonium.

前記ステップ（３）において、温度は室温〜１００℃であることが好ましい。   In the step (3), the temperature is preferably room temperature to 100 ° C.

本発明の製造方法は、従来の製造方法と比べると、有機溶媒を使わないため、汚染と製造操作の複雑性を低下すると共に、操作者に安全な操作環境を与える。   Compared with the conventional manufacturing method, the manufacturing method of the present invention does not use an organic solvent, thereby reducing contamination and complexity of the manufacturing operation and providing a safe operating environment for the operator.

以下、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれら実施例のみに限定されるものではない。   EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples.

実施例１
塩化テトラエチルアンモニウム３００ｇ（即ち、１．１８１ｍｏｌ）と、テトラフルオロホウ酸アンモニウム１９０ｇ（即ち、１．１８１ｍｏｌ）と、純水４５０ｇとを混合し、撹拌しつつ８０℃に加熱して完全に溶解させ、３０℃付近まで自然冷却し、遠心分離でテトラフルオロホウ酸テトラエチルアンモニウムの粗製品３００ｇの固体を得た。含水率は約３．５％であり、収率は７３％であった。 Example 1
300 g of tetraethylammonium chloride (ie 1.181 mol), 190 g of ammonium tetrafluoroborate (ie 1.181 mol) and 450 g of pure water are mixed and heated to 80 ° C. with stirring to completely dissolve. The mixture was naturally cooled to about 30 ° C. and centrifuged to obtain a solid product of 300 g of a tetraethylammonium tetrafluoroborate crude product. The water content was about 3.5% and the yield was 73%.

以下は、反応物と生成物の水に対する溶解度のパラメータである。
ＮＨ４Ｃｌの水に対する溶解度は３０℃で０．７７ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。
ＮＨ４ＢＦ４の水に対する溶解度は３０℃で０．３５ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。
Ｎ（Ｃ２Ｈ５）４ＢＦ４の水に対する溶解度は３０℃で０．２２ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。
Ｎ（Ｃ２Ｈ５）４Ｃｌの水に対する溶解度は３０℃で１．４１ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。 The following are the solubility parameters of the reactants and products in water.
The solubility of NH 4 Cl in water is 0.77 mol / 100 g water at 30 ° C., and the solubility increases with increasing temperature.
The solubility of NH 4 BF 4 in water is 0.35 mol / 100 g water at 30 ° C., and the solubility increases with increasing temperature.
The solubility of N (C 2 H 5 ) 4 BF 4 in water is 0.22 mol / 100 g water at 30 ° C., and the solubility increases with increasing temperature.
The solubility of N (C 2 H 5 ) 4 Cl in water is 1.41 mol / 100 g water at 30 ° C., and the solubility increases with increasing temperature.

上記４つの塩において、ＮＨ４Ｃｌは、３０℃で水に対する溶解度Ｓ３＝０．７７ｍｏｌ／１００ｇ水であり、ＮＨ４ＢＦ４は、３０℃で水に対する溶解度Ｓ１＝０．３５ｍｏｌ／１００ｇ水であり、Ｎ（Ｃ２Ｈ５）４ＢＦ４は、３０℃で水に対する溶解度Ｓ２＝０．２２ｍｏｌ／１００ｇ水であり、Ｎ（Ｃ２Ｈ５）４Ｃｌは、３０℃で水に対する溶解度Ｓ２＝１．４１ｍｏｌ／１００ｇ水であり、また、Ｋ１＝Ｓ１／Ｓ４＝１．５９、Ｋ２＝Ｓ２／Ｓ４＝６．４、Ｋ３＝Ｓ３／Ｓ４＝４．０５であった。 In the above four salts, NH 4 Cl has water solubility S3 = 0.77 mol / 100 g water at 30 ° C., and NH 4 BF 4 has water solubility S1 = 0.35 mol / 100 g water at 30 ° C. , N (C 2 H 5 ) 4 BF 4 has a water solubility S2 = 0.22 mol / 100 g water at 30 ° C., and N (C 2 H 5 ) 4 Cl has a water solubility S2 = 1 at 30 ° C. 0.41 mol / 100 g water, and K1 = S1 / S4 = 1.59, K2 = S2 / S4 = 6.4, and K3 = S3 / S4 = 4.05.

実施例２
臭化メチルトリｎ−ブチルアンモニウム２２０ｇ（即ち、０．７９ｍｏｌ）と、テトラフルオロホウ酸アンモニウム８２．５ｇ（即ち、０．７９ｍｏｌ）と、純水２８０ｇとを混合し、撹拌しつつ６０℃まで加熱し、３０℃付近まで自然冷却し、遠心分離でテトラフルオロホウ酸テトラエチルアンモニウムの粗製品２８０ｇの個体を得た。含水率は約９．２％であり、収率は９２％であった。 Example 2
Methyl tri-n-butylammonium bromide 220 g (ie 0.79 mol), ammonium tetrafluoroborate 82.5 g (ie 0.79 mol) and 280 g of pure water were mixed and heated to 60 ° C. with stirring. The mixture was naturally cooled to around 30 ° C. and centrifuged to obtain 280 g of a crude product of tetraethylammonium tetrafluoroborate. The water content was about 9.2% and the yield was 92%.

以下は、反応物と生成物の水に対する溶解度のパラメータである。
臭化メチルトリｎ−ブチルアンモニウムの水に対する溶解度は−３℃で１．１９ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。即ち、３０℃の場合は、Ｓ２＞１．１９ｍｏｌ／１００ｇ水であった。
テトラフルオロホウ酸アンモニウムは、３０℃で水に対する溶解度Ｓ２＝０．２２ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。
臭化アンモニウムは、３０℃で水に対する溶解度Ｓ３＝０．８５ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。
テトラフルオロホウ酸メチルトリｎ−ブチルアンモニウムの水に対する溶解度は３０℃で０．０１２ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。 The following are the solubility parameters of the reactants and products in water.
The solubility of methyltri-n-butylammonium bromide in water is 1.19 mol / 100 g water at −3 ° C., and the solubility increases with increasing temperature. That is, in the case of 30 degreeC, it was S2> 1.19 mol / 100g water.
Ammonium tetrafluoroborate has a solubility S2 = 0.22 mol / 100 g water in water at 30 ° C., and the solubility increases with increasing temperature.
Ammonium bromide has a solubility in water of S3 = 0.85 mol / 100 g water at 30 ° C., and the solubility increases with increasing temperature.
The solubility of tetratriborate methyltri-n-butylammonium in water is 0.012 mol / 100 g water at 30 ° C., and the solubility increases with increasing temperature.

実施例３
臭化エチルトリｎ−ブチルアンモニウム２６２ｇ（即ち、０．８９ｍｏｌ）と、テトラフルオロホウ酸アンモニウム９３．６ｇ（即ち、０．８９ｍｏｌ）と、純水３００ｇとを混合し、撹拌しつつ７０℃まで加熱し、３０℃付近まで自然冷却し、遠心分離してテトラフルオロホウ酸エチルトリｎ−ブチルアンモニウムの粗製品２５２ｇの個体を得た。含水率は約１０．４％であり、収率は８４％であった。 Example 3
262 g of ethyl tri-n-butylammonium bromide (ie 0.89 mol), 93.6 g of ammonium tetrafluoroborate (ie 0.89 mol) and 300 g of pure water were mixed and heated to 70 ° C. with stirring. The mixture was naturally cooled to around 30 ° C. and centrifuged to obtain 252 g of a crude product of ethyl trifluoroborate tri-n-butylammonium tetrafluoroborate. The water content was about 10.4% and the yield was 84%.

以下は、反応物と生成物の水に対する溶解度のパラメータである。
臭化エチルトリｎ−ブチルアンモニウムの水に対する溶解度は０℃で２．３２ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。即ち、３０℃の場合は、Ｓ２＞２．３２ｍｏｌ／１００ｇ水であった。
テトラフルオロホウ酸アンモニウムは、３０℃で水に対する溶解度Ｓ１＝０．２２ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。
臭化アンモニウムは、３０℃で水に対する溶解度Ｓ３＝０．８５ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。
テトラフルオロホウ酸エチルトリｎ−ブチルアンモニウムの水に対する溶解度は３０℃で０．０１５ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。 The following are the solubility parameters of the reactants and products in water.
The solubility of ethyltri-n-butylammonium bromide in water is 2.32 mol / 100 g water at 0 ° C., and the solubility increases with increasing temperature. That is, in the case of 30 degreeC, it was S2> 2.32 mol / 100g water.
Ammonium tetrafluoroborate has a solubility S1 = 0.22 mol / 100 g water in water at 30 ° C., and the solubility increases with increasing temperature.
Ammonium bromide has a solubility in water of S3 = 0.85 mol / 100 g water at 30 ° C., and the solubility increases with increasing temperature.
The solubility of tetrafluoroborate ethyltri-n-butylammonium in water is 0.015 mol / 100 g water at 30 ° C., and the solubility increases with increasing temperature.

実施例４
臭化プロピルトリｎ−ブチルアンモニウム５１５ｇ（即ち、１．６７ｍｏｌ）と、テトラフルオロホウ酸アンモニウム１７５ｇ（即ち、１．６７ｍｏｌ）と、純水５００ｇとを混合し、撹拌しつつ８０℃まで加熱し、完全に溶解させ、３０℃付近まで自然冷却し、遠心分離でテトラフルオロホウ酸プロピルトリｎ−ブチルアンモニウム粗製品４１５ｇの固体を得た。含水率は約５％であり、収率は７８％であった。 Example 4
515 g of propyltri-n-butylammonium bromide (i.e. 1.67 mol), 175 g of ammonium tetrafluoroborate (i.e. 1.67 mol) and 500 g of pure water were mixed and heated to 80C with stirring, It was completely dissolved, naturally cooled to around 30 ° C., and centrifuged to obtain 415 g of a solid product of propyltrifluoroborate propyltri-n-butylammonium. The water content was about 5% and the yield was 78%.

以下は、反応物と生成物の水に対する溶解度のパラメータである。
臭化プロピルトリｎ−ブチルアンモニウムの水に対する溶解度は０℃で３．０５ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。即ち、３０℃の場合は、Ｓ２＞３．０５ｍｏｌ／１００ｇ水であった。
テトラフルオロホウ酸アンモニウムは、３０℃で水に対する溶解度Ｓ１＝０．２２ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。
臭化アンモニウムは、３０℃で水に対する溶解度Ｓ３＝０．８５ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。
テトラフルオロホウ酸プロピルトリｎ−ブチルアンモニウムの水に対する溶解度は０℃で０．００８６ｍｏｌ／１００ｇ水であり、温度上昇とともに溶解度は大きくなる。 The following are the solubility parameters of the reactants and products in water.
The solubility of propyltri-n-butylammonium bromide in water is 3.05 mol / 100 g water at 0 ° C., and the solubility increases with increasing temperature. That is, in the case of 30 degreeC, it was S2> 3.05 mol / 100g water.
Ammonium tetrafluoroborate has a solubility S1 = 0.22 mol / 100 g water in water at 30 ° C., and the solubility increases with increasing temperature.
Ammonium bromide has a solubility in water of S3 = 0.85 mol / 100 g water at 30 ° C., and the solubility increases with increasing temperature.
The solubility of propyltri-n-butylammonium tetrafluoroborate in water is 0.0086 mol / 100 g water at 0 ° C., and the solubility increases with increasing temperature.

Claims (8)

テトラフルオロホウ酸第四級アンモニウム塩の製造方法であって、下記の一般式
Figure 2009269917
 （ここで、反応物Ｍ１におけるＭはアルカリ金属イオンまたはＮＨ４ ＋を示し、
反応物Ｍ２におけるＲ１、Ｒ２、Ｒ３、Ｒ４はそれぞれ独立に炭素数１〜５の炭化水素基を示し、
Ｘは、Ｃｌ−、Ｂｒ−、Ｉ−若しくは硫酸モノアルキルエステル酸基を示す。）に従って、
前記物質の水に対する溶解度Ｓは、ＳＭ１／ＳＭ４及びＳＭ２／ＳＭ４が１．０以上であり、且つ、ＳＭ１及びＳＭ２が０．１５ｍｏｌ／１００ｇ水以上である、という関係を満たし、
（１）適量の反応物Ｍ１とＭ２を秤量し、適量の水に入れ、
（２）ステップ（１）における反応物を混合し、撹拌で加熱反応を行い、
（３）反応系を所定の温度まで加熱し、３０℃付近まで自然冷却し、
（４）遠心分離し、テトラフルオロホウ酸第四級アンモニウム塩の粗製品である固体を回収するステップを通じて、テトラフルオロホウ酸第四級アンモニウム塩を得る製造方法。 A method for producing a tetrafluoroboric acid quaternary ammonium salt having the following general formula
Figure 2009269917
 (Here, M in the reactant M 1 represents an alkali metal ion or NH 4 + ,
R 1 , R 2 , R 3 and R 4 in the reactant M 2 each independently represent a hydrocarbon group having 1 to 5 carbon atoms,
X represents a Cl − , Br − , I − or sulfuric acid monoalkyl ester acid group. )
The solubility S of the substance in water satisfies the relationship that S M1 / S M4 and S M2 / S M4 are 1.0 or more and that S M1 and S M2 are 0.15 mol / 100 g water or more. ,
(1) an appropriate amount of the reaction M 1 and M 2 were weighed, placed in an appropriate amount of water,
(2) The reactants in step (1) are mixed and subjected to a heating reaction with stirring,
(3) The reaction system is heated to a predetermined temperature, naturally cooled to around 30 ° C.,
(4) A production method for obtaining a tetrafluoroboric acid quaternary ammonium salt through a step of recovering a solid which is a crude product of the tetrafluoroboric acid quaternary ammonium salt by centrifugation. 前記炭化水素基Ｒ１、Ｒ２、Ｒ３、Ｒ４のうちの二つは互いに連結されている請求項１記載の製造方法。 The production method according to claim 1 , wherein two of the hydrocarbon groups R 1 , R 2 , R 3 , and R 4 are connected to each other. 前記炭化水素基Ｒ１、Ｒ２、Ｒ３、Ｒ４は分岐を含む請求項１記載の製造方法。 The manufacturing method according to claim 1 , wherein the hydrocarbon groups R 1 , R 2 , R 3 , and R 4 include a branch. 前記炭化水素基Ｒ１、Ｒ２、Ｒ３、Ｒ４はヒドロキシ基、エーテル基若しくはエステル基を有する請求項１記載の製造方法。 The manufacturing method according to claim 1 , wherein the hydrocarbon groups R 1 , R 2 , R 3 and R 4 have a hydroxy group, an ether group or an ester group. 前記Ｍ３とＭ４の溶解度の比ＳＭ３／ＳＭ４は１以上である請求項１記載の製造方法。 The manufacturing method according to claim 1, wherein the solubility ratio S M3 / S M4 of M 3 and M 4 is 1 or more. 前記Ｍ１はテトラフルオロホウ酸アンモニウム或いはテトラフルオロホウ酸ナトリウムである請求項１記載の製造方法。 The manufacturing method according to claim 1, wherein M 1 is ammonium tetrafluoroborate or sodium tetrafluoroborate. 前記Ｍ２はハロゲン化テトラエチルアンモニウム、ハロゲン化メチルトリｎ−ブチルアンモニウム、ハロゲン化エチルトリｎ−ブチルアンモニウム、及びハロゲン化プロピルトリｎ−ブチルアンモニウムのいずれか一つである請求項１記載の製造方法。 The method according to claim 1, wherein M 2 is any one of tetraethylammonium halide, methyltrin-butylammonium halide, ethyltrin-butylammonium halide, and propyltrin-butylammonium halide. 前記ステップ（３）における前記所定の温度は室温〜１００℃である請求項１記載の製造方法。   The manufacturing method according to claim 1, wherein the predetermined temperature in the step (3) is room temperature to 100 ° C.
JP2009111188A 2008-04-30 2009-04-30 Method for producing quaternary ammonium tetrafluoroborate Active JP5075870B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200810066948.1 2008-04-30
CN200810066948.1A CN101570491B (en) 2008-04-30 2008-04-30 Method for preparing tetrafluoroborate

Publications (2)

Publication Number Publication Date
JP2009269917A true JP2009269917A (en) 2009-11-19
JP5075870B2 JP5075870B2 (en) 2012-11-21

Family

ID=41229990

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2009111188A Active JP5075870B2 (en) 2008-04-30 2009-04-30 Method for producing quaternary ammonium tetrafluoroborate

Country Status (2)

Country Link
JP (1) JP5075870B2 (en)
CN (1) CN101570491B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014509072A (en) * 2011-01-21 2014-04-10 コーニング インコーポレイテッド Electrolyte synthesis for ultracapacitors
KR20140059820A (en) * 2011-08-30 2014-05-16 코닝 인코포레이티드 Electrolyte synthesis for ultracapacitors
TWI584318B (en) * 2012-11-20 2017-05-21 康寧公司 Electrolyte solution for ultracapacitors and method of forming the same
CN110922333A (en) * 2019-10-10 2020-03-27 浙江工业大学 Method for preparing tetraethyl ammonium tetrafluoroborate by electrodialysis technology

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017031B (en) * 2014-04-21 2017-09-29 天津大学 A kind of preparation method of ultracapacitor electrolytic salt tetraethyl tetrafluoroborate
CN107793442B (en) * 2017-10-19 2019-12-31 常州大学 Preparation method of tetrafluoroborate quaternary ammonium salt
CN108147937A (en) * 2017-12-21 2018-06-12 常州大学 A kind of preparation method of quaternary ammonium salt

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1087574A (en) * 1996-09-09 1998-04-07 Sutera Chemiphar Kk Production of quaternary alkylammonium salt
JP2000086671A (en) * 1998-09-17 2000-03-28 Sumitomo Seika Chem Co Ltd Production of quaternary alkylammonium tetrafluoroborate
JP2000226360A (en) * 1999-02-04 2000-08-15 Mitsubishi Rayon Co Ltd Production of quaternary alkylammonium salt
JP2001106656A (en) * 1999-08-04 2001-04-17 Mitsubishi Chemicals Corp Production of quaternary ammonium salt
JP2006257039A (en) * 2005-03-18 2006-09-28 Koei Chem Co Ltd Method for producing quaternary ammonium salt

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4194296B2 (en) * 2002-05-14 2008-12-10 ステラケミファ株式会社 Method for purifying quaternary alkyl ammonium salt and method for producing quaternary alkyl ammonium salt
DE10250808B3 (en) * 2002-10-31 2004-04-08 Honeywell Specialty Chemicals Seelze Gmbh Preparation of electrolyte containing tetraalkylammonium tetrafluoroborate, used in electrochemical cell or capacitor, involves mixing tetraalkylammonium halide and metal tetrafluoroborate in (partly) water-miscible organic solvent
CN100561619C (en) * 2006-08-21 2009-11-18 深圳新宙邦科技股份有限公司 The preparation method of aluminium electrolytic capacitor, quaternary ammonium salt for super capacitor
KR100869291B1 (en) * 2006-08-31 2008-11-18 에스케이케미칼주식회사 Electrolyte solution and super capacitor including the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1087574A (en) * 1996-09-09 1998-04-07 Sutera Chemiphar Kk Production of quaternary alkylammonium salt
JP2000086671A (en) * 1998-09-17 2000-03-28 Sumitomo Seika Chem Co Ltd Production of quaternary alkylammonium tetrafluoroborate
JP2000226360A (en) * 1999-02-04 2000-08-15 Mitsubishi Rayon Co Ltd Production of quaternary alkylammonium salt
JP2001106656A (en) * 1999-08-04 2001-04-17 Mitsubishi Chemicals Corp Production of quaternary ammonium salt
JP2006257039A (en) * 2005-03-18 2006-09-28 Koei Chem Co Ltd Method for producing quaternary ammonium salt

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014509072A (en) * 2011-01-21 2014-04-10 コーニング インコーポレイテッド Electrolyte synthesis for ultracapacitors
KR20140059820A (en) * 2011-08-30 2014-05-16 코닝 인코포레이티드 Electrolyte synthesis for ultracapacitors
JP2014529191A (en) * 2011-08-30 2014-10-30 コーニング インコーポレイテッド Electrolyte synthesis for ultracapacitors
TWI563526B (en) * 2011-08-30 2016-12-21 Corning Inc Electrolyte solution and method of forming the same
TWI584318B (en) * 2012-11-20 2017-05-21 康寧公司 Electrolyte solution for ultracapacitors and method of forming the same
CN110922333A (en) * 2019-10-10 2020-03-27 浙江工业大学 Method for preparing tetraethyl ammonium tetrafluoroborate by electrodialysis technology
CN110922333B (en) * 2019-10-10 2022-11-25 浙江工业大学 Method for preparing tetraethyl ammonium tetrafluoroborate by electrodialysis technology

Also Published As

Publication number Publication date
CN101570491A (en) 2009-11-04
JP5075870B2 (en) 2012-11-21
CN101570491B (en) 2014-03-05

Similar Documents

Publication Publication Date Title
JP5075870B2 (en) Method for producing quaternary ammonium tetrafluoroborate
KR102300703B1 (en) Solvent-free alkane sulfonation
EP1505057B1 (en) Method of purifying quaternary alkylammonium salt
CN108530380B (en) Synthesis method of N-methyl-1, 2-benzisothiazolin-3-one
CN106008262A (en) Preparation method of 4,5-dicyan base-2-trifluoro-methylimidazole and prepared intermediate and salt thereof
WO2014061482A1 (en) Ionic liquid
CN104030906A (en) Method for preparing 9-fluorenone by liquid-phase oxidation
JP2006527243A (en) Preparation of aryldiazonium salts and reaction with nucleophiles.
JP3947490B2 (en) 3,3 &#39;, 5,5&#39;-tetramethyl-4,4&#39;-biphenol, method for producing the same, and method for producing an epoxy resin composition
JP2001247306A (en) Method for synthesizing ionic metal complex and method for purifying the same
JP2013082636A (en) Magnetic ionic liquid compound and method of dissolving and collecting cellulose using the same
JP6512970B2 (en) Purification method of 6-hydroxy-2-naphthoic acid glycidyl ether ester
US9272995B2 (en) Process for producing ionic liquids
EP2155653B1 (en) Process for preparing alkyl alkoxybenzoates in one step
CN106349189B (en) The preparation method of 9,9- double [4- (2,3- glycidoxy ethyoxyl) phenyl] fluorenes
CN101234977A (en) Method for preparing 3,7-di(2,4-dinitrophenoxy)-2-naphthoic acid
JP2006265198A (en) Method for producing quinoline derivative
CN101250111B (en) Method for preparing 1,4-di(2,6-dinitro-4-trifluoromethyl phenoxy) benzene
CN101230005B (en) Method for preparing 1,3,5-tri(2,4-dinitrophenoxy) benzene
CN101234979B (en) Method for preparing 3,5-di(2,4-dinitrophenoxy)toluene
CN101353307A (en) Preparation of 3,5-bis(2,6- dinitro-4-trifluoromethyl phenoxy)-2-naphthoic acid
CN101234987A (en) Method for preparing 4,4&#39;-di(2,4-dinitrophenoxy)diphenyl ether
CN101245016A (en) Process for producing 1,4-bis(2,4-dinitrophenoxy)-2- naphthoic acid
CN101279918A (en) Preparation of 1,3,5-tri(2,6-dinitro- trifluoromethylphenoxy) benzene
CN101230006A (en) Method for preparing 2,7-di(2,4-dinitrophenoxy) naphthalene

Legal Events

Date Code Title Description
A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20090805

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20111220

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20120319

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20120731

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20120827

R150 Certificate of patent or registration of utility model

Ref document number: 5075870

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20150831

Year of fee payment: 3

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250