TWI237015B - Process for the preparation of quaternary alkylammonium salts represented by R1R2R3R4N+ to BF4- - Google Patents

Abstract

The present invention relates to a process for the preparation of quaternary alkylammonium salts capable of obtaining highly pure product represented by R1R2R3R4N+ to BF4- without recrystallization. The process is provided by which quaternary alkylammonium salts of the following general formula: R1R2R3R4N+ to BF4- (wherein R1, R2, R3 and R4 are each independently C1-5 alkyl) can be easily prepared at high purity even without recrystallization. This process is characterized by reacting a quaternary ammonium halide of the general formula: R1R2R3R4N+ to X1- (wherein X1 is Cl or Br) with HBF4 (fluoboric acid) in an alcohol.

Description

1237015 V. Description of the invention (1) Industrial scope of application: The present invention relates to a method for producing a quaternary alkyl ammonium salt, and a more detailed description relates to an organic electrolyte used as, for example, an electrolytic capacitor or a battery. As the electrolyte, a method for producing a quaternary alkylammonium salt represented by RiR2r3R4N + · BF4- is quite useful. Conventional technology: In the past, a quaternary alkylammonium salt was prepared by reacting a quaternary alkyl group with gasification of ammonium, bromide, or hydroxide, and reaction with an aqueous solution of fluoroboric acid or hexafluorophosphoric acid.

Another example is disclosed in Japanese Patent Application Laid-Open No. 5-2 8 6 9 8 1, which is prepared by using anhydrous hydrofluoric acid as a solvent. In addition, as disclosed in Japanese Unexamined Patent Publication No. 1 1 to 3 1 0 555, it is prepared by reacting a tetrafluoroalkyl ammonium fluoride hydrofluoride with boron trifluoride or a complex thereof. Also disclosed in Japanese Patent Application Laid-Open No. H-3 1 5055, which is prepared by reacting a tetraalkylammonium bicarbonate with fluoroboric acid. The problem to be solved by the invention: The method for reacting quaternary acid or aqueous solution of hexafluorophosphoric acid for gasification, desertification or hydrogenation of four-stage burning base, due to the lack of stomach and gas-grade ammonium salts The solubility to water is large, so the yield is not good. Four of 1 is therefore concentrated to increase yield. In addition, like this, there are many raw materials such as chlorine and bromine, and the purity of the product is reduced. No capacitor or electrolyte is used for the product. Therefore, in order to make the electrolysis

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5. Description of the invention (2) The recrystallization is repeated. In addition, the method of using anhydrous hydrofluoric acid as a solvent has a problem in treatment, and because hydrogen fluoride cannot be completely removed, it must be recrystallized with methanol. In the method for producing a reaction of boron compound or soy complex, anhydrous hydrofluoric acid must be used when synthesizing the hydrofluoric acid salt of a tetraalkylammonium fluoride. In addition, after reacting the hydrofluoric acid salt of quaternary alkyl beryllium fluoride with boron difluoride or its complex, it is necessary to remove excess hydrofluoric acid and excess boron trifluoride complex. Warm up. The problem to be solved by the present invention is to solve the difficulties of the conventional method described above. In more detail, it is to provide a method for producing a quaternary alkyl ammonium salt. This method does not perform any recrystallization or uses anhydrous hydrofluoric acid. A method for producing a quaternary alkylammonium salt that can easily produce a high-purity target substance. Means for solving the problem: The main point of the present invention is a method for producing a quaternary alkylammonium salt represented by · Βίν, This method is characterized by ...

A process in which the quaternary ammonium halide represented by Xi (where h, & and & represent the same or different carbon number 丨 -5, Xi represents C1 or Br), and react with jjbf in. 〃 4; In addition, the gist of the present invention is directed to a method for producing a quaternary alkylammonium salt represented by Βίν, which is characterized by using χ "(wherein the ratio, &, & and d Same or different carbon number

1237015 Fifth, the description of the invention (3) "Xt" represents the four-stage burned halogen halide, which reacts with HBF4 in alcohol, and then performs a drying process. The alkyl group of the quaternary ammonium salt of the present invention refers to a carbon number as small as 5, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, n-pentyl , Isopentyl, third pentyl. The alkyl group of the quaternary ammonium salt is composed of one type of the above-mentioned alkyl groups, a combination of two types, or a combination of two or more types.溶剂 The alcohol used as the solvent is a low-aliphatic alcohol such as 曱 ol, ethanol, n-propanol, isopropanol, and the like, and 最佳 ol and ethanol are most preferable. Furthermore, although the reaction is carried out at an appropriate ordinary temperature, the reaction may be carried out at elevated temperatures. , $, Ming is the method of removing the hydrogen halide (Η) that is a by-product of the drying process after reacting the quaternary alkyl ammonium halide with hbf4, which is produced by vaporizing tetraethylammonium and HBF4 in methanol. The reaction formula for the reaction situation is shown in (1). ~ (C2H5) 4NC1 + HBF4 = (C2H5) NBF4 + HC1 (1) ^ The ammonium salt and hydrogen chloride of the target are formed. Because the solubility of ammonium salt in methanol is small, Precipitation in the solution. Hydrogenated gas is evaporated during the reaction, while = is attached to the crystal when the ammonium salt is separated from the solution. Since the hydrogen chloride is vaporized through 11, only the separated ammonium salt is dried to obtain a high Purity products. In addition, in order to improve the purity of the South, alcohol washing can also be performed. In particular, the removal of moisture is quite effective. Moreover, drying is carried out at 30-20 0 ° C, preferably 60-1 50 ° C ,

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Page 6 1237015 V. Description of the invention (4) ~-For the effective removal of by-products HXi and moisture 轫 τ and zi 乂 are rational phases. 1-1.5 moles and 1 mole of quaternary alkyl ammonium halide

The addition of HBF ears in order to reduce the acid content seems to be more rational. Example 4: The following shows a representative example of the present invention, and a more detailed description. Furthermore, these examples are merely illustrative examples, and, of course, it is needless to say that this test X is not limited to these examples. (Example 1) 828.5 g (5 mol) of vaporized tetraethylammonium was mixed with 30% 0.001 to 1 463 g (HBF4 5 mol), and the crystals of the j 4 formazan solution were precipitated by stirring. Stir for 1 hour. Tetraethylammonium fluoroborate was used to cool the solution to about TC, and after crystals were fully analyzed, the crystals were dried in a nitrogen stream at 105t for 20 hours. ~%, 867.2 g (yield 80. %), The product purity is 9 " (Example 2) Tetraethylammonium i 〇5 J g (5 Mo 1463 g) (HBF4 5 Mo u / day, Japanese / with 30 / ° '4 ferment bath The crystals of the liquid precipitate out of the ears), and mix for 1 hour. The solution is cooled to Q. The plant & , Nitrogen, and dried at 105 ° C for 20 hours. "The yield is 867.2 g (yield 80%), the purity of the product is M"

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%, Impurities Br is below 3 ppm, Na, Ca, Mg, AI, Fe, and Cr are each 1 p p m or less. (Example 3) Tetraethylammonium fluoroacetate obtained in Example 2 was suspended in isopropanol, and crystals were obtained from the suspension, and dried in a nitrogen stream at i 0 5 0c for 20 hours. Moisture in the product is below 15 ppm. (Example 4) 1 051 g (5 mol) of tetraethylammonium bromide was mixed with 30% HBF4 methanol solution (144 6 3 g (Η B F4 5 mol)) and stirred; dropped for 1 hour. Crystals of tetraethylammonium fluoroside acid precipitated. The solution was cooled to 0 ° C, and the crystals were fully analyzed, and then the solution was filtered. After obtaining the crystals, the drying temperature was changed to perform drying. Table 1 shows the analysis results of the drying temperature and the impurities (moisture) after drying. Drying temperature and residual impurity (moisture) concentration Table 1 Drying temperature 30 50 60 70 90 110 130 140 150 160 170 200 Impurity (water) concentration (ppm) 80 30 20 20 20 20 20 20 20 20 20 20 (Example 5 ) In this example, tetraethylammonium fluoborate before drying in Example 1 was tested. At this time, hundreds to thousands of P P m of C1 remain in the product. Na, Ca, Mg, A1, Fe, and Cr are each 1 ppm or less. Invention effect:

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Claims (1)

Μ-1237015 XT 'VI. Application scope of patent t 1 · A method for producing a quaternary alkylammonium salt represented by heart 1? 21 ^ 1? 41 ^ · bf4-, which is characterized in that R1 R2 RsR4 Ν + · A process in which a quaternary alkyl ammonium halide represented by Xl (where Rl, D, I, and R4 represent the same or different carbon number 5 alkyl group, \ represents C1 or meter), reacts with HBF4 in rhenium . 2. The method for producing a quaternary alkylammonium salt represented by RlR2R3R4N + · Β1-4 as described in item 1 of the scope of the patent application, wherein the quaternary alkyl group and HBF4 are reacted in alcohol, and then The process of washing with alcohol is performed. 3 · —A method for producing a quaternary alkynyl ammonium salt represented by κΛΚ3Κ4Ν + · BF4-, characterized in that M2κ3Μ + · χι- (wherein R1, dagger, K and R4 represent the same or different carbon numbers The alkyl group of 5 is a quaternary alkyl ammonium halide represented by C1 * Br), and reacts with HBF4 in an alcohol, and then a drying process is performed. 4. The production method of the quaternary alkylammonium salt indicated by BFV as described in item 3 of the scope of patent application, wherein the aforementioned drying is performed at 30-200 ° C. 5. The method for producing a quaternary alkylammonium salt represented by Ri R2 R3 R4 N + · BFr as described in claims 3 to 4 of the scope of the patent application, wherein the alcohol is washed after drying. 2015-3857-PF; Frank.ptd Page 10