JP2001048846A - Quaternary ammonium salt and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stabilized quaternary ammonium salt without causing lowering, etc. of quality by storage, etc., and excellent in storage stability and provide a method for producing the above ammonium salt. SOLUTION: This quaternary ammonium salt represented by the formula Q+.X (Q+ is quaternary ammonium cation; and X is BF4 or PF6) is obtained by coating the surface of the ammonium salt with an organic solvent having <25 permittivity at 25 deg.C and >=50 deg.C and <=150 deg.C boiling point. A method for coating the quaternary ammonium salt comprises suspending or immersing crystal of quaternary ammonium salt represented by the formula into an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a quaternary ammonium salt and a method for producing the same. More specifically, the present invention relates to a quaternary ammonium salt whose surface is coated with a specific solvent and a method for producing the same. Quaternary ammonium salts are used for electrolytes for electrochemical devices such as batteries and electrolytic capacitors, surfactants,
Used in a wide range of fields as phase transfer catalysts, softeners, antistatic agents such as detergents, dispersants such as asphalt and cement, disinfectants, preservatives, antiblocking agents for fertilizers and granules, and anticoagulants. .

The quaternary ammonium tetrafluoroborate or hexafluorophosphate according to the present invention is extremely hard to absorb moisture and hardly causes decomposition of the quaternary ammonium salt due to moisture, so that it maintains high purity even after long-term storage. And is particularly suitable as an electrolyte for a non-aqueous electrolyte.

[0003]

2. Description of the Related Art Quaternary ammonium salts used in electrolytes such as quaternary ammonium tetrafluoroborate or hexafluorophosphate are originally known.
Since the salt itself is very easy to absorb moisture and easily hydrolyze, in the manufacturing process or in storage and handling, due to the unavoidable water content, the salt is hydrolyzed as in the following formula to generate hydrogen fluoride, There is a problem such as solidification.

[0004]

[Formula 2] _{^{Q + · BF 4 - + xH}} 2 O → Q + · B (O
^{_{H) x F (4-X}} ) - + xHF Q + · PF 6 - + xH 2 O → Q + · PO x F (6-2x)
^- + 2xHF

(Where Q ⁺ has the same meaning as in formula (I))

In particular, it has been conventionally known that impurities such as hydrogen fluoride adversely affect the performance of an electrolytic solution. For a quaternary ammonium salt for an electrolyte, in order to remove impurities such as hydrogen fluoride, Prior to use, purification by recrystallization or the like is performed again.

[0007]

However, performing such recrystallization each time is complicated as an operation.
Moreover, it is not economically preferable. An object of the present invention is to provide a stabilized quaternary ammonium salt which does not cause deterioration in quality due to storage handling and the like, and a method for producing the same.

[0008]

Means for Solving the Problems The present inventors have made intensive studies in view of such circumstances, and as a result, by coating a quaternary ammonium salt with a specific solvent, a quaternary ammonium salt having excellent storage stability can be easily obtained. Thus, the present invention has been completed.

That is, the gist of the present invention is that the surface is coated with an organic solvent having a relative dielectric constant at 1.25 ° C. of less than 25 and a boiling point at normal pressure of 50 ° C. or more and 150 ° C. or less. The following general formula (I)
A quaternary ammonium salt represented by

[0010]

## STR3 ## Q ⁺ · ^X - (I)

[0011] (wherein, Q ⁺ represents a quaternary ammonium cation, X ^- is BF ₄ ^- shows the ^- or PF ₆₎

2. A method for coating a quaternary ammonium salt, comprising suspending or impregnating crystals of the quaternary ammonium salt represented by the formula (I) in an organic solvent.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Quaternary ammonium salts used in the present invention, quaternary ammonium salt represented by formula (I), i.e., Q ⁺ · BF ₄ ^- comprising quaternary ammonium tetrafluoroborate and Q ⁺ ·
PF ₆ ^- is a quaternary ammonium hexafluorophosphate made.

[0014]

[Of 4] Q ⁺ · ^X - (I)

[0015] (wherein, Q ⁺ represents a quaternary ammonium cation, X ^- is BF ₄ ^- shows the ^- or PF ₆₎

The following are specific examples of Q ⁺ . Trialkylamine with quaternized nitrogen: tetramethylammonium, ethyltrimethylammonium,
Diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl-n
-Propylammonium, trimethylisopropylammonium, ethyldimethyl-n-propylammonium, ethyldimethylisopropylammonium, diethylmethyl-n-propylammonium, diethylmethylisopropylammonium, dimethyldi-n-propylammonium, dimethyl-n-propylisopropylammonium, dimethyl Diisopropylammonium, triethyl-n-propylammonium, n-butyltrimethylammonium, isobutyltrimethylammonium, t-butyltrimethylammonium, triethylisopropylammonium, ethylmethyldi-n-propylammonium, ethylmethyl-n-propylisopropylammonium, ethylmethyldiisopropylammonium , N-butyl Tyldimethylammonium, isobutylethyldimethylammonium, t-butylethyldimethylammonium, diethyldi-n-propylammonium, diethyl-n-propylisopropylammonium, diethyldiisopropylammonium, methyltri-n-propylammonium, methyldi-n-propylisopropylammonium, Methyl-n-propyldiisopropylammonium, n-butyltriethylammonium, isobutyltriethylammonium, t-
Butyltriethylammonium, di-n-butyldimethylammonium, diisobutyldimethylammonium,
Di-t-butyldimethylammonium, n-butylisobutyldimethylammonium, n-butyl-t-butyldimethylammonium, isobutyl-t-butyldimethylammonium and the like.

Aliphatic cyclic amine in which nitrogen is quaternized: N, N-dimethylpyrrolidium, N-ethyl-N-
Methylpyrrolidium, N, N-diethylpyrrolidium,
1,1,2-trimethylpyrrolidinium, 1,1,3-
Trimethylpyrrolidinium, 1-ethyl-1,2-dimethylpyrrolidinium, 1-ethyl-1,3-dimethylpyrrolidinium, 2-ethyl-1,1-dimethylpyrrolidinium, 3-ethyl-1, 1-dimethylpyrrolidinium, 1,1-diethyl-2-methylpyrrolidinium,
1,1-diethyl-3-methylpyrrolidinium, 1,2
-Diethyl-1-methylpyrrolidinium, 1,3-diethyl-1-methylpyrrolidinium, 1,1,2-triethylpyrrolidinium, 1,1,3-triethylpyrrolidinium, 1,1,2 , 2-tetramethylpyrrolidinium, 1,1,2,3-tetramethylpyrrolidinium,
1,1,2,4-tetramethylpyrrolidinium, 1,
1,2,5-tetramethylpyrrolidinium, 1,1,
3,4-tetramethylpyrrolidinium, 1,1,3,3
-Tetramethylpyrrolidinium, 2-ethyl-1,1,1
2-trimethylpyrrolidinium, 2-ethyl-1,1,1,
3-trimethylpyrrolidinium, 3-ethyl-1,1,
2-trimethylpyrrolidinium, 3-ethyl-1,1,
3-trimethylpyrrolidinium, 2-ethyl-1,1,1,
4-trimethylpyrrolidinium, 4-ethyl-1,1,
2-trimethylpyrrolidinium, 2-ethyl-1,1,1,
5-trimethylpyrrolidinium, 5-ethyl-1,1,1
2-trimethylpyrrolidinium, 3-ethyl-1,1,
4-trimethylpyrrolidinium, 4-ethyl-1,1,
3-trimethylpyrrolidinium, 1-ethyl-1,2,2
2-trimethylpyrrolidinium, 1-ethyl-1,2,2
3-trimethylpyrrolidinium, 1-ethyl-1,3,
3-trimethylpyrrolidinium, 1-ethyl-1,2,2
4-trimethylpyrrolidinium, 1-ethyl-1,2,2
5-trimethylpyrrolidinium, 1-ethyl-1,3,
4-trimethylpyrrolidinium, 2,2-diethyl-
1,1-dimethylpyrrolidinium, 2,3-diethyl-
1,1-dimethylpyrrolidinium, 3,3-diethyl-
1,1-dimethylpyrrolidinium, 2,4-diethyl-
1,1-dimethylpyrrolidinium, 2,5-diethyl-
1,1-dimethylpyrrolidinium, 3,4-diethyl-
1,1-dimethylpyrrolidinium, 1,2-diethyl-
1,2-dimethylpyrrolidinium, 1,2-diethyl-
1,3-dimethylpyrrolidinium, 1,3-diethyl-
1,2-dimethylpyrrolidinium, 1,3-diethyl-
1,3-dimethylpyrrolidinium, 1,2-diethyl-
1,4-dimethylpyrrolidinium, 1,4-diethyl-
1,2-dimethylpyrrolidinium, 1,2-diethyl-
1,5-dimethylpyrrolidinium, 1,5-diethyl-
1,2-dimethylpyrrolidinium, 1,3-diethyl-
1,4-dimethylpyrrolidinium, 1,1,2,2,3
-Pentamethylpyrrolidinium, 1,1,2,2,4-
Pentamethylpyrrolidinium, 1,1,2,2,5-pentamethylpyrrolidinium, 1,1,2,3,4-pentamethylpyrrolidinium, 1,1,2,3,5-pentamethyl Pyrrolidinium, 1,1,3,3,4-pentamethylpyrrolidinium, 1,1,3,3,5-pentamethylpyrrolidinium, 1-ethyl-1,2,2,3-tetramethyl Pyrrolidinium, 1-ethyl-1,2,2,4
-Tetramethylpyrrolidinium, 1-ethyl-1,2,2
2,5-tetramethylpyrrolidinium, 1-ethyl-
1,2,3,4-tetramethylpyrrolidinium, 1-ethyl-1,2,3,5-tetramethylpyrrolidinium,
1-ethyl-1,2,4,5-tetramethylpyrrolidinium, 1-ethyl-1,3,3,4-tetramethylpyrrolidinium, 1-ethyl-1,3,3,5-tetramethyl Pyrrolidinium, 1-ethyl-1,3,4,5-tetramethylpyrrolidinium, 2-ethyl-1,1,2,3
-Tetramethylpyrrolidinium, 2-ethyl-1,1,1
2,4-tetramethylpyrrolidinium, 2-ethyl-
1,1,2,5-tetramethylpyrrolidinium, 2-ethyl-1,1,3,3-tetramethylpyrrolidinium,
2-ethyl-1,1,3,4-tetramethylpyrrolidinium, 2-ethyl-1,1,3,5-tetramethylpyrrolidinium, 2-ethyl-1,1,4,4-tetramethyl Pyrrolidinium, 2-ethyl-1,1,4,5-tetramethylpyrrolidinium, 2-ethyl-1,1,5,5
-Tetramethylpyrrolidinium, 3-ethyl-1,1,
2,2-tetramethylpyrrolidinium, 3-ethyl-
1,1,2,3-tetramethylpyrrolidinium, 3-ethyl-1,1,2,4-tetramethylpyrrolidinium,
3-ethyl-1,1,2,5-tetramethylpyrrolidinium, 3-ethyl-1,1,3,4-tetramethylpyrrolidinium, 3-ethyl-1,1,4,4-tetramethyl Pyrrolidinium, 3-ethyl-1,1,4,5-tetramethylpyrrolidinium, 1,1,2,2,3,3-hexamethylpyrrolidinium, 1,1,2,2,3 4-
Hexamethylpyrrolidinium, 1,1,2,2,3,5
-Hexamethylpyrrolidinium, 1,1,2,2,4
4-hexamethylpyrrolidinium, 1,1,2,2
4,5-hexamethylpyrrolidinium, 1,1,2,2
2,5,5-hexamethylpyrrolidinium, 1,1,
2,3,3,4-hexamethylpyrrolidinium, 1,
1,2,3,3,5-hexamethylpyrrolidinium,
1,1,2,3,4,4-hexamethylpyrrolidinium, 1,1,2,3,5,5-hexamethylpyrrolidinium, 1,1,2,3,4,5-hexamethyl Pyrrolidinium and the like.

A morpholine ring having a quaternized nitrogen:
N, N-dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N, N-diethylmorpholinium, 3,4,4-trimethylmorpholinium, 2,4
4-trimethylmorpholinium, 3-ethyl-4,4-
Dimethylmorpholinium, 3,4-dimethyl-4-ethylmorpholinium, 2,4-dimethyl-4-ethylmorpholinium, 3-methyl-4,4-diethylmorpholinium, 2,4-dimethyl- 4-ethylmorpholinium,
2-methyl-4,4-diethylmorpholinium, 3,4
-Diethyl-4-methylmorpholinium, 2,4-diethyl-4-methylmorpholinium, 3,4,4-triethylmorpholinium, 2,4,4-triethylmorpholinium, 3,3,4 2,4-tetramethylmorpholinium, 2,3,4,4-tetramethylmorpholinium,
2,4,4,5-tetramethylmorpholinium, 3,
4,4,5-tetramethylmorpholinium, 2,2
4,4-tetramethylmorpholinium, 2,4,4,6
-Tetramethylmorpholinium, 2,4,4-trimethyl-3-ethylmorpholinium, 2-ethyl-3,4
4-trimethylmorpholinium, 2,4,4-trimethyl-5-ethylmorpholinium, 2-ethyl-4,4
5-trimethylmorpholinium, 3-ethyl-4,4,
6-trimethylmorpholinium, 2-ethyl-4,4,
5-trimethylmorpholinium, 2-ethyl-4,4,
6-trimethylmorpholinium, 2,3-dimethyl-
4,4-diethylmorpholinium, 2,5-dimethyl-
4,4-diethylmorpholinium, 3,5-dimethyl-
4,4-diethylmorpholinium, 2,6-dimethyl-
4,4-diethylmorpholinium, 2,4-dimethyl-
3,4-diethylmorpholinium, 2,4-diethyl-
3,4-dimethylmorpholinium, 2,4-dimethyl-
4,5-diethylmorpholinium, 2,4-diethyl-
4,5-dimethylmorpholinium, 3,4-diethyl-
4,5-dimethylmorpholinium, 2,4-diethyl-
4,6-dimethylmorpholinium, 2,3-diethyl-
4,4-dimethylmorpholinium, 2,5-diethyl-
4,4-dimethylmorpholinium, 3,5-diethyl-
4,4-dimethylmorpholinium, 2,6-diethyl-
4,4-dimethylmorpholinium, 2,3,4,4,6
-Pentamethylmorpholinium, 2,3,4,4,5-
Pentamethylmorpholinium, 2,6,4,4-tetramethyl-3-ethylmorpholinium, 2,4,4,5-
Tetramethyl-3-ethylmorpholinium, 2-ethyl-3,4,4,6-tetramethylmorpholinium, 2-
Ethyl-3,4,4,5-tetramethylmorpholinium, 2,3,4,4,5,6-hexamethylmorpholinium and the like.

Imidazoline ring quaternized with nitrogen: N, N'-dimethylimidazolinium, N-ethyl-N'-methylimidazolinium, N, N'-diethylimidazolinium, 1,2 1,3-trimethylimidazolinium, 1,3,4-trimethylimidazolinium, 1
-Ethyl-2,3-dimethylimidazolinium, 1-ethyl-3,4-dimethylimidazolinium, 1-ethyl-3,5-dimethylimidazolinium, 2-ethyl-
1,3-dimethylimidazolinium, 4-ethyl-1,
3-dimethylimidazolinium, 1,2-diethyl-3
-Methylimidazolinium, 1,4-diethyl-3-methylimidazolinium, 1,5-diethyl-3-methylimidazolinium, 1,3-diethyl-2-methylimidazolinium, 1,3-diethyl -4-methylimidazolinium, 1,2,3-triethylimidazolinium,
1,3,4-triethylimidazolinium, 1,2,2
3,4-tetramethylimidazolinium, 1-ethyl-
2,3,4-trimethylimidazolinium, 1-ethyl-2,3,5-trimethylimidazolinium, 1-ethyl-3,4,5-trimethylimidazolinium, 2-ethyl-1,3,4 -Trimethylimidazolinium, 4-
Ethyl-1,2,3-trimethylimidazolinium,
1,2-diethyl-3,4-dimethylimidazolinium, 1,3-diethyl-2,4-dimethylimidazolinium, 1,4-diethyl-2,3-dimethylimidazolinium, 2,4-diethyl -1,3-dimethylimidazolinium, 4,5-diethyl-1,3-dimethylimidazolinium, 1,2,3-triethyl-4-methylimidazolinium, 1,2,4-triethyl-3- Methyl imidazolinium, 1,2,5-triethyl-3-methyl imidazolinium, 1,3,4-triethyl-2-methyl imidazolinium, 1,3,4-triethyl-5-methyl imidazolinium, 1,4,5-triethyl-3-
Methyl imidazolinium, 1,2,3,4,5-pentamethyl imidazolinium and the like.

Tetrahydropyrimidine ring having a quaternized nitrogen: N, N'-dimethyltetrahydropyrimidinium, N-ethyl-N'-methyltetrahydropyrimidinium, N, N'-diethyltetrahydropyrimidinium 1,2,3-trimethyltetrahydropyrimidinium, 1,3,4-trimethyltetrahydropyrimidinium, 1,3,5-trimethyltetrahydropyrimidinium, 1-ethyl-2,3-dimethyltetrahydropyrimidinium , 1-ethyl-3,4-dimethyltetrahydropyrimidinium, 1-ethyl-3,5-dimethyltetrahydropyrimidinium, 1-ethyl-3,6-dimethyltetrahydropyrimidinium, 2-ethyl-1,3 −
Dimethyltetrahydropyrimidinium, 4-ethyl-
1,3-dimethyltetrahydropyrimidinium, 5-ethyl-1,3-dimethyltetrahydropyrimidinium,
1,2,3,4-tetramethyltetrahydropyrimidinium, 1,2,3,5-tetramethyltetrahydropyrimidinium, 1-ethyl-2,3,4-trimethyltetrahydropyrimidinium, 1-ethyl- 2,3,5-trimethyltetrahydropyrimidinium, 1-ethyl-
2,3,6-trimethyltetrahydropyrimidinium,
2-ethyl-1,3,4-trimethyltetrahydropyrimidinium, 2-ethyl-1,3,5-trimethyltetrahydropyrimidinium, 4-ethyl-1,2,3-trimethyltetrahydropyrimidinium, 4- Ethyl-
1,3,5-trimethyltetrahydropyrimidinium,
4-ethyl-1,3,6-trimethyltetrahydropyrimidinium, 5-ethyl-1,2,3-trimethyltetrahydropyrimidinium, 5-ethyl-1,3,4-trimethyltetrahydropyrimidinium, 1, 2-diethyl-3,4-dimethyltetrahydropyrimidinium,
1,2-diethyl-3,5-dimethyltetrahydropyrimidinium, 1,2-diethyl-3,6-dimethyltetrahydropyrimidinium, 1,3-diethyl-2,4-
Dimethyltetrahydropyrimidinium, 1,3-diethyl-2,5-dimethyltetrahydropyrimidinium,
1,4-diethyl-2,3-dimethyltetrahydropyrimidinium, 1,4-diethyl-3,5-dimethyltetrahydropyrimidinium, 1,4-diethyl-3,6-
Dimethyltetrahydropyrimidinium, 1,5-diethyl-2,3-dimethyltetrahydropyrimidinium,
1,5-diethyl-3,4-dimethyltetrahydropyrimidinium, 1,5-diethyl-3,6-dimethyltetrahydropyrimidinium, 2,4-diethyl-1,3-
Dimethyltetrahydropyrimidinium, 2,5-diethyl-1,3-dimethyltetrahydropyrimidinium,
4,5-diethyl-1,3-dimethyltetrahydropyrimidinium, 4,6-diethyl-1,3-dimethyltetrahydropyrimidinium, 1,2,3,4,5-pentamethyltetrahydropyrimidinium, , 2,3,4,
6-pentamethyltetrahydropyrimidinium, 1,
2,3,4,5,6-hexamethyltetrahydropyrimidinium, methyldiazabicyclononenium, ethyldiazabicyclononenium, methyldiazabicycloundecenium, ethyldiazabicycloundecenium and the like.

When the nitrogen of the piperazine ring is quaternized:
N, N, N ', N'-tetramethylpiperazinium, N
-Ethyl-N, N ', N'-trimethylpiperazinium, N, N-diethyl-N', N'-dimethylpiperazinium, N, N, N'-triethyl-N'-methylpiperazinium, N, N, N ', N'-tetraethylpiperazinium, 1,1,2,4,4-pentamethylpiperazinium, 1,1,3,4,4-pentamethylpiperazinium, 1,1 , 2,3,4,4-hexamethylpiperazinium, 1,1,2,4,4,5-hexamethylpiperazinium, 1,1,2,4,4,6-hexamethylpiperazinium 1,1,3,4,4,5-hexamethylpiperazinium, 1-ethyl-1,2,4,4-tetramethylpiperazinium, 1-ethyl-1,3,4,4-tetra Methylpiperazinium, 2-ethyl-1,1,4,
4-tetramethylpiperazinium, 1-ethyl-1,
2,4,4-tetramethylpiperazinium, 1-ethyl-1,3,4,4-tetramethylpiperazinium, 1,
1-diethyl-2,4,4-trimethylpiperazinium, 1,4-diethyl-1,2,4-trimethylpiperazinium, 1,2-diethyl-1,4,4-trimethylpiperazinium, 1 , 3-diethyl-1,4,4-trimethylpiperazinium and the like.

When the nitrogen of the piperidine ring is quaternized:
N, N-dimethylpiperidinium, N-ethyl-N-methylpiperidinium, N, N-diethylpiperidinium, 1,1,2-trimethylpiperidinium, 1,1,
3-trimethylpiperidinium, 1,1,4-trimethylpiperidinium, 1,1,2,2-tetramethylpiperidinium, 1,1,2,3-tetramethylpiperidinium, 1,1, 2,4-tetramethylpiperidinium,
1,1,2,5-tetramethylpiperidinium, 1,
1,2,6-tetramethylpiperidinium, 1,1,
3,3-tetramethylpiperidinium, 1,1,3,4
-Tetramethylpiperidinium, 1,1,3,5-tetramethylpiperidinium, 1-ethyl-1,2-dimethylpiperidinium, 1-ethyl-1,3-dimethylpiperidinium, 1-ethyl -1,4-dimethylpiperidinium, 1-ethyl-1,2,3-trimethylpiperidinium, 1-ethyl-1,2,4-trimethylpiperidinium, 1-ethyl-1,2,5- Trimethylpiperidinium, 1-ethyl-1,2,6-trimethylpiperidinium, 1-ethyl-1,3,4-trimethylpiperidinium, 1-ethyl-1,3,5-trimethylpiperidinium, 1,1-diethyl-2-methylpiperidinium,
1,1-diethyl-3-methylpiperidinium, 1,1
-Diethyl-4-methylpiperidinium, 1,1-diethyl-2,3-dimethylpiperidinium, 1,1-diethyl-2,4-dimethylpiperidinium, 1,1-diethyl-2,5- Dimethylpiperidinium, 1,1-diethyl-2,6-dimethylpiperidinium, 1,1-diethyl-3,4-dimethylpiperidinium, 1,1-diethyl-3,5-dimethylpiperidinium, 2-ethyl-
1,1,3-trimethylpiperidinium, 2-ethyl-
1,1,4-trimethylpiperidinium, 2-ethyl-
1,1,5-trimethylpiperidinium, 2-ethyl-
1,1,6-trimethylpiperidinium, 3-ethyl-
1,1,2-trimethylpiperidinium, 3-ethyl-
1,1,4-trimethylpiperidinium, 3-ethyl-
1,1,5-trimethylpiperidinium, 3-ethyl-
1,1,6-trimethylpiperidinium, 4-ethyl-
1,1,2-trimethylpiperidinium, 4-ethyl-
1,1,3-trimethylpiperidinium, 1,2-diethyl-1,3-dimethylpiperidinium, 1-ethyl-
1,2,4-trimethylpiperidinium, 1,2-diethyl-1,5-dimethylpiperidinium, 1,2-diethyl-1,6-dimethylpiperidinium, 1,3-diethyl-1,5 -Dimethylpiperidinium, 1,3-diethyl-1,4-dimethylpiperidinium, 1,3-diethyl-1,5-dimethylpiperidinium, 1,3-diethyl-1,6-dimethylpiperidinium , 1,4-diethyl-1,2-dimethylpiperidinium, 1,4-diethyl-1,3-dimethylpiperidinium, 1,1,2-
Triethyl-3-methylpiperidinium, 1,1,2-
Triethyl-4-methylpiperidinium, 1,1,2-
Triethyl-5-methylpiperidinium, 1,1,2-
Triethyl-6-methylpiperidinium, 1,1,3-
Triethyl-2-methylpiperidinium, 1,1,3-
Triethyl-4-methylpiperidinium, 1,1,3-
Diethyl-5-methylpiperidinium, 1,1,3-triethyl-6-methylpiperidinium, 1,1,4-diethyl-2-methylpiperidinium, 1,1,4-diethyl-3-methyl Piperidinium, 2-ethyl-1,1
-Dimethylpiperidinium, 3-ethyl-1,1-dimethylpiperidinium, 4-ethyl-1,1-dimethylpiperidinium, 2,3-diethyl-1,1-dimethylpiperidinium, 2,4 -Diethyl-1,1-dimethylpiperidinium, 2,5-diethyl-1,1-dimethylpiperidinium, 2,6-diethyl-1,1-dimethylpiperidinium, 3,4-diethyl-1, 1-dimethylpiperidinium, 3,5-diethyl-1,1-dimethylpiperidinium, 1,2-diethyl-1-methylpiperidinium, 1,3-diethyl-1-methylpiperidinium, 1, 4-diethyl-1-methylpiperidinium,
1,2,3-triethyl-1-methylpiperidinium,
1,2,4-triethyl-1-methylpiperidinium,
1,2,5-triethyl-1-methylpiperidinium,
1,2,6-triethyl-1-methylpiperidinium,
1,3,4-triethyl-1-methylpiperidinium,
1,3,5-triethyl-1-methylpiperidinium,
1,1,2-triethylpiperidinium, 1,1,2-
Triethylpiperidinium, 1,1,4-triethylpiperidinium, 1,1,2,3-tetraethylpiperidinium, 1,1,2,4-tetraethylpiperidinium, 1,1,2,5- Tetraethylpiperidinium,
1,1,2,6-tetraethylpiperidinium, 1,
1,3,4-tetraethylpiperidinium, 1,1,
3,5-tetraethylpiperidinium and the like.

The pyridine ring having a quaternized nitrogen: N
-Methylpyridinium, N-ethylpyridinium, 1,
2-dimethylpyrimidinium, 1,3-dimethylpyrimidinium, 1,4-dimethylpyrimidinium, 1-ethyl-2-methylpyrimidinium, 2-ethyl-1-methylpyrimidinium, 1-ethyl -3-methylpyrimidinium, 3-ethyl-1-methylpyrimidinium, 1-ethyl-4-methylpyrimidinium, 4-ethyl-1-methylpyrimidinium, 1,2-diethylpyrimidinium, 1,3-diethylpyrimidinium, 1,4-diethylpyrimidinium, 1,2,3-trimethylpyridinium, 1,2,4-trimethylpyridinium, 1,3,4
-Trimethylpyridinium, 1,3,5-trimethylpyridinium, 1,2,5-trimethylpyridinium,
1,2,6-trimethylpyridinium, 1-ethyl-
2,3-dimethylpyridinium, 1-ethyl-2,4-
Dimethylpyridinium, 1-ethyl-2,5-dimethylpyridinium, 1-ethyl-2,6-dimethylpyridinium, 1-ethyl-3,4-dimethylpyridinium, 1
-Ethyl-3,5-dimethylpyridinium, 2-ethyl-1,3-dimethylpyridinium, 2-ethyl-1,4
-Dimethylpyridinium, 2-ethyl-1,5-dimethylpyridinium, 2-ethyl-1,6-dimethylpyridinium, 3-ethyl-1,2-dimethylpyridinium,
3-ethyl-1,4-dimethylpyridinium, 3-ethyl-1,5-dimethylpyridinium, 3-ethyl-1,
6-dimethylpyridinium, 4-ethyl-1,2-dimethylpyridinium, 4-ethyl-1,3-dimethylpyridinium, 1,2-diethyl-3-methylpyridinium, 1,2-diethyl-4-methylpyridinium, 1 ,
2-diethyl-5-methylpyridinium, 1,2-diethyl-6-methylpyridinium, 1,3-diethyl-2
-Methylpyridinium, 1,3-diethyl-4-methylpyridinium, 1,3-diethyl-5-methylpyridinium, 1,3-diethyl-6-methylpyridinium,
1,4-diethyl-2-methylpyridinium, 1,4-
Diethyl-3-methylpyridinium, 2,3-diethyl-1-methylpyridinium, 2,4-diethyl-1-methylpyridinium, 2,5-diethyl-1-methylpyridinium, 2,6-diethyl-1-methylpyridinium , 3,4-diethyl-1-methylpyridinium, 3,
5-diethyl-1-methylpyridinium, 1,2,3
4,5-pentamethylpyridinium, 1,2,3,4
6-pentamethylpyridinium, 1,2,3,5,6-
Pentamethylpyridinium, 1,2,3,4,5,6-
Hexamethylpyridinium and the like.

N-N-N-dimethylimidazolium, N-ethyl-
N'-methylimidazolium, N, N'-diethylimidazolium, 1,2,3-trimethylimidazolium,
1,3,4-trimethylimidazolium, 1-ethyl-
2,3-dimethylimidazolium, 1-ethyl-3,4
-Dimethylimidazolium, 1-ethyl-3,5-dimethylimidazolium, 2-ethyl-1,3-dimethylimidazolium, 4-ethyl-1,3-dimethylimidazolium, 1,2-diethyl-3-methyl Imidazolium, 1,4-diethyl-3-methylimidazolium,
1,5-diethyl-3-methylimidazolium, 1,3
-Diethyl-2-methylimidazolium, 1,3-diethyl-4-methylimidazolium, 1,2,3-triethylimidazolium, 1,3,4-triethylimidazolium, 1,2,3,4-tetra Methylimidazolium, 1-ethyl-2,3,4-trimethylimidazolium, 1-ethyl-2,3,5-trimethylimidazolium, 1-ethyl-3,4,5-trimethylimidazolium, 2-ethyl- 1,3,4-trimethylimidazolium, 4-ethyl-1,2,3-trimethylimidazolium, 1,2-diethyl-3,4-dimethylimidazolium, 1,3-diethyl-2,4-dimethylimidazo Lium, 1,4-diethyl-2,3-dimethylimidazolium, 1,4-diethyl-2,5-dimethylimidazolium, 2,4-diethyl -1,3-dimethylimidazolium, 4,5-diethyl-1,3-dimethylimidazolium, 1,2,3-triethyl-4-methylimidazolium, 1,2,4-triethyl-3-methylimidazolium , 1,2,5-triethyl-3-methylimidazolium, 1,3,4-triethyl-2-methylimidazolium, 1,3,4-triethyl-5-methylimidazolium, 1,4,5-triethyl -3-methylimidazolium, 1,2,3,4,5-pentamethylimidazolium and the like.

Of these Q ⁺ , triethylmethylammonium, diethyldimethylammonium and ethyltrimethylammonium are preferred. As the anion, PF ₆ ^- it is preferred ^- BF ₄ than. Therefore,
Among the quaternary ammonium salts represented by the formula (I), particularly preferred are triethylmethylammonium tetrafluoroborate, diethyldimethylammonium tetrafluoroborate and ethyltrimethylammonium tetrafluoroborate.

The organic solvent used for coating these quaternary ammonium salts includes a dielectric constant at 25 ° C. of less than 25, preferably less than 20, and a boiling point at normal pressure of 50 ° C. to 150 ° C. Preferably, it is 60 ° C. or more and 120 ° C. or less. A low dielectric constant solvent having a relative dielectric constant of less than 20 hardly absorbs water and has a low solubility of the quaternary ammonium salt itself, so that it has an effect of preventing hydrolysis of the salt and preventing fixation between crystals of the salt. Further, if the boiling point at normal pressure is 50 ° C or less, it is not preferable because the composition easily evaporates during handling and changes in composition, and if it is 150 ° C or more, it is difficult to remove it during use. This is not preferred because of the high possibility of causing

Preferred examples of such an organic solvent include, for example, n-propanol, isopropanol, n
-Butanol, methyl acetate, ethyl acetate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl ethyl ketone, methyl isobutyl ketone, n-hexane, n-heptane, toluene and the like. Of these, n-butanol, dimethyl carbonate, and toluene are particularly preferred. These may be used in combination, or an organic solvent containing the organic solvent as a main component substantially as long as the storage stability of the quaternary ammonium salt intended for the present invention is not impaired. Can also.

The method of coating the surface of the quaternary ammonium salt with an organic solvent is not particularly limited, and specific examples thereof include, for example, the method of preparing a crystal obtained by a recrystallization operation using a solvent and the solvent of the present invention. After stirring and then filtering to obtain quaternary ammonium salt crystals impregnated with the solvent,
After recrystallization, a method of obtaining a quaternary ammonium salt impregnated with the solvent by rinsing the cake with the solvent of the present invention after centrifugation or solid-liquid separation with a filter is used. Among these methods, the method of rinsing the cake with the solvent of the present invention is preferred.

The solvent content at this time is 1 to
It must be in the range of 25% by weight, preferably in the range of 5 to 15% by weight. If the solvent content is low, the effect of the low dielectric constant organic solvent is unlikely to appear. Conversely, if it is too large, it is not preferable in terms of handling such as liberation of the liquid, and it is not economically preferable. When using a quaternary ammonium salt which has been subjected to a coating treatment with an organic solvent to improve the storage stability, it can be used after removing the organic solvent by a vacuum drying treatment immediately before use. In particular, when used as a non-aqueous electrolyte for an electric double layer capacitor, a quaternary ammonium salt coated with an organic solvent is directly dissolved in an electrolyte solvent, and then the organic solvent is selectively removed under reduced pressure. It is possible to

[0030]

EXAMPLES The method of the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist. Example 1 Triethyl methyl ammonium tetrafluoroborate (50 wt%) of a solution of triethyl methyl ammonium methyl carbonate (Et ₃ MeN ⁺ .CH ₃ CO ₃ ⁻ ) in methanol and a hydrofluoric acid aqueous solution (42 wt%) were used. 221.9 g of crude crystals of Et ₃ MeN ⁺ .BF ₄ ⁻ ) were obtained. Next, a recrystallization operation was performed with 500 ml of a mixed solvent of methanol and isopropanol at a volume ratio of 1: 1. The obtained slurry was subjected to solid-liquid separation at 700 G at room temperature by a small centrifuge. The recrystallization and solid-liquid separation operations were performed once more, and then the surface was coated with n-butanol by rinsing twice with 100 ml of n-butanol (dielectric constant: 18, boiling point: 117.7 ° C.). 173.1 g of triethylmethylammonium tetrafluoroborate (Et ₃ MeN ⁺ .BF ₄ ⁻ ) white solid
Was obtained (containing 95% by weight as a BF ₄ salt). Chemical analysis, the purity of the obtained triethylmethylammonium tetrafluoroborate is at least 99.0% by BF ₄ standard, the content of fluorine ions as impurities by ion chromatography was 100 weight ppm. This was placed in a glass petri dish and left in air having a dew point of -20 ° C for 24 hours. As a result, there was no change in the fluorine ion content. Also, there was no change in the appearance of the crystals.

[0031] Example 2 Triethylmethylammonium tetraethylammonium ethyl carbonate instead of methyl carbonate ^{_{(Et 4 N + · C 2}} H 5 CO 3 -) except using the procedure of Example 1, tetraethyl Ammonium tetrafluoroborate (Et ₄ N ⁺ BF ₄
^- ) White solid 1 of triethylmethylammonium tetrafluoroborate (Et ₃ MeN ⁺ .BF ₄ ⁻ ) coated with n-butanol from 241.2 g of the crude crystals of 1)
91.8 g were obtained (containing 95% by weight as a BF ₄ salt).
Chemical analysis, the purity of the obtained triethylmethylammonium tetrafluoroborate 99 BF ₄ standards.
It was 0% or more, and the content of fluorine ions, which was an impurity by ion chromatography, was 120 ppm by weight. This was placed in a glass petri dish and left in air having a dew point of -20 ° C for 24 hours. As a result, there was no change in the fluorine ion content. Also, there was no change in the appearance of the crystals.

Example 3 The same operation as in Example 2 was carried out except that an aqueous solution of hexafluorophosphoric acid (60% by weight) was used instead of the aqueous solution of borofluoric acid, and tetraethylammonium hexafluorophosphate (Et ₄ N ⁺・ PF
₆ ^- from) the crude crystals 262.8G, surface coated triethylmethylammonium tetrafluoroborate (Et ₃ MeN ⁺ · BF ₄ in n- butanol ^- to give a white solid 231.8g of) as (BF ₄ salt 95% by weight). Chemical analysis, the purity of the obtained triethylmethylammonium tetrafluoroborate is at least 99.0% by BF ₄ standard, the content of fluorine ions as impurities by ion chromatography was 200 weight ppm. This was placed in a glass petri dish and left in air having a dew point of -20 ° C for 24 hours. As a result, there was no change in the fluorine ion content. Also, there was no change in the appearance of the crystals.

Example 4 The procedure of Example 1 was repeated, except that the solvent to be rinsed was changed from n-butanol to toluene (dielectric constant: 2, boiling point: 110.6 ° C.). A borate white solid was obtained (containing 95% by weight as BF ₄ salt). As a result of the chemical analysis, the purity of the obtained triethylmethylammonium tetrafluoroborate is 99.0% or more based on BF ₄ , and the content of fluorine ion, which is an impurity by ion chromatography, is the lower limit of quantification.
It was 0 ppm by weight. This was placed in a glass petri dish and left in air having a dew point of -20 ° C for 24 hours. As a result, there was no change in the fluorine ion content. Also,
There was no change in the appearance of the crystals.

Example 5 The solvent to be rinsed was changed from n-butanol to dimethyl carbonate (dielectric constant 2.8, boiling point 90.1).
C)) to obtain a white solid of triethylmethylammonium tetrafluoroborate coated with dimethyl carbonate in the same manner as in Example 1 (containing 95% by weight as a BF ₄ salt). Chemical analysis, the purity of the obtained triethylmethylammonium tetrafluoroborate is at least 99.0% by BF ₄ standard, the content of fluorine ions as impurities by ion chromatograph 150
It was ppm by weight. This was placed in a glass petri dish and left in air having a dew point of -20 ° C for 24 hours. As a result, there was no change in the fluorine ion content. Also,
There was no change in the appearance of the crystals.

Example 6 The solvent to be rinsed was changed from n-butanol to methyl ethyl ketone (dielectric constant 18, boiling point 79.
6 ° C.) to obtain a white solid of triethylmethylammonium tetrafluoroborate whose surface was coated with methyl ethyl ketone (BF _4).
95% by weight as salt). Chemical analysis, the purity of the obtained triethylmethylammonium tetrafluoroborate is at least 99.0% by BF ₄ standard, the content of fluorine ions as impurities by ion chromatography was 200 weight ppm. This was placed in a glass petri dish and left in air having a dew point of -20 ° C for 24 hours. As a result, there was no change in the fluorine ion content.
Also, there was no change in the appearance of the crystals.

Example 7 Triethylmethylammonium whose surface was coated with methyl acetate in the same manner as in Example 1 except that the solvent to be rinsed was changed from n-butanol to methyl acetate (relative dielectric constant 7, boiling point 57.8 ° C.). A white solid of tetrafluoroborate was obtained (95% by weight as BF ₄ salt).
Content). Chemical analysis, the purity of the obtained triethylmethylammonium tetrafluoroborate is at least 99.0% by BF ₄ standard, the content of fluorine ions as impurities by ion chromatography is quantitative limit 8
It was 0 ppm by weight. This was placed in a glass petri dish and left in air having a dew point of -20 ° C for 24 hours. As a result, there was no change in the fluorine ion content. Also,
There was no change in the appearance of the crystals.

COMPARATIVE EXAMPLE 1 A solvent to be rinsed was a mixed solvent of methanol and isopropanol in a volume ratio of 1: 1 (methanol: relative dielectric constant: 33, boiling point: 64.5 ° C., isopropanol: relative dielectric constant: 18.3, boiling point: 82.4 ° C.) 165.5 g of triethylmethylammonium tetrafluoroborate white solid whose surface was coated with methanol and isopropanol was obtained in the same manner as in Example 1 except for changing to (B).
95% by weight as F ₄ salt). Chemical analysis, the purity of the obtained triethylmethylammonium tetrafluoroborate is at least 99.0% by BF ₄ standard, the content of fluorine ions as impurities by ion chromatography was 100 weight ppm. This was placed in a glass petri dish and left in air having a dew point of -20 ° C for 24 hours. The content of fluorine ions was 700 ppm.
Increased. Further, the crystals were consolidated in a block shape.

Comparative Example 2 50.0 g of the white solid of triethylmethylammonium tetrafluoroborate obtained in Comparative Example 1 was dried under reduced pressure at 80 ° C. for 2 hours. As a result, 47.8 g of a white solid solidified in a rice cake shape was obtained. Chemical analysis, the purity of the obtained triethylmethylammonium tetrafluoroborate is at least 99.0% by BF ₄ standard, the content of fluorine ions as impurities by ion chromatography was 80 weight ppm. This was put in a glass petri dish and left for 24 hours in air having a dew point of −20 ° C., and the content of fluorine ions increased to 2000 ppm. Originally, some mochi-shaped crystals were deliquescent.

Reference Example 1 The surface obtained in Example 1 was n-
Triethylmethylammonium tetrafluoroborate coated with butanol (Et ₃ MeN ⁺ .BF ₄ ⁻ )
Was dissolved in 440 g of high-purity propylene carbonate for an electrolyte, and 1 g of a white solid was obtained under reduced pressure of 5 mmHg.
The mixture was heated to 00 ° C., part of n-butanol and propylene carbonate was distilled off, and 500 g of an electrolytic solution was recovered. The amount of fluorine ions contained in the electrolyte is 40 ppm
Met.

Reference Example 2 Triethylmethylammonium tetrafluoroborate (Et ₃ MeN) whose surface obtained in Comparative Example 1 was coated with methanol and isopropanol
⁺ • BF ₄ ⁻ ) except that a white solid of 20% was used in the electrolyte prepared in the same manner as in Reference Example 1.
It was 0 ppm.

Reference Example 3 Triethylmethylammonium tetrafluoroborate (Et ₃ M) obtained in Comparative Example 2
eN ⁺ .BF ₄ ⁻ ) except that 100 g of a white solid was used, and the electrolyte solution prepared in the same manner as in Reference Example 1 had a fluorine ion content of 540 ppm.

According to the present invention, it is possible to obtain a stabilized quaternary ammonium salt having excellent storage stability and a method for producing the same, which do not cause deterioration in quality due to storage handling and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideo Nagaoka 1 Toho-cho, Yokkaichi-shi, Mie F-term in Mitsubishi Chemical Corporation Yokkaichi Office (reference) 4H006 AA05 AD40

Claims (6)

[Claims] 1. A method according to the following general formula (I), wherein the surface is coated with an organic solvent having a relative dielectric constant at 25 ° C. of less than 25 and a boiling point at normal pressure of 50 ° C. or more and 150 ° C. or less. Represented quaternary ammonium salts. [Formula 1] Q ⁺ · ^X - in (I) (formula, Q ⁺ represents a quaternary ammonium cation, X ^-
Is BF ₄ ^- or PF ₆ ^- shows a) 2. The method according to claim 1, wherein the organic solvent is n-propanol, isopropanol, n-butanol, methyl acetate, ethyl acetate,
The quaternary ammonium salt according to claim 1, wherein the quaternary ammonium salt is at least one selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl ethyl ketone, methyl isobutyl ketone, n-hexane, n-heptane and toluene. 3. The quaternary ammonium salt according to claim 1, wherein the content of the organic solvent is 1 to 25% by weight based on the quaternary ammonium salt. 4. A method for coating a quaternary ammonium salt, comprising suspending or impregnating crystals of a quaternary ammonium salt represented by the formula (I) in an organic solvent. 5. An organic solvent comprising n-propanol, isopropanol, n-butanol, methyl acetate, ethyl acetate,
The method for coating a quaternary ammonium salt according to claim 4, wherein the method is at least one selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl ethyl ketone, methyl isobutyl ketone, n-hexane, n-heptane and toluene. . 6. The method for coating a quaternary ammonium salt according to claim 4, wherein the content of the organic solvent is 1 to 25% by weight based on the quaternary ammonium salt.