JP2002003466A - New fluorine-containing compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fluorine-containing nitrile compound containing a sulfonic group and a cyano group and to provide a method for producing the same. SOLUTION: A compound represented by formula FSO2CF2[CF2OCF(CF3)]nCN ((n) is 0, 1, 2 or 3) is hydrolyzed in the presence of a tertiary amine and brought into contact with an acid type ion exchange resin to give the fluorine-containing nitrile compound represented by formula HOSO2CF2[CF2OCF(CF3)]nCN ((n) is 1, 2 or 3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sulfonic acid group (-
The present invention relates to a novel fluorine-containing nitrile compound containing (SO ₃ H) and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in the field of fuel cells, sulfonic acid group-containing perfluorocarbon polymers having a structure of formula (4) (hereinafter referred to as perfluorocarbon sulfonic acid polymers) have been used as proton conductors in membranes and catalyst layers. Are mainly used.

[0003]

Embedded image

(Where the ratio x: y of x and y is approximately 2
0: 1 to 2: 1, m is 0, 1, or 2 and n is
It is an integer of 1 to 12. )

[0005] This copolymer comprises CF ₂ = CF ₂ and CF ₂ = CFO [CF
₂ CF (CF ₃ ) O] _m (CF ₂ ) _n SO ₂ F is subjected to radical copolymerization to obtain a copolymer having a fluorosulfonyl group (—SO ₂ F) at a terminal of a side chain. It is synthesized by hydrolyzing a group with a base and then performing ion exchange with a protonic acid. Usually, a polymer having m = 1 and n = 2 is used.

[0006] The above-mentioned perfluorocarbon sulfonic acid polymer does not contain any hydrogen in its structure, so it is extremely stable chemically and physically and can operate a fuel cell at a relatively high temperature. , And the battery performance was greatly improved. Therefore, it is preferable that the fuel cell be operated at a higher temperature in order to reduce catalyst poisoning due to carbon monoxide contained in hydrogen gas of the fuel. However, when the polymer is formed into a film or the like, its shape is held by perfluorocarbon chains, but since this is a non-crosslinked polymer, its strength and durability at higher temperatures are: There is a problem that it is not always enough.

[0007] In order to overcome the above-mentioned problems, it is basically considered preferable to use a crosslinked perfluorocarbon sulfonic acid polymer. Was unknown.

On the other hand, as a crosslinkable perfluorocarbon polymer, a polymer having a —CN group in a side chain is known (see JP-A-6-340710).

Specifically, for example, perfluorocarbon polymers represented by the formulas (5) and (6) having the following repeating units are exemplified.

[0010]

Embedded image (Where n is an integer of 1 to 12)

[0011]

Embedded image (Where m = 1, 2 and n = 1 to 4)

The compound represented by the above formula is replaced with tetraphenyltin, triphenyltin hydroxide, Zn (C
_{7 F 15 CO 2) 2,} Co (C 7 F 15 CO 2) 2, 1- perfluorooctane sulfonic acid, 2-ethylhexylamine, generates a triazine ring by trimerization reaction of formula (7) aniline as a catalyst By doing so, a crosslinked perfluorocarbon polymer is formed.

[0013]

Embedded image Furthermore, a crosslinked perfluorocarbon polymer can be obtained by performing the same reaction on a perfluorocarbon compound having two —CN groups in the molecule (for example, US Pat. No. 3,317,484). Specific examples of the perfluorocarbon compound having two —CN groups in the molecule include compounds represented by the following formulas (8-1) to (8-1).
Compounds represented by (8-5) are exemplified, and among these, those having a boiling point higher than around room temperature can be suitably used.

[0014]

Embedded image Therefore, a perfluorocarbon compound having both a —SO ₃ H group and a —CN group was synthesized, and a perfluorocarbon polymer having a —CN group in a side chain as in formulas (5) and (6), or a compound represented by formula (8-1) It is considered that a cross-linked perfluorocarbon polymer containing a sulfonic acid group can be obtained by mixing with a perfluoro compound having a plurality of -CN groups such as (8-5).

However, a perfluoro compound having both a —SO ₃ H group and a —CN group has not been known.

[0016]

DISCLOSURE OF THE INVENTION The present invention relates to a novel compound which has both a sulfonic acid group and a cyano group, is itself useful as an electrolyte, and is capable of performing a triazine ring-forming reaction by trimerization of a cyano group. An object is to provide a fluorine-containing compound and a method for producing the same.

[0017]

According to the present invention, the formula
A novel sulfonic acid group-containing fluorine-containing nitrile compound represented by (1) is provided.

[0018]

Embedded image (Where n = 0, 1, 2, or 3) According to the present invention, the formula (2)

[0019]

Embedded image (Where n = 0, 1, 2, or 3)

Wherein the fluorosulfonyl group of the fluorine-containing compound represented by the formula is hydrolyzed in the presence of a tertiary amine, and is then contacted with an acid-type ion exchange resin.
A method for producing a fluorine-containing nitrile compound represented by (1),
Is provided.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The fluorinated nitrile compound of the present invention can be prepared, for example, by a two-stage reaction [I] according to the following scheme.
(A), (b) and [II] (c), (d).

[0023]

Embedded image

[I] The reaction of (a) and (b) is represented by the formula (1)
The formula as a starting material for the synthesis of the compound of the present invention represented by
This is a reaction for synthesizing the fluorosulfonyl group-containing fluorine-containing compound represented by (2).

The first reaction (a) of the fluorine-containing compound as a starting material is a selective amidation reaction of a fluoroformyl group (—COF) of a carboxylic acid fluoride derivative which is an acid halide. Specifically, the amidation is performed according to the formula (9)

[0026]

Embedded image (Where n has the previously defined meaning.)

The fluorine-containing compound (carboxylic acid fluoride derivative) represented by the above formula is brought into contact with NH ₃ in an aprotic solvent at a low temperature to selectively amidate only the fluoroformyl group. .

The temperature at which NH ₃ is brought into contact with the compound of formula (9) is -100 ° C. to 30 ° C., preferably -8 ° C., in order to increase the amidation selectivity for the fluoroformyl group.
A low temperature of 0 ° C to -30 ° C is desirable.

The aprotic solvent used in the reaction includes
For example, diethyl ether, tetrahydrofuran, diphenyl ether, hexane, octane, fluorobenzene, bromobenzene, 2H, 3H-perfluoropentane, 1H-perfluorohexane, 1,1-dichloro-
2,2,3,3,3-pentafluoropropane, 1,3
Dichloro-1,1,2,2,3-pentafluoropropane, dimethylformamide, dimethylacetamide,
Methylene chloride, carbon tetrachloride, monoglyme, diglyme and the like can be suitably used.

The amount of NH ₃ used is 0.8 to 1.5 times, preferably 1.0 to 1.0 times the carboxylic acid fluoride derivative represented by the formula (9) in order to improve the selectivity of amidation. １．２1.2 times mol.

In this amidation reaction, in order to selectively amidate the fluoroformyl group, it is important to carry out the reaction in a state where the concentration of the fluorine-containing compound is excessive with respect to the NH ₃ concentration. For this purpose, it is desirable that the entire amount of the fluorine-containing compound is charged into a reaction vessel, and NH ₃ is dividedly supplied to the fluorine-containing compound by, for example, dropping.

The reaction time may vary depending on the reaction temperature, the NH ₃ molar ratio, the amount of the aprotic solvent used (that is, the concentration of the reaction solute) and the like, but is usually 0.5 to 30 hours, preferably about 1 to 24 hours. is there.

On the other hand, the reaction (b) in the latter stage is a nitrile reaction in which the carboxylic acid amide formed by the reaction formula (a) is converted in an aprotic dry solvent similar to the case of the above amidation. It reacts with a dehydrating agent to produce nitriles.

The reaction temperature for nitrilation is from -30 to 100.
° C, preferably in the range of -20 to 60 ° C. If the temperature is too low, the reaction rate decreases, and if the temperature is too high, side reactions cannot be ignored.

As the dehydrating agent, ordinary dehydrating agents can be used, and examples thereof include phosphorus pentoxide, acetic anhydride, trifluoroacetic anhydride, phthalic anhydride, phosphorus oxychloride, and thionyl chloride.

As described above, in the nitrilation reaction using a dehydrating agent that becomes an acid after dehydration, it is preferable that a basic compound that traps a by-produced acid coexist with the dehydrating agent.

Preferred basic compounds are tertiary amines in which an H atom is not directly bonded to N. In the present specification, a tertiary amine is, in addition to a tertiary aliphatic amine,
It also includes pyridines and other heterocyclic compounds having no N—H bond. Specific examples include trimethylamine,
Triethylamine, tri (n-propyl) amine, tri (i-propyl) amine, tri (n-butyl) amine,
Tripentylamine, trihexylamine, triheptylamine, tri (n-octylamine), tri (i-octyl) amine, trinonylamine, tridecylamine, triundecylamine, tridodecylamine, N,
N-dimethyl-n-butylamine, N, N-dimethyl-
Tertiary aliphatic amines such as n-octylamine, N, N, N ', N'-tetramethylethylenediamine; aliphatic unsaturated tertiary amines such as trivinylamine and triallylamine; dimethylaniline, diethylaniline, tribenzy Aromatic tertiary amines such as ruamine and triphenylamine;
Pyridine, α-methylpyridine (α-picoline), β-methylpyridine (β-picoline), γ-methylpyridine (γ-picoline), 2,6-dimethylpyridine (2.6)
-Lutidine), 2,4-dimethylpyridine (2,4-lutidine), 2,4,6-trimethylpyridine (2,4
6-collidine), pyridazine, pyrazine, pyrimidine,
1,5-diazabicyclo [4,3,0] -5-nonene, 1,5-diazabicyclo [4,3,0] non-5-
Heterocyclic tertiary amines containing a nitrogen atom, such as ene, N-methylmorpholine and 1-methylpiperidine. In the above scheme, pyridine is used as the basic compound, and the reaction is performed at 0 ° C.

The amount of the dehydrating agent used may vary depending on the type of the dehydrating agent, the amount of the amide to be dehydrated, etc., and is 1.0 to 5.0 mol, preferably 1.0 to 5.0 mol per mol of the carbamoyl group.
About 3.0 mol.

The amount of the basic compound used can vary depending on the type of the basic compound, the amount of the dehydrating agent, and the like.
Usually, it is about 0.5 to 4.0 mol, preferably about 1.0 to 3.0 mol, per 1 mol of the dehydrating agent.

The reaction time for nitrilation can vary depending on the reaction temperature, the molar ratio of the dehydrating agent, the amount of the aprotic solvent used (that is, the concentration of the reaction solute) and the like, but is usually 0.5 to 30 hours, preferably 1 to 24 hours. About an hour.

By the above operation, the carbamoyl group of the amide compound is converted to a cyano group by the reaction with a dehydrating agent such as trifluoroacetic anhydride and phosphorus pentoxide (formula (b)).

Thus, the resulting fluoronitrile is
As a phase composed mostly of the fluoronitrile, the two phases are separated from the solvent phase containing the dehydrating agent and the residue of the reaction with the dehydrating agent. Next, the fluoronitrile-containing phase is subjected to liquid-
By separating from the solvent phase by a liquid separating means and washing with water, it is possible to obtain fluoronitrile in high yield. Usually, ultimately, high-purity fluoronitrile is isolated by distilling and purifying the fluoronitrile-containing phase.

The yield of fluoronitrile from fluoroamides according to this method is high, at least 50% or more, usually more than 70%.

It should be noted that, in addition to the above-mentioned method in which the nitrilation reaction is carried out in an aprotic solvent described above, a method in which a dehydrating agent such as phosphorus pentoxide is mixed without a solvent and heated to 100 to 300 ° C. may be employed. Can be.

[II] (c) and (d) are reactions in the second stage, and the fluorosulfonyl group-containing fluorine-containing compound of the formula (2) obtained as described above is converted to a compound of the formula (c) The hydrosulfonyl group (FSO _2- ) is hydrolyzed in the presence of a tertiary amine according to the formula (1), and then contacted with an acid-type ion-exchange resin as shown in formula (d) to obtain a compound represented by formula (1). The sulfonic acid group-containing fluorine-containing nitrile compound of the invention is obtained.

The present invention is characterized in that hydrolysis is carried out in the presence of a tertiary amine instead of an alkali such as potassium hydroxide, sodium hydroxide and potassium carbonate.

The tertiary amine is not particularly limited, and for example, various tertiary amines described in the above nitrilation reaction can be suitably used.

The amount of water used for the hydrolysis is usually determined by the formula
It is preferable to use stoichiometrically about equimolar amount to the fluorosulfonyl group-containing fluorine-containing compound of (2). When the amount of water used is smaller than this, hydrolysis is not sufficiently performed, and when too much water is used, hydrolysis of the cyano group is induced, which is not preferable.

In the present invention, the fluorosulfonyl group
The hydrolysis is performed in the presence of the tertiary amine described above.
(In the above scheme, pyridine is used as the tertiary amine.
Here is an example using. ). As the hydrolysis progresses
HF is released and sulfonic acid groups are formed (H_Two O
+ FSO_Two − → HF + HOSO_Two -), In the present invention
Tertiary amine traps this released HF
In particular, it is believed that the sulfonic acid groups formed are neutralized. You
That is, for example, a tertiary amine is converted to NR¹ R^Two R^Three (R ¹ ~ R
^Three Represents alkyl or the like. ), This is the next (1)
0) and (11).

[0050]

Embedded image

For this purpose, the amount of the tertiary amine to be used is generally at least 2 to 15 times, preferably 3 to 10 times the mol of the compound (2) containing a fluorosulfonyl group.

The hydrolysis temperature is -50 to 30 ° C, preferably about -30 to 10 ° C. The hydrolysis reaction is
Since the reaction proceeds relatively easily, it is not necessary to carry out the treatment with too much heating, and it is preferable to carry out the treatment at the above-mentioned temperature from the viewpoint of preventing side reactions. The reaction time may vary depending on the reaction temperature, but is usually 0.5 to 24 hours, preferably about 1 to 4 hours.

The apparatus for carrying out the hydrolysis reaction is not particularly limited, but includes a stirrer, a thermometer, a heating / cooling apparatus, a temperature controller, a water and / or tertiary amine dropping apparatus or a quantitative apparatus. A stirred tank type reaction vessel equipped with a supply device and the like is preferable. In addition, a continuous reaction operation can be performed using a tubular reaction vessel.

It is preferable to use an aprotic solvent as the solvent for carrying out the hydrolysis. For example, tetrahydrofuran (THF), diethyl ether, diphenyl ether, methyl-t-butyl ether, dioxane, anisole, diphenyl ether, (perfluorobutyl) methyl ether, (perfluorobutyl) ethyl ether, monoglyme, diglyme, triglyme, tetraglyme, etc. Ethers; hexane, heptane,
Hydrocarbons such as octane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as fluorobenzene, bromobenzene, chlorobenzene and dichlorobenzene; 2H, 3H-perfluoropentane;
1H-perfluorohexane, 1H-perfluorooctane, 1H-perfluorodecane, 1H, 4H-perfluorobutane, 1H, 1H, 1H, 2H, 2H-perfluorohexane, 1H, 1H, 1H, 2H, 2H- Perfluorooctane, 1H, 1H, 1H, 2H, 2H-perfluorodecane, 3H, 4H-perfluoro (2-methylpentane), 2H, 3H-perfluoro (2-methylpentane), 1,1-dichloro- 2,2,3,3,3
-Pentafluoropropane, 1,3-dichloro-1,
1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, perfluoro (2-butyltetrahydrofuran), 3,3-dichloro-1,1,1
Fluoroalkane compounds such as 1,2,2-pentafluoropropane, 1,1,2-trichloro-1,2,2-trifluoroethane and perfluorooctane; other acetone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexa Methylphosphoramide, sulfolane, acetonitrile, ethylene carbonate, propylene carbonate, γ-butyrolactone, chloroform, methylene chloride, carbon tetrachloride, and the like can be suitably used, but these are merely examples, and are not limited thereto. is not.

The water and the tertiary amine used in the hydrolysis reaction may be charged all at once to the reaction vessel, but may be added to the reaction system successively or continuously using a dropping device or a metering pump. It is also preferable to carry out the reaction while controlling the reaction temperature so as to be in the above preferable temperature range. When a tubular reaction vessel is used, water and tertiary amine supply ports are provided in each part of the reaction tube, and water and tertiary amine are separately introduced from the supply ports to control the temperature, that is, control the reaction rate. Can also be performed.

In the present invention, the reaction solution after hydrolysis is contacted with a solid acid to release the sulfonic acid group-containing fluorine-containing nitrile compound represented by the formula (1). Usually, a salt is formed when it is brought into contact with an acid. In order to facilitate separation from the salt, a solid acid, preferably a polymer acid, is used as the acid. Particularly preferably, an acid-type ion exchange resin is used.

The acid-type ion-exchange resin is used as a base synthetic resin such as polystyrene cross-linked with a small amount of divinylbenzene.
Any water-insoluble sulphonic acid group, carboxyl group, phenolic hydroxyl group or the like can be used, but a strongly acidic one is preferable, and a sulfonic acid group-containing one is particularly preferable.

The form of the ion exchange resin is not particularly limited, and may be an irregular (crushed) form.
Spherical or granular ones are preferably used.

The particle size is 180 to 1700 μm.
m, preferably about 250 to 850 μm, and an ion exchange capacity of 3 to 7 meq / g dry resin, preferably about 4.5 to 6.5 meq / g dry resin is desirable.

The total volume of the ion-exchange resin is preferably sufficiently large in consideration of the amount of the tertiary amine used in excess.

The method of contacting the reaction solution after hydrolysis with the ion-exchange resin can be of various forms. For example, the reaction solution and the ion-exchange resin are charged into a stirred tank type vessel, and the ion-exchange resin is stirred. The ion exchange reaction can proceed while the exchange resin is suspended. More preferably, the ion exchange resin is filled in a tower-shaped container to form a fixed layer (column), and a reaction solution is supplied from the tip of the fixed layer to perform ion exchange. The supplied reaction solution is ion-exchanged while moving in the packed bed made of the ion exchange resin, and the sulfonic acid group-containing fluorine-containing nitrile compound of the formula (1) is released.

On the other hand, since the tertiary amine is retained by the ion exchange resin and does not flow out, the reaction solution flowing out from the other end of the column contains substantially all of the target sulfonic acid group-containing fluorine-containing nitrile compound. It is thought that it is.

The sulfonic acid group-containing fluorine-containing nitrile compound of the present invention is usually supplied to a distillation apparatus or a concentrating apparatus by supplying a reaction solution subjected to an ion exchange treatment to a distillation apparatus or a concentrating apparatus, and a solvent (distillate) of an apparatus obtained by distilling off a solvent or the like. (Remaining liquid).

By the above reaction, the yield of the fluorine-containing nitrile compound of the present invention represented by the formula (1) based on the fluorosulfonyl compound (formula (2)) is as high as at least 70%, usually at least 80%. Yield. In the formula (1), n is 0, 1, 2, or 3, and the number of n of the fluorinated nitrile compound is determined according to the n of the fluorinated compound of the formula (2) as a starting material. Where n =
The compound of formula (3) (1) can be obtained most easily. Here, the fluorinated nitrile of the formula (3) is also a nitrile compound synthesized in Examples described later.

[0065]

Embedded image

The fluorinated nitrile compound of the formula (1) having a sulfonic acid group and a cyano group at both terminals of the present invention is a compound having a triazine ring represented by the formula (12) by a trimerization reaction of the terminal cyano group. Can be converted to

[0067]

Embedded image (In the formula, n represents the meaning already defined in the formula (1).)

The triazine ring forming reaction is described in, for example,
The method can be carried out by a method known per se described in JP-A-7-17793 or JP-A-6-340710.

That is, bismuth, copper, lead, barium,
Cadmium, tin, thallium, cadmium, metal catalysts, tetraphenyl tin, such as indium oxide, _{triphenyltin, Zn (C 7 F 15 CO} 2) 2, 1- perfluorooctane sulfonic acid or a metal oxide such as silver oxide, In the presence of a catalyst, without solvent or in a solvent such as carbon tetrachloride, cyclohexanone, dioxane, dimethyl sulfoxide, fluorinated benzene, nitrobenzene, monoglyme, diglyme, triglyme, at 0 to 400 ° C, preferably 25 to 25 ° C.
The trimerization reaction (triazine ring formation reaction) of the nitrile fluoride compound of the formula (1) may be performed at a temperature of about 0 ° C. for about 1 to 200 hours. Usually, the catalyst is used in an amount of about 0.01 to 10% by mass of the nitrile compound of the formula (1).

The triazine compound represented by the formula (12) has three sulfonic acid groups in one molecule and is useful as an intermediate of a low molecular weight electrolyte or a polymer electrolyte.

The fluorinated nitrile compound of the formula (1) of the present invention is mixed with a dinitrile compound or a fluorinated polymer having a cyano group in a side chain to carry out a triazine ring-forming reaction, thereby obtaining a sulfonic acid group. Can be converted to a crosslinked polymer containing

The triazine ring-containing low molecular weight electrolyte or polymer electrolyte having a sulfonic acid group or the like obtained as described above can be used as an electrolyte for a lithium secondary battery when converted to a lithium salt type (—SO ₃ Li). Can be
The acid type (—SO ₃ H) can be suitably used as a polymer for a membrane or an electrode layer of a solid polymer electrolyte fuel cell.

[0073]

The present invention will be described below in detail with reference to examples and comparative examples.

Example 1 (1) In a 3 L four-necked flask-type reaction vessel equipped with a stirrer, a thermometer, and a dewar type dry ice cooler, 1 part of diethyl ether was used as a solvent.
450 ml, FSO ₂ C which is a fluoroformyl compound
346 g (1 mo) of F ₂ CF ₂ OCF (CF ₃ ) COF
1) After charging and purging with nitrogen, the mixture was cooled to -70 ° C. While cooling NH ₃ with a dry ice cooler, 17 g (1 mol) of liquefied NH ₃ was added dropwise with stirring to carry out an amidation reaction. After the completion of the dropwise addition of NH ₃ , 0.5
The reaction was completed by stirring for 2 hours, and the temperature was returned to room temperature over 2 hours.

Thereafter, the crude reaction solution was washed three times with pure water, and the organic phase was separated with a separating funnel. After the water content of the organic phase was removed with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain FSO ₂ CF ₂ CF ₂ as a white solid.
303 g (0.839 mol) of a fluoroamide represented by OCF (CF ₃ ) CONH ₂ was obtained.

(2) Next, 1200 g of dimethylformamide as a solvent was placed in a 3 L four-necked flask-type reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a condenser.
70 ml) and the fluoroamide FSO ₂ obtained above.
_{CF 2 CF 2 OCF (CF 3} ) of CONH ₂ 286g
(0.834 mol) to prepare a dimethylformamide solution, which was cooled to 0 ° C. Thereto, 221 g (1.05 mol) of trifluoroacetic anhydride as a dehydrating agent was slowly dropped over 0.5 hour. After the completion of the dropwise addition, 167 g (2.11 mol) of pyridine as an acceptor for the acid generated during nitrilation was slowly added dropwise over 1 hour. During this time, the reaction temperature was kept between 2 and 4 ° C.

After completion of the dropwise addition, the mixture was stirred for 0.5 hour to complete the reaction.
And 350 g of pure water is added from a dropping funnel.
Left till the end. Separation leakage of the lower phase of the reaction crude liquid separated into two phases
After distilling with pure water and washing with pure water three times,
Nitrile FSO_Two CF_Two CF _Two OCF (CF_Three ) CN2
01 g (0.583 mol, yield 70.3%) was obtained.

Boiling point 89 ° C., ¹⁹ F-NMR ((CD ₃ )
₂ C = O solvent, CFCl ₃ standard, δ ppm) 46.1
(1F, s), -79.8 (1F, dd), -82.8
(1F, d) -83.1 (3F, s), -111.7
(2F, s), -114.4 (1F, m)

(3) Subsequently, a stirrer, a thermometer, and a three-way
, Two-liter, four-port hood with dewar
650 ml of THF in a Lasco-type reaction vessel, obtained above
FSO _Two CF_Two CF_Two OCF (CF_Three 130 g of CN
(0.4 mol), and after cooling with nitrogen, cool to 0 ° C.
Was. There, 226 g of tertiary amine pyridine (7.
15 mol) and 7.2 g (0.4 mol) of water
The liquid was slowly added dropwise with stirring to carry out a hydrolysis reaction.
After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours to complete the reaction.

An excess of ion exchange resin (SK 1BN,
Made by Mitsubishi Chemical Corporation, ion exchange group: sulfonic acid group, ion exchange capacity: 5.7 meq / g dry resin or more, particle size: 50
(0-650 μm) was packed in a column to form a fixed layer of an ion-exchange resin, through which the reaction solution was slowly passed from above and allowed to flow out from below.

The reaction solution thus subjected to the ion exchange treatment is charged into a rotary concentrator (evaporator), and the solvent and the like are distilled off under reduced pressure by evaporation, and a sulfonic acid group-containing fluoronitrile HOSO ₂ CF is obtained as a concentrated solution.
_{2 CF 2 OCF (CF 3)} CN 109.2g (0.3
38 mol, yield 84%).

¹⁹ F-NMR ((CD ₃ ) ₂ C ＝ O solvent,
CFCl ₃ standard, δ ppm) -81.3 (1F, d
d), -84.7 (3F, s), -84.9 (1F, d
d) -114.8 (1F, m), -119.2 (2F,
s)

[0083] LC / MS [Frit-FAB ^- (fast neutral atom bombardment), collision atom: Xe] by [M-H] ^- was detected a strong peak m / z = 322 corresponding to.

Comparative Example 1 A stirrer, thermometer, dropping funnel,
50 ml of methanol and 21.26 g of potassium carbonate were placed in a 200 ml three-necked flask-type reaction vessel equipped with a cooling tube.
(0.15 mol), and after cooling with nitrogen, cooled to 0 ° C. There, the FSO ₂ CF ₂ CF ₂ synthesized in Example 1
10 g (0.03 mol) of OCF (CF ₃ ) CN was slowly added dropwise to carry out a hydrolysis reaction. After dropping,
The reaction was completed by stirring at room temperature for 3 hours.

When the ¹⁹ F-NMR analysis was performed on the supernatant, the peak at 46.1 ppm derived from the —SO ₂ F group disappeared, suggesting that the hydrolysis reaction was completed. The peak at -114.4 ppm, which indicates the presence, also disappeared, indicating that the cyano group had also reacted. That is, it can be seen that the hydrolysis of the fluorosulfonyl group by an alkali such as potassium carbonate has a problem that the cyano group is also reacted at the same time.

Comparative Example 2 An evaporator was used without passing a part of the reaction intermediate product in Example 1, ie, a part of the reaction crude liquid after the hydrolysis reaction using pyridine and water, through an ion exchange resin column. And concentrated. Excessive concentrated sulfuric acid was added to the concentrated solution, and distillation under reduced pressure was performed. The cyano group in the distilled portion was confirmed by ¹⁹ F-NMR measurement, and it was found that the cyano group had reacted and deteriorated. That is,
It can be seen that conversion to a sulfonic acid type using a mineral acid like concentrated sulfuric acid inevitably involves the reaction of a cyano group.

[0087]

The fluorinated nitrile compound represented by the formula (1) having a sulfonic acid group and a cyano group at both ends of the present invention is a novel, intermediate compound of a triazine ring-containing low molecular weight electrolyte or polymer electrolyte. Useful as a body.

According to the method of the present invention, the compound of formula (2) is used as a starting material to hydrolyze a fluoroformyl group in the presence of a tertiary amine, and this is contacted with an acid type ion exchange resin. As a result, the fluorinated nitrile compound of the formula (1) can be obtained with a high yield.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01M 8/10 H01M 8/10 10/40 10/40 B // C07D 251/24 C07D 251/24 F term (Reference) 4H006 AA01 AA02 AB46 AC61 AD11 AD32 BA51 BB15 BB25 BB61 BC10 BC19 BC34 BE60 5G301 CD01 CE10 5H026 AA06 CX05 5H029 AJ05 AJ11 AM16 DJ09 EJ12

Claims (3)

[Claims] 1. A fluorine-containing nitrile compound represented by the formula (1). Embedded image (Where n = 0, 1, 2, or 3) (2) Formula (2) (Where n = 0, 1, 2 or 3) wherein the fluorosulfonyl group of the fluorinated compound is hydrolyzed in the presence of a tertiary amine, and then contacted with an acid-type ion exchange resin. The method for producing a fluorine-containing nitrile compound represented by the formula (1) according to claim 1. 3. A fluorine-containing nitrile compound represented by the formula (3). Embedded image