KR102162624B1 - Organic solvent solution of sulfonimide having polymerizable functional group with reduced halide - Google Patents

Abstract

The present invention is a form such as storage of sulfonimide having a polymerizable functional group with improved stability against natural polymerization, while reducing halides, which were difficult to manufacture by the conventional method, and a method for preparing a sulfone imide solution, and a sulfone A method for removing halogen ions in an imide solution is provided.
The present invention is an organic solvent solution of sulfonimide represented by the general formula (1), wherein the content of halogen ions relative to the amount of sulfonimide in the solution is 1000 ppm or less, a method for producing an organic solvent solution and a sulfonimide solution And a method of removing halogen ions in a sulfonimide solution.

Description

Organic solvent solution of sulfonimide having polymerizable functional group with reduced halide

The present invention relates to an organic solvent solution of a sulfonimide having an industrially important polymerizable functional group as a raw material for manufacturing a member of an electronic material such as a capacitor or a lithium secondary battery.

Conventionally, the following method is known as a method for producing sulfonimide. That is, a method of obtaining an amine salt of a sulfonimide by reacting a sulfonyl halide, a sulfonamide, and a tertiary amine, and an alkali metal salt of the sulfonimide by reacting the amine salt of the sulfonimide obtained by the above method. It is a method of obtaining a metal salt (see, for example, Patent Document 1 and Patent Document 2).

Patent Document 1: Japanese Patent No. 4088351 (Example) Patent Document 2: Japanese Patent Laid-Open Publication No. 2014-169271 (paragraphs 0174-0177)

In Patent Document 1, in the synthesis of lithium styrenyltrifluoromethylbis-sulfonylimide described on pages 27 to 28, styrenesulfonyl chloride is dissolved in a mixture of acetonitrile and triethylamine, A yellow solution was obtained by reacting with fluoromethylsulfonamide, and the resulting alkali metal salt of sulfonimide was distilled off with acetonitrile, a reaction solvent, and then diethyl ether was added and stirred. After removal, diethyl ether was distilled off to obtain a yellow solid, which was purified by recrystallization from dichloromethane (CH ₂ Cl ₂ ) to obtain a pale yellow powder (59% yield). There is a description.

As a result of the present inventors trying to obtain an alkali metal salt of sulfonimide according to the above method, it is difficult to distill the solvent, and thus, it has become an oil-like state. This was thought to be because the alkali metal salt of sulfonimide has very high affinity for a solvent. Further, the present inventors tried to recrystallize this using dichloromethane using this as an organic solvent, but precipitation of crystals could not be confirmed. Further, although recrystallization from other organic solvents was also attempted, precipitation of crystals could not be confirmed in any of them.

In addition, the alkali metal salt of sulfonimide, such as the oil, not only contains a large amount of alkali metal halides, but also naturally polymerizes rapidly at room temperature in the same state as oil, so storage at low temperatures is required, and handling It was troublesome.

In Patent Document 2, in the section of Example 16: 4-styrenesulfonyl (trifluoromethanesulfonyl)imide described in paragraphs 0174 to 0177, in tetrahydrofuran, in the presence of argon, 4-styrene sulfonyl chloride (CH ₂ =CHC ₆ H ₄ SO ₂ Cl) was reacted with trifluoromethane-sulfonamide (CF ₃ SO ₂ NH ₂ ) and hydrochloric acid (DABCO), filtered, hydrochloric acid removed, and anhydrous lithium chloride Processed. Soon, a precipitate of hydrochloric acid was formed, and after that, after stirring, filtration, evaporation and drying, the lithium salt of trifluoromethane-sulfonyl(4-styrenesulfonyl)imide was recovered. There is a description to the effect that the produced alkali metal salt of sulfonimide was isolated by distilling tetrahydrofuran as a reaction solvent.

As a result of the present inventors trying to obtain an alkali metal salt of sulfonimide according to this method, the alkali metal salt of sulfonimide is difficult to distill out of the solvent, resulting in an oil-like state. This was thought to be due to the very high affinity for solvents.

The remaining of the halide in such sulfonimide is not preferable for use in electronic materials such as capacitors and lithium secondary batteries, and generally, the halide is preferably removed as much as possible. However, since sulfonimide has a very high affinity for water, in the case of attempting to remove a halide by washing with water, the sulfonimide is eluted into the aqueous layer and the yield is greatly reduced. There was an assignment.

Therefore, in the production of a sulfonimide having a polymerizable functional group, a method of efficiently removing by-produced halides without lowering the yield, and a method of stably storing and transporting by-products against natural polymerization was required. .

The object of the present invention is to be proposed in view of these conventional facts, and the storage of sulfonimide having a polymerizable functional group with improved stability against natural polymerization while reducing halides, which were difficult to manufacture by the conventional method. It is to provide a method for preparing a sulfonimide solution, and a method for removing halogen ions in a sulfonimide solution.

The inventors of the present invention believe that the storage of sulfonimide having a polymerizable functional group with improved stability against natural polymerization while reducing halides, a method for preparing a sulfonimide solution, and removal of halogen ions in a sulfonimide solution With the aim of providing a method, research has been eagerly conducted.

As a result, it was found that sulfonimide has a very high affinity for water, and it is difficult to selectively remove only by-product halides by washing with water, the agent containing halides obtained by synthesis.

In addition, the synthesized sulfonimide and accompanying halides are extracted with water from the reaction solution, and are purposely made into an aqueous solution of sulfonimide containing halides, and then in the presence of a specific organic solvent such as dimethyl carbonate or diethyl carbonate. , It was found that by dissolving a specific salt such as lithium chloride in the aqueous solution, only sulfonimide can be selectively extracted into an organic solvent. In addition, by drying the organic solvent solution containing sulfonimide with a dehydrating agent, an organic solvent solution of sulfonimide having a polymerizable functional group having a reduced halide can be prepared in good yield. Surprisingly, in this solution It was found that the natural polymerization of sulfonimide hardly proceeds. Further, by adding a polymerization inhibitor to this solution, it was found that natural polymerization of sulfonimide can be suppressed for a longer period of time, and the present invention has been completed.

That is, the present invention is the general formula (1)

[Formula 1]

(In formula (1), R ¹ is fluorine, C1-C10 linear or branched chain alkyl having an arbitrary number of substituents, C2-C10 alkenyl, C2-C10 alkynyl, 4-vinylphenyl , (Meth)acryloyloxy, (meth)acryloyloxyalkyl, or cyclic alkyl having 3 to 10 carbon atoms,

R ² represents a monovalent alkali metal ion or a quaternary ammonium ion,

R ³ represents a C 2 to C 10 linear or branched alkenyl, 4-vinylphenyl, (meth)acryloyloxy, or (meth)acryloyloxyalkyl having an arbitrary number of substituents.) It is an organic solvent solution of sulfonimide to be obtained, and the content of halogen ions relative to the amount of sulfonimide in the solution is 1000 ppm or less.

As the organic solvent, aromatic hydrocarbons, alcohols, ketones, esters, ethers, carbonate esters, aprotic polar solvents, or mixtures thereof can be used.

The content of the halogen ion relative to the amount of the sulfonimide is preferably 200 ppm or less, further preferably 100 ppm or less, and particularly preferably 60 ppm or less. In addition, the content of the halogen ion is preferably the content of the chloride ion.

In the general formula (1), it is preferable that R ¹ is trifluoromethyl. In addition, in General Formula (1), it is preferable that R ² is a lithium ion. Moreover, in General Formula (1), it is preferable that R ³ is vinyl, acrylic, or 4-vinylphenyl.

Further, the present invention relates to a method for preparing an organic solvent solution of sulfonimide in which a salt is dissolved in an aqueous solution of sulfonimide in the presence of an organic solvent to extract the sulfonimide into an organic solvent. 1 selected from the group consisting of hydrocarbons, alcohols, ketones, esters, ethers, carbonate esters such as dimethyl carbonate or diethyl carbonate, and aprotic polar solvents such as acetonitrile and N-methylpyrrolidone The present invention relates to a method for preparing an organic solvent solution of the sulfonimide described above using a species or a combination of two or more.

Further, the present invention relates to a method for removing halogen ions in which a salt is dissolved in an aqueous solution of a sulfonimide containing a halogen ion in the presence of an organic solvent to extract the sulfonimide into an organic solvent.

The organic solvent solution of sulfonimide having a polymerizable functional group of the present invention has improved stability against natural polymerization, which was a conventional problem, and also reduced halogen compounds, so it is used in the field of electronic materials such as capacitors and lithium secondary batteries. , Very useful.

The present invention, as above, general formula (1)

[Formula 1]

It relates to an organic solvent solution of a sulfonimide represented by, wherein the content of halogen ions relative to the amount of sulfonimide in the solution is 1000 ppm or less.

In formula (1), R ¹ is fluorine, a straight or branched chain alkyl having 1 to 10 carbon atoms having an arbitrary number of substituents, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, 4-vinylphenyl, (Meth)acryloyloxy, (meth)acryloyloxyalkyl, or cyclic alkyl having 3 to 10 carbon atoms. Here, a substituent in a C1-C10 linear or branched chain alkyl may not exist, or may have 1 or more.

R ¹ is specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, isopropyl, t-butyl, trifluoromethyl, tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl , Benzyl, phenylethyl, 3-phenylpropyl, vinyl, allyl, 3-butenyl, 4-pentenyl, 2-methyl-2-butenyl, 4-vinylphenyl, (meth)acryloyloxymethyl, 2- (Meth)acryloyloxyethyl, 3-(meth)acryloyloxypropyl, etc. are mentioned, and although one or more substituents may be provided at an arbitrary position, trifluoromethyl is especially preferable among these.

R ² represents a monovalent alkali metal ion or a quaternary ammonium ion. R ² specifically includes lithium ions, sodium ions, potassium ions, triethyl ammonium ions, diisopropylethyl ammonium ions, tripropyl ammonium ions, and pyridinium ions, and among these, lithium ions are particularly preferred. .

R ³ represents a C2-C10 linear or branched alkenyl, 4-vinylphenyl, (meth)acryloyloxy, or (meth)acryloyloxyalkyl having an arbitrary number of substituents. Here, a substituent in a C2-C10 linear or branched alkenyl may not exist, or may have 1 or more.

R ³ is specifically, vinyl, allyl, 3-butenyl, 4-pentenyl, 2-methyl-2-butenyl, 4-vinylphenyl, (meth)acryloyloxymethyl, 2-(meth)acrylo Monooxyethyl, 3-(meth)acryloyloxypropyl, etc. are mentioned, and although it may have a substituent at an arbitrary position, vinyl, allyl, and 4-vinylphenyl are especially preferable among these.

As the organic solvent, aromatic hydrocarbons, alcohols, ketones, esters, ethers, carbonate esters, aprotic polar solvents, or mixtures thereof can be used. The organic solvent is specifically, benzene, toluene, o-xylene, m-xylene, p-xylene, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl ether, methyl tertiary butyl ether, isopropyl ether , Tetrahydrofuran, dioxane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, and mixtures thereof. However, among these, a water-insoluble solvent is preferable, and dimethyl carbonate and diethyl carbonate are particularly preferable.

As the organic solvent solution of sulfonimide represented by the general formula (1) of the present invention, a method for producing an organic solvent solution having a halogen ion content of 1000 ppm or less with respect to the sulfonimide will be described.

The sulfonimide represented by general formula (1) of the present invention is general formula (2)

[Formula 2]

(In formula (2), R ¹ is fluorine, straight or branched chain alkyl having 1 to 10 carbon atoms having an arbitrary number of substituents, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, 4-vinylphenyl , (Meth)acryloyloxy, (meth)acryloyloxyalkyl, or a cyclic alkyl having 3 to 10 carbon atoms is reacted with a base by reacting a sulfonamide represented by General Formula (3)

[Formula 3]

(In formula (3), R ¹ is fluorine, straight or branched chain alkyl having 1 to 10 carbon atoms having an arbitrary number of substituents, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, 4-vinylphenyl , (Meth)acryloyloxy, (meth)acryloyloxyalkyl, or cyclic alkyl having 3 to 10 carbon atoms,

R ² represents a monovalent alkali metal ion or a quaternary ammonium ion), a step of obtaining a salt of a sulfonamide represented by general formula (3), and a salt of a sulfonamide represented by general formula (3) and general formula (4)

[Formula 4]

(In formula (4), R ³ represents a C 2 to C 10 linear or branched alkenyl, 4-vinylphenyl, (meth)acryloyloxy, or (meth)acryloyl having a substituent having 2 to 10 carbon atoms Represents oxyalkyl,

X represents a halogen atom. It is obtained by a method including a step of reacting a sulfonyl halide represented by) to obtain a sulfonimide represented by the general formula (1).

Here, as the base to react with the sulfonamide, alkali metal salts such as lithium hydride, lithium hydroxide, sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate, or amines such as triethylamine, tributylamine, and pyridine may be used. May be, but lithium hydride, lithium hydroxide, or sodium carbonate is particularly preferred.

The reaction according to the production of the sulfonimide represented by the general formula (1) may be carried out in the presence of a solvent or may be carried out without using a solvent.

Examples of the solvent used include linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, aliphatic halogen compounds, aromatic hydrocarbons, aromatic halogen compounds, alcohols, ketones, esters, ethers, carbonate esters, aprotic Polar solvents or mixtures thereof can be used. The organic solvent is specifically, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, 2-methylbutane, 2- Methylpentane, 3-methylpentane, 2-methylhexane, 3-methylhexane, methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1-chloropropane, 1, 2-dichloropropane, 1, 3-dichloropropane , 1-chlorobutane, 2-chlorobutane, 1, 2-dichlorobutane, 1, 3-dichlorobutane, 1, 4-dichlorobutane, 2, 3-dichlorobutane, dibromomethane, bromoform, tetrabromide Carbon, 1, 1-dibromoethane, 1-bromopropane, 2-bromopropane, 1, 2-dibromopropane, 1, 3-dibromopropane, 1-bromobutane, 2-bro Mobutane, 1, 2-dibromobutane, 1, 3-dibromobutane, 1, 4-dibromobutane, 2, 3-dibromobutane, benzene, toluene, o-xylene, m- Xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene , 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclo Hexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl ether, methyl tertiary butyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, and mixtures thereof, and the like. Among these, ethyl acetate, acetonitrile, or N, N-dimethylformamide is particularly preferred. .

In addition, the amount of the solvent according to the present preparation method is not particularly limited, but it is preferably 1 to 100 by weight relative to the sulfonamide represented by General Formula (2), and in order to shorten the reaction time, the weight ratio is 1 to 30 It is more preferable than this.

The amount of base used in the process of obtaining the salt of the sulfonamide represented by the general formula (3) of the present invention is not particularly limited, but in order to quantitatively proceed the reaction, 2 equivalents to 10 equivalents to the raw material sulfonamide It is preferable to use an equivalent, and in order to suppress the polymerization reaction which is a side reaction, 2 to 3 equivalents are more preferable.

The reaction according to the production of the sulfonimide represented by the general formula (1) can be carried out at 0°C to 80°C, but in order to suppress the polymerization reaction as a side reaction, it is preferably carried out at 0°C to 60°C.

In addition, the reaction according to the preparation of the salt of sulfonimide represented by the general formula (1) can be carried out in any of an open atmosphere reactor or a closed system reactor such as an autoclave, and the reaction pressure is atmospheric pressure. It is possible both under pressure or under pressure.

The sulfonimide and the by-product halide represented by the general formula (1) synthesized according to the above method were extracted from the reaction solution with water, and the sulfonimide represented by the general formula (1) deliberately containing the halide After obtaining an aqueous solution, in the presence of a specific organic solvent such as dimethyl carbonate or diethyl carbonate, a specific salt such as lithium chloride is dissolved in the aqueous solution, and only sulfonimide is selectively extracted with an organic solvent, and the organic solvent solution is dehydrated. By drying by, as an organic solvent solution of sulfonimide represented by the general formula (1), the content of halogen ions relative to the amount of sulfonimide is 1000 ppm or less, preferably 200 ppm or less, even more preferably An organic solvent solution of 100 ppm or less, particularly preferably 60 ppm or less can be obtained. In addition, the content of the halogen ion is preferably the content of the chloride ion.

As the organic solvent, aromatic hydrocarbons, alcohols, ketones, esters, ethers, carbonate esters, aprotic polar solvents, or mixtures thereof can be used. The organic solvent is specifically, benzene, toluene, o-xylene, m-xylene, p-xylene, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl ether, methyl tertiary butyl ether, isopropyl ether , Tetrahydrofuran, dioxane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, and mixtures thereof. However, among these, a water-insoluble solvent is preferable, and dimethyl carbonate or diethyl carbonate is particularly preferable.

In addition, the amount of water and organic solvent used according to the present manufacturing method is not particularly limited, but it is preferable to set it as a weight ratio of 1 to 100 with respect to the sulfonimide represented by the general formula (1), reducing manufacturing cost and transportation cost. In order to make it, the weight ratio is more preferably 1 to 30.

Examples of the salts include halides of alkali metals, sulfates of alkali metals, hydrogen sulfates of alkali metals, sulfites of alkali metals, hydrogen sulfite salts of alkali metals, thiosulfates of alkali metals, nitrates of alkali metals, nitrites of alkali metals. , Alkali metal phosphate, alkali metal monohydrogen phosphate, alkali metal dihydrogen phosphate, alkali metal carbonate, alkali metal hydrogen carbonate, alkali metal acetate, alkaline earth metal halide, amine hydrochloride, Hydrobromide of amines, hydroiodide of amines, or mixtures thereof can be used.

Salts, specifically, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, lithium sulfate, sodium sulfate, potassium sulfate, sulfuric acid Lithium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, lithium sulfite, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, lithium thiosulfate, sodium thiosulfate, potassium thiosulfate, lithium nitrate, sodium nitrate , Potassium nitrate, lithium nitrite, sodium nitrite, potassium nitrite, lithium phosphate, sodium phosphate, potassium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, carbonic acid Lithium, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium acetate, sodium acetate, potassium acetate, magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, calcium fluoride, calcium chloride, calcium bromide, Calcium iodide, trimethylamine hydrochloride, trimethylamine hydrobromide, trimethylamine hydroiodide, triethylamine hydrochloride, triethylamine hydrobromide, triethylamine hydroiodide, tripropylamine hydrochloride, tripropylamine hydrobromide, Tripropylamine hydroiodide, pyridine hydrochloride, pyridine hydrobromide, pyridine hydroiodide, and mixtures thereof. Among these, the solubility in water at 20°C is 0.3 or more in weight ratio with respect to water. It is preferred, and lithium chloride or sodium chloride is particularly preferred.

In addition, the amount of the salt according to the present production method is not particularly limited, but it is preferably 1 to 10 in terms of weight ratio with respect to the sulfonimide represented by the general formula (1), and in order to reduce the manufacturing cost, the weight ratio is 1 to 10. 3 is even more preferable.

Examples of the dehydrating agent include molecular sieve, zeolite, aluminum oxide, calcium chloride, active anhydrous calcium sulfate, magnesium sulfate (anhydrous), phosphorus oxide (V), potassium carbonate (anhydrous), potassium hydroxide, silica gel, sodium hydroxide. , Sodium sulfate (anhydrous), zinc chloride, or mixtures thereof, and the like, among them, molecular sieves and zeolites are particularly preferred.

In addition, the amount of the dehydrating agent according to the present manufacturing method is not particularly limited, but it is preferably 5 or less in terms of weight ratio with respect to the sulfonimide represented by the general formula (1), and in order to reduce the manufacturing cost, 2 or less in terms of weight ratio. Is more preferable.

Examples of the polymerization inhibitor include 4-tertiary butyl pyrocatechol, tertiary butyl hydroquinone, 1, 4-benzoquinone, 2, 6-ditertiary butyl-p-cresol, 2, 6-ditertiary butyl phenol, hydro Although quinone, 4-methoxyphenol, or a mixture thereof can be used, among these, 4-tertiary butyl pyrocatechol is particularly preferred.

In addition, the amount of the polymerization inhibitor according to the present production method is not particularly limited, but it is preferable to be 1000 ppm or less in terms of weight ratio with respect to the sulfonimide represented by the general formula (1). In order to reduce the production cost, the weight ratio 300 ppm or less is even more preferable.

Example

Hereinafter, the present invention will be described by way of examples, but they do not limit the present invention.

And the content of the chloride ion was quantified according to JIS K8001 by the turbidity method (hereinafter, referred to as "chloride ion analysis"). The stability against natural polymerization was evaluated by measuring the polymerization conversion rate by gel permeation chromatography analysis (hereinafter referred to as “GPC analysis”). In addition, about the compound obtained by the present invention, the generation of the target compound in the reaction system and the reaction product were identified by nuclear magnetic resonance analysis (hereinafter referred to as "NMR analysis").

[Chloride ion analysis]

Turbidimeter: manufactured by U-Tech, TN100

Preparation of a calibration curve: 0.1 g of a standard aqueous solution of sodium chloride (1 mg/mL, 0.1 mg/mL, 0.01 mg/mL) was added to 0.1 g of water to make 20 mL, 5 mL of nitric acid (1+2) and an aqueous silver nitrate solution (20 g/mL) L) Add 1 mL, shake and mix, and let stand for 15 minutes. Using a turbidimeter, each turbidity of the solution is measured, and the turbidity versus chloride ion concentration is plotted.

How to prepare a measurement sample: Add water to about 0.1 g of the sample to make 20 mL, add 5 mL of nitric acid (1+2) and 1 mL of silver nitrate aqueous solution (20 g/L), shake and mix, and then stand for 15 minutes. Using a turbidimeter, the turbidity of the sample solution is measured, and the chloride ion concentration is obtained from the calibration curve.

[GPC analysis]

Model: HLC-8320GPC, manufactured by Tosoh Corporation

Column: TSK guardcolumn AW-H/TSK AW-3000/TSK AW-6000

Eluent: A 90:10 wt% solution in volume ratio of sodium sulfate buffer (0.05 mol/L) and acetonitrile

Column temperature: 40°C, flow rate: 0.6 ml/min

Detector: RI detector, injection volume: 10 μl

Calibration curve: Prepared from the peak top molecular weight and elution time of monodisperse polystyrene sulfonate sodium (3 K, 15 K, 41 K, 300 K, 1000 K, 2350 K, 5000 K) manufactured by Sowa Kagaku.

[NMR analysis]

Device: Bruker Biospin, AV-400M

Preparation method of the measurement sample: The sample was dissolved in about 0.7 mL of dimethylsulfoxide-d6 (99.5%) containing about 0.05% tetramethylsilane as an internal standard, and ¹ H-NMR and ¹⁹ F-NMR were measured. .

(Example 1) Synthesis of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide in diethyl carbonate solution

A stirrer and a thermometer were attached to a 100 mL four-necked flask, and 0.20 g (75.9 mmol) of lithium hydride and 28.50 g of anhydrous acetonitrile were added, followed by cooling to 0°C while stirring. Then, what dissolved 5.65 g (37.9 mmol) of trifluoromethanesulfonamide in 28.50 g of anhydrous acetonitrile was added dropwise. Subsequently, 21.00 g (37.9 mmol) of a 37 mol% 4-styrenesulfonyl chloride/toluene solution was added dropwise, and further stirring was continued at room temperature for 17 hours. After adding 60.00 g of toluene to the obtained reaction solution and stirring for 30 minutes, the inorganic salt was removed by filtration. 0.03 g of a 40% lithium nitrite aqueous solution was added, and the solvent was distilled off with a rotary evaporator, and then 60.00 g of water was added to obtain an aqueous solution of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide.

Next, a stirrer and a thermometer were attached to a 100 mL four-necked flask, and 15.00 g of lithium chloride and 60.00 g of diethyl carbonate were added, followed by cooling to 0°C while stirring. Then, the aqueous solution of the lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was added dropwise, further stirred at room temperature for 30 minutes, and then liquid-separated. As a result, the target product, lithium 4 -A diethyl carbonate solution of styrenesulfonyl (trifluoromethylsulfonyl) imide was obtained in a yield of 75% (molar conversion, relative to the starting material trifluoromethanesulfonamide).

Further, 0.002 g (0.01 mmol) of 4-tertiary butyl pyrocatechol was added to the diethyl carbonate solution of the obtained lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide.

The content of the chloride ion relative to the amount of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was measured by the above chloride ion analysis, and as a result, it was 187 ppm.

The NMR analysis results were as follows.

¹ H-NMR (400 MHz, DMSO-d6): δ(ppm) 7.70 (d, J=8.0 Hz, 2H), 7.55 (d, J=8.0 Hz, 2H), 7.24-7.10 (dd, J=12.0 Hz, 20.0 Hz, 1H), 5.93 (d, J=20.0 Hz, 1H), 5.37 (d, J=12.0 Hz, 1H); ¹⁹ F-NMR (376 MHz, DMSO-d6): δ(ppm)-77.89(s).

(Example 2)

Lithium zeolite 3.00 g was added to the diethyl carbonate solution of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide obtained in Example 1, allowed to stand for 17 hours, and then filtered. As a result, the target product, lithium 4 -A diethyl carbonate solution of styrenesulfonyl (trifluoromethylsulfonyl) imide was obtained in a yield of 60% (molar conversion, relative to the starting material trifluoromethanesulfonamide).

The content of the chloride ion relative to the amount of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was measured by the above chloride ion analysis and found to be 8 ppm.

After storing the obtained solution at room temperature for 6 months, as a result of measurement by the GPC analysis, only the peak derived from the monomer of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was detected, and the peak derived from the polymer. Was not detected.

The NMR analysis results were as follows.

¹ H-NMR (400 MHz, DMSO-d6): δ(ppm) 7.70 (d, J=8.0 Hz, 2H), 7.55 (d, J=8.0 Hz, 2H), 7.24-7.10 (dd, J=12.0 Hz, 20.0 Hz, 1H), 5.93 (d, J=20.0 Hz, 1H), 5.37 (d, J=12.0 Hz, 1H); ¹⁹ F-NMR (376 MHz, DMSO-d6): δ(ppm)-77.89(s).

(Example 3) Synthesis of dimethyl carbonate solution of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide

As a result of replacing diethyl carbonate as the extraction solvent in Example 2 with dimethyl carbonate, a dimethyl carbonate solution of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide as the target product was in a yield of 57% (in terms of molar, To the starting material trifluoromethanesulfonamide).

The content of chloride ions relative to the amount of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was measured by the above chloride ion analysis, and as a result, it was 55 ppm.

The NMR analysis results were as follows.

¹ H-NMR (400 MHz, DMSO-d6): δ(ppm) 7.70 (d, J=8.0 Hz, 2H), 7.55 (d, J=8.0 Hz, 2H), 7.24-7.10 (dd, J=12.0 Hz, 20.0 Hz, 1H), 5.93 (d, J=20.0 Hz, 1H), 5.37 (d, J=12.0 Hz, 1H); ¹⁹ F-NMR (376 MHz, DMSO-d6): δ(ppm)-77.89(s).

(Comparative Example 1)

The aqueous solution of 4-styrenesulfonyl(trifluoromethylsulfonyl)imide of Example 1 was obtained in a yield of 77% (molar conversion, relative to the starting material trifluoromethanesulfonamide).

The content of chloride ions relative to the amount of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was measured by the above chloride ion analysis, and as a result, it was 4467 ppm.

The NMR analysis results were as follows.

¹ H-NMR (400 MHz, DMSO-d6): δ(ppm) 7.70 (d, J=8.0 Hz, 2H), 7.55 (d, J=8.0 Hz, 2H), 7.24-7.10 (dd, J=12.0 Hz, 20.0 Hz, 1H), 5.93 (d, J=20.0 Hz, 1H), 5.37 (d, J=12.0 Hz, 1H); ¹⁹ F-NMR (376 MHz, DMSO-d6): δ(ppm)-77.89(s).

(Comparative Example 2)

As a result of performing liquid separation without adding lithium chloride in Example 1, the target product, lithium 4-styrenesulfonyl (trifluoromethylsulfonyl)imide, could not be obtained.

(Comparative Example 3)

When water in Example 1 was not added and left to stand at room temperature for 1 hour in an oil-like state, natural polymerization proceeded and solidified.

(Comparative Example 4)

After storing the obtained solution at room temperature for 1 month without adding 4-tertiary butyl pyrocatechol in Example 1, as a result of measurement by the GPC analysis, lithium 4-styrenesulfonyl (trifluoromethylsulfonyl ) Only the peak derived from the monomer of imide was detected, and the peak derived from the polymer was not detected, but after storing for an additional 5 months, as a result of measurement by the GPC analysis, lithium 4-styrenesulfonyl (trifluoromethyl With respect to the monomer of sulfonyl)imide, a polymer having a weight average molecular weight of 27,000 was detected in a peak area ratio of 3%.

Industrial availability

The organic solvent solution of a sulfonimide having a polymerizable functional group having a reduced halogen compound obtained by the present invention is industrially very useful as a raw material for manufacturing a member of an electronic material such as a capacitor or a lithium secondary battery.

Claims (5)

delete delete Reacting a sulfonamide and a sulfonyl halide to prepare a reaction solution containing a sulfonimide represented by the following formula (1) and a halide;
Adding water to the reaction solution to prepare an aqueous sulfonimide solution containing a halide; And
As a method for preparing a sulfonimide organic solvent solution comprising; adding an organic solvent and a salt to the sulfonimide aqueous solution to extract the sulfonimide with an organic solvent,
A method for producing a sulfonimide organic solvent solution, wherein the content of the halogen ion relative to the amount of sulfonimide in the sulfonimide organic solvent solution is 1000 ppm or less.
[Formula 1]

(In formula (1), R1 represents fluorine, C1-C10 straight or branched chain alkyl having an arbitrary number of substituents, C2-C10 alkenyl, or C2-C10 alkynyl,
R2 represents a monovalent alkali metal ion or a quaternary ammonium ion,
R3 represents 4-vinyl phenyl.) The method of claim 3,
Organic solvent solution of sulfonimide in which the organic solvent is one or a combination of two or more selected from the group consisting of aromatic hydrocarbons, alcohols, ketones, esters, ethers, carbonate esters, and aprotic polar solvents Manufacturing method. A method for removing halogen ions, wherein an organic solvent and a salt are added to an aqueous solution of the sulfonimide of the following formula (1) containing halogen ions to extract the sulfonimide with an organic solvent.
[Formula 1]

(In formula (1), R1 represents fluorine, C1-C10 straight or branched chain alkyl having an arbitrary number of substituents, C2-C10 alkenyl, or C2-C10 alkynyl,
R2 represents a monovalent alkali metal ion or a quaternary ammonium ion,
R3 represents 4-vinyl phenyl.)