WO2018021185A1 - ハロゲン化物が低減された重合性官能基を有するスルホンイミドの有機溶剤溶液 - Google Patents
ハロゲン化物が低減された重合性官能基を有するスルホンイミドの有機溶剤溶液 Download PDFInfo
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- WO2018021185A1 WO2018021185A1 PCT/JP2017/026476 JP2017026476W WO2018021185A1 WO 2018021185 A1 WO2018021185 A1 WO 2018021185A1 JP 2017026476 W JP2017026476 W JP 2017026476W WO 2018021185 A1 WO2018021185 A1 WO 2018021185A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
- C07C311/49—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom to nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
Definitions
- the present invention relates to an organic solvent solution of a sulfonimide having an industrially important polymerizable functional group as a raw material for producing a member of an electronic material such as a capacitor or a lithium secondary battery.
- the following methods are known as methods for producing sulfonimide. That is, a method for obtaining a sulfonimide amine salt by reacting a sulfonyl halide, a sulfonamide, and a tertiary amine, and a reaction of an alkali metal salt with the amine salt of the sulfonimide obtained by the above method. This is a method for obtaining an alkali metal salt. (For example, see Patent Document 1 and Patent Document 2)
- Patent No. 4088351 Example JP 2014-169271 A (paragraphs 0174 to 0177)
- Patent Document 1 in the section of synthesis of lithium styryl trifluoromethylbis-sulfonylimide described on pages 27 to 28, styrenesulfonyl chloride is dissolved in a mixture of acetonitrile and triethylamine, and trifluoromethylsulfonamide and A yellow solution is obtained by reaction, and the resulting suspension of the alkali metal salt of sulfonimide is removed by filtration after removing the suspension, which is obtained by distilling off acetonitrile as a reaction solvent, adding diethyl ether and stirring. The 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).
- dichloromethane CH 2 Cl 2
- the inventors of the present invention tried to obtain an alkali metal salt of sulfonimide according to the above-mentioned method, but it was difficult to distill off the solvent, resulting in an oil-like state. This seems to be because the alkali metal salt of sulfonimide has a very high affinity for the solvent. Furthermore, the present inventors tried to recrystallize this using dichloromethane as an organic solvent, but could not confirm the precipitation of crystals. Moreover, although recrystallization from other organic solvents was attempted, no crystal precipitation could be confirmed.
- oil-like sulfonimide alkali metal salt described above not only contains a large amount of alkali metal halide, but also spontaneously polymerizes rapidly at room temperature in an oil-like state, and therefore must be stored at a low temperature. The handling was complicated.
- Example 16 4-styrenesulfonyl (trifluoromethanesulfonyl) imide described in paragraphs 0174 to 0177, 4-styrenesulfonyl chloride (CH 2 ⁇ CHC 6 H) in tetrahydrofuran in the presence of argon. 4 SO 2 Cl) was reacted with trifluoromethane-sulfonamide (CF 3 SO 2 NH 2 ) and hydrochloric acid (DABCO), filtered, removed with hydrochloric acid, and then treated with anhydrous lithium chloride.
- 4-styrenesulfonyl (trifluoromethanesulfonyl) imide described in paragraphs 0174 to 0177, 4-styrenesulfonyl chloride (CH 2 ⁇ CHC 6 H) in tetrahydrofuran in the presence of argon. 4 SO 2 Cl) was reacted with trifluoromethane-sulfonamide (CF 3 SO 2 NH 2
- the inventors of the present invention tried to obtain an alkali metal salt of sulfonimide according to this method. As a result, it was difficult for the alkali metal salt of sulfonimide to distill off the solvent, and it became an oil-like state. This seems to be due to the very high affinity for the solvent.
- Such a remaining halide in the sulfonimide is not preferable for use in electronic materials such as capacitors and lithium secondary batteries, and it is generally desirable to remove halide as much as possible.
- sulfonimide has a very high affinity for water, there is a problem that when the halide is removed by washing with water, elution of the sulfonimide into the aqueous layer occurs and the yield is greatly reduced. It was.
- An object of the present invention has been proposed in view of the conventional situation, and a polymerizable functional group having reduced halide, which was difficult to produce by the conventional method, and improved stability against natural polymerization.
- An object of the present invention is to provide a form such as storage of a sulfonimide having a group, a method for producing a sulfonimide solution, and a method for removing halogen ions in the sulfonimide solution.
- the inventors of the present invention have disclosed a form such as storage of a sulfonimide having a polymerizable functional group with reduced halide and improved stability against natural polymerization, a method for producing a sulfonimide solution, and a halogen in a sulfonimide solution. In order to provide a method for removing ions, intensive research was conducted.
- sulfonimide has an extremely high affinity for water, and it is difficult to selectively remove only by-produced halides by washing with water-containing agents obtained by synthesis. I understood.
- the synthesized sulfonimide and the accompanying halide are extracted from the reaction solution with water to make an aqueous solution of a sulfonimide containing a halide, and then in the presence of a specific organic solvent such as dimethyl carbonate or diethyl carbonate. It was found that only a sulfonimide can be selectively extracted into an organic solvent by dissolving a specific salt such as lithium chloride in the aqueous solution. Furthermore, by drying an organic solvent solution containing a sulfonimide with a dehydrating agent, an organic solvent solution of a sulfonimide having a polymerizable functional group with reduced halide can be produced in a high yield.
- R 1 is fluorine, linear or branched alkyl having 1 to 10 carbon atoms having any number of substituents, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, 4 -Represents 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 linear or branched alkenyl having 2 to 10 carbon atoms having any number of substituents, 4-vinylphenyl, (meth) acryloyloxy, or (meth) acryloyloxyalkyl. And an organic solvent solution having a halogen ion content of 1000 ppm or less with respect to the amount of the sulfon
- organic solvent aromatic hydrocarbons, alcohols, ketones, esters, ethers, carbonates, aprotic polar solvents, or a mixture thereof can be used.
- the halogen ion content relative to the amount of sulfonimide is preferably 200 ppm or less, more preferably 100 ppm or less, and particularly preferably 60 ppm or less.
- the halogen ion content is preferably chloride ion content.
- R 1 is preferably trifluoromethyl.
- R 2 is preferably a lithium ion.
- R 3 is preferably vinyl, acrylic or 4-vinylphenyl.
- the present invention also relates to a method for producing 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, and the sulfonimide is extracted into the organic solvent.
- a salt is dissolved in an aqueous solution of sulfonimide in the presence of an organic solvent, and the sulfonimide is extracted into the organic solvent.
- 1 selected from the group consisting of hydrocarbons, alcohols, ketones, esters, ethers, carbonate esters such as dimethyl carbonate and diethyl carbonate, and aprotic polar solvents such as acetonitrile and N-methylpyrrolidone. It is invention which concerns on the manufacturing method of the organic solvent solution of said sulfonimide using the seed
- the present invention also relates to a method for removing halogen ions, in which a salt is dissolved in an aqueous solution of sulfonimide containing halogen ions in the presence of an organic solvent, and the sulfonimide is extracted into the organic solvent.
- the organic solvent solution of sulfonimide having a polymerizable functional group of the present invention has improved stability against natural polymerization, which has been a problem in the past, and further has reduced halogen compounds, so that capacitors, lithium secondary batteries, etc. It is extremely useful in the field of electronic materials.
- the present invention relates to the general formula (1)
- R 1 is fluorine, linear or branched alkyl having 1 to 10 carbon atoms having any number of substituents, alkenyl having 2 to 10 carbons, alkynyl having 2 to 10 carbons, 4- Vinylphenyl, (meth) acryloyloxy, (meth) acryloyloxyalkyl or cyclic alkyl having 3 to 10 carbon atoms.
- the substituent in the linear or branched alkyl having 1 to 10 carbon atoms may be absent, or may have one 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, and 3- (meth) acryloyloxypropyl and the like may be mentioned, which may have one or more substituents at any position, and among these, trifluoromethyl is particularly preferable.
- R 2 represents a monovalent alkali metal ion or a quaternary ammonium ion.
- R 2 include lithium ion, sodium ion, potassium ion, triethylammonium ion, diisopropylethylammonium ion, tripropylammonium ion, and pyridinium ion, and among these, lithium ion is particularly preferable.
- R 3 represents a linear or branched alkenyl having 2 to 10 carbon atoms having any number of substituents, 4-vinylphenyl, (meth) acryloyloxy, or (meth) acryloyloxyalkyl.
- the substituent in the straight-chain or branched alkenyl having 2 to 10 carbon atoms may be absent or may have one or more.
- R 3 is specifically vinyl, allyl, 3-butenyl, 4-pentenyl, 2-methyl-2-butenyl, 4-vinylphenyl, (meth) acryloyloxymethyl, 2- (meth) acryloyloxyethyl, and 3 -(Meth) acryloyloxypropyl and the like may be mentioned, which may have a substituent at any position, among which vinyl, allyl and 4-vinylphenyl are particularly preferred.
- organic solvent aromatic hydrocarbons, alcohols, ketones, esters, ethers, carbonates, aprotic polar solvents, or a mixture thereof can be used.
- organic solvent include 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, carbonic acid Examples thereof include
- the sulfonimide represented by the general formula (1) of the present invention is represented by the general formula (2).
- R 1 is fluorine, linear or branched alkyl having 1 to 10 carbon atoms having any number of substituents, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, 4 -Representing a phenylamide, (meth) acryloyloxy, (meth) acryloyloxyalkyl, or cyclic alkyl having 3 to 10 carbon atoms) and a base to react with a base represented by the general formula (3)
- R 1 is fluorine, linear or branched alkyl having 1 to 10 carbon atoms having any number of substituents, alkenyl having 2 to 10 carbon atoms, alkynyl having 2 to 10 carbon atoms, 4 -Represents vinylphenyl, (meth) acryloyloxy, (meth) acryloyl
- R 3 is a linear or branched alkenyl having 2 to 10 carbon atoms and a straight chain or branched alkenyl, 4-vinylphenyl, (meth) acryloyloxy, or (meth) acryloyloxy having a substituent having 2 to 10 carbon atoms.
- alkali metal salts such as lithium hydride, lithium hydroxide, sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate, or triethylamine, tributylamine, pyridine, etc.
- Amines can be used, but lithium hydride, lithium hydroxide, or sodium carbonate is particularly preferred.
- the reaction relating 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.
- Solvents used include linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, aliphatic halogen compounds, aromatic hydrocarbons, aromatic halogen compounds, alcohols, ketones, esters, Ethers, carbonates, aprotic polar solvents, or mixtures thereof can be used.
- organic solvent examples include 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, carbon
- the amount of the solvent used in the present production method is not particularly limited, but it is preferably 1 to 100 by weight with respect to the sulfonamide represented by the general formula (2), in order to shorten the reaction time. More preferably, the weight ratio is 1 to 30.
- the amount of the base used in the step of obtaining the sulfonamide salt represented by the general formula (3) of the present invention is not particularly limited, but in order to proceed the reaction quantitatively, the raw material sulfone is used. It is preferable to use 2 equivalents to 10 equivalents with respect to the amide, and 2 equivalents to 3 equivalents are more preferable in order to suppress the polymerization reaction which is a side reaction.
- the reaction relating to the production of the sulfonimide represented by the general formula (1) can be carried out at 0 ° C. to 80 ° C., but it is carried out at 0 ° C. to 60 ° C. in order to suppress the side-reaction polymerization reaction. It is preferable to do this.
- reaction relating to the production of the sulfonimide salt represented by the general formula (1) can be carried out either in an open-air reactor or in a closed reactor such as an autoclave. Can be under atmospheric pressure or under pressure.
- the sulfonimide represented by the general formula (1) synthesized according to the above method and the by-product halide are extracted from the reaction solution with water, and the aqueous solution of the sulfonimide represented by the general formula (1) containing the halide is intentionally included.
- a specific organic solvent such as dimethyl carbonate or diethyl carbonate
- a specific salt such as lithium chloride is dissolved in this aqueous solution, and only sulfonimide is selectively extracted into the organic solvent.
- the organic solvent solution of the sulfonimide represented by the general formula (1) has a halogen ion content of 1000 ppm or less, preferably 200 ppm or less, more preferably Gives an organic solvent solution of 100 ppm or less, particularly preferably 60 ppm or less.
- the halogen ion content is preferably chloride ion content.
- organic solvent aromatic hydrocarbons, alcohols, ketones, esters, ethers, carbonates, aprotic polar solvents, or a mixture thereof can be used.
- organic solvent include 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, carbonic acid
- examples include benzen
- the amount of water and organic solvent used in the production method is not particularly limited, but is preferably 1 to 100 by weight with respect to the sulfonimide represented by the general formula (1).
- Production cost and transportation In order to reduce the cost, the weight ratio is more preferably 1 to 30.
- the above salts include alkali metal halides, alkali metal sulfates, alkali metal hydrogen sulfates, alkali metal sulfites, alkali metal hydrogen sulfites, alkali metal thiosulfates, alkali metal nitrates, Alkali metal nitrite, alkali metal phosphate, alkali metal monohydrogen phosphate, alkali metal dihydrogen phosphate, alkali metal carbonate, alkali metal hydrogen carbonate alkali metal acetate, alkali Earth metal halides, amine hydrochlorides, amine hydrobromides, amine hydroiodides, or mixtures thereof can be used.
- Salts are specifically lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, iodide.
- the amount of salt used in the production method is not particularly limited, but is preferably 1 to 10 by weight with respect to the sulfonimide represented by the general formula (1), in order to reduce the production cost. Is more preferably 1 to 3 by weight.
- Examples of the dehydrating agent include molecular sieves, zeolite, aluminum oxide, calcium chloride, activated anhydrous calcium sulfate, magnesium sulfate (anhydrous), phosphorus oxide (V), potassium carbonate (anhydrous), potassium hydroxide, silica gel, sodium hydroxide. Sodium sulfate (anhydrous), zinc chloride, or a mixture thereof.
- molecular sieves and zeolite are particularly preferable.
- the amount of the dehydrating agent used in the present production method is not particularly limited, but is preferably 5 or less by weight with respect to the sulfonimide represented by the general formula (1), in order to reduce the production cost. Is more preferably 2 or less by weight.
- polymerization inhibitor examples include 4-tertiarybutylpyrocatechol, tertiarybutylhydroquinone, 1,4-benzoquinone, 2,6-ditertiarybutyl-p-cresol, 2,6-ditertiarybutylphenol, hydroquinone, 4 -Methoxyphenol or a mixture thereof can be used, among which 4-tertiarybutylpyrocatechol is particularly preferred.
- the amount of polymerization prohibition used in the present production method is not particularly limited, but is preferably 1000 ppm or less by weight with respect to the sulfonimide represented by the general formula (1), in order to reduce the production cost. Is more preferably 300 ppm or less by weight.
- chloride ion analysis The content of chloride ions was quantified by a turbidimetric method (hereinafter referred to as “chloride ion analysis”) according to JIS K8001.
- the stability against natural polymerization was evaluated by measuring the polymerization conversion rate by gel permeation chromatography analysis (hereinafter referred to as “GPC analysis”).
- GPC analysis gel permeation chromatography analysis
- NMR analysis nuclear magnetic resonance analysis
- Turbidimeter TN100, manufactured by UTEC Preparation of calibration curve: Water is added to 0.1 g of a standard aqueous solution of sodium chloride (1 mg / mL, 0.1 mg / mL, 0.01 mg / mL) to make 20 mL, and 5 mL of nitric acid (1 + 2) and an aqueous silver nitrate solution (20 g / L) ) Add 1mL and shake, then leave it for 15 minutes. The turbidity of the solution is measured using a turbidimeter, and the turbidity against the chloride ion concentration is plotted.
- Preparation method of measurement sample Water is added to about 0.1 g of a sample to make 20 mL, 5 mL of nitric acid (1 + 2) and 1 mL of an aqueous silver nitrate solution (20 g / L) are added and shaken, and then left for 15 minutes. The turbidity of the sample solution is measured using a turbidimeter, and the chloride ion concentration is determined from the calibration curve described above.
- a stirrer and a thermometer were attached to a 100 mL four-necked flask, and after adding 0.20 g (75.9 mmol) of lithium hydride and 28.50 g of anhydrous acetonitrile, the mixture was cooled to 0 ° C. with stirring. Next, a solution prepared by dissolving 5.65 g (37.9 mmol) of trifluoromethanesulfonamide in 28.50 g of anhydrous acetonitrile was added dropwise.
- the content of chloride ion relative to the amount of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was measured by the above chloride ion analysis and found to be 187 ppm.
- Example 2 3.00 g of lithium zeolite was added to the diethyl carbonate solution of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide obtained in Example 1, and after standing for 17 hours, filtration was performed. A diethyl carbonate solution of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was obtained in a yield of 60% (in terms of moles, relative to the starting material trifluoromethanesulfonamide). The content of 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.
- the content of chloride ion relative to the amount of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was measured by the above chloride ion analysis and found to be 55 ppm.
- the content of chloride ion relative to the amount of lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was measured by the above chloride ion analysis and found to be 4467 ppm.
- Example 3 When water was not added in Example 1 and allowed to stand at room temperature for 1 hour in an oil-like state, spontaneous polymerization proceeded and solidified.
- Example 4 The 4-tert-butylpyrocatechol in Example 1 was not added, and the resulting solution was stored at room temperature for 1 month and then measured by the above GPC analysis. As a result, lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was obtained. Only the monomer-derived peak was detected, and the polymer-derived peak was not detected, but after storage for another 5 months, it was measured by the above GPC analysis. As a result, lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was obtained. 3% of the polymer having a weight average molecular weight of 27,000 was detected in terms of the peak area ratio with respect to the above monomer.
- the organic solvent solution of sulfonimide having a polymerizable functional group reduced in halogen compounds obtained by the present invention is industrially extremely useful as a raw material for producing electronic material members such as capacitors and lithium secondary batteries. It is.
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Abstract
Description
R2は1価のアルカリ金属イオン、又は第四級アンモニウムイオンを示し、
R3は任意の数の置換基を有する炭素数2~10の直鎖若しくは分岐鎖アルケニル、4-ビニルフェニル、(メタ)アクリロイルオキシ、又は(メタ)アクリロイルオキシアルキルを示す。)で表されるスルホンイミドの有機溶剤溶液であり、前記溶液中のスルホンイミドの量に対するハロゲンイオンの含有量が1000ppm以下である有機溶剤溶液に関する。
R2は1価のアルカリ金属イオン又は第四級アンモニウムイオンを示す。)で表されるスルホンアミドの塩を得る工程、及び一般式(3)で表されるスルホンアミドの塩と一般式(4)
Xはハロゲン原子を示す。)で表されるスルホニルハライドを反応させて、一般式(1)で表されるスルホンイミドを得る工程を含む方法により得られる。
また、本製造方法に係る重合禁止の使用量は特に制限されないが、一般式(1)で表されるスルホンイミドに対して重量比で1000ppm以下にするのが好ましく、製造コストを低減させるためには、重量比で300ppm以下がさらに好ましい。
濁度計:ユーテック社製、 TN100
検量線の作製:塩化ナトリウムの標準水溶液(1mg/mL、0.1mg/mL、0.01mg/mL)0.1gに水を加えて20mLとし、硝酸(1+2)5mL及び硝酸銀水溶液(20g/L)1mLを加えて振り混ぜた後、15分間放置する。濁度計を用いて、溶液の濁度をそれぞれ測定し、塩化物イオン濃度に対する濁度をプロットする。
測定サンプルの調製方法: 試料約0.1gに水を加えて20mLとし、硝酸(1+2)5mL及び硝酸銀水溶液(20g/L)1mLを加えて振り混ぜた後、15分間放置する。濁度計を用いて、試料溶液の濁度を測定し、上記した検量線より塩化物イオン濃度を求める。
機種:東ソー株式会社製、 HLC-8320GPC
カラム:TSK guardcolumn AW-H/TSK AW-3000/TSK AW-6000
溶離液:硫酸ナトリウム緩衝液(0.05mol/L)とアセトニトリルの体積比90:10wt%溶液
カラム温度:40℃、流量:0.6ml/min
検出器:RI検出器、注入量:10μl
検量線:創和科学製の単分散ポリスチレンスルホン酸ナトリウム(3K、15K、41K、300K、1000K、2350K、5000K)のピークトップ分子量と溶出時間から作成した。
装置:ブルカー・バイオスピン社製、 AV-400M
測定サンプルの調製方法:内部標準物質として約0.05%のテトラメチルシランを含むジメチルスルホキシド-d6(99.5%)約0.7mLに試料を溶解し、1H-NMRおよび19F-NMRを測定した。
1H-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);19F-NMR (376 MHz, DMSO-d6): δ (ppm)-77.89(s).
実施例1で得られたリチウム 4-スチレンスルホニル(トリフルオロメチルスルホニル)イミドの炭酸ジエチル溶液にリチウムゼオライト3.00gを加えて、17時間静置した後、ろ過を行ったところ、目的物であるリチウム 4-スチレンスルホニル(トリフルオロメチルスルホニル)イミドの炭酸ジエチル溶液が60%の収率(モル換算で、出発原料トリフルオロメタンスルホンアミドに対する)で得られた。
リチウム 4-スチレンスルホニル(トリフルオロメチルスルホニル)イミドの量に対する塩化物イオンの含有量を上記の塩化物イオン分析により測定したところ、8 ppmであった。
1H-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);19F-NMR (376 MHz, DMSO-d6): δ (ppm)-77.89(s).
1H-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);19F-NMR (376 MHz, DMSO-d6): δ (ppm)-77.89(s).
実施例1の4-スチレンスルホニル(トリフルオロメチルスルホニル)イミドの水溶液は77%の収率(モル換算で、出発原料トリフルオロメタンスルホンアミドに対する)で得られた。
1H-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);19F-NMR (376 MHz, DMSO-d6): δ (ppm)-77.89(s).
実施例1における塩化リチウムを加えず、分液を行ったところ、目的物であるリチウム 4-スチレンスルホニル(トリフルオロメチルスルホニル)イミドは得られなかった。
実施例1における水を加えず、オイル様の状態にて室温で1時間静置したところ、自然重合が進行し、固結した。
実施例1における4-ターシャリブチルピロカテコールを加えず、得られた溶液を室温で1か月間保存した後、上記のGPC分析により測定したところ、リチウム 4-スチレンスルホニル(トリフルオロメチルスルホニル)イミドのモノマー由来のピークのみが検出され、ポリマー由来のピークは検出されなかったが、さらに5か月間保存した後、上記のGPC分析により測定したところ、リチウム 4-スチレンスルホニル(トリフルオロメチルスルホニル)イミドのモノマーに対して、重量平均分子量27,000のポリマーがピーク面積比で3%検出された。
Claims (5)
- 一般式(1)
R2は1価のアルカリ金属イオン、又は第四級アンモニウムイオンを示し、
R3は任意の数の置換基を有する炭素数2~10の直鎖若しくは分岐鎖アルケニル、4-ビニルフェニル、(メタ)アクリロイルオキシ、又は(メタ)アクリロイルオキシアルキルを示す。)で表されるスルホンイミドの有機溶剤溶液であり、前記溶液中のスルホンイミドの量に対するハロゲンイオンの含有量が1000ppm以下である有機溶剤溶液。 - 有機溶剤として、芳香族炭化水素類、アルコール類、ケトン類、エステル類、エーテル類、炭酸エステル類、及び非プロトン性の極性の溶剤からなる群より選ばれる1種又は2種以上の組合せを用いた請求項1に記載のスルホンイミドの有機溶剤溶液。
- 有機溶剤存在下で、スルホンイミドの水溶液に塩を溶解させ、スルホンイミドを有機溶剤へ抽出するスルホンイミドの有機溶剤溶液の製造方法。
- 有機溶剤が、芳香族炭化水素類、アルコール類、ケトン類、エステル類、エーテル類、炭酸エステル類、及び非プロトン性の極性の溶剤からなる群より選ばれる1種又は2種以上の組合せである、請求項3に記載のスルホンイミドの有機溶剤溶液の製造方法。
- 有機溶剤存在下で、ハロゲンイオンを含むスルホンイミドの水溶液に塩を溶解させ、スルホンイミドを有機溶剤へ抽出する、ハロゲンイオンの除去方法。
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