JP2011098897A - Cyclic carbonate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound that has high thermal stability, can easily be produced, and has high ion conductivity. <P>SOLUTION: The compound is represented by formula (1). In formula (1), R<SP>1</SP>and R<SP>2</SP>represent a methylene group respectively, or a substituted or unsubstituted 2-20C alkylene group, Z represents an ionic functional group, m and n represent an integer of 0 to 5 respectively, satisfying 1≤n+m≤5, and p represents an integer of 1 to 100. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a cyclic carbonate containing an ionic functional group, a method for producing the same, and a molded article formed from the cyclic carbonate containing an ionic functional group.

As an electrolyte material used in electrochemical devices such as lithium-ion batteries, lithium-ion capacitors, and electric double layer capacitors, an electrolytic solution in which an electrolyte is mainly dissolved in an organic solvent has been used so far. Therefore, the development of polymer solid electrolytes and gel electrolytes has been actively promoted.
However, since these materials are solid electrolytes, it is difficult to obtain high conductivity, which hinders practical use. Therefore, development has been advanced in which an ionic liquid is impregnated into a separator, a film, or the like. An ionic liquid is a molten salt that is liquid at room temperature, and is non-volatile, non-flammable, and exhibits ionic conductivity. Therefore, application to various electrochemical devices is expected.

  Patent Document 1 describes that a non-aqueous electrolyte can be made flame-retardant using a non-volatile room temperature molten salt, and an ionic liquid having excellent recycling characteristics can be used for an electrochemical device. In Patent Document 1, a room temperature molten salt is a salt that is composed of a cation and an anion and is in a liquid state at room temperature. This room temperature molten salt is a definition for a salt that is non-volatile due to its strong ionic bonding and has the characteristics of flame retardancy.

JP 2006-260952 A

  However, although the ionic liquid does not require high-temperature treatment, it does not have good thermal stability at room temperature, so it must be dissolved in a solvent such as acetone to be added to the electrolyte film, The solubility was low and it was difficult to increase the content, and workability was poor.

  An object of the present invention is to provide a novel ionic liquid that is liquid at room temperature and excellent in thermal stability, a method for producing the same, and a molded body using the compound.

  Therefore, as a result of various studies, the present inventors have found that a novel compound having a structure in which an ionic functional group and a cyclic carbonate structure are linked by an ether bond exhibits high ionic conductivity, is liquid at room temperature, The present invention has been completed by finding that it is excellent in stability and can be used as a solid electrolyte material or the like without using an organic solvent.

  That is, this invention provides the compound represented by following formula (1).

(In the formula (1), R ¹ and R ² each represent a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, Z represents an ionic functional group, and m and n represent 0 to 5 respectively. And is a number satisfying 1 ≦ n + m ≦ 5, and p is an integer of 1 to 100.)

  The present invention also includes a step of reacting a compound represented by the formula (2) with a halogenated glycidyl compound in the presence of a base and a solvent to obtain a compound represented by the formula (3); The manufacturing method of the compound represented by following formula (1) including the process with which the compound represented by these and carbon dioxide are made to react in catalyst presence and a solvent presence is provided.

(In the formula (2), R ² represents a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and Z represents an ionic functional group.)

(In Formula (3), R ¹ and R ² each independently represents a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and Z represents an ionic functional group.)

(In Formula (1), R ¹ and R ² each independently represents a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, Z represents an ionic functional group, and m and n are Each is an integer of 0 to 5, and represents a number satisfying 1 ≦ n + m ≦ 5, and p is an integer of 1 to 100.)

  Moreover, this invention provides the resin composition containing an epoxy resin and the compound represented by following formula (1), and this epoxy resin is (A) the ionic compound which has one epoxy group, (B) A resin obtained from a compound having two or more epoxy groups and (C) a compound having two or more amino groups is preferable.

(In Formula (1), R ¹ and R ² each independently represents a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, Z represents an ionic functional group, and m and n are 0. An integer of ˜5, which represents a number satisfying 1 ≦ n + m ≦ 5, and p is an integer of 1 to 100.)

  The compound (1) of the present invention is liquid at room temperature, has excellent thermal stability, high ionic conductivity, and high compatibility with the electrolyte film. Therefore, the resin containing the compound (1) of the present invention is useful as an electrolyte and an antistatic agent for electrochemical devices such as batteries and capacitors.

1 is a diagram showing a ¹ H-NMR spectrum (in DMSO-d ₆ ) of Sample 1. FIG. It is a figure which shows the thermal stability (TGA) of the sample 1. FIG. It is a figure which shows the glass transition temperature of sample 1, and melting | fusing point (DSC result). FIG. 3 is a diagram showing a ¹ H-NMR spectrum (in DMSO-d ₆ ) of Sample 2. It is a figure which shows the thermal stability (TGA) of the sample 2. FIG.

The compound (1) of the present invention is an ionic cyclic carbonate having an alkyleneoxy (—OR ² —) spacer. In the formula (1), the ionic functional group represented by Z is partially electrostatically charged at the binding pH of the compound to the resin, and is further charged or different at the release pH of the compound from the resin. Charged to one of the polarities.

  The ionic functional group may be either an anionic functional group or a cationic functional group. A counter cation may be bonded to the anionic functional group to form a salt, and the cationic functional group may be bonded to the counter anion to form a salt.

As the anionic functional group, an anionic functional group derived from an acid is preferable. Specifically, a carboxylic acid group (carboxylate group), a sulfonic acid group (sulfonate group), a sulfuric acid group (sulfate group), a phosphoric acid group. (Phosphonate group), sulfonylamide group, sulfonylimide group and the like can be mentioned, among which carboxylic acid group and sulfonic acid group are preferable, and sulfonic acid group is particularly preferable. The counter cation capable of binding to the acid-derived anionic functional group is preferably a metal cation or an organic ammonium cation, and more preferably an alkali metal cation.
That is, examples of the salt formed by the anionic functional group and the counter cation include an alkali metal salt of an acid and a salt of an acid and an organic amine. Examples of the alkali metal salt include Na salt, K salt, Li salt and the like. Specific examples of the alkali metal salt of an acid include -COO ^- Na ⁺ , -COO ^- K ⁺ , -SO ₃ ^- Na ⁺ , -SO ₃ ^- Li ^{+ and the} like.

The salt of the acid and an organic ^{amine, -COO - N + R a R} b R c, -SO 3 - N + R d R e R f (R a, R b, R c, R d, R e and R ^f independently represents a hydrogen atom or a substituent such as an alkyl group having 1 to 5 carbon atoms.

Further, the cationic functional group is not particularly limited as long as it has a cation, but it is an onium ion; for example, an ammonium ion (ammonium group) such as a cyclic or acyclic trialkylammonium ion; an imidazolium ion (imidazolium group) ); Pyridinium ion (pyridinium group); phosphonium ion (phosphonium group); sulfonium ion (sulfonium group).
More specifically, a tri (C1-C12 alkyl) ammonium ion, an imidazolium ion which 1 to 3 C1-C12 alkyl groups may substitute are mentioned.

  As said tri (C1-C12 alkyl) ammonium ion, group represented by following formula (4) is preferable.

(In Formula (4), R <^14> , R <^15> and R < ¹⁶ > show a C1-C5 alkyl group each independently.)
As R <^14> , R <^15> and R < ¹⁶ >, a C1-C3 alkyl group is preferable, and a methyl group, an ethyl group, n-propyl group, and an isopropyl group are mentioned, A methyl group is especially preferable.

  Moreover, as an imidazolium ion which the said C1-C12 alkyl group may substitute, group represented by following formula (5) is preferable.

(In the formula (5), R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
In the above R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ , the alkyl group having 1 to 5 carbon atoms is preferably the same as R ¹⁴ described above.

The counter anion bonded to the cationic functional group is not particularly limited as long as it has a negative charge, and examples thereof include a halogen ion, an organic acid anion, and an inorganic acid anion. Examples of the organic acid anion include a carboxylic acid anion, an organic sulfone anion, an organic phosphate anion, a sulfonylamino anion, and a disulfonylamide anion. Examples of inorganic acid anions include sulfonic acid anions and Lewis acid anions. Specific examples of preferred counter anions include Br ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (FSO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , F (HF) _n ⁻ , CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ ⁻ , (CF ₃ CF ₂ SO ₂ ) ₂ N ⁻ , CF ₃ CF ₂ CF ₂ COO ^{− and the} like. BF ₄ ⁻ , PF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ and (FSO ₂ ) ₂ N ⁻ are more preferable, and PF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ and (FSO ₂ ) ₂ N ⁻ are particularly preferable.

Of R ¹ and R ^{2 in} formula (1), the unsubstituted alkylene group having 2 to 20 carbon atoms is an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a butylene group, a pentamethylene group, or a hexamethylene group. An octamethylene group, and the like, and an ethylene group, a propylene group, and a trimethylene group are preferable. These alkylene groups may be substituted with a hydroxy group, a halogen atom, an alkoxy group, an aryl group, an aralkyl group or the like.
Of the unsubstituted alkylene group having 2 to 20 carbon atoms, a linear or branched alkylene group having 2 to 10 carbon atoms is preferable, and a linear or branched alkylene group having 2 to 6 carbon atoms is more preferable. A linear or branched alkylene group having 2 to 4 carbon atoms is particularly preferred.

p is an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, and particularly preferably 1 to 10. Further, the p OR ^{2 s} may be the same or different.

  m and n are each an integer of 0 to 5, and are numbers satisfying 1 ≦ m + n ≦ 5, preferably 0 or 1, particularly when m = 0, n = 1, or when m = 1 and n = The case of 1 is preferable.

  The compound of the formula (1) can be produced, for example, according to the following reaction formula.

(In the formula, R ¹ , R ² , Z and m, n, and p are the same as above.)

  That is, a compound of formula (2) and a halogenated glycidyl compound are reacted in the presence of a base and a solvent to obtain a compound of formula (3), and a compound of the formula (3) and carbon dioxide are reacted in the presence of a solvent. A compound of formula (1) is obtained.

  Examples of compounds of formula (2) include choline chloride, polyoxyethylene choline, 1- (2-hydroxyethyl) -2,3-dimethylimidazolium chloride, 2,3-dimethyl-1- (polyoxyethyleneimidazo And polyoxyalkylene compounds having a lithium) chloride ionic functional group. Examples of the halogenated glycidyl compound include epichlorohydrin and epibromohydrin.

  Bases used for the reaction of the compound of formula (2) with the halogenated glycidyl compound include sodium hydride, lithium hydride, potassium hydride, alkyl lithium, alkyl sodium, alkyl magnesium, alkyl magnesium halide, lithium amide, sodium amide. And strong metal bases such as sodium hydroxide, lithium hydroxide and potassium hydroxide. As the solvent, dimethylformamide, N-methylpyrrolidone, acetone, ether, dimethyl sulfoxide, dimethylacetamide, tetrahydrofuran, dimethoxyethane and the like are used.

  In order to obtain the compound of the formula (3) in high yield, it is desirable to use 1 to 10 equivalents of the halogenated glycidyl compound with respect to the compound of the formula (2). The reaction may be performed at 0 to 150 ° C. for 1 to 50 hours.

Catalysts used for the reaction of the compound of formula (3) with carbon dioxide include LiBr, NaBr, KBr, (CH ₃ ) ₄ N ⁺ Br ⁻ , (C ₂ H ₅ ) ₄ N ⁺ Br ⁻ , (n− ^{_{C 4 H 9) 4 N +}} Br -, C 6 H 5 CH 2 (CH 3) 3 N + Br - bromide salt such as; LiCl, NaCl, KCl, ( CH 3) 4 N + Cl -, (C 2 ^{_{H 5) 4 n + Cl -}} , (n-C 4 H 5) 4 n + Cl -, C 6 H 5 CH 2 (CH 3) 3 n + Cl - chloride salt such as; LiI, NaI, KI, ^{_{(CH 3) 4 n + I}} -, (C 2 H 5) 4 n + I -, (n-C 4 H 9) 4 n + I -, C 6 H 5 CH 2 (CH 3) 3 n + I ^- products salt and the like such as. As the solvent, dimethylformamide, N-methylpyrrolidone, acetone, ether, dimethyl sulfoxide, dimethylacetamide, tetrahydrofuran, dimethoxyethane and the like are used.

Carbonation of the compound of the formula (3) with carbon dioxide is carried out in an amount of 0.05 to 50% by weight, preferably 0.1% of a catalyst such as LiBr in an excess amount of CO ₂ atmosphere with respect to the compound of the formula (3). It is preferable to carry out the reaction by adding -20% by weight, more preferably 0.2-10% by weight. The reaction may be performed at 0 to 150 ° C. for 1 to 50 hours.

  The compound of the formula (1) obtained by the above reaction is liquid at room temperature, has excellent thermal stability, and exhibits high conductivity. Therefore, using the compound represented by the formula (1) of the present invention, for example, an electrolyte material used in an electrochemical device such as a lithium ion battery, a lithium ion capacitor, or an electric double layer capacitor can be formed.

  The compound of formula (1) is preferably used as an electrolyte material by being contained in an epoxy resin. Such a resin composition of the present invention comprises a compound represented by the formula (1): (A) an ionic compound having one epoxy group; and (B) a compound having two or more epoxy groups; (C) It can be obtained by including it in a resin obtained from a compound having two or more amino groups.

  (A) As an ionic compound which has one epoxy group, the compound represented by Formula (6) is mentioned.

(In the above formula (6), L represents a glycidyl group, M represents an ionic functional group, .q showing a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms R ²¹ are each independently from 1 to 100 Is an integer.)

  When producing the resin composition of the present invention, (A) the amount of the ionic compound having one epoxy group is 1 to 40% by weight, more preferably 1 to 40% by weight, from the viewpoint of causing the epoxy resin to act as an electrolyte. It is preferably 30% by weight, in particular 1 to 25% by weight.

In addition, the larger the number of repeating units (x) of the ionic compound having (A) one epoxy group in formula (6) and the number of repeating units (y) of (B), the greater the degree of freedom of the polymer. A resin having high ionic conductivity is obtained. In addition, examples of the alkylene group represented by R ²¹ and the ionic functional group represented by M in Formula (6) are the same as those described above for R ² and Z. q is preferably from 1 to 50, particularly preferably from 1 to 20.

  (B) Examples of the compound having two or more epoxy groups include compounds having two or more epoxy groups such as an epoxy group, a glycidyl group, a glycidyloxy group, and a glycidylamino group. Moreover, as a compound which has 2 or more epoxy groups, Preferably the compound which has 2-5 pieces, More preferably, 2-3 pieces, More preferably, 2 epoxy groups is mentioned.

Specific examples of the compound (B) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, and brominated bisphenol A type. Epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, spiro ring type epoxy resin, bisphenol alkane type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, brominated cresol novolak type epoxy resin , Trishydroxymethane type epoxy resin, tetraphenylolethane type epoxy resin, alicyclic epoxy resin, alcohol type epoxy resin, ethylene glycol diglycidyl ether, Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ether, fatty acid-modified epoxy resin, toluidine Type epoxy resin, aniline type epoxy resin, aminophenol type epoxy resin, hindered-in type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, dimer acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl Ether, silicone-modified epoxy resin, silicon-containing epoxy resin, urethane-modified epoxy resin, NBR-modified epoxy Shi resin, CTBN modified epoxy resins, epoxidized polybutadiene. Among these, these compounds can be used alone or in combination of two or more.
Among these, as the component (B), a compound represented by the following formula (7) is preferable.

(In the above formula (7), R ²² represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, and r is an integer of 1 to 100.)

R ²² is preferably a substituted or unsubstituted alkylene group having 2 or 3 carbon atoms. Specific examples of R ²² include an ethylene group and a propylene group, and an ethylene group is particularly preferable.
Moreover, as r, 1-50, especially 1-20 are preferable. The r R ²² Os may be the same or different.

  Preferable specific examples of component (B) include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether is particularly preferable.

  The amount of the compound (B) having two epoxy groups used in the production of the resin composition of the present invention is 1 to 90% by weight, more preferably 5 to 80% by weight, particularly from the viewpoint of preventing the ionic liquid from eluting. It is preferably 10 to 70% by weight.

  Next, (C) the compound having two or more amino groups used in the production of the resin composition of the present invention is represented by the formula (8) and acts as a curing agent.

(In the above formula (7), R ^{23 to} R ²⁶ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ^{27 to} R ²⁹ each independently represents a methylene group, Or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and s is an integer of 9 to 100.)

In R ^{23 to} R ²⁶ in Formula (8), the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms.
As the R ²³ to R ²⁶ in the formula (8), a hydrogen atom, preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably a hydrogen atom.

In R ²⁷ and R ²⁸ in formula (8), the methylene group or the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms is preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. More preferably, it is a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms.

  Specific examples of the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, a pentamethylene group, a hexamethylene group, and the like. A trimethylene group is preferred.

Further, preferred specific examples of R ²⁷ and R ²⁸ include an ethylene group and a trimethylene group, and a trimethylene group is particularly preferred.

R ²⁹ is preferably a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms. Examples of the group that can be substituted with an alkylene group include a hydroxy group. Preferable specific examples include those similar to R ²⁷ and R ²⁸ described above, and ethylene group and glyceryl group are particularly preferable.

Examples of the group that can be substituted for the alkylene group represented by R ²⁷ , R ²⁸ , and R ²⁹ include a hydroxy group, a (meth) acrylate group, and a group derived from an acid anhydride.

  Here, as the number of repeating units (s) in formula (8) increases, the flexibility as a polymer improves, so the degree of freedom of the ionic functional group immobilized on the polymer increases and the ionic conductivity improves. Can be made. In order to improve the ion conductivity, the number of repeating units (s) of the diamine compound (C) is 9 to 100, preferably 9 to 99, and more preferably 20 to 99, s. More preferably, s is 20-90.

The formula (8) _{^{-R 27 (-OR 29 -) s}} OR 28 - When the specifically shown, alkylene poly (oxyalkylene) group; alkylene poly (glycerol) group hydroxy is substituted such as an alkylene group; methoxy Alkoxy group-substituted alkylene poly (oxy) alkylene groups such as ethoxy and n-propoxy; (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate, (poly) glycerin (meth) acrylate and the like ( (Meth) acrylate group; groups substituted with groups derived from acid anhydrides such as acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, pyromellitic anhydride, and the like. Furthermore, -R ²⁷ in a compound of formula (8) in the present invention ^{(B) (-OR 29 -)} s OR 28 - The ethylene poly (oxyethylene group, propylene poly (alkylenepoly of oxypropylene) group (Oxyalkylene) group is more preferable, In the above examples, (meth) acryl means acryl or methacryl.

In the production of the resin composition of the present invention, in addition to (C) the diamine compound of formula (8), other curing agents can also be used. Examples of such other curing agents include amine compounds, phenols, and acid anhydrides.
Examples of amine compounds other than the above formula (8) include diethylamine, diethylenetriamine (DETA), triethylenetetramine, tetraethylenepentamine (TEPA), 1,6-hexamethylenediamine, dipropylenetriamine (DPTA), 1,2- Bis (2-aminoethoxy) ethane, diethylaminopropylamine, aminoethylpiperazine, mensendiamine, metaxylylenediamine, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, methylenedianiline, metaphenylenediamine, isophoronediamine, m-xylenediamine 4,4′-methylenebis (cyclohexylamine) and the like.

  The phenol is not particularly limited as long as it has a phenolic hydroxyl group. Co) polymers and their halides, alkyl group-substituted products and the like.

Acid anhydrides include hexahydrophthalic anhydride (HPA), tetrahydrophthalic anhydride (THPA), pyromellitic anhydride (PMDA), chlorendic anhydride (HET), nadic anhydride (NA), and methyl nadic anhydride (MNA), dodecynyl succinic anhydride (DDSA), phthalic anhydride (PA), methylhexahydrophthalic anhydride (MeHPA), maleic anhydride and the like.
Curing agents other than these compounds of formula (8) can be used alone or in combination of two or more.

  The amount of the compound of the formula (8) used in the production of the resin composition of the present invention is 30 to 80% by weight, preferably 40 to 40%, from the viewpoint of causing the epoxy resin to exert an effect of enhancing ion conductivity. 75% by weight, more preferably 45 to 70% by weight is preferred. Moreover, a curing accelerator can be used in combination with a curing catalyst as necessary for the purpose of accelerating the curing reaction. By reacting these polymers, the flexibility as a self-supporting film is further improved, and the polymer itself freely moves freely, so that the ion conductivity can be increased.

  The resin composition of the present invention further swells the compound (D) represented by the formula (1) in the resin obtained from the component (A), the component (B) and the component (C), thereby further ionic conduction. Can increase the sex.

  Other additives (E) include, for example, carboxylic acids, dibasic acid dihydrazides, imidazoles, organic boron, organic phosphines, guanidines, perchloric acids, sulfonic acids, sulfonylamides, bissulfonylimides, and the like. Salt, lithium tetrafluoroborate, lithium hexafluorophosphate and the like, and these can be used alone or in combination of two or more.

  As said additive (E), the compound represented by following formula (9) is preferable at the point of ion conductivity.

(In the above formula (9), X represents a halogen atom or a trihalogenomethyl group.)
As the halogen in X, a fluorine atom is preferable.

  When using the said component (E), the said usage-amount is 1 to 30 weight%, Furthermore, 5 to 25 weight% is preferable.

  The content mass ratio (A: B: C) of the component (A), the component (B), and the component (C) of the resin composition of the present invention is 1 to 90: 0.5 to 40: 2 to 95, and 5-80: 0.5-35: 2-95 are preferable. Moreover, in the resin composition of this invention, ion conductivity improves by enlarging the mass of (A), (D), (E) component. In particular, the ion conductivity is improved by increasing the mass ratio of the component (A).

In the present invention, from the viewpoint of ion conductivity, the resin composition obtained as described above is preferably swollen with a swelling agent to obtain a swollen resin composition.
The swelling agent is preferably an electrolyte solution, specifically, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, vinylene carbonate, γ-butyrolactone, dimethoxyethane, propane sultone, butane sultone, and these. A mixture is mentioned. In terms of ion conductivity, the swelling agent may be swollen by containing the additive (E). Moreover, the said swelling should just be performed by a well-known method, and 1.5-50 are preferable and 2-20 are more preferable at the point of ionic conductivity of swelling resin. Here, the swelling degree can be obtained by W _swollen / W _dry where the weight of the swollen resin is W _swollen (g) and the weight of the dry resin is W _dry (g).

  In the resin composition obtained in the present invention, since the compound represented by the formula (1) has an oxyspacer (ether bond) in the monomer, it has a high thermal stability at room temperature and exists in a liquid state, and has no solvent. Therefore, it is useful as a polymer electrolyte membrane.

  In addition, in the production of the resin composition of the present invention, the resin before adding the component (D) is, for example, each component (A), (B) and (C), and, if necessary, a solvent or other It can be produced by mixing the ingredients. As a method for producing this resin, a conventionally known method can be used as appropriate, and each component may be added at once or in an arbitrary order and stirred, mixed, and dispersed. Moreover, since this resin has a short time from mixing the compound (A), the compound (B), and the compound (C) to curing, the component (I) containing the compound (A) and the compound (B) By storing each of the component (II) containing the compound (C), the storage stability is easily improved.

  The resin composition according to the present invention includes an electrolyte such as a lithium salt, an inorganic filler, an adhesion aid, a polymer additive, a reactive diluent, a leveling agent, a wettability improver, a surfactant, and a plastic as necessary. Agents, antistatic agents, inorganic fillers, antifungal agents, humidity control agents, flame retardants, and the like may be included. These additives can be used as long as the effects of the present invention are not impaired.

  By heat-curing the assembled resin composition of the present invention, a molded body in which ionic functional groups are fixed and elution of ionic functional groups is prevented can be obtained. In addition, the obtained molded product has characteristics such as mechanical characteristics, electrical characteristics, adhesiveness, heat resistance, chemical resistance, and solvent resistance unique to epoxy resins, and excellent ionic conductivity in a swollen state. In addition, it has characteristics as an electrolyte. In particular, it is preferable to use a thermosetting film. By using a film, an antistatic film, a heat-resistant film, a flame retardant film, an adhesive film, an ion conductive film, a conductive film, an electrolyte film for a battery, and a capacitor. It is particularly useful for an electrolyte film for use. In particular, the film of the present invention is preferably used for battery applications and capacitor applications.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

The reagents used in this example are as follows.
Choline chloride, epichlorohydrone, sodium hydride (50-72 wt% in oil), lithium bromide (anhydrous), toluene (special grade), diethyl ether (special grade), dichloromethane (special grade) are purchased from Wako Pure Chemical Industries And used as is. Glycidyltrimethylammonium chloride (containing 25 wt% water) (GTMACI) was purchased from Fluka and used as it was. Carbon dioxide (liquefied carbon dioxide) was purchased from Fukutoei Acid and used as it was. Polyethylene glycol diglycidyl ether (Mw = 526, PEGGE) and polyethylene glycol bis (3-aminopropyl) (Mw = 1500, PEGBA1500) were purchased from Aldrich and used as they were. Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) was purchased from Wako Pure Chemical Industries, Ltd., and was used after being dried by heating at 120 ° C. for 3 hours under vacuum. NN-dimethylformamide (DMF) was used after distillation under reduced pressure from above calcium hydride.

The analysis of the sample used for the present Example and the comparative example is as follows.
The IR spectrum was measured by the ATR method using a NICOLET iS10 with SMART iTR sampling unit manufactured by Thermo Scientific. 1H-NMR was measured with a Varian UNITY INOVA 400 using DMSO-d6 as a solvent, and the chemical shift was determined using residual protons in DMSO-d6 as a reference. Thermogravimetric analysis (TGA) was measured with a TG-DTA6200 manufactured by Seiko Instruments Inc. by using an aluminum pan and raising the temperature in a nitrogen stream of 50 mL / min at 10 ° C./min. In differential scanning calorimetry (DSC), a DSC6200 manufactured by Seiko Instruments Inc. was used, and the sample was sealed in an aluminum pan, heat-treated at 100 ° C. for 5 minutes, rapidly cooled to −80 ° C. with liquid nitrogen, and 10 mL / min. The temperature was raised at 10 ° C./min in a nitrogen stream. The ion conductivity measurement was performed by measuring impedance by a four-terminal AC method using a stainless steel plate electrode, and analyzing by Nyquist plot to obtain ion conductivity. (HIOKI 3532-80 Chemical impedance meter, 9140 4-terminal probe, voltage: 50 mV, measurement frequency: 4 Hz to 1 MHz)

Production Example 1
Preparation of lithium 3-glycidyloxypropane sulfonate (LiGPS) Hydrogen in a DMF (4 mL) solution of 2,3-epoxy-1-propanol (1.48 g, 20.0 mmol) and propane sultone (2.44 g, 20 mmol) After adding lithium chloride (176 mg, 22 mmol) and stirring at room temperature for 20 hours, acetone (100 mL) was added to the reaction mixture to precipitate the product. The precipitate was collected, washed with acetone, and the obtained solid was vacuum-dried to obtain the target compound (2.21 g, 10.9 mmol) in a yield of 54.7%.

ATR-IR: 751, 800, 851, 891, 910, 1045, 1076, 1104, 1166, 1221, 2876, 2940 cm ⁻¹ .
¹ H-NMR δ in CD ₃ OD: 2.00-2.13 (m, 2H), 2.63 (dd, J = 2.8, 5.2 Hz, 1H), 2.81 (dd, J = 4.4, 5.2 Hz, 1H), 2.92 (t, J = 7.8 Hz, 2H), 3.10-3.20 (m, 1H), 3.37 (dd, J = 6.0). , 11.4 Hz, 1H), 3.57-3.68 (m, 2H), 3.79 (dd, J = 2.8, 11.4 Hz, 1H).

Production Example 2
Preparation of 2-glycidyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (GETMATFSSI) To a 12 mL aqueous solution of choline chloride (6.98 g, 50.0 mmol) at room temperature, lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) ( (14.4 g, 50.0 mmol) of 12 mL aqueous solution was added, and after stirring for 24 h, the lower layer liquid was recovered, washed twice with pure water (10 mL), and then vacuum-dried at 70 ° C. for 3 hours to give a choline bis ( Trifluoromethanesulfonyl) imide salt (14.2 g, 36.9 mmol) was obtained in 74% yield. While cooling a DMF (16 mL) solution of this choline TFSI salt (6.14 g, 16 mmol) and epichlorohydrin (4.44 g, 48 mmol) with water, sodium hydride (about 50 wt% oil dispersion, 1 g, about 21 mmol) Was slowly added and stirred. After 20 hours, diethyl ether (200 mL) was added, and the precipitate was recovered and washed twice with diethyl ether (10 mL). After adding pure water (5 mL) and stirring, the lower layer liquid was recovered and purified water (5 mL) was used. After washing, vacuum drying was performed at room temperature for 3 hours to obtain the target compound (4.47 g, 10.2 mmol) in a yield of 64%.

ATR-IR: 739, 788, 866, 895, 926, 969, 1049, 1130, 1175, 1325, 1346, 1476, 1487 cm ⁻¹ .
¹ H-NMR δ in CD ₃ OD: 2.67 (dd, J = 2.7, 5.0 Hz, 1H), 2.85 (dd, J = 4.2, 5.0 Hz, 1H), 3. 16-3.28 (m, 1H), 3.21 (s, 9H), 3.41 (dd, J = 6.3, 11.6 Hz, 1H), 3.62-3.68 (m, 2H) ), 3.96 (dd, J = 2.1, 11.6 Hz, 1H), 3.75-4.05 (m, 2H).

Production Example 3
Synthesis of bis (trifluoromethanesulnyl) imide salt of propylene carbonate substituted with trimethylammonium through an ethyleneoxy spacer (TAEPCTFSI: Sample 1) A magnetic rotor, GEMATFSI (4.4 g, 10 mmol) in a 100 mL eggplant flask, DMF (10 mL) and LiBr (87 mg, 1 mmol) were added, a three-way cock with a 2 L rubber balloon filled with carbon dioxide was attached, the flask was evacuated and replaced with carbon dioxide, and the mixture was stirred at 100 ° C. at 16 ° C. Stir for hours. After allowing to cool to room temperature, the mixture was poured into toluene (300 mL), and the precipitate was collected, washed twice with toluene (10 mL), washed twice with distilled water (5 mL), and vacuum dried. The target compound TAEPCTFSI (3.81 g, 7.87 mmol) was obtained with a yield of 79%.

IR (neat, ATR) 718, 740, 765, 792, 878, 957, 1045, 1132, 1175, 1325, 1345, 1480, 1790 cm ⁻¹ .
¹ H-NMR δ (DMSO-d ₆ ) 3.08 (s, 9H), 3.52-3.57 (m, 2H), 3.64 (dd, J = 3.1, 11.1 Hz, 1H ), 3.75 (dd, J = 2.5, 11.1 Hz, 1H), 3.86-3.93 (m, 2H), 4.32 (dd, J = 5.5, 8.6 Hz, 1H), 4.55 (dd, J = 8.6, 8.7 Hz, 1H), 4.95-5.02 (m, 1H).

Production Example 4
Synthesis of bis (trifluoromethanesulfonyl) imide salt of propylene carbonate substituted with trimethylammonium (TAPPCTFSI: Sample 2) (.04 g, 25 wt% water content, 30.0 mmol) in DMF (30 mL) was added, and the inside of the flask was replaced with carbon dioxide gas under reduced pressure. The reaction mixture was heated to 50 ° C. with stirring for 12 hours. After cooling to room temperature, the reaction mixture was poured into 300 mL of dichloromethane with stirring. A viscous liquid precipitated. The precipitate was collected by decantation, washed twice with dichloromethane (10 mL), distilled water (20 mL) was added to the crude product, and a solution of LiTFSI (8.61 g, 30 mmol) in distilled water (25 mL) was stirred at room temperature. As a result, a white solid immediately precipitated. After stirring for 10 hours, the mixture was filtered through a glass filter to recover a solid. The obtained solid was washed 3 times with distilled water (5 mL), and the collected solid was vacuum-dried to obtain the desired TAPCTFSI (9.45 g, 21.5 mmol) in a yield of 72%. The melting point was 80.7-81.0 ° C.

IR (neat, ATR) 721, 740, 765, 792, 952, 968, 1050, 1077, 1135, 1180, 1333, 1480, 1490, 1795 cm ⁻¹ .
¹ H-NMR δ (DMSO-d ₆ ) 3.13 (s, 9H), 3.64 (d, J = 14.8 Hz, 1H), 3.92 (dd, J = 9.2, 14.8 Hz, 1H), 4.18 (dd, J = 7.6, 8.6 Hz, 1H), 4.7 (dd, J = 8.4, 8.6 Hz, 1H), 5.42 (m, 1H).

Synthesis of polymer film using epoxy resin and amine curing agent After adding methanol to a mixture of epoxy resin, ionic epoxy, amine curing agent (stoichiometric amount with respect to all epoxy groups), knead the mixture well, After pouring into a fluororesin mold and evaporating methanol, the mixture was heated at 100 ° C. for 7 hours. After cooling to room temperature, the fluororesin mold was removed to obtain a yellow transparent or colorless transparent epoxy former. A cured product (15 mm × 5 mm) was cut out and immersed in 50 mL of methanol for 2 hours, and then the formed body was taken out and washed with methanol. After performing this operation three times, it was air-dried overnight, and further heat-dried at 100 ° C. for 3 hours using an electric dryer to synthesize a polymer film made of an epoxy cured resin having an ionic group.

Example 1
Preparation of polymer film-1
Polymer film (thick film) of PEGGE / LiGPS-1.0 / PEFBA1500 synthesized by the above method (100 ° C., heated and dried for 3 hours) 8.4 mg (5.5 mm × 6.0 mm × 0.41 mm) ), Soaked in TAEPCTFSI (67 mg), heated at 100 ° C. for 20 hours, removed the membrane from the TAEPCTFSI solution, and wiped off the excess TAEPCTFSI on the surface with Kimwipe. (26.6 mg, 6.0 mm × 7.0 mm × 0.44 mm, TAEPCTFSI content 68 wt%) was obtained. The ionic conductivity was 1.4 × 10 ⁻² [S / m].

Example 1
Preparation of polymer film-2
10.6 mg (6 mm × 6 mm × 0.41 mm) of PEGGE / LiGPS-1.0 / PEFBA1500 polymer film (thick film) (100 ° C., heated and dried for 3 hours) synthesized in the same manner as in Example 1 was cut out. , LiTFSI (12.6 mg) was dissolved in TAEPCTFSI (85 mg) and immersed in a solution obtained by heating at 100 ° C. for 20 hours. Thus, LiTFSI / TAEPCTFSI-added PEGGE / LiGPS-1.0 / PEGBA1500 (33.5 mg, 6.5 mm × 6.5 mm × 0.51 mm, LiTFSI / TAEPCTFSI content 68 wt%) was obtained. The ionic conductivity was 5.3 × 10 ⁻³ [S / m].

Comparative Example 1
Preparation of polymer film-3
PEGGE / LiGPS-1.0 / PEGBA1500 polymer film (thick film) synthesized in the same manner as in Example 1 and Example 2 (100 ° C., heat-dried for 3 hours) 16.2 mg (5.5 mm × 7 mm × 0.41 mm) was cut out, immersed in an acetone (30 mg) solution of TAPCTFSI (16.2 mg) obtained by the above synthesis method for 3 hours, and then heated and dried at 100 ° C. for 3 hours to obtain TAPCTFSI-added PEGGE / LiGPS-1. 0 / PEFBA1500 (31 mg, 6 mm × 8 mm × 0.47 mm, TAPCTFSI content 48 wt%) was obtained. The ionic conductivity was 1.2 × 10 ⁻³ [S / m].

  Table 1 shows the evaluation results of Examples 1 and 2 and Comparative Example 1.

  From the results of Example 1 according to the present invention, it was confirmed that the electrolyte film in which the ether carbonate-containing cyclic carbonate was swollen exhibited high conductivity.

  From the results of Example 2 according to the present invention, it was confirmed that the electrolyte film obtained by swelling an ether-bonded cyclic carbonate to which lithium bis (trifluoromethanesulfonyl) imide was added exhibited a certain degree of conductivity.

  From the results of Comparative Example 1, it was confirmed that the electrolyte film in which propylene carbonate was swollen did not have high conductivity as compared with Example 1 and Example 2.

Claims (7)

A compound represented by the following formula (1).

(In the formula (1), R ¹ and R ² each represent a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, Z represents an ionic functional group, and m and n represent 0 to 5 respectively. And is a number satisfying 1 ≦ m + n ≦ 5, and p is an integer of 1 to 100.) A step of reacting a compound represented by the following formula (2) with a halogenated glycidyl compound in the presence of a base and a solvent to obtain a compound represented by the following formula (3);
A method for producing a compound represented by the following formula (1), comprising a step of reacting a compound represented by the following formula (3) with carbon dioxide in the presence of a catalyst and a solvent.

(In the formula (2), R ² represents a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and Z represents an ionic functional group.)

(In Formula (3), R ¹ and R ² each represent a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and Z represents an ionic functional group.)

(In the formula (1), R ¹ and R ² each represent a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, Z represents an ionic functional group, and m and n represent 0 to 5 respectively. And is a number satisfying 1 ≦ n + m ≦ 5, and p is an integer of 1 to 100.) A resin composition comprising an epoxy resin and the compound according to claim 1.

(In the formula (1), R ¹ and R ² each represent a methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, Z represents an ionic functional group, and m and n represent 0 to 5 respectively. And is a number satisfying 1 ≦ m + n ≦ 5, and p is an integer of 1 to 100.) The epoxy resin is
(A) an ionic compound having one epoxy group;
(B) a compound having two or more epoxy groups;
(C) The resin composition according to claim 3, which is a resin obtained from a compound having two or more amino groups. The (A) is a compound represented by the following formula (8), the (B) is a compound represented by the following formula (9), and the (C) is represented by the following formula (10). The resin composition according to claim 3 or 4, which is a compound to be produced.

(In Formula (8), L represents a glycidyl group, M represents an ionic functional group, R ²⁰ represents a substituted or unsubstituted alkylene group having 2 to ²⁰ carbon atoms, and q is an integer of 1 to 100. .)

(In Formula (9), R ²¹ represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, and r is an integer of 1 to 100.)

(In the formula (10), R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ²⁶ and R ²⁷ are each independently Represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R ²⁸ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and s is an integer of 9 to 100.)   The molded object shape | molded using the resin composition of any one of Claims 3-5.   An electrolyte film for a battery or a capacitor formed using the resin composition according to claim 3.

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