JP2013113683A - Method for evaluating ion liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for evaluating ion liquid for evaluating thermostability of the ion liquid, and to provide a method for selecting the ion liquid for allowing easy selection of the ion liquid according to a use by using this technology.SOLUTION: In a method for evaluating ion liquid, thermostability of the ion liquid, and a compound to be generated by thermal decomposition of the ion liquid are evaluated by analyzing the ion liquid using thermal mass analysis (TGA) and heat desorption-gas chromatograph mass analysis (TDS-GCMS).

Description

  The present invention relates to a method for evaluating an ionic liquid (hereinafter also simply referred to as “evaluation method”), and more particularly, to a method for evaluating the thermal stability of an ionic liquid.

  An ionic liquid is a novel substance having various excellent physical properties as a liquid, and is expected to be used in fields and directions that cannot be considered from conventional salts and liquids. For example, high thermal stability is one of the remarkable features of ionic liquids. In addition, the ionic liquid has characteristics as a recyclable solvent.

  The application of ionic liquids to capacitors and lithium ion batteries is expected, and the development of various types of ionic liquids is being studied and promoted. As a technique related to such an ionic liquid, for example, Patent Document 1 discloses an ionic liquid property measuring method for measuring an intensity suggestion value suggesting the strength of an acid or a base in an ionic liquid or an ionic liquid solution using an ISFET sensor. It is disclosed.

JP 2008-64578 A (Claims etc.)

  By the way, in selecting an ionic liquid to be used for various applications, the thermal stability of the ionic liquid, the composition of a compound generated by thermal decomposition of the ionic liquid, and the like are important. However, at present, there is no established method for evaluating these characteristics of ionic liquids. Therefore, it is necessary to actually apply various ionic liquids to intended applications and evaluate their suitability for such applications. There is a problem that it takes a lot of time to select an optimum ionic liquid from among the existing ionic liquids.

  Accordingly, an object of the present invention is to solve the above-described problems and provide a technique for evaluating the thermal stability of an ionic liquid, and by using this technique, an ionic liquid can be easily selected according to the application. Is to make it possible.

  As a result of intensive studies, the present inventor has performed thermal mass spectrometry (Thermogravimetric Analysis, TGA) and thermal desorption-gas chromatograph mass spectrometry (Thermal Desorption Spectroscopy-Gas Chromatography Mass SpectroMS, DS) using DSC. The inventors have found that the above problems can be solved by using the technique, and have completed the present invention.

  That is, the method for evaluating an ionic liquid according to the present invention includes analyzing the ionic liquid using thermal mass spectrometry and thermal desorption-gas chromatography mass spectrometry, so that the thermal stability of the ionic liquid and the ion It is characterized by evaluating a compound produced by thermal decomposition of a liquid.

  Moreover, the selection method of the ionic liquid of this invention selects an ionic liquid using the evaluation result by the evaluation method of the said ionic liquid of this invention.

  According to the present invention, the above-described configuration makes it possible to evaluate the thermal stability of the ionic liquid, whereby the optimum ionic liquid can be easily selected according to the application. It was.

Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, the thermal stability of the ionic liquid and the ionic liquid are analyzed by analyzing the ionic liquid using thermal mass spectrometry (TGA) and thermal desorption-gas chromatograph mass spectrometry (TDS-GCMS). Is a compound that is evaluated by thermal decomposition.

  Here, TGA is an analytical method for measuring the mass change of a sample while heating or cooling and changing the temperature or keeping it at a constant temperature, and is a thermal method including thermal decomposition of the sample. It is a technology that can know the reaction process. In the present invention, by analyzing the ionic liquid by TGA, the thermal stability (decomposition temperature) of the ionic liquid can be evaluated, and the heat resistant temperature can be obtained. More specifically, in the present invention, by measuring the weight of the ionic liquid while heating, the volatile impurities contained in the ionic liquid, and at a higher temperature, the thermal decomposition product (product), respectively, It becomes possible to quantify.

  TDS-GCMS is an analysis method in which a sample is heated and heated with a TDS apparatus, degassed from the sample is collected, and the collected degass is measured with a GCMS apparatus. In the present invention, by analyzing the ionic liquid by TDS-GCMS, it is possible to qualitatively evaluate the composition of decomposition products (volatile components) generated by thermal decomposition of the ionic liquid. It is possible to easily determine whether or not industrialization is possible.

  As described above, in the present invention, since the ionic liquid is analyzed by combining the above TGA and TDS-GCMS, the thermal stability of the ionic liquid can be easily evaluated, and the ionic liquid is thermally decomposed. Thus, it was possible to simultaneously evaluate the resulting compounds. Thereby, since the evaluation method of the thermal stability of an ionic liquid can be established, when an ionic liquid is selected using the evaluation result by this evaluation method, when applying an ionic liquid to various uses In addition, the optimum ionic liquid can be easily selected. Therefore, it is possible to save time and cost required for selecting an ionic liquid by eliminating the waste of time and work for actually applying various ionic liquids to each application.

The present invention can be applied to any ionic liquid and is not particularly limited. Specifically, such an ionic liquid can be represented by the following formula (I) or (II).
[A] ⁺ _n [Y] ⁿ⁻ (I)
(In the formula (I), n represents 1, 2, 3 or 4, [A] ⁺ represents a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Y] ⁿ⁻ represents 1 Represents a tetravalent anion)
[A ¹ ] ⁺ [A ² ] ⁺ [Y] ⁿ⁻ (II−a), where n = 2
[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ⁿ⁻ (II−b), where n = 3
[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ⁿ⁻ (II−c), where n = 4
(In the formula, [A ¹ ] ⁺ to [A ⁴ ] ⁺ each independently represents a quaternary ammonium cation, an oxonium cation, a sulfonium cation, or a phosphonium cation, and [Y] ^n- represents 1 to 4 valences. Represents an anion of

As the cation [A] ⁺ of the ionic liquid, oxygen, phosphorus, sulfur, and particularly a nitrogen atom, for example, at least 1, preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. Individual, particularly preferably, compounds containing 1 to 2 nitrogen atoms can be used. These may have additional heteroatoms such as oxygen, sulfur or phosphorus atoms. Nitrogen atoms are good carriers of the positive charge of the cation of the ionic liquid, from which protons or alkyl groups can be transferred to an anion in equilibrium to form an electrically neutral molecule.

  When the nitrogen atom is the positively charged carrier of the cation of the ionic liquid, in the synthesis of the ionic liquid, the cation can first be synthesized by quaternizing the nitrogen atom of the amine or nitrogen-containing heterocyclic compound. . Quaternization of amines or nitrogen-containing heterodry compounds can be performed by alkylation of nitrogen atoms, and salts with different anions can be synthesized depending on the alkylating reagent used. If there is no possibility that the desired anion is pre-formed during quaternization, this can be synthesized in a further synthetic step. For example, a complex anion is formed by reacting a halide with a Lewis acid using ammonium halide as a starting material. As another method, halide ions can be exchanged with desired anions. This can be done by addition of a metal salt with solidification of the formed metal halide or replacement of the halide ion with a strong acid (hydrohalic acid is liberated) via an ion exchanger.

Alkyl group which may be quaternized nitrogen atom in the amines or nitrogen-containing heterocyclic compounds, for _example, C 1 _{-C 18} alkyl, preferably _C 1 _{-C 10} alkyl, particularly preferably _C 1 -C ₆ alkyl Especially preferred is methyl. An alkyl group can be unsubstituted or can contain one or more identical or different substituents.

  In the present invention, at least one 5-membered to 6-membered heterocyclic group containing at least one nitrogen atom and optionally an oxygen or sulfur atom, particularly those containing a 5-membered heterocyclic group are used. Can do. Other suitable compounds contain at least one 5- to 6-membered heterocyclic group containing 1, 2 or 3 nitrogen atoms and sulfur or oxygen atoms, more preferably 2 nitrogen atoms. Things. In the present invention, an aromatic heterocyclic compound is more preferable.

  In the present invention, the compound preferably has a molecular weight of less than 1000 g / mol, more preferably less than 500 g / mol, and even more preferably less than 300 g / mol.

As the cation in the present invention, specifically, compounds having structures represented by the following formulas (III-a) to (III-w) and oligomers having these structures can be preferably used.

In the present invention, as other cations, compounds having the following structures and oligomers having these structures may be used.

  Here, R in the above structural formula is a hydrogen atom, unsubstituted, interrupted, or organic having 1 to 20 carbon atoms substituted with 1 to 5 heteroatoms or functional groups, Represents a saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or aromatic aliphatic group.

Also, R ^{1 to} R ⁹ in the above structural formula are independently of each other a hydrogen atom, a sulfo group, unsubstituted or interrupted, or substituted with 1 to 5 heteroatoms or functional groups. Represents an organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or aromatic aliphatic group having from 1 to 20 carbon atoms.

Furthermore, the carbon atom in the above structural formula, that is, R ^{1 to} R ⁹ bonded to other than the hetero atom may be a halogen atom or a functional group. Here, the heteroatom means all heteroatoms capable of exchanging —CH ₂ —, —CH═, —C≡ or ═C═ group. As the hetero atom, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. Especially, -O -, - S -, - SO -, - SO 2 -, - NR '-, - N =, - PR' -, - PR '2 - and SiR' ₂ - a and, R 'is The remainder of the carbon-containing group. In the above formula (III), when bonded to a carbon atom (not bonded to a heteroatom), R ^{1 to} R ⁹ may be bonded via a heteroatom.

Examples of the functional group include —OH (hydroxyl), ═O (particularly as a carbonyl group), —NH ₂ (amino), —NHR, —NR ₂ , ═NH (imino), —COOH (carboxyl), — CONH ₂ (carboxamide), —SO ₃ H (sulfo) and CN (cyano) can be mentioned, and preferably —OH (hydroxyl), ═O (particularly as a carbonyl group), —NH ₂ (amino), ═ NH (imino), —COOH (carboxyl), —CONH ₂ (carboxamide), —SO ₃ H (sulfo) and CN (cyano). The functional group may be bonded through a heteroatom such as —O— (ether) or —S— (thioether), and further —COO— (ester), —CONH— Secondary amide) or CONR ′-(tertiary amide) may be bonded via an atomic group. For example, di- (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ alkoxycarbonyl or C ₁ -C ₄ alkoxy can be mentioned.

  In the present invention, examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of R include methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, and 1-pentyl. 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2 -Pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3 -Dimethyl-1-butyl, 2-d 1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (n-butoxy Carbonyl) ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and Propylsulfo Acid or hydroxyl, halogen, phenyl, _cyano, unbranched C 1 -C ₆ alkoxycarbonyl and / or SO ₃ H with one or more substituted carbons have 1 to 20 or branched chain _C 1 -C ₁₈ alkyl or, for example, R ^A O— (CHR ^B —CH ₂ —O) _m —CHR ^B —CH ₂ — or R ^A O— (CH ₂ CH ₂ CH ₂ CH ₂ O) _m —CH ₂ CH ₂ CH ₂ CH ₂ O- (wherein, ^{R a} and ^{R B} is preferably hydrogen, methyl or ethyl, m is preferably 0 to 3), in particular 3-oxabutyl, 3-oxapentyl, 3 , 6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and Glycol, butylene glycol and oligomers thereof having _{1 to} 100 units and hydrogen or C _{1 to} C ₈ alkyl as a terminal group, such as 3,6,9,12-tetraoxatetradecyl, and vinyl, allyl, For example, N, N-di-C ₁ -C ₆ alkylamino, such as N, N-dimethylamino and N, N-diethylamino may be used.

In the present invention, R ^{1 to} R ⁹ are preferably independently of each other hydrogen, halogen, or a functional group, but (i) C _{1 to} C ₁₈ alkyl or these are functional groups, aryl, alkyl, aryl Substituted with oxy, alkoxy, halogen, heteroatoms and / or heterocyclic groups and / or interrupted with one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups It may be what you have. Further, (ii) or C ₂ -C ₁₈ alkenyl, these functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, substituted with heteroatoms and / or heterocyclic group, and / or one or more It may be interrupted by an oxygen and / or sulfur atom and / or one or more substituted or unsubstituted imino groups, (iii) C ₆ -C ₁₂ aryl, and these are functional groups, aryl, alkyl, aryloxy _May be substituted with alkoxy, halogen, heteroatoms and / or heterocyclic groups, (iv) C ₅ -C ₁₂ cycloalkyl and these are functional groups, aryl, alkyl, aryloxy, alkoxy, halogen It may be those substituted with heteroatoms and / or heterocyclic group, (v) C ₅ C ₁₂ or cycloalkenyl, they functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, may be those substituted with heteroatoms and / or heterocyclic group, (vi) oxygen, nitrogen and / or sulfur It may be a 5- to 6-membered heterocyclic group containing atoms and optionally substituted with a functional group, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocyclic group. (Vii) Both two adjacent groups are preferably substituted with a functional group, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocyclic group, optionally with one or more It may be an unsaturated, saturated or aromatic ring interrupted by oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups.

As the above (i), methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl) 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl -1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3 -Methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl , 3,3-Dime 1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl 1,1,3,3-tetramethylbutyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1 -Octadecyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl α, α-dimethylbenzyl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyano Propyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, methoxy, ethoxy, formyl, 1,3-dioxolan-2-yl, 1 , 3-Dioxolan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxy Propyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-amino Propyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethyl Aminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3- Phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3- Ethoxypropyl, 4-ethoxy C _m F _{2 (m−a) + (1−b)} H where sibutyl, 6-ethoxyhexyl, acetyl, m is 1-30, 0 ≦ a ≦ m, and b = 0 or 1. _{2a + b (e.g., CF 3, C 2 F 5} , CH 2 CH 2 -C (m-2) F 2 (m-2) +1, C 6 F 13, C 8 F 17, C 10 F 21, C 12 R ₂₅ ), chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl-2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl Butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa-octyl, 11-hydroxy-3,6,9-tolyoxa -Undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14 -Hydroxy-5,10-dioxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy -4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy 4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6- Dioxa-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12- Mention may be made of trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

As the (ii), vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl _{or, C m F 2 (m-} a) - a _{(1-b) H 2a-} b Can be mentioned. Here, m ≦ 30, 0 ≦ a ≦ m, and b = 0 or 1 may be used.

As (iii), preferably, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, Diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4 6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4 -Dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _{(5-a )} can be mentioned H _a. Here, 0 ≦ a ≦ 5.

As (iv) above, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chloro Cyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, m ≦ 30, 0 ≦ a ≦ m, b = 0 or 1, C _m F _{2 (m−a)-(1-b)} H _2a−b and Mention may be made, for example, of saturated or unsaturated bicyclic systems such as norbornyl or norbornenyl.

(V) is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexanedienyl, or m ≦ 30 and 0 ≦ a ≦ m. b = 0 or _1, it can be mentioned _{C n F 2 (m-a} ) -3 (1-b) H 2a-3b.

  Examples of (vi) include furyl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxyfuryl, dimethoxypyridyl, or difluoropyridyl. it can.

As (vii), 1,3-propylene, 1,4-butylene, 1,5-pentylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa-1 , 3-propylene, 1-oxa-1,3-propenylene, 3-oxa-1,5-pentylene, 1-aza-1,3-propenylene, 1-C ₁ -C ₄ alkyl-1-aza-1, Mention 3-propenylene, 1,4-buta-1,3-dienylene, 1-aza-1,4-buta-1,3-dienylene or 2-aza-1,4-buta-1,3-dienylene Can do.

  When the substituents (i) to (vii) above contain an oxygen, sulfur atom, substituted or unsubstituted imino group, the number of these is not limited, but these are 5 or less, preferably 4 in the substituent. Or less, more preferably 3 or less. When the substituent contains a heteroatom, at least 1 carbon atom, preferably at least 2 carbon atoms, are present between the 2 heteroatoms.

In the present invention, more preferably, R ^{1 to} R ⁹ are independently of each other hydrogen, such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1, -Propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl 2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl 2,3-dimethyl 1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -Ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nona Fluoroisobutyl, undecylfluoropentyl, undecylfluoro Sopenchiru, 6-hydroxyhexyl, and, and substituted groups such as propyl sulfonic acid, Ya substituent these hydroxyl, halogen, phenyl, cyano, C ₁ -C ₆ alkoxycarbonyl, substituted one or more SO 3 _H , Branched C ₁ -C ₁₈ alkyl and, for example, R ^A O— (CHR ^B —CH ₂ —O) _m —CHR ^B —CH ₂ — or R ^A O— (CH ₂ CH ₂ CH ₂ CH ₂ O) _{m -CH 2 CH 2 CH 2 CH} 2 O- ( wherein, ^{R a} and ^{R B} is preferably hydrogen, methyl or ethyl, m is preferably 0-3), in particular, 3-oxabutyl 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6 , 9,12-tetraoxaspiro tridecyl and, 3,6,9,12 like tetraoxatetracosane decyl, glycols having _C 1 -C ₈ alkyl as 1 to 100 units and a hydrogen or terminal groups, butylene glycol And oligomers thereof and vinyl, allyl such as N, N-di-C ₁ -C ₆ alkylamino such as N, N-dimethylamino and N, N-diethylamino.

More preferably, R ^{1 to} R ⁹ are independently of each other hydrogen or, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl or 1-octyl, phenyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (n-butoxycarbonyl) ethyl, N, N-dimethylamino, N, N-diethylamino, chlorine, and _{CH 3 O- (CH 2 CH 2} O) m -CH 2 CH 2 - and _{CH 3 CH 2 O- (CH 2} CH 2 O) m -CH 2 CH 2 - ( m is at 0-3 wherein C ₁ -C ₁₈ alkyl, such as

In the present invention, the pyridinium ion (III-a) more preferably used is as follows: (1) ^{one of} R ^{1 to} R ⁵ is methyl, ethyl or chlorine, and the remaining R ^{1 to} R ⁵ are hydrogen. (2) R ³ is dimethylamino and the remaining R ¹ , R ² , R ⁴ and R ⁵ are hydrogen, (3) R ^{1 to} R ⁵ are all hydrogen, 4) R ² is carboxyl or carboxamide and the remaining R ¹ , R ² , R ⁴ and R ⁵ are hydrogen, (5) R ¹ and R ² , or R ² and R ³ are 1, 4-buta-1,3-dienylene, and the remaining R ¹ , R ² , R ⁴ and R ⁵ are hydrogen, and in particular, (3) or ¹ of R ^{1 to} R ⁵ One of which is methyl or ethyl and the remaining radicals R ^{1 to} R ⁵ are hydrogen Is preferred.

  In the present invention, pyridinium ions (III-b) more preferably used include 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- ( 1-octyl) pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2-methylpyridinium 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2- Methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2 Methylpyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1- Octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2 -Dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1- (1-butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3- Ethylpyridinium and 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1- (1-dodecyl) -2-methyl-3 Ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethyl pyridinium, and 1- (1-hexadecyl) -2-methyl-3 can be mentioned ethyl pyridinium.

Particularly preferably used pyridazinium ions (III-b) are those in which R ^{1 to} R ⁴ are hydrogen, or one of R ^{1 to} R ⁴ is methyl or ethyl, and the remaining group R ¹ to R ⁴ can be exemplified are hydrogen.

In the present invention, as a pyrimidinium ion (III-c) more preferably used, R ¹ is hydrogen, methyl or ethyl, and R ^{2 to} R ⁴ are independently of each other hydrogen or methyl. And R ¹ is hydrogen, methyl or ethyl, R ² and R ⁴ are methyl, and R ³ is hydrogen.

The pyrazinium ion (III-d) more preferably used in the present invention is ^{one in} which R ¹ is hydrogen, methyl or ethyl, and R ^{2 to} R ⁴ are independently of each other hydrogen or methyl. R ¹ is hydrogen, methyl or ethyl, R ² and R ⁴ are methyl, R ³ is hydrogen, R ^{1 to} R ⁴ are methyl, R ^{1 to} R ⁴ May be methyl or hydrogen.

In the present invention, imidazolium ion (III-e) more preferably used is that R ¹ is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, Mention may be made of allyl, 2-hydroxyethyl or 2-cyanoethyl and R ^{2 to} R ⁴ independently of one another are hydrogen, methyl or ethyl.

  Specific examples of suitable imidazolium ions (III-e) include 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) imidazolium, 1- (1-octyl) imidazolium, 1- (1-dodecyl) imidazolium, 1- (1-tetradecyl) imidazolium, 1- (1-hexadecyl) imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3- Ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-o Til) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1 -(1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethyl Imidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethyl Imidazolium, 1,4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5 -Tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazoli And 1,4,5-trimethyl-3-octylimidazolium.

In the present invention, the pyrazolium ions (III-f), (III-g) or (III-g ′) which are more preferably used include R ¹ is hydrogen, methyl or ethyl, and R ^{2 to} R ⁴ Which are, independently of one another, hydrogen or methyl.

In the present invention, examples of the pyrazolium ion (III-h) more preferably used include those in which R ^{1 to} R ⁴ are each independently hydrogen or methyl.

In the present invention, examples of the 1-pyrazolium ion (III-i) more preferably used include those in which R ^{1 to} R ⁶ are each independently hydrogen or methyl.

In the present invention, as 2-pyrazolium ion (III-j) or (III-j ′) more preferably used, R ¹ is hydrogen, methyl or phenyl, and R ^{2 to} R ⁶ are independent of each other. And those that are hydrogen or methyl.

In the present invention, 3-pyrazolium ion (III-k) or (III-k ′) that can be more preferably used includes, as R ¹ and R ² , independently of one another, hydrogen, methyl, ethyl or phenyl And R ^{3 to} R ⁶ are each independently hydrogen or methyl.

In the present invention, as imidazolinium ion (III-l) that can be more preferably used, R ¹ and R ² independently of one another are hydrogen, methyl, ethyl, 1-butyl or phenyl, Mention may be made of those in which ³ and R ⁴ are independently of each other hydrogen, methyl or ethyl, and R ⁵ and R ⁶ are independently of each other hydrogen or methyl.

In the present invention, the imidazolinium ion (III-m) or (III-m ′) that can be more preferably used includes R ¹ and R ² independently of one another, hydrogen, methyl or ethyl, Mention may be made of those in which R ^{3 to} R ⁶ are independently of each other hydrogen or methyl.

In the present invention, the imidazolinium ion (III-n) or (III-n ′) that can be used more preferably includes R ^{1 to} R ³ independently of one another, hydrogen, methyl or ethyl, Mention may be made of those in which R ^{4 to} R ⁶ are independently of each other hydrogen or methyl.

In the present invention, as thiazolium ions (III-o), (III-o ′) and oxazolium ions (III-p) that can be more preferably used, R ¹ is hydrogen, methyl, ethyl or phenyl. And R ² and R ³ independently of one another are hydrogen or methyl.

In the present invention, 1,2,4-triazolium ions (III-q), (III-q ′) or (III-q ″) that can be used more preferably include R ¹ and R ² as Independently of each other, mention may be made of those which are hydrogen, methyl, ethyl or phenyl and R ³ is hydrogen, methyl or phenyl.

In the present invention, 1,2,3-triazolium ions (III-r), (III-r ′) or (III-r ′ ′) that can be more preferably used include R ¹ is hydrogen, methyl Or ethyl and R ² and R ³ , independently of one another, are hydrogen or methyl, or R ² and R ³ are both 1,4-buta-1,3-dienylene. Can do.

In the present invention, pyrrolidinium ions (III-s) that can be more preferably used include: R ¹ is hydrogen, methyl, ethyl, or phenyl; and R ^{2 to} R ⁹ are each independently hydrogen or Mention may be made of methyl.

As the imidazolidinium ion (III-t) that can be more preferably used in the present invention, R ^{1 to} R ⁴ are independently of each other hydrogen, methyl, ethyl or phenyl, R ² and R ³ and Mention may be made of those in which R ^{5 to} R ⁸ are independently of each other hydrogen or methyl.

In the present invention, ammonium ions (III-u) that can be used more preferably include those in which R ^{1 to} R ³ are each independently C _{1 to} C ₁₈ alkyl, or R ¹ and R ² are And 1,5-pentylene or 3-oxa-1,5-pentylene, and R ³ is C ₁ -C ₁₈ alkyl, 2-hydroxyethyl or 2-cyanoethyl. Particularly preferred are methyl-tri- (1-butyl) ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.

  Tertiary amines that can derive quaternary ammonium ions of general formula (III-u) by quaternization with R include diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine. , Diethylhexylamine, diethyloctylamine, diethyl- (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctyl Amine, di-n-propyl- (2-ethylhexyl) amine, diisopropylethylamine, diisopropyl-n-propylamine, diisopropylbutylamine, diisopropylpentylamine, diisopropylhexylamine, diisopropyloctylamine, diisopropyl -(2-ethylhexyl) -amine, di-n-butylethylamine, di-n-butyl-n-propylamine, di-n-butyl-n-pentylamine, di-n-butylhexylamine, di-n- Butyloctylamine, di-n-butyl- (2-ethylhexyl) -amine, Nn-butylpyrrolidine, N-sec-butylpyrrolidine, N-tert-butylpyrrolidine, Nn-pentylpyrrolidine, N, N- Dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-di-n-butylcyclohexylamine, Nn-propylpiperidine, N-isopropylpiperidine, Nn-butylpiperidine, N-sec-butylpiperidine, N-tert-butylpiperidine, Nn-pentylpiperidine, Nn-butyl Ruphorin, N-sec-butylmorpholine, N-tert-butylmorpholine, Nn-pentylmorpholine, N-benzyl-N-ethylaniline, N-benzyl-Nn-propylaniline, N-benzyl-N-isopropyl Aniline, N-benzyl-Nn-butylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di-n-butyl-p-toluidine, diethylbenzylamine And di-n-propylbenzylamine, di-n-butylbenzylamine, diethylphenylamine, di-n-propylphenylamine and di-n-butylphenylamine.

  In the present invention, suitable tertiary amines include diisopropylethylamine, diethyl-tert-butylamine, diisopropylbutylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine, and pentyl. Isomeric tertiary amines can be mentioned, and more preferred tertiary amines can include di-n-butyl-n-pentylamine and pentyl isomeric tertiary amines. A more preferred tertiary amine having three identical substituents can include triallylamine.

Examples of the guanidinium ion (III-v) that can be preferably used in the present invention include those in which R ^{1 to} R ⁵ are methyl, and more preferable guanidinium ion (III-v) is: N, N, N ′, N ′, N ′ ′, N ′ ′-hexamethylguanidinium.

In the present invention, as the corinium ion (III-w) that can be preferably used, R ¹ and R ² are each independently methyl, ethyl, 1-butyl or 1-octyl, and R ³ is Hydrogen, methyl, ethyl, acetyl, —SO ₂ OH or PO (OH) ₂ , or R ¹ is methyl, ethyl, 1-butyl or 1-octyl, and R ² is —CH ₂ —CH _{2. A 2-} OR ⁴ group, wherein R ³ and R ⁴ are independently of each other hydrogen, methyl, ethyl, acetyl, —SO ₂ OH or PO (OH) ₂ , or R ¹ is —CH ₂ —CH ₂ OR ⁴ group, R ² is —CH ₂ —CH ₂ —OR ⁵ group, and R ^{3 to} R ⁵ are independently of each other hydrogen, methyl, ethyl, acetyl, —SO ₂ OH. or PO _{(OH) 2} Mention may be made of a certain thing.

As more preferred corinium ion (III-w), R ³ is hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy- 3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy- 5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9- Trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy Ci-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

  Particularly preferred corinium ions (III-w) include trimethyl-2-hydroxyethylammonium, dimethyl-bis-2-hydroxyethylammonium or methyl-tris-2-hydroxyethylammonium.

In the present invention, phosphonium ions (III-x) that can be preferably used include R ^{1 to} R ³ independently of one another, C _{1 to} C ₁₈ alkyl, particularly butyl, isobutyl, 1-hexyl or 1-hexyl. Mention may be made of octyl.

  Of the above heterocyclic cations, pyridinium ions, pyrazolinium, pyrazolium ions, imidazolinium and imidazolium ions are preferred, and ammonium and corinium ions are more preferred.

  In the present invention, particularly preferable ions include 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- ( 1-dodecyl) pyridinium, 1- (1-tetradecyl) pyridinium, 1- (1-hexadecyl) pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2- Methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-tetradecyl)- 2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2- Tilpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1 -(1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1 , 5-diethyl-2-methylpyridinium, 1- (1-butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium, 1- (1-octyl) ) -2-methyl-3-ethylpyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradeci) ) -2-methyl-3-ethylpyridinium, 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium, 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) imidazolium, 1- (1-octyl) imidazolium, 1- (1-dodecyl) imidazolium, 1- (1-tetradecyl) imidazolium, 1- (1-hexadecyl) imidazolium, 1,3-dimethylimidazolium, 1- Ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-hex Sadecyl) -3-methylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3 -Dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium and 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4 -Trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4 , 5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-buty Mention may be made of imidazolium, 1,4,5-trimethyl-3-octylimidazolium, trimethyl-2-hydroxyethylammonium, dimethyl-bis-2-hydroxyethylammonium, and methyl-tris-2-hydroxyethylammonium. .

で示されるカルボン酸イミド、ビス（スルホニル）イミドおよびスルホニルイミドや、一般式：

で示されるメチドを挙げることができる。 Next, as an anion of the ionic liquid, in principle, all anions can be used. Examples of the anion [Y] ⁿ⁻ of the ionic liquid include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₃ ) ₂ N ⁻ , Halides and halogen-containing compounds represented by CF ₃ CO ₂ , CCl ₃ CO ₂ , CN ⁻ , SCN ⁻ , OCN ⁻ , and general formulas: SO ₄ ²⁻ , HSO ₄ ⁻ , SO ₃ ²⁻ , HSO ₃ ⁻ , _{^{R a OSO 3 -, R a}} SO 3 - sulfate represented by, and sulfites and sulfonates of the general _{^{formula: PO 4 3-, HPO 4 2-}} , H 2 PO 4 -, R a PO 4 2- Phosphonic acid represented by the general formulas: R ^a HPO ₃ ⁻ , R ^a R ^b PO ₂ , R ^a R ^b PO ₃ ^— , and phosphates represented by HR ^a PO ₄ ⁻ and R ^a R ^b PO ₄ ^— Salts and phosphinates, Phosphate represented by the general formulas: PO ₃ ³⁻ , HPO ₃ ²⁻ , H ₂ PO ₃ ⁻ , R ^a PO ₃ ²⁻ , R ^a HPO ₃ ⁻ , R ^{a Rb} PO ₃ ⁻ , and the general formula : R ^a R ^b PO ₂ , R ^a HPO ₂ , R ^a R ^b PO ⁻ , phosphonite and phosphite represented by R ^a HPO ⁻ , and carboxylic acid represented by the general formula: R ^a COO ⁻ And general formulas: BO ₃ ³⁻ , HBO ₃ ²⁻ , H ₂ BO ₃ ⁻ , R ^a R ^b BO ₃ ⁻ , R ^a HBO ₃ ⁻ , R ^a BO ₃ ²⁻ , B (OR ^a ) (OR ^b ) ) (OR ^c ) (OR ^d ) ⁻ , B (HSO ₄ ) ⁻ , B (R ^a SO ₄ ) ⁻ , and general formulas: R ^a BO ₂ ²⁻ , R ^a R ^b BO ⁻ Or boronic acid salt represented by the general formula: SiO ₄ ⁴⁻ , HSiO ₄ ³⁻ , H ₂ SiO ₄ ²⁻ , H ₃ SiO ₄ ⁻ , R ^a SiO ₄ ^{3 −} , R ^a R ^b SiO ₄ ²⁻ , R ^a R ^b R ^c SiO ₄ ⁻ , HR ^a SiO ₄ ²⁻ , H ₂ R ^a SiO ₄ ⁻ , HR ^a R ^b SiO ₄ ^— , silicates and silicate esters, and general formulas: R ^a SiO ₃ ³⁻ , R ^a R ^b SiO ₂ ²⁻ , R ^a R ^b R ^c SiO ⁻ , R ^a Alkyl- or arylsilane salts represented by R ^b R ^c SiO ₃ ⁻ , R ^a R ^b R ^c SiO ₂ , R ^a R ^b R ^c SiO ₃ ²⁻ , or a general formula:

Carboxylic acid imide, bis (sulfonyl) imide and sulfonylimide represented by the general formula:

Can be mentioned.

In the above structural formula, R ^a , R ^b , R ^c and R ^d are independently of each other hydrogen, (i) C ₁ -C ₃₀ alkyl, (ii) one or more non-adjacent oxygen and / or sulfur atoms, And / or C ₂ -C ₁₈ alkyl, (iii) C ₆ -C ₁₄ aryl, (iv) C ₅ -C ₁₂ cycloalkyl, (v) or oxygen interrupted by one or more substituted or unsubstituted imino groups Represents a 5-membered to 6-membered heterocyclic group containing a nitrogen and / or sulfur atom. Where two of these are both unsaturated, saturated, or aromatic, optionally interrupted by one or more oxygen and / or sulfur atoms, and / or one or more unsubstituted or substituted imino groups A ring can be formed, and (i) to (v) can each be substituted with a functional group, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocyclic group.

  In the present invention, as (i), for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4- Trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, α, α- Dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonyl Ethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolane-2 -Yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxy Propyl, 2-octyloxyethyl, chloromethyl, trichloromethyl, trifluoromethyl, 1,1-dimethylbutyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2 -Phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2- Droxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2 -Hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl, and their functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and And / or those substituted with a heterocyclic group.

  In the present invention, as (ii), for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7- Hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5,10 -Oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-dioxaundecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5- Xanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5 , 10-oxatetradecyl, and their functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or substituted with heterocyclic groups.

Among these, when two substituents form a ring, they together are, for example, 1,3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1- Oxa-1,3-propylene, 2-oxa-1,3-propenylene, 1-aza-1,3-propenylene, 1-C ₁ -C ₄ alkyl-1-aza-1,3-propenylene, 1,4 It is preferably -buta-1,3-dienylene, 1-aza-1,4-buta-1,3-dienylene or 2-aza-1,4-buta-1,3-dienylene.

  In the present invention, the number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is not particularly limited, but is limited by the size of the substituent or ring unit. In general, there are 5 or less, preferably 4 or less, or particularly preferably 3 or less in a particular substituent. Also, it is generally preferred that at least 1, preferably at least 2 carbon atoms are present between 2 heteroatoms.

  Substituted and unsubstituted imino groups can include, for example, imino, methylimino, isopropylimino, n-butylimino, or tert-butylimino.

Here, the “functional group” means, for example, carboxyl, carboxamide, hydroxyl, di- (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ alkoxycarbonyl, cyano or C ₁ -C ₄ alkoxy below. To do. In this _case, C 1 -C ₄ alkyl are methyl, ethyl, propyl, isopropyl, n- butyl, sec- butyl or tert- butyl.

  In the present invention, (iii) includes, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethyl Phenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2, 4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4 -Or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl and their functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or The thing substituted by the heterocyclic group can be mentioned.

  In the present invention, as (iv), for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, Saturated or unsaturated bicyclic systems such as butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, and norbornyl or norbornenyl, and their functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or Or the thing substituted by the heterocyclic group can be mentioned.

  In the present invention, (v) is, for example, furyl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxyfuryl, dimethoxypyridyl, difluoro List pyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl and those substituted with these functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocyclic groups Can do.

The above ionic liquids may be used alone or in combination of two or more. In the present invention, an imidazolium cation is particularly preferable. More preferably, the 1- and 3-positions or the 1-, 2- and 3-positions of the imidazolium ring are substituted with a (C ₁ -C ₆ ) alkyl group. As the imidazolium cation, 1-ethyl-3-methylimidazolium, 1,3-dimethylimidazolium or 1-butyl-3-methylimidazolium cation is particularly suitable.

In the present invention, neither the cation of the ionic liquid nor the corresponding anion is particularly limited. Anions include halides, perchloric acid, pseudohalides, sulfuric acid, especially hydrogen sulfate, sulfurous acid, sulfonic acid, phosphoric acid, alkyl phosphates, particularly mono- and / or dialkyl phosphate anions (preferred alkyl groups are methyl And an carboxylic acid anion, particularly a C _{1 to} C ₆ carboxylate anion (preferably an acetic acid or propionate anion). Halide ions are present as chloride, bromide and / or iodide ions, pseudohalide ions are present as cyanide, thiocyanate and / or cyanate ions, and C ₁ -C ₆ carboxylic acids It is particularly preferred that the ions are present as formic acid, acetic acid, propionic acid, butyric acid, hexanoic acid, maleic acid, fumaric acid, oxalic acid, lactic acid, pyruvic acid, methanesulfonic acid, tosylate and / or alkanesulfate ions.

The following suitable anions may also be mentioned: R ^a —COO ⁻ , R ^a —SO ₃ ^— , R ^a R ^b PO ₄ ^— (wherein R ^a and R ^b have the above-mentioned meanings). In particular, there are anions of (CH ₃ O) ₂ PO ₂ and (C ₂ H ₅ O) ₂ PO ₂ and benzoate anions, preferably (C ₂ H ₅ O) ₂ PO ₂ and benzoic acid anions. included.

  In the present invention, a cation and an anion can be appropriately combined. Particularly preferable ionic liquids include 1-ethyl-3-methylimidazolium acetate, 1,3-dimethylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1 -Ethyl-3-methylimidazolium diethyl phosphate, 1-methyl-3-methylimidazolium dimethyl phosphate, 1-methyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium octanoate, Examples include 1,3-diethylimidazolium acetate and 1-ethyl-3-methylimidazolium propionate. Of these, 1-ethyl-3-methylimidazolium acetate, 1,3-dimethylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1- Methyl-3-methylimidazolium dimethyl phosphate, 1,3-diethylimidazolium acetate and 1-ethyl-3-methylimidazolium propionate.

  In the present invention, the cation and anion can be appropriately selected according to the purpose. Particularly preferred anions and cations are shown below.

The ^anion, R a COO ^- (wherein ^{R a} is preferably an alkyl, especially _C 1 -C ₈ alkyl, more preferably _C 1 -C ₃ alkyl or phenyl); phosphate (preferably dialkyl - Phosphate, especially di- (C ₁ -C ₃ alkyl) phosphate, dimethyl-phosphate, diethyl-phosphate and di-n-propyl phosphate are particularly preferred; phosphonates (especially O-alkylalkyl-phosphonates, O-methyl) Methyl-phosphonate, O-methyl-ethyl-phosphonate, O-ethyl-methyl-phosphonate and O-ethylethyl-phosphonate are particularly preferred).

  Examples of the cation include compounds of the above formula (III-e), particularly 1-ethyl-3-methylimidazolium (EMIM), 1-butyl-3-methylimidazolium (BMIM), 1-ethyl-2,3-dimethyl. Imidazolium (EMMIM) and 1-butyl-2,3-dimethylimidazolium (BMMIM); compounds of the above formula (III-a), preferably N-alkyl-pyridinium, more preferably N-methylpyridinium, N-ethyl Pyridinium, N-methyl-2-methylpyridinium, N-methyl-3-methylpyridinium, N-ethyl-2-methylpyridinium and N-ethyl-3-methylpyridinium; compounds of formula (III-f) above, preferably Mention may be made of 1,2,4-trimethylpyrazolium.

In the present invention, R ^a COO ⁻ as an anion, ^a combination of the compound of the above formula (III-e) as a cation, a phosphate as an anion, and a combination of the compound of the above formula (III-e) as a cation are particularly preferable. It is.

Hereinafter, the present invention will be described more specifically with reference to examples.
The ethyl-3-methylimidazolium diethylene phosphate as the ionic liquid was analyzed by thermogravimetric analysis and TDS-GCMS according to the following.

<Thermogravimetric analysis (TGA)>
When a new ionic liquid was heated in an environment of 140 ° C., about 5.4 masses of components contained as impurities during synthesis were confirmed in the initial stage of heating. Further, when the heating was further continued, a weight reduction was gradually confirmed.

<Heat desorption-gas chromatograph mass spectrometry (TDS-GCMS)>
First, a new ionic liquid is heated under the following conditions to adsorb the generated gas, then desorbed by heating and analyzed by GCMS (TDS-GCMS) to remove volatile impurities contained in the ionic liquid. analyzed. Regarding the analysis conditions, the heating temperature was 140 ° C., the heating time was 5 minutes, and GC / MS manufactured by Agilent was used as the analyzer.

  As a result of the analysis, impurities contained as ionic liquid synthetic raw materials such as methylimidazole and triethyl phosphate were detected.

  Next, the ionic liquid repeatedly used for fiber spinning at 100 ° C. was analyzed under the same conditions. As a result of analysis, the components detected in the new ionic liquid are not detected, and there are components estimated to be generated by oxidative decomposition, such as components having a structure that is presumed that the components of the ionic liquid are oxidized, and acetic acid. was detected. This point almost coincided with the result of 1H-NMR analysis performed on the same ionic liquid sample.

  In addition, when the ionic liquid sample for analysis was heated in a nitrogen atmosphere, the detected amount of the oxidizing component was small. This is considered to be because the oxidation of the ionic liquid was suppressed. This point was supported by the fact that no carbonyl group (oxide) was detected in the FT-IR (Fourier transform infrared spectrophotometer) spectrum evaluation for the same ionic liquid sample.

  As a result of the above, by conducting analysis using TGA and TDS-GCMS, the thermal stability of ionic liquids, which are generally considered to have high thermal stability, can be evaluated for volatile components such as impurities and thermal decomposition behavior. Was confirmed.

Claims (2)

  To evaluate the thermal stability of the ionic liquid and the compounds produced by thermal decomposition of the ionic liquid by analyzing the ionic liquid using thermal mass spectrometry and thermal desorption-gas chromatography mass spectrometry. An ionic liquid evaluation method characterized by the above.   An ionic liquid is selected using an evaluation result obtained by the ionic liquid evaluation method according to claim 1.