Inorganic-organic hybrid ionic liquid

Abstract

Provided is a composite of an ionic liquid and a polyacid, which has performance suitable for use as an acid catalyst or a proton conductor and is in a liquid state at room temperature. 【Solution means】A composite represented by the general formula (I): Z p L q X. In the formula (I), Z represents an amphoteric ion compound represented by the general formula (II), JPEG2026113438000012.jpg22170 L represents T m+ (T is any one of the elements H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ag, and m is an integer of 1 to 3 corresponding to the above elements.), and X is [MQ 12 O 40 n- (M is any one of the elements P, Si, Ge, Co, As, Fe, Al, Zn or B or H2, Q is any one of the elements W or Mo, and n is an integer of 1 to 6 corresponding to the above elements), etc., p represents a number of 1 to 6, and q represents a number of 0 to 5.​

Description

Technical Field

[0001] The present invention relates to a composite composed of an acid catalyst, an ionic liquid (particularly an imidazolium salt-based ionic liquid) that can be used as a proton conductor, and a polyacid.

Background Art

[0002] Ionic liquids are ionic substances in a liquid state at room temperature and are expected to be applied as electrolytes and catalysts. As ionic liquids, for example, alkylammonium-based ionic liquids, imidazolium salt-based ionic liquids, etc. are known. On the other hand, inorganic cluster anions called polyacids are known to exhibit strong acidity and proton conductivity when the counter cation is a proton. These ionic liquids and polyacids can be complexed, and for example, the following complexes are known.

[0003] Non-Patent Document 1 describes a composite composed of an alkylammonium-based ionic liquid having a polyether chain: (CH3)(C 18 H 37 )N + [(CH2CH2O) n H][(CH2CH2O) m H]Cl - and a polyacid: H3PW 12 O 40 It is also described that the composite is in a liquid state at room temperature. Note that the composite of Non-Patent Document 1 has not been obtained as a single crystal, and its molecular structure is not clear.

[0004] Non-Patent Document 2 describes a composite composed of an imidazolium-based ionic liquid, a pyridinium-based ionic liquid or an alkylammonium-based ionic liquid having a sulfo group and a polyacid, that is, [(CH3)C3H3N2 + (C3H6-SO3H)]3PW 12 O 40 3- 、[C5H5N + (C3H6-SO3H)]3PW 12 O 403- (C2H5)3N+(C3H6-SO3H)]3PW 12 O 40 3- The document mentions C, and also states that the composite is in a solid state at room temperature. Furthermore, Non-Patent Document 2 suggests that the composite may be used as an acid catalyst in the esterification reaction of citric acid and 1-butanol. However, the composite described in Non-Patent Document 2 has not been obtained as a single crystal, and its molecular structure is not clear. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] AB Bourlinos, K. Raman, R. Herrera, Q. Zhang, LA Archer, EP Giannelis, “A Liquid Derivative of 12-Tungstophosphoric Acid with Unusually High Conductivity”, J. Am. Chem. Soc. 2004, 126, 15358. [Non-Patent Document 2] Y. Leng, J. Wang, D. Zhu, X. Ren, H. Ge, L. Shen, “Heteropolyanion-Based Ionic Liquids: Reaction-Induced Self-Separation Catalysts for Esterification”, Angew. Chem. Int. Ed. 2009, 48, 168. [Disclosure of the Invention] [Problems that the invention aims to solve]

[0006] As described in Non-Patent Literature 2, it is expected that an ionic liquid with improved acid catalytic activity and proton conductivity can be obtained by compounding an ionic liquid, such as an imidazolium salt system into which sulfo groups have been introduced, with a strongly acidic polyacid. However, no such compound that remains liquid at room temperature has been obtained to date. A compound that remains liquid at room temperature would be useful in applications as a catalyst or proton conductor, and could, for example, be used as a catalyst that facilitates phase separation even in liquid-phase reactions.

[0007] The present invention aims to provide a composite of an ionic liquid and a polyacid that has properties suitable for applications such as acid catalysts and proton conductors, and that remains in a liquid state at room temperature. [Means for solving the problem]

[0008] The inventors of this invention have identified a sulfonate group (-SO3 - Based on the discovery that a complex (inorganic-organic hybrid ionic liquid) that remains liquid at room temperature can be obtained by compounding an imidazolium-based ionic liquid, which has an alkylene group of a certain number of carbon atoms and an alkylpolyoxyethylene group or alkyl group of a certain length introduced together with a neutral polyacid compound (e.g., heteropoly acid) in a solvent, and that single crystals can be obtained by slowly volatilizing this liquid complex, and that crystal structure analysis was successful and revealed to contain protons, the present invention was completed.

[0009] In other words, the present invention provides the following in one aspect. [Section 1] A complex represented by the following general formula (I). Z p L q X (I) In formula (I), Z represents a zwitterionic compound represented by the following general formula (II): [ka] In formula (II), R1 is R'―(OC2H5) r —(R' represents an alkyl group with 1 to 5 carbon atoms, and r represents an integer from 1 to 5.) or represents an alkyl group with 8 to 18 carbon atoms, R 2 This represents an alkylene group with 2 to 5 carbon atoms. R 3 is a sulfonate group (―SO3 - ), carboxylate group (―COO - ) or phosphate group (―PO4 3- ), represents, L is T m+ (T represents one of the elements H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, or Ag, and m is an integer from 1 to 3 corresponding to the above element.) X is [MQ 12 O 40 ] n- (M is one of the elements P, Si, Ge, Co, As, Fe, Al, Zn, or B, or H2; Q is one of the elements W or Mo; and n is an integer from 1 to 6 corresponding to the above elements.) [M'2Q' 18 O 62 ] 6- (M' is either P or As, and Q' is either W or Mo.) [Mo6O 19 ] 2- [Mo8O 26 ] 4- [V 10 O 28 ] 6- , or [W 10 O 32 ] 4- This represents a polyacid, p represents a number from 1 to 6. q represents a number from 0 to 5. The value of (net charge of Z × p) + (charge of L × q) is equal to the absolute value of the charge of X. [Section 2] The aforementioned R 1 ga R'―(OC2H5) r —(The definition is the same as above.) A composite as described in item 1. [Section 3] The aforementioned R 3The complex described in item 1, wherein represents an alkylene group (propylene group) with 3 carbon atoms. [Section 4] The aforementioned R 3 is a sulfonate group (―SO3 - The complex described in item 1, which represents ). [Section 5] A catalyst comprising a complex described in any one of items 1 to 4. [Section 6] A proton conductor comprising a composite as described in any one of items 1 to 4. [Section 7] The complex represented by the following general formula (I): Z p L q X (I) In formula (I), Z represents a zwitterionic compound represented by the following general formula (II): [ka] In formula (II), R 1 is R'―(OC2H5) r —(R' represents an alkyl group with 1 to 5 carbon atoms, and r represents an integer from 1 to 5.) or represents an alkyl group with 8 to 18 carbon atoms, R 2 This represents an alkylene group with 2 to 5 carbon atoms. R 3 is a sulfonate group (―SO3 - ), carboxylate group (―COO - ) or phosphate group (―PO4 3- ), represents, L is T m+ (T represents one of the elements H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, or Ag, and m is an integer from 1 to 3 corresponding to the above element.) X is [MQ 12 O 40 ] n- (M is one of the elements P, Si, Ge, Co, As, Fe, Al, Zn, or B, or H2; Q is one of the elements W or Mo; and n is an integer from 1 to 6 corresponding to the above elements.) [M'2Q' 18O 62 ] 6- (M' is either P or As, and Q' is either W or Mo.) [Mo6O 19 ] 2- [Mo8O 26 ] 4- [V 10 O 28 ] 6- , or [W 10 O 32 ] 4- This represents a polyacid, p represents a number from 1 to 6. q represents a number from 0 to 5. The value of (net charge of Z × p) + (charge of L × q) is equal to the absolute value of the charge of X. A method for manufacturing, A method for producing Z, comprising the step of reacting a reaction material containing a zwitterionic compound represented by the following general formula (II) for the composition of Z, a reaction material for the composition of L, and a reaction material for the composition of X in a quantity ratio that satisfies the definitions of p and q. [Section 8] The aforementioned R 1 ga R'―(OC2H5) r A manufacturing method described in item 7, which represents (the definition is the same as above). [Section 9] The aforementioned R 3 The manufacturing method described in item 7, wherein represents an alkylene group (propylene group) having 3 carbon atoms. [Section 10] The aforementioned R 3 is a sulfonate group (―SO3 - The manufacturing method described in item 7, which represents ). [Effects of the Invention]

[0010] The composite according to the present invention (inorganic-organic hybrid ionic liquid) is in a liquid state even at room temperature, and due to its ionic liquid properties and ease of phase separation in liquid-phase reactions, it can be easily recovered and reused, making it suitable as an acid catalyst for hydrolysis reactions, oxidation reactions, hydration reactions, etc. Furthermore, the composite according to the present invention has a certain level of proton conductivity (preferably with a conductivity of 10⁻¹⁰). 3 Scm-1 Because it is a proton conductor exhibiting a specific order of magnitude, it can be used as a practical proton transport agent, for example, for inclusion in fuel cell separators. The composite according to the present invention also exhibits excellent heat resistance (thermal stability), and can maintain a certain level of proton conductivity (conductivity) even at relatively high temperatures (e.g., above 100°C). Furthermore, by using the composite according to the present invention, which is in a liquid state at room temperature, and removing the solvent, it is possible to prepare a solid composite in the form of a powder or plate, or to recover it as a single crystal. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 shows the powder X-ray analysis pattern of the composite: PE3ImSO3-PMo12 obtained as a powdered solid according to Example 1-2. [Figure 2] Figure 2 shows the crystal structure of the composite obtained as a single crystal in Example 1-2: PE3ImSO3-PMo12 (hydrogen atoms and solvent molecules are omitted). [Figure 3] Figure 3 shows the powder X-ray analysis pattern of the composite obtained as a powdered solid according to Example 2-2: PE3ImSO3-PW12. [Figure 4] Figure 4 shows the crystal structure of the composite obtained as a single crystal in Example 2-2: PE3ImSO3-PW12 (hydrogen atoms and solvent molecules are omitted). [Figure 5] Figure 5 shows the crystal structure of the composite EPE3ImSO3-PMo12 obtained as plate-like crystals in Example 3 (hydrogen atoms and solvent molecules are omitted). [Figure 6] Figure 6 shows the crystal structure of the composite EPE3ImSO3-PW12 obtained as a plate-like crystal in Example 4 (hydrogen atoms and solvent molecules are omitted). [Modes for carrying out the invention]

[0012] -Complex- The complex of the present invention is represented by the general formula (I). In formula (I), Z corresponds to an imidazolium salt compound, and X corresponds to a polyacid. Z p L q X (I)

[0013] In formula (I), Z represents a zwitterionic compound represented by the following general formula (II). The zwitterionic compound represented by general formula (II) corresponds to a compound referred to as an "imidazolium salt-based ionic liquid" in this specification.

Chemical formula

[0014] In formula (II), R 1 represents R’-(OC2H5) r -(where R’ represents an alkyl group having 1 to 5 carbon atoms and r represents an integer of 1 to 5) or an alkyl group having 8 to 18 carbon atoms. In one embodiment of the present invention, it is preferable that R’ represents an alkyl group having 1 carbon atom (methyl group) and r represents 3, that is, R 1 represents CH3-(OC2H5)3-.

[0015] In formula (II), R 2 represents an alkylene group having 2 to 5 carbon atoms, and R 3 represents a sulfonate group (―SO3 - ), a carboxylate group (―COO - ) or a phosphate group (―PO4 3- ). Since the net charge of the zwitterionic compound of formula (II) is such that the charge of the quaternary ammonium ion of the imidazolium ring is +1, when R 3 is a sulfonate group or a carboxylate group with a charge of -1, it becomes 0, and when R 3 is a sulfate group with a charge of -3, it becomes -2. In one embodiment of the present invention, it is preferable that R 2 represents an alkylene group having 3 carbon atoms (propylene group) and / or R 3 represents a sulfonate group (―SO3 - ).

[0016] In equation (I), L is T m+ (T represents one of the elements H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, or Ag, and m is an integer from 1 to 3 corresponding to the above element.)

[0017] In equation (I), X is [MQ 12 O 40 ] n- (M is one of the elements P, Si, Ge, Co, As, Fe, Al, Zn, or B, or H2; Q is one of the elements W or Mo; and n is an integer from 1 to 6 corresponding to the above elements.) [M'2Q' 18 O 62 ] 6- (M' is either P or As, and Q' is either W or Mo.) [Mo6O 19 ] 2- [Mo8O 26 ] 4- [V 10 O 28 ] 6- , or [W 10 O 32 ] 4- This represents a polyacid represented by [MQ 12 O 40 ] n- and [M'2Q' 18 O 62 ] 6- These can be collectively referred to as "heteropoly acids," and [Mo6O 19 ] 2- [Mo8O 26 ] 4- [V 10 O 28 ] 6- and [W 10 O 32 ] 4- These can be collectively referred to as "isopolyacids". In one embodiment of the present invention, X is a heteropolyacid, for example [MQ 12 O 40 ] n- It is preferable to represent this.

[0018] In equation (I), p represents a number (integer or decimal) from 1 to 6, and q represents a number (integer or decimal) from 0 to 5. The value of [Net charge of Z (0 or -2) × p] + [Charge of L (+1 to 3) × q] is equal to the absolute value of [Charge of X] (-1 to -6).

[0019] The definitions of p and q essentially mean that in the present invention, the complex consisting of the imidazolium salt compound has a sum of the positive charge (1 × p) and negative charge (1 × p or 3 × p) of p zwitterionic compounds Z and the positive charge (valence of L: 1 to 3 × q) of q metals L, which is equal to the absolute value of the negative charge (-1 to -6) of the polyacid X, and therefore the net charge of the entire compound is 0. As can be seen from the fact that q may be 0, the complex consisting of the imidazolium salt compound of the present invention does not necessarily have to contain metal L.

[0020] In one embodiment of the present invention, the compound represented by general formula (I) is the complex "PE3ImSO3-PMo" in Examples 1-1 and 1-2 described below. 12 This corresponds to the following, and in formula (I), Z, i.e., the compound represented by general formula (II), is a zwitterionic compound (R) represented by the following formula (II-1). 1 is CH3―(OC2H5)3―, R 2 H is -C3H6- (an alkylene group with 3 carbon atoms, i.e., a propylene group), R 3 ( is a sulfonate group), and L is H + And X is [PMo 12 O 40 ] 3- That is the case. [ka]

[0021] In one embodiment of the present invention, the compound represented by general formula (I) is the complex "PE3ImSO3-PW" in Examples 2-1 and 2-2 described below. 12 This corresponds to the above formula (II-1), where Z, i.e., the compound represented by formula (II), is a zwitterionic compound represented by formula (II-1), and L is H+ And X is [PW 12 O 40 ] 3- That is the case.

[0022] In one embodiment of the present invention, the compound represented by general formula (I) is the complex "EPE3ImSO3-PMo" in Example 3 below. 12 This corresponds to the following, and in formula (I), Z, i.e., the compound represented by general formula (II), is a zwitterionic compound (R) represented by the following formula (II-2). 1 is C2H5―(OC2H5)3―, R 2 H is -C3H6- (an alkylene group with 3 carbon atoms, i.e., a propylene group), R 3 ( is a sulfonate group), and L is H + And X is [PMo 12 O 40 ] 3- That is the case. [ka]

[0023] In one embodiment of the present invention, the compound represented by general formula (I) is the complex "EPE3ImSO3-PW" in Example 4 below. 12 This corresponds to the above formula (II-2), where Z, i.e., the compound represented by formula (II), is a zwitterionic compound represented by formula (II-2), and L is H + And X is [PW 12 O 40 ] 3- That is the case.

[0024] In one embodiment of the present invention, the compound represented by general formula (I) is the complex "C" in Example 5 described below. 10 ImSO3-PMo 12 This corresponds to the following, and in formula (I), Z, i.e., the compound represented by general formula (II), is a zwitterionic compound (R) represented by the following formula (II-3). 1 is C 10 H 23 —(C10 alkyl group), R 2H is -C3H6- (an alkylene group with 3 carbon atoms, i.e., a propylene group), R 3 ( is a sulfonate group), and L is H + And X is [PMo 12 O 40 ] 3- That is the case. [ka]

[0025] In one embodiment of the present invention, the compound represented by general formula (I) is the complex "C" in Example 6 described below. 10 ImSO3-PW 12 This corresponds to the above formula (II-3), where Z, i.e., the compound represented by formula (II), is a zwitterionic compound represented by formula (II-3), and L is H + And X is [PW 12 O 40 ] 3- That is the case.

[0026] Those skilled in the art will understand that the composite of the present invention is not limited to the above embodiments, and that various embodiments can be taken within the scope of the definition of general formula (I), taking into consideration the similarity of the chemical properties of the components defined as Z, L, and X.

[0027] -Method for manufacturing the composite- The method for producing the composite of the present invention is based on the general formula (I):Z p L qA method for producing a composite represented by X, comprising the step of reacting a reaction material containing a zwitterionic compound represented by general formula (II) for constituting Z (sometimes referred to herein as "reaction material Z"), a reaction material for constituting L (sometimes referred to herein as "reaction material L"), and a reaction material for constituting X (sometimes referred to herein as "reaction material X") in a quantity ratio that satisfies the definitions of p and q. The definitions and embodiments of general formula (I) and general formula (II) in the method for producing the composite of the present invention can be applied similarly to the matters described herein in relation to the composite of the present invention, and these definitions and embodiments can also be applied similarly to the reaction materials Z, L, and X used to carry out the method for producing the composite of the present invention. The selection of reaction materials Z, L, and X and the design of production conditions, etc. in the method for producing the composite of the present invention can be appropriately carried out according to the application of the obtained composite.

[0028] The zwitterionic compound represented by general formula (II) corresponding to Z can be expressed by applying known methods to imidazolium with R. 1 The area corresponding to and R 2 and R 3 By introducing the corresponding site, it can be synthesized in advance. Generally, (1) imidazole is reacted with an appropriate reagent (compound) to produce R in formula (II). 1 (2) The compound obtained by (1) above is reacted with an appropriate reagent, R 2 and R 3 By introducing a corresponding site, zwitterionic compounds represented by general formula (II) can be synthesized. 2 and R 3 These can be introduced in one step by using a reagent to which the corresponding sites are bound. The compound obtained by (1) above is also available commercially. A purified product, reaction solution, etc., containing such a zwitterionic compound represented by general formula (II) can be used as the reaction raw material Z.

[0029] The desired polyacid corresponding to X can be obtained commercially or synthesized in advance using known methods, and a purified product, reaction solution, etc., containing such polyacid can be used as the reaction raw material X.

[0030] The predetermined element corresponding to L may originate from the raw materials for synthesizing the predetermined polyacid corresponding to X, and may be bonded to the polyacid, or the initially bonded element may be replaced with other elements as needed. For example, if X is [PMo 12 O 40 ] 3- When representing this, the reaction raw material for constructing X is H3[PMo], which has H bonded to L. 12 O 40 ] can be used, but the compound can be used as both reaction material X and reaction material L. As seen in these embodiments, in the method for producing the composite of the present invention, reaction material L does not need to be a different substance from reaction material X, and may be the same substance.

[0031] The reaction materials Z, L, and X can be reacted by mixing them in a suitable solvent at room temperature in sufficient quantities to satisfy the definitions of p and q in general formula (I). Examples of reaction solvents include ethanol, acetonitrile, and acetone. After the reaction, the composite of the present invention can be recovered as a liquid substance (e.g., a highly viscous oily substance) by removing the solvent, for example, at atmospheric pressure and room temperature, yielding a composite with properties suitable for applications such as electrolytes and catalysts. Furthermore, by removing the solvent from the liquid composite of the present invention, the composite can be recovered as a solid substance (e.g., a powder or plate-like substance), yielding a composite with properties suitable for applications such as electrodes. The composite of the present invention can also be recovered as a single crystal by slowly removing the solvent, for example, at atmospheric pressure and room temperature, with ethanol being a preferred solvent in this case. The composite of the present invention can reversibly change between a solid (e.g., powder) state and a liquid state; for example, the composite in the former state can be converted to the latter state by exposing it to the vapor of a solvent (e.g., ethanol).

[0032] -Applications of the composite- The applications of the composite of the present invention are not particularly limited, and it can be used in the same applications as conventional composites composed of imidazolium salt-based ionic liquids and polyacids, or in the same applications as imidazolium salt-based ionic liquids or polyacids, respectively, based on the functional and property characteristics depending on the type of zwitterionic compound (Z) and polyacid (X) in general formula (I). For example, the composite of the present invention can be used as an acid catalyst because it can contain dissociable protons when H is selected as L in general formula (I), and it can also be used as an oxidation catalyst because the polyacid has oxidizing power. On the other hand, the composite of the present invention can also be used as a luminescent material when a rare earth element is selected as L in general formula (I). The composite of the present invention can also be used as a catalyst for electrochemical reactions by taking advantage of the redox ability of the polyacid, and can also be suitably used as a device for electrochemical reactions by taking advantage of its proton conductivity.

[0033] The composite material of the present invention has a certain level of proton conductivity. The level of proton conductivity of the composite material of the present invention is not particularly limited and may be at an appropriate level depending on the application, but the conductivity (electrical conductivity) should be, for example, at least 1 × 10⁻⁶. -5 Scm -1 Preferably at least 1 × 10 -4 Scm -1 Therefore, 1 × 10 -3 Scm -1 That is the case.

[0034] In one embodiment of the present invention, the composite of the present invention can be used as a catalyst for various reactions. Reactions in which the composite of the present invention can be used include, for example, hydrolysis reactions (e.g., the reaction to produce benzoic acid and methanol from methyl benzoate), hydration reactions (e.g., the reaction to produce t-butyl alcohol from isobutene and water), and oxidation reactions (e.g., the reaction to produce methacrylic acid from methacrylaldehyde (methacrolein)). The composite of the present invention may be used as a catalyst itself, or a preparation, product, etc., obtained by combining the composite of the present invention with other raw materials, components, etc., may be used as a catalyst.

[0035] In one embodiment of the present invention, the composite material of the present invention can be used as a proton conductor. The proton conductor can be used, for example, as a proton transport agent used as an electrolyte membrane (proton exchange membrane) in a hydrogen-oxygen fuel cell. The composite material of the present invention may be used as a proton conductor itself, or a preparation, product, etc., obtained by combining the composite material of the present invention with other raw materials, components, etc., may be used as a proton conductor such as a proton transport agent. [Examples]

[0036] [Synthesis Example 1] Synthesis of Ionic Liquid: PE3ImSO3 [ka]

[0037] 1,3-propanesultone (1.71 mmol, 9.20 g) was added to a toluene solution (3.5 mL) of 1-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-imidazole (1.71 mmol, 0.36 g), and the reaction was carried out under reflux conditions for 12 hours. After washing the reaction mixture with hexane, the solvent was removed to obtain 3-(1-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-imidazolium-3-yl)propanesulfonate (denoted as "PE3ImSO3" in this example) (0.551 g, yield: 95%).

[0038] [Synthesis Example 2] Synthesis of Ionic Liquid: EPE3ImSO3 [ka]

[0039] 1,3-propanesultone (3.0 mmol, 0.37 g) was added to a toluene solution (7.0 mL) of 1-(2-(2-(2-ethoxyethoxy)ethoxy)ethyl)imidazole (3.0 mmol, 0.70 g), and the reaction was carried out under reflux conditions for 12 hours. After washing the reaction mixture with hexane and removing the solvent, 3-(1-(2-(2-(2-ethoxyethoxy)ethoxy)ethyl)imidazole-3-ium-3-yl)propane-1-sulfonate (denoted as "EPE3ImSO3" in this example) was obtained (0.92 g, yield: 86%).

[0040] [Synthesis Example 3] Ionic Liquid: C 10 ImSO3 synthesis [ka]

[0041] 1,3-propanesultone (4.2 mmol, 0.99 g) was added to a toluene solution (8.5 mL) of 1-decylimidazole (4.2 mmol, 0.99 g) and the reaction was carried out under reflux conditions for 12 hours. After washing the reaction mixture with hexane, the solvent was removed and 3-(1-decyl-1H-imidazole-3-ium-3-yl)propane-1-sulfonate (in this example, "C" was used). 10 It is denoted as "ImSO3". A sample was obtained (1.26g, yield: 84%).

[0042] [Example 1-1] Composite: PE3ImSO3-PMo 12 Manufacturing of (oil-based substances) Phosphorus molybdate n-hydrate (H3PMo 12 O 40 • nH2O, in this example, "PMo 12 Dissolve 0.44 g of the polyacid (labeled as "[product name]" in 2 mL of ethanol. To this polyacid solution, add 2 mL of ethanol solution containing 0.20 g of PE3ImSO3 obtained according to Synthesis Example 1, and stir. Remove the solvent from the resulting solution using a rotary evaporator (EYELA N-1300V) and a diaphragm vacuum pump (EYELA NVP-2100) to obtain a highly viscous oily substance (0.54 g, yield: 85%). Elemental analysis: Calcd(C 36 H 93 N4S2PMo 12 O 63 ): C: 15.24, H: 3.30, N: 1.96%. Found: C: 15.13, H: 3.21, N: 2.11%.

[0043] [Examples 1-2] Composite: PE3ImSO3-PMo 12 Manufacturing of (powdered solids, single crystals) Phosphorus molybdate n-hydrate (H3PMo 12 O 40Dissolve 1.31 g of nH2O in 5 mL of ethanol. Add 2 mL of an ethanol solution containing 0.60 g of PE3ImSO3 obtained according to Synthesis Example 1 to this polyacid solution and stir. Divide the resulting solution into two equal parts (A and B). Remove the solvent from solution A at atmospheric pressure and room temperature, and remove the solvent from the resulting oily substance by vacuum drying at room temperature (using a freeze dryer) to obtain a powdered solid (0.54 g, yield: 85%) (Figure 1). Remove the solvent from solution B at atmospheric pressure and room temperature to obtain a single crystal (Figure 2). Crystal data: triclinic, P-1 (#2), a = 13.23830(15), b = 15.05140(17), c = 20.8328(4) Å, α = 83.1683(12), β = 89.4274(12), γ = 79.2280(9)°, V = 4048.62(10) Å 3 , Z = 2, R1= 0.0699 (I > 2σ(I)), wR2= 0.2077 (all data). FT-IR (KBr disk) (powder): 3143 (w), 3113 (w), 2960(w), 2925(w), 2868(w), 1631(w), 1562(w), 1446(w), 1352(w), 1208(w) , 1161(w), 1136(w), 1108(w)1063(m), 958(s), 881(m), 797(s), 607(w), 502(w). Elemental analysis (crystal): Calcd(C 26 H 67 N4S2PMo 12 O 60 ): C: 11.82, H: 2.56, N: 2.12%. Found: C: 11.91, H: 2.59, N: 1.98%.

[0044] Solid (powder) composite: PE3ImSO3-PMo 12 When exposed to ethanol vapor, the composite material became a liquid (Figure 2). These results clearly demonstrate that the change between the solid (powder) and liquid states occurs reversibly depending on the presence or absence of ethanol vapor.

[0045] Composite in liquid state (oil-like) obtained in Example 1-1: PE3ImSO3-PMo 12 The conductivity is 3.6 × 10 -5 ~3.4×10 -4 S cm -1 The temperature range was (20-100 °C). The solid-state (powdered solid) composite obtained in Example 1-2: PE3ImSO3-PMo 12 The conductivity is 8.8 × 10 -7 ~5.6×10 -4 S cm -1 The temperature range was (20-100°C).

[0046] [Example 2-1] Composite: PE3ImSO3-PW 12 Manufacturing of (oil-based substances) Phosphate tungstic acid n hydrate (H3PW) 12 O 40 • nH2O, in this example, "PW 12 Dissolve 0.65 g of the polyacid (labeled as "[product name]" in ethanol (2 mL). To this polyacid solution, add 2 mL of ethanol solution containing PE3ImSO3 (0.20 g) obtained according to Synthesis Example 1, and stir. Remove the solvent from the resulting solution using a rotary evaporator (EYELA N-1300V) and a diaphragm vacuum pump (EYELA NVP-2100) to obtain a highly viscous oily substance (0.58 g, yield: 82%). Elemental analysis: Calcd(C 36.5 H 83 N5S 2.5 PW 12 O 61 ): C: 11.28, H: 2.15, N: 1.80%. Found: C: 11.19, H: 2.28, N: 1.60%.

[0047] [Example 2-2] Composite: PE3ImSO3-PW 12 Manufacturing of (powdered solids, single crystals) Phosphate tungstic acid n hydrate (H3PW) 12 O 40Dissolve 1.70 g of nH2O in 5 mL of ethanol. Add 5 mL of an ethanol solution containing 0.52 g of PE3ImSO3 obtained according to Synthesis Example 1 to this polyacid solution and stir. Divide the resulting solution into two equal parts (A and B). Remove the solvent from solution A at atmospheric pressure and room temperature, and remove the solvent from the resulting oily substance by vacuum drying at room temperature (using a freeze-dryer) to obtain a powdered solid (1.93 g, yield: 87%) (Figure 3). Remove the solvent from solution B at atmospheric pressure and room temperature to obtain a single crystal (Figure 4). Crystal data: triclinic, P-1 (#2), a = 13.1608(4), b = 15.3076(4), c = 20.2396(6) Å, α = 84.058(2), β = 88.332(2), γ = 79.320(2)°, V = 3985.1(2) Å 3 , Z = 2, R1= 0.0960 (I > 2σ(I)), wR2= 0.3154 (all data). FT-IR (KBr disk) (powder): 3146 (w), 3112 (w), 2938(w), 2877(w), 1636(w), 1559(w), 1457(w), 1352(w), 1201(w), 1166(w), 11 39(w), 1079(m), 1041(w), 978(s), 897(m), 806(s), 619(w), 594(w), 518(m), 445(w). Elemental analysis (crystal): Calcd(C 32.5 H 71 N5S 2.5 PW 12 O 59 ): C: 10.29, H: 1.88, N: 1.85%. Found: C: 10.31, H: 1.91, N: 1.87%.

[0048] Composite in liquid state (oil-like) obtained in Example 2-1: PE3ImSO3-PW 12 The conductivity of the liquid (oil-like) composite obtained in Example 1-1 is PE3ImSO3-PMo 12 The conductivity (3.6 × 10 -5 ~3.4×10 -4 S cm-1 It is considered to be equivalent to (20-100°C). Composite in solid state (powdered solid) obtained in Example 2-2: PE3ImSO3-PW 12 The conductivity is 2.8 × 10⁻⁶. -6 ~2.1×10 -3 S cm -1 The temperature range was (20-100°C).

[0049] [Example 3] Composite: EPE3ImSO3-PMo 12 Manufacturing of (oil-like substances / plate-like crystals) Phosphorus molybdate n-hydrate (H3PMo 12 O 40 • 0.65 g of nH2O was dissolved in 2.5 mL of ethanol. To this polyacid solution, 2.5 mL of an ethanol solution containing 0.10 g of EPE3ImSO3 obtained according to Synthesis Example 2 was added and stirred. The solvent was gradually evaporated from the resulting solution to obtain a highly viscous oily substance (0.75 g, yield: 85%). When the solvent was continued to evaporate, green plate-like crystals EPE3ImSO3-PMo were found in the oily substance. 12 A precipitate formed. The solvent was then evaporated to obtain a glassy solid (Figure 5). FT-IR (KBr disk): 2934 (w), 1637 (m), 1562 (w), 1469 (w), 1349 (w), 1212 (w), 1173 (w), 1121 (w), 1095 (w), 1064 (m), 957 (s), 876 (m), 802 (s), 741 (m), 595 (w), 506 (w), 476 (w). Elemental analysis: Calcd(C 42 H 101 N6S3PMo 12 O 68 ): C: 16.50, H: 3.33, N: 2.75%. Found: C: 16.31;, H: 3.38, N: 2.69%. Crystal data: monoclinic, C2 / c (#15), a = 36.502(5), b = 10.7724(13), c = 23.247(3) Å, α = 90.000, β = 129.027(9), γ = 90.000°, V = 7101.1(18) Å 3 , Z = 4, R1= 0.0737 (I > 2σ(I)), wR2= 0.2053 (all data).

[0050] [Example 4] Composite: EPE3ImSO3-PW 12 Manufacturing of (oil-based substances / liquid crystals / plate-like crystals) Phosphate tungstic acid n hydrate (H3PW) 12 O 40 • 0.97 g of nH2O was dissolved in 2.5 mL of ethanol. To this polyacid solution, 2.5 mL of an ethanol solution containing 0.32 g of PE3ImSO3 obtained according to Synthesis Example 2 was added and stirred. The solvent was slowly evaporated to obtain a highly viscous oily substance (1.0 g, yield: 80%). Further evaporation of the solvent yielded liquid crystals and colorless plate-like crystals EPEImSO3(n=3)-PW 12 It precipitated (Figure 6). FT-IR(KBr disk): 3162 (w), 3107 (w), 2922 (w), 2863 (w), 1636 (w), 1559 (w), 1471 (w), 1351 (w), 1216 (w), 1173 (w), 1123 (w), 1080 (s), 1039 (w), 979 (s), 896 (m), 811 (s), 742 (m), 643 (w), 596 (w), 520 (w), 463 (w), 410 (w). Elemental analysis: Calcd(C 35 H 100 N5S 2.5 PW 12 O 71 ): C: 10.39, H: 2.49, N: 1.73%. Found: C: 10.14, H: 2.27, N: 1.70%. Crystal data: monoclinic, C2 / c (#15), a = 36.78(4), b = 10.734(11), c = 23.512(7) Å, α = 90.000, β = 129.655(16), γ = 90.000°, V = 7147(10) Å 3 , Z = 4, R1= 0.0468 (I > 2σ(I)), wR2= 0.1402 (all data).

[0051] [Example 5] Composite: C 10 ImSO3-PMo 12 (oil-like) manufacturing Phosphorus molybdate n-hydrate (H3PMo 12 O 40 • 0.18 g of nH2O was dissolved in ethanol (2.5 mL). To this polyacid solution, the C obtained according to Synthesis Example 3 was added. 10 A 2.5 mL ethanol solution containing 0.10 g of ImSO3 was added and the mixture was stirred. The solvent was gradually evaporated from the resulting solution, or removed using a rotary evaporator, to obtain a highly viscous oily substance (0.23 g, yield: 83%). FT-IR (KBr disk): 3158 (w), 3107 (w), 2957 (w), 2924 (m), 2854 (m), 1635 (w), 1562 (w), 1466 (w), 1168 (m), 1062 (m), 1044 (w), 957 (s), 880 (m), 800 (s), 741 (m), 617 (w), 526 (w), 502 (w), 459 (w), Elemental analysis: Calcd(C 70 H 141 N8S4PMo 12 O 55 ): C: 25.59, H: 4.33, N: 3.41%. Found: C: 25.72 H: 4.42, N: 3.71%.

[0052] [Example 6] Composite: C 10 ImSO3-PW 12 (oil-like) manufacturing Phosphate tungstic acid n hydrate (H3PW)12 O 40 • 0.18 g of nH2O was dissolved in ethanol (2.5 mL). To this polyacid solution, the C obtained according to Synthesis Example 3 was added. 10 A 2.5 mL ethanol solution containing 0.10 g of ImSO3 was added and the mixture was stirred. The solvent was gradually evaporated from the resulting solution, or removed using a rotary evaporator, to obtain a highly viscous oily substance (0.22 g, yield: 79%). FT-IR (KBr disk): 3149 (w), 3124 (w), 2955 (w), 2928 (m), 2858 (w), 1636 (w), 1561 (w), 1467 (w), 1168 (w), 1079 (m), 1045 (w), 979 (s), 898 (m), 812 (s), 743 (w), 667 (w), 641 (w), 625 (w), 596 (w), 524 (m), 437 (w). Elemental analysis: Calcd(C 52 H 109 N6S3PW 12 O 53 ): C: 17.37, H: 3.13, N: 2.03%. Found: C: 17.40, H: 2.98, N: 2.49%.

Claims

1. A complex represented by the following general formula (I). Z ｐ L ｑ X (I) In formula (I), Z represents a zwitterionic compound represented by the following general formula (II): 【Chemistry 1】 In formula (II), R １ is R'-(OC ２ H ５ ) ｒ —(R' represents an alkyl group with 1 to 5 carbon atoms, and r represents an integer from 1 to 5.) or represents an alkyl group with 8 to 18 carbon atoms, R ２ This represents an alkylene group with 2 to 5 carbon atoms. R ３ represents a sulfonate group (―SO ３ － ), a carboxylate group (―COO － ), or a phosphate group (―PO ４ ３－ ), and L is T ｍ＋ (T represents one of the elements H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, or Ag, and m is an integer from 1 to 3 corresponding to the above element.) X is [MQ １２ O ４０ ] ｎ－ (M is one of the elements P, Si, Ge, Co, As, Fe, Al, Zn, or B or H) ２ Here, Q is either the element W or Mo, and n is an integer from 1 to 6 corresponding to the above element. ) [M' ２ Q' １８ O ６２ ] ６－ (M' is either the element P or As, and Q' is either the element W or Mo.) [Mo ６ O １９ ] ２－ [Mo ８ O ２６ ] ４－ [V １０ O ２８ ] ６－ , or [W １０ O ３２ ] ４－ This represents a polyacid, p represents a number from 1 to 6. q represents a number from 0 to 5. The value of (net charge of Z × p) + (charge of L × q) is equal to the absolute value of the charge of X.

2. The aforementioned R １ ga R'―(OC ２ H ５ ) ｒ — (The definition is the same as above.) The composite according to claim 1.

3. The aforementioned R ３ The composite according to claim 1, wherein represents an alkylene group (propylene group) having 3 carbon atoms.

4. The aforementioned R ３ is a sulfonate group (-SO ３ － The composite according to claim 1, which represents ).

5. A catalyst comprising the complex according to any one of claims 1 to 4.

6. A proton conductor comprising the composite according to any one of claims 1 to 4.

7. The complex represented by the following general formula (I): Z ｐ L ｑ X (I) In formula (I), Z represents a zwitterionic compound represented by the following general formula (II): 【Chemistry 2】 In formula (II), R １ is R'-(OC ２ H ５ ) ｒ —(R' represents an alkyl group with 1 to 5 carbon atoms, and r represents an integer from 1 to 5.) or represents an alkyl group with 8 to 18 carbon atoms, R ２ This represents an alkylene group with 2 to 5 carbon atoms. R ３ The sulfonate group (-SO ３ － ), carboxylate group (-COO － ) or phosphate group (-PO ４ ３－ ), represents, L is T ｍ＋ (T represents one of the elements H, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, or Ag, and m is an integer from 1 to 3 corresponding to the above element.) X is [MQ １２ O ４０ ] ｎ－ (M is one of the elements P, Si, Ge, Co, As, Fe, Al, Zn, or B or H) ２ Here, Q is either the element W or Mo, and n is an integer from 1 to 6 corresponding to the above element. ) [M' ２ Q' １８ O ６２ ] ６－ (M' is either the element P or As, and Q' is either the element W or Mo.) [Mo ６ O １９ ] ２－ [Mo ８ O ２６ ] ４－ [V １０ O ２８ ] ６－ , or [W １０ O ３２ ] ４－ This represents a polyacid, p represents a number from 1 to 6. q represents a number from 0 to 5. The value of (net charge of Z × p) + (charge of L × q) is equal to the absolute value of the charge of X. A method for manufacturing, A method for producing Z, comprising the step of reacting a reaction material containing a zwitterionic compound represented by the following general formula (II) for the composition of Z, a reaction material for the composition of L, and a reaction material for the composition of X in a quantity ratio that satisfies the definitions of p and q.

8. The aforementioned R １ ga R'―(OC ２ H ５ ) ｒ A manufacturing method according to claim 7, which represents (the definition is the same as above).

9. The aforementioned R ３ The manufacturing method according to claim 7, wherein represents an alkylene group (propylene group) having 3 carbon atoms.

10. The aforementioned R ３ is a sulfonate group (-SO ３ － The manufacturing method according to claim 7, which represents ).

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