JP2012184197A - Metal complex and adsorbent, occlusion material, and separation material consisting of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal complex having gas adsorption property, gas occlusion property, and gas separation property.SOLUTION: The metal complex includes: a dicarboxylic acid compound (I) represented by formula (I); at least one metal ion selected from metal ions belonging to the group 2, the groups 7-10, and the group 12 in the periodic table; and a specific organic ligand (e.g. 1,2- bis(4-pyridyl)ethane) bidentately coordinatable with the metal ion. In the formula: R, R, R, R, Rand Rare the same or different mutually and each a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a formyl group, an acyloxy group, an alkoxycarbonyl group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group or a halogen atom.

Description

  The present invention relates to a metal complex and an adsorbent, occlusion material, and separation material comprising the same. More specifically, the present invention relates to a metal complex comprising a specific dicarboxylic acid compound, at least one metal ion, and a specific organic ligand capable of bidentate coordination with the metal ion. The metal complex of the present invention is an adsorbent for adsorbing carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, water vapor or organic vapor, It is preferable as an occlusion material for occlusion and a separation material for separation.

  So far, various adsorbents have been developed in fields such as deodorization and exhaust gas treatment. Activated carbon is a representative example, and is widely used in various industries such as air purification, desulfurization, denitration, and removal of harmful substances by utilizing the excellent adsorption performance of activated carbon. In recent years, the demand for nitrogen has increased for semiconductor manufacturing processes, etc., and as a method for producing such nitrogen, a method of producing nitrogen from air by pressure swing adsorption method or temperature swing adsorption method using molecular sieve charcoal is used. Has been. Molecular sieve charcoal is also applied to various gas separation and purification such as hydrogen purification from methanol cracked gas.

  When separating mixed gas by pressure swing adsorption method or temperature swing adsorption method, generally, molecular sieve charcoal or zeolite is used as the separation adsorbent, and separation is performed by the difference in the equilibrium adsorption amount or adsorption rate. . However, when separating the mixed gas based on the difference in the amount of equilibrium adsorption, the conventional adsorbents cannot selectively adsorb only the gas to be removed, so the separation factor becomes small, and the size of the apparatus is inevitable. . In addition, when separating the mixed gas based on the difference in adsorption speed, only the gas to be removed can be adsorbed depending on the type of gas, but it is necessary to perform adsorption and desorption alternately, and in this case, the apparatus still has to be large. I didn't get it.

  On the other hand, polymer metal complexes that cause a dynamic structural change by an external stimulus have been developed as adsorbents that give better adsorption performance (see Non-Patent Document 1 and Non-Patent Document 2). When this new dynamic structure change polymer metal complex is used as a gas adsorbent, a unique phenomenon is observed in which gas adsorption does not adsorb up to a certain pressure, but gas adsorption starts when a certain pressure is exceeded. Yes. In addition, a phenomenon has been observed in which the adsorption start pressure varies depending on the type of gas.

  When this phenomenon is applied to, for example, an adsorbent in a pressure swing adsorption type gas separation apparatus, very efficient gas separation is possible. In addition, the pressure swing width can be narrowed, contributing to energy saving. Furthermore, since it can contribute to miniaturization of the gas separation device, it is possible to increase cost competitiveness when selling high-purity gas as a product, of course, even when high-purity gas is used inside its own factory Since the cost required for the equipment that requires high purity gas can be reduced, the manufacturing cost of the final product can be reduced.

  However, the present situation is that cost reduction by further downsizing of the apparatus is required, and in order to achieve this, further improvement in adsorption performance and storage performance is required.

  A polymer comprising an aromatic dicarboxylic acid derivative, at least one divalent metal selected from copper, rhodium, chromium, molybdenum, palladium, zinc and tungsten, and an organic ligand capable of bidentate coordination with the metal A metal complex is disclosed (see Patent Document 1). However, what is described in the examples is a polymer metal complex composed of terephthalic acid, copper ion, and pyrazine, and dicarboxylic acid compounds other than terephthalic acid and organic ligands capable of bidentate coordination adsorb gas. No mention is made of the effect on the behavior.

  An aromatic dicarboxylic acid derivative, at least one divalent metal selected from copper, rhodium, chromium, molybdenum, palladium, zinc and tungsten, and an organic ligand having a pKa of 4 or more capable of bidentate coordination with the metal A polymer metal complex consisting of is disclosed (see Patent Document 2). However, what is described in the examples is a polymer metal complex composed of terephthalic acid, a copper ion, and 1,4-diazabicyclo [2.2.2] octane, which is a dicarboxylic acid compound other than terephthalic acid or a bidentate. No mention is made of the effect of coordinating organic ligands on gas adsorption behavior.

  A polymer metal complex composed of 2,6-naphthalenedicarboxylic acid, copper ion, and 1,2-bis (4-pyridyl) ethane is known (see Non-Patent Document 3). However, the amount of carbon dioxide adsorbed is small and the performance is insufficient. No mention is made of the effect of metal ions on gas adsorption behavior.

JP 2000-109485 A JP 2001-348361 A

Kazuhiro Uemura, Susumu Kitagawa, Future Materials, Volume 2, 44-51 (2002) Ryotaro Matsuda, Susumu Kitagawa, Petrotech, Vol. 26, 97-104 (2003) P. Kanoo, R.A. Matsuda, M .; Higuchi, S .; Kitagawa, T .; K. Maji, Chemistry of Materials, Vol. 21, pages 5860-5866 (2009)

  Therefore, an object of the present invention is to provide a metal complex that can be used as a gas adsorbent having a larger adsorption amount than the conventional one, a gas storage material having a larger effective occlusion amount than the conventional one, or a gas separation material that exhibits higher selectivity than the conventional one. It is to provide.

  The present inventors have intensively studied, and by using a metal complex comprising a dicarboxylic acid compound (I), at least one metal ion, and an organic ligand (II) capable of bidentate coordination with the metal ion, The inventors have found that the object can be achieved, and have reached the present invention.

That is, according to the present invention, the following is provided.
(1) The following general formula (I);

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each is a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group, a formyl group, an acyloxy group) A dicarboxylic acid compound (I) represented by an alkoxycarbonyl group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group or a halogen atom), group 2 of the periodic table, At least one metal ion selected from ions of metals belonging to Groups 7 to 10 and Group 12, and the following general formula (II);

(Wherein X and Y are the same or different and are CH ₂ , CH (OH), NH, an oxygen atom or a sulfur atom, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a formyl group, an acyloxy group, an alkoxycarbonyl group, a nitro group, a cyano group, an amino group, or a monoalkylamino. A metal complex comprising an organic ligand (II) capable of bidentate coordination to the metal ion represented by: a group, a dialkylamino group, an acylamino group, or a halogen atom.
(2) The metal complex according to (1), wherein the jungle gym skeleton has a structure in which a plurality of interpenetrations occur.
(3) The metal complex according to (1) or (2), wherein the metal ion is a zinc ion.
(4) The metal complex according to any one of (1) to (3), wherein the organic ligand (II) capable of bidentate coordination is 1,2-bis (4-pyridyl) ethane.
(5) An adsorbent comprising the metal complex according to any one of (1) to (4).
(6) The adsorbent is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or The adsorbent according to (5), which is an adsorbent for adsorbing organic vapor.
(7) An occlusion material comprising the metal complex according to any one of (1) to (4).
(8) The storage material is a storage material for storing carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, water vapor or organic vapor. The occlusion material according to (7).
(9) A separating material comprising the metal complex according to any one of (1) to (4).
(10) The separator is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or The separation material according to (8), which is a separation material for separating organic vapor.
(11) The separation according to (8), wherein the separation material is a separation material for separating methane and carbon dioxide, hydrogen and carbon dioxide, nitrogen and carbon dioxide, methane and ethane, ethane and ethylene, or air and methane. Wood.
(12) Dicarboxylic acid compound (I), at least one metal salt selected from salts of metals belonging to Groups 2, 7-10 and 12 of the periodic table, and bidentate coordination to the metal ion The method for producing a metal complex according to (1), wherein the organic ligand (II) is reacted in a solvent and precipitated.

  According to the present invention, the dicarboxylic acid compound (I), at least one metal ion selected from ions of metals belonging to Groups 2, 7-10 and 12 of the periodic table, and bidentate coordination to the metal ions The metal complex which consists of possible organic ligand (I) can be provided.

  Since the metal complex of the present invention is excellent in the adsorption performance of various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxidation It can be used as an adsorbent for storing materials, nitrogen oxides, siloxane, water vapor or organic vapor.

  Moreover, since the metal complex of the present invention is excellent in the occlusion performance of various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, It can also be used as a storage material for storing water vapor or organic vapor.

  Furthermore, since the metal complex of the present invention is excellent in the separation performance of various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, It can also be used as a separating material for separating sulfur oxides, nitrogen oxides, siloxanes, water vapor or organic vapors.

The jungle gym skeleton formed by coordination of an organic ligand (II) capable of bidentate coordination at the axial position of the metal ion in the skeleton consisting of the carboxylate ion and the metal ion of the dicarboxylic acid compound (I) It is a schematic diagram. It is a schematic diagram of a three-dimensional structure in which the jungle gym skeleton is double interpenetrated. It is a schematic diagram of the structural change accompanying adsorption / desorption of the metal complex of this invention. 3 is a crystal structure of the metal complex obtained in Synthesis Example 1. 3 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 1. FIG. 3 is a crystal structure of a metal complex obtained in Comparative Synthesis Example 1. 3 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 1. FIG. It is a crystal structure of the metal complex obtained in Comparative Synthesis Example 2. 4 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 2. FIG. It is a crystal structure of the metal complex obtained in Comparative Synthesis Example 3. 4 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 3. FIG. It is the result of having measured the adsorption isotherm of the carbon dioxide in 195K by the capacitance method about the metal complex obtained by the synthesis example 1, the comparative synthesis example 1, and the comparative synthesis example 2. FIG. It is the result of having measured the adsorption adsorption isotherm of ethylene in 195K by the capacitance method about the metal complex obtained by the synthesis example 1, the comparative synthesis example 2, and the comparative synthesis example 3. FIG. It is the result of having measured the adsorption-desorption isotherm of the carbon dioxide in 195K by the capacitance method about the metal complex obtained by the synthesis example 1. FIG. It is the result of having measured the adsorption-desorption isotherm of the carbon dioxide in 195K by the capacitance method about the metal complex obtained by the comparative synthesis example 1. FIG. It is the result of having measured the adsorption-desorption isotherm of the carbon dioxide in 195K by the capacitance method about the metal complex obtained by the comparative synthesis example 2. FIG. It is the result of having measured the adsorption-desorption isotherm of the carbon dioxide and methane in 195K by the capacitance method about the metal complex obtained by the synthesis example 1. FIG. It is the result of having measured the adsorption-desorption isotherm of the carbon dioxide and methane in 195K by the capacitance method about the metal complex obtained by the comparative synthesis example 2. FIG. It is the result of having measured the adsorption-desorption isotherm of the carbon dioxide and methane in 195K by the capacitance method about the metal complex obtained by the comparative synthesis example 3. FIG. It is the result of having measured the adsorption-and-desorption isotherm of ethylene and ethane in 195K by the capacitance method about the metal complex obtained by the synthesis example 1. FIG. It is the result of having measured the adsorption-and-desorption isotherm of ethylene and ethane in 195K by the capacitance method about the metal complex obtained by the comparative synthesis example 2. FIG. It is the result of having measured the adsorption-and-desorption isotherm of ethylene and ethane in 195K by the capacitance method about the metal complex obtained by the comparative synthesis example 3. FIG.

  The metal complex of the present invention comprises a dicarboxylic acid compound (I), at least one metal ion selected from ions of metals belonging to Groups 2, 7-10, and 12 of the periodic table, and two metal ions. It consists of an organic ligand (II) capable of coordination.

  As a metal ion used for manufacture of a metal complex, magnesium ion, calcium ion, manganese ion, cobalt ion, nickel ion, zinc ion, and cadmium ion are preferable, and zinc ion is more preferable. The metal ion is preferably a single metal ion, but may be a mixed metal complex containing two or more metal ions. Moreover, the metal complex of this invention can also mix and use 2 or more types of metal complexes which consist of a single metal ion.

  The metal complex includes a dicarboxylic acid compound (I), at least one metal salt selected from the salts of metals belonging to Groups 2, 7 to 10, and 12 of the periodic table, and a bidentate coordination to the metal ion. The possible organic ligand (II) can be produced by reacting in a solvent at normal pressure for several hours to several days and depositing it. For example, an aqueous solution or an organic solvent solution of a metal salt and an organic solvent solution containing a dicarboxylic acid compound (I) and an organic ligand (II) capable of bidentate coordination are mixed and reacted under normal pressure. Thus, the metal complex of the present invention can be obtained.

  The dicarboxylic acid compound (I) used in the present invention is represented by the following general formula (I):

It is represented by In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each is a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a formyl group, an acyloxy group, An alkoxycarbonyl group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group, or a halogen atom.

Among the substituents that can constitute R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , the alkyl group or alkoxy group preferably has 1 to 5 carbon atoms. Examples of the alkyl group include a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and a pentyl group, and an alkoxy group. Examples of methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, and examples of acyloxy group include acetoxy group, n-propanoyloxy group , N-butanoyloxy group, pivaloyloxy group, benzoyloxy group, examples of alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, examples of monoalkylamino group include methylamino group However, as an example of a dialkylamino group, a dimethylamino group is acyl Examples of amino group, an acetylamino group, examples of the halogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, and the like, respectively. Examples of the substituent that the alkyl group may have include an alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group). Etc.), amino group, monoalkylamino group (such as methylamino group), dialkylamino group (such as dimethylamino group), formyl group, epoxy group, acyloxy group (acetoxy group, n-propanoyloxy group, n-butanoyl) Oxy group, pivaloyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, etc.), carboxylic acid anhydride group (—CO—O—CO—R group) (R Is an alkyl group having 1 to 5 carbon atoms). 1-3 are preferable and, as for the number of the substituents of an alkyl group, one is more preferable.

  As the dicarboxylic acid compound (I), 2,6-naphthalenedicarboxylic acid is preferable.

  As salts of metals belonging to Groups 2, 7-10 and 12 of the periodic table used for the production of metal complexes, magnesium salts, calcium salts, manganese salts, iron salts, cobalt salts, nickel salts, zinc salts and cadmium salts Etc., and zinc salts are preferred. The metal salt is preferably a single metal salt, but two or more metal salts may be mixed and used. As these metal salts, organic acid salts such as acetate and formate, and inorganic acid salts such as hydrochloride, hydrobromide, sulfate, nitrate and carbonate can be used.

  The organic ligand (II) capable of bidentate coordination used in the present invention has the following general formula (II):

It is represented by In the formula, X and Y are the same or different and are CH ₂ , CH (OH), NH, an oxygen atom or a sulfur atom, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ^13. And R ¹⁴ are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom.

  When one or both of X and Y are CH (OH), an asymmetric carbon may be formed, but the bidentate organic ligand (II) is an optical isomer or a mixture thereof, for example, a racemate. May be.

Of the substituents that can constitute R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , the alkyl group preferably has 1 to 5 carbon atoms. Examples of the alkyl group include a straight or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and a pentyl group, and a halogen atom. Examples of are fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the substituent that the alkyl group may have include an alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, etc. ), Amino group, monoalkylamino group (such as methylamino group), dialkylamino group (such as dimethylamino group), formyl group, epoxy group, acyloxy group (acetoxy group, n-propanoyloxy group, n-butanoyloxy) Group, pivaloyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, etc.), carboxylic acid anhydride group (—CO—O—CO—R group) (R is And an alkyl group having 1 to 5 carbon atoms). 1-3 are preferable and, as for the number of the substituents of an alkyl group, one is more preferable.

Examples of the bidentate organic ligand (II) include 1,2-bis (4-pyridyl) ethane (X═Y═CH ₂ ), 1,2-bis (4-pyridyl) -glycol. (X = Y = CH (OH)) and 4,4'-dipyridyl sulfide (X = Y = S) can be used, and among these, 1,2-bis (4-pyridyl) ethane is preferred. Here, the organic ligand capable of bidentate coordination means a neutral ligand having two sites coordinated to a metal by a lone pair.

  The mixing ratio of the dicarboxylic acid compound (I) to the bidentate organic ligand (II) when producing the metal complex is as follows: dicarboxylic acid compound (I): bidentate organic ligand (II) = 1: 5-8: 1 is preferable, and a molar ratio of 1: 3-6: 1 is more preferable. Even if the reaction is carried out in a range other than this, the desired metal complex can be obtained, but this is not preferable because the yield is lowered and the side reaction is also increased.

  The mixing ratio of the metal salt to the bidentate organic ligand (II) when producing the metal complex is as follows: metal salt: bidentate organic ligand (II) = 3: 1 to 1 : Within the range of the molar ratio of 3: 3, and more preferably within the range of the molar ratio of 2: 1 to 1: 2. In other ranges, the yield of the target metal complex decreases, and purification of the metal complex obtained by leaving unreacted raw materials becomes difficult.

  The molar concentration of the dicarboxylic acid compound (I) in the mixed solution for producing the metal complex is preferably 0.005 to 5.0 mol / L, and more preferably 0.01 to 2.0 mol / L. Even if the reaction is performed at a concentration lower than this, the desired metal complex can be obtained, but this is not preferable because the yield decreases. If the concentration is higher than this, the solubility is lowered and the reaction does not proceed smoothly.

  The molar concentration of the metal salt in the mixed solution for producing the metal complex is preferably 0.005 to 5.0 mol / L, and more preferably 0.01 to 2.0 mol / L. Even if the reaction is performed at a concentration lower than this, the desired metal complex can be obtained, but this is not preferable because the yield decreases. Further, at a concentration higher than this, unreacted metal salt remains, and purification of the obtained metal complex becomes difficult.

  The molar concentration of the bidentate organic ligand (II) in the mixed solution for producing the metal complex is preferably 0.001 to 5.0 mol / L, and preferably 0.005 to 2.0 mol / L. More preferred. Even if the reaction is performed at a concentration lower than this, the desired metal complex can be obtained, but this is not preferable because the yield decreases. If the concentration is higher than this, the solubility is lowered and the reaction does not proceed smoothly.

  As a solvent used for producing the metal complex, an organic solvent, water, or a mixed solvent thereof can be used. Specifically, methanol, ethanol, propanol, diethyl ether, dimethoxyethane, tetrahydrofuran, hexane, cyclohexane, heptane, benzene, toluene, methylene chloride, chloroform, acetone, ethyl acetate, acetonitrile, N, N-dimethylformamide, water or These mixed solvents can be used. The reaction temperature is preferably 253 to 423K.

  A metal complex having good crystallinity has high purity and good adsorption performance. The completion of the reaction can be confirmed by quantifying the remaining amount of the raw material by gas chromatography or high performance liquid chromatography. After completion of the reaction, the obtained mixed solution is subjected to suction filtration to collect a precipitate, washed with an organic solvent, and then vacuum dried at about 373 K for several hours to obtain the metal complex of the present invention.

  The metal complex of the present invention obtained as described above is an organic ligand capable of bidentate coordination to the axial position of the metal ion in the skeleton composed of the carboxylate ion and the metal ion of the dicarboxylic acid compound (I) ( II) has a three-dimensional structure in which the jungle gym skeleton formed by coordination is doubly interpenetrated. A schematic diagram of a jungle gym skeleton is shown in FIG. 1, and a schematic diagram of a three-dimensional structure in which the jungle gym skeleton is double-interpenetrated is shown in FIG.

  In this specification, the “jungle gym skeleton” means an organic ligand capable of bidentate coordination at the axial position of the metal ion in the skeleton composed of the carboxylate ion and metal ion of the dicarboxylic acid compound (I). It is defined as a jungle gym-like three-dimensional structure formed by connecting two-dimensional lattice-like sheets composed of dicarboxylic acid compound (I) and metal ions.

In the present specification, “a structure in which multiple jungle gym skeletons interpenetrate” is defined as a three-dimensional integrated structure in which a plurality of jungle gym skeletons penetrate each other so as to fill the pores.
It can be confirmed, for example, by crystal X-ray analysis, powder X-ray crystal structure analysis, etc. that the metal complex has “a structure in which the jungle gym skeleton has multiple interpenetrations”.

  Since the three-dimensional structure in the metal complex of the present invention can be changed in the synthesized crystal, the structure and size of the pores change with the change. The conditions for changing the structure depend on the type of substance to be adsorbed, the adsorption pressure, and the adsorption temperature. That is, in addition to the difference in the interaction between the pore surface and the substance (the strength of the interaction is proportional to the magnitude of the Lennard-Jones potential of the substance), the degree of structural change varies depending on the adsorbed substance, and thus high selectivity is achieved. To express. FIG. 3 shows a schematic diagram of the structural change accompanying the adsorption / desorption. In the present invention, the dicarboxylic acid compound represented by the general formula (I) is used to control the strength of the interaction between the pore surface and the gas molecule, and the bidentate coordination represented by the general formula (II) is possible. By controlling the pore diameter using a simple organic ligand, high gas adsorption performance, high gas storage performance and high gas separation performance are manifested. After the adsorbed substance is desorbed, it returns to its original structure, so the pore size also returns.

  Although the selective adsorption mechanism is estimated, even if it does not follow the mechanism, it is included in the technical scope of the present invention as long as it satisfies the requirements defined in the present invention.

  Since the metal complex of the present invention is excellent in the adsorption performance of various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, C 1-4 hydrocarbon (methane, ethane, ethylene, acetylene, etc.), Noble gas (such as helium, neon, argon, krypton, xenon), hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane (such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane), water vapor or organic vapor It is preferable as an adsorbent for adsorbing. The organic vapor means a vaporized organic substance that is liquid at normal temperature and pressure. Examples of such organic substances include alcohols such as methanol and ethanol; amines such as trimethylamine; aldehydes such as acetaldehyde; aliphatic hydrocarbons having 5 to 16 carbon atoms; aromatic hydrocarbons such as benzene and toluene; acetone And ketones such as methyl ethyl ketone; halogenated hydrocarbons such as methyl chloride and chloroform.

  Further, since the metal complex of the present invention is excellent in the occlusion performance of various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, C 1-4 hydrocarbons (methane, ethane, ethylene, acetylene, etc. ), Noble gases (helium, neon, argon, krypton, xenon, etc.), hydrogen sulfide, ammonia, water vapor, organic vapor, etc. The organic vapor means a vaporized organic substance that is liquid at normal temperature and pressure. Examples of such organic substances include alcohols such as methanol and ethanol; amines such as trimethylamine; aldehydes such as acetaldehyde; aliphatic hydrocarbons having 5 to 16 carbon atoms; aromatic hydrocarbons such as benzene and toluene; acetone And ketones such as methyl ethyl ketone; halogenated hydrocarbons such as methyl chloride and chloroform.

  Furthermore, since the metal complex of the present invention is excellent in the separation performance of various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms (methane, ethane, ethylene, acetylene, etc. ), Noble gases (such as helium, neon, argon, krypton, xenon), hydrogen sulfide, ammonia, sulfur oxides, nitrogen oxides, siloxanes (such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane), water vapor or organic vapors It is also preferable as a separating material for separating, particularly carbon dioxide in methane, carbon dioxide in hydrogen, carbon dioxide in nitrogen, ethane in methane, ethylene in ethane or methane in air, It is suitable for separation by swing adsorption method or temperature swing adsorption method. The organic vapor means a vaporized organic substance that is liquid at normal temperature and pressure. Examples of such organic substances include alcohols such as methanol and ethanol; amines such as trimethylamine; aldehydes such as acetaldehyde; aliphatic hydrocarbons having 5 to 16 carbon atoms; aromatic hydrocarbons such as benzene and toluene; acetone And ketones such as methyl ethyl ketone; halogenated hydrocarbons such as methyl chloride and chloroform.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Analysis and evaluation in the following examples and comparative examples were performed as follows.

(1) Single crystal X-ray crystal structure analysis The obtained single crystal was mounted on a gonio head and measured using a single crystal X-ray diffractometer.
Details of the measurement conditions are shown below.
<Analysis conditions>
Apparatus: SMART APEX II Ultra manufactured by Bruker AXS Co., Ltd.
X-ray source: MoKα (λ = 0.10773Å) 50 kV 24 mA
Condenser mirror: Helios
Detector: CCD
Collimator: Φ0.42mm
Analysis software: SHELXTL

(2) Measurement of powder X-ray diffraction pattern Using an X-ray diffractometer, a range of diffraction angle (2θ) = 5 to 50 ° was scanned at a scanning speed of 1 ° / min, and measured by a symmetric reflection method. Details of the measurement conditions are shown below.
<Analysis conditions>
Apparatus: RINT2400 manufactured by Rigaku Corporation
X-ray source: CuKα (λ = 1.5418Å) 40 kV 200 mA
Goniometer: Vertical goniometer Detector: Scintillation counter Step width: 0.02 °
Slit: Divergent slit = 0.5 °
Receiving slit = 0.15mm
Scattering slit = 0.5 °

(3) Measurement of adsorption / desorption isotherm Measurement was carried out by a volumetric method using a gas adsorption amount measuring device. At this time, prior to the measurement, the sample was dried at 373 K and 50 Pa for 10 hours to remove adsorbed water and the like. Details of the measurement conditions are shown below.
<Analysis conditions>
Device: Nippon Bell Co., Ltd. BELSORP-18
Equilibrium waiting time: 500 seconds

<Synthesis Example 1>
In a nitrogen atmosphere, 5.83 g (20 mmol) of zinc nitrate hexahydrate, 4.24 g (20 mmol) of 2,6-naphthalenedicarboxylic acid and 1.81 g (10 mmol) of 1,2-bis (4-pyridyl) ethane were added to N , N-dimethylformamide was dissolved in 800 mL and stirred at 403 K for 24 hours. The results of taking out part of the precipitated crystals and conducting single crystal X-ray structural analysis are shown below. The composition of the skeleton of this complex was zinc ion: 2,6-naphthalenedicarboxylic acid: 1,2-bis (4-pyridyl) ethane = 2: 2: 1. The crystal structure is shown in FIG. FIG. 4 shows that this complex has a structure in which the jungle gym skeleton is triple interpenetrated.
Monoclinic (C2 / c)
a = 18.813 (2) Å
b = 18.357 (2) Å
c = 12.7207 (16) Å
α = 90.00 °
β = 122.0240 (10) °
γ = 90.00 °
V = 3724.5 (8) ^{３ 3}
Z = 8
R = 0.0622
Rw = 0.2872
The precipitated metal complex was collected by suction filtration and then washed with methanol three times. Then, it dried at 373 K and 50 Pa for 8 hours, and obtained 6.32 g (yield 87%) of the target metal complex. FIG. 5 shows a powder X-ray diffraction pattern of the obtained metal complex.

<Comparative Synthesis Example 1>
Under a nitrogen atmosphere, copper sulfate pentahydrate 0.251 g (1.0 mmol), 2,6-naphthalenedicarboxylic acid 0.220 g (1.0 mmol) and 1,2-bis (4-pyridyl) ethane 0.0978 g ( 0.53 mmol) was dissolved in 50 mL of a mixed solvent of toluene and methanol having a volume ratio of toluene: methanol = 1: 1, and stirred at 393 K for 36 hours. The results of taking out part of the precipitated crystals and conducting single crystal X-ray structural analysis are shown below. The composition of the skeleton of this complex was copper ion: 2,6-naphthalenedicarboxylic acid: 1,2-bis (4-pyridyl) ethane = 2: 2: 1. The crystal structure is shown in FIG. FIG. 6 shows that this complex has a structure in which the jungle gym skeleton is triple interpenetrated.
Monoclinic (C2 / c)
a = 17.094 (3) Å
b = 19.605 (3) Å
c = 11.782 (2) Å
α = 90.00 °
β = 113.950 (4) °
γ = 90.00 °
V = 3608.5 (10) Å ³
Z = 8
R = 0.0576
Rw = 0.903
The precipitated metal complex was recovered by suction filtration, and then washed with methanol three times. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex 0.214g (yield 55%). FIG. 7 shows a powder X-ray diffraction pattern of the obtained metal complex.

<Comparative Synthesis Example 2>
Under a nitrogen atmosphere, 2.81 g (9.5 mmol) of zinc nitrate hexahydrate, 2.05 g (9.5 mmol) of 2,6-naphthalenedicarboxylic acid and 0.739 g (4.7 mmol) of 4,4′-bipyridyl were added. The mixture was dissolved in 800 mL of a mixed solvent of N, N-dimethylformamide and ethanol having a volume ratio of N, N-dimethylformamide: ethanol = 1: 1 and stirred at 363 K for 48 hours. The results of taking out part of the precipitated crystals and conducting single crystal X-ray structural analysis are shown below. The composition of the skeleton of this complex was zinc ion: 2,6-naphthalenedicarboxylic acid: 1,2-bis (4-pyridyl) ethane = 2: 2: 1. The crystal structure is shown in FIG. FIG. 8 shows that this complex has a structure in which the jungle gym skeleton is double interpenetrated.
Triclinic (P-1)
a = 12.9758 (15) Å
b = 13.1095 (15) Å
c = 13.9258 (16) Å
α = 85.310 (2) °
β = 70.710 (2) °
γ = 84.193 (2) °
V = 2221.5 (4) Å ³
Z = 2
R = 0.0488
Rw = 0.0953
The precipitated metal complex was recovered by suction filtration, and then washed with methanol three times. Then, it dried at 373 K and 50 Pa for 8 hours, and obtained the target metal complex 3.09g (yield 91%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Comparative Synthesis Example 3>
Under a nitrogen atmosphere, 4.28 g (15 mmol) of zinc nitrate hexahydrate, 3.18 g (15 mmol) of 2,6-naphthalenedicarboxylic acid and 1.34 g of trans-1,2-bis (4-pyridyl) ethene (7. 4 mmol) was dissolved in 600 mL of N, N-dimethylformamide and stirred at 373 K for 24 hours. The results of taking out part of the precipitated crystals and conducting single crystal X-ray structural analysis are shown below. The composition of the skeleton of this complex was zinc ion: 2,6-naphthalenedicarboxylic acid: trans-1,2-bis (4-pyridyl) ethene = 2: 2: 1. The crystal structure is shown in FIG. From FIG. 10, it can be seen that this complex has a structure in which the jungle gym skeleton is double interpenetrated.
Monoclinic (P2 (1) / c)
a = 16.1578 (5) Å
b = 18.8070 (6) Å
c = 18.1039 (5) Å
α = 90.00 °
β = 92.6150 (10) °
γ = 90.00 °
V = 5495.7 (3) Å ³
Z = 4
R = 0.0477
Rw = 0.1331
The precipitated metal complex was recovered by suction filtration, and then washed with methanol three times. Then, it dried at 373 K and 50 Pa for 8 hours, and obtained 4.61 g (yield 85%) of the target metal complex. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Example 1>
For the metal complex obtained in Synthesis Example 1, the adsorption isotherm of carbon dioxide at 195 K was measured. The results are shown in FIG.

<Comparative Example 1>
The adsorption complex isotherm of carbon dioxide at 195K was measured for the metal complex obtained in Comparative Synthesis Example 1. The results are shown in FIG.

<Comparative example 2>
For the metal complex obtained in Comparative Synthesis Example 2, the adsorption isotherm of carbon dioxide at 195 K was measured. The results are shown in FIG.

  From FIG. 12, it is clear that the metal complex of the present invention is excellent as a carbon dioxide adsorbent because it has a large amount of carbon dioxide adsorbed.

<Example 2>
For the metal complex obtained in Synthesis Example 1, an adsorption isotherm of ethylene at 195 K was measured. The results are shown in FIG.

<Comparative Example 3>
For the metal complex obtained in Comparative Synthesis Example 2, an ethylene adsorption isotherm at 195K was measured. The results are shown in FIG.

<Comparative example 4>
For the metal complex obtained in Comparative Synthesis Example 3, the adsorption isotherm of ethylene at 195 K was measured. The results are shown in FIG.

  From FIG. 13, it is clear that the metal complex of the present invention is excellent as an adsorbent for ethylene because it has a large amount of adsorption of ethylene.

<Example 3>
For the metal complex obtained in Synthesis Example 1, the adsorption and desorption isotherm of carbon dioxide at 195 K was measured. The results are shown in FIG.

<Comparative Example 5>
For the metal complex obtained in Comparative Synthesis Example 1, the adsorption and desorption isotherm of carbon dioxide at 195 K was measured. The results are shown in FIG.

<Comparative Example 6>
For the metal complex obtained in Comparative Synthesis Example 2, the adsorption and desorption isotherm of carbon dioxide at 195 K was measured. The results are shown in FIG.

  From the comparison between FIG. 14, FIG. 15 and FIG. 16, it is clear that the metal complex of the present invention has a large amount of occluded carbon dioxide and is therefore excellent as an occluded material for carbon dioxide.

<Example 4>
For the metal complex obtained in Synthesis Example 1, the adsorption and desorption isotherms of carbon dioxide and methane at 195 K were measured. The results are shown in FIG.

<Comparative Example 7>
For the metal complex obtained in Comparative Synthesis Example 2, the adsorption and desorption isotherms of carbon dioxide and methane at 195 K were measured. The results are shown in FIG.

<Comparative Example 8>
The adsorption and desorption isotherms of carbon dioxide and methane at 195 K were measured for the metal complex obtained in Comparative Synthesis Example 3. The results are shown in FIG.

  From comparison between FIG. 17, FIG. 18 and FIG. 19, the metal complex of the present invention selectively adsorbs carbon dioxide and has a large amount of carbon dioxide adsorbed, so that it is excellent as a separator for methane and carbon dioxide. it is obvious.

<Example 5>
For the metal complex obtained in Synthesis Example 1, the adsorption and desorption isotherms of ethylene and ethane at 195 K were measured. The results are shown in FIG.

<Comparative Example 9>
For the metal complex obtained in Comparative Synthesis Example 2, the adsorption and desorption isotherms of ethylene and ethane at 195 K were measured. The results are shown in FIG.

<Comparative Example 10>
For the metal complex obtained in Comparative Synthesis Example 3, the adsorption and desorption isotherms of ethylene and ethane at 195 K were measured. The results are shown in FIG.

  From comparison of FIG. 20, FIG. 21 and FIG. 22, it is clear that the metal complex of the present invention selectively adsorbs ethylene and has a large amount of adsorbed ethylene, so that it is excellent as a separator for ethane and ethylene. .

Claims (12)

The following general formula (I);

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each is a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group, a formyl group, an acyloxy group) A dicarboxylic acid compound (I) represented by an alkoxycarbonyl group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group or a halogen atom), group 2 of the periodic table, Ions of metals belonging to Groups 7-10 and 12 and the following general formula (II);

(Wherein X and Y are the same or different and are CH ₂ , CH (OH), NH, an oxygen atom or a sulfur atom, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a formyl group, an acyloxy group, an alkoxycarbonyl group, a nitro group, a cyano group, an amino group, or a monoalkylamino. A metal complex comprising an organic ligand (II) capable of bidentate coordination to the metal ion represented by: a group, a dialkylamino group, an acylamino group, or a halogen atom.   The metal complex according to claim 1, wherein the jungle gym skeleton has a structure in which a plurality of interpenetrations occur.   The metal complex according to claim 1 or 2, wherein the metal ion is a zinc ion. The metal complex according to claim 1, wherein the bidentate organic ligand (II) is 1,2-bis (4-pyridyl) ethane. An adsorbent comprising the metal complex according to claim 1. The adsorbent is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or organic vapor. The adsorbent according to claim 5, which is an adsorbent for adsorbing. The occlusion material which consists of a metal complex in any one of Claims 1-4. The occlusion material is an occlusion material for occluding carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, water vapor or organic vapor. The occlusion material according to 7. The separating material which consists of a metal complex in any one of Claims 1-4.   The separation material is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or organic vapor. The separation material according to claim 9, which is a separation material for separation.   The separating material is methane and carbon dioxide, hydrogen and carbon dioxide, nitrogen and carbon dioxide, methane and ethane. The separation material according to claim 9, which is a separation material for separating ethylene and ethane or air and methane.   Dicarboxylic acid compound (I), at least one metal salt selected from salts of metals belonging to Groups 2, 7-10 and 12 of the periodic table, and an organic configuration capable of bidentate coordination with the metal ion The method for producing a metal complex according to claim 1, wherein the ligand (II) is reacted and precipitated in a solvent.