JP2013040147A - Metal complex and adsorbing material, storing material, separating material comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal complex having excellent gas adsorbing performance, gas storing performance, and gas separating performance.SOLUTION: The metal complex comprises anionic ligands, at least one metal ion selected from metal ions belonging to second to fifth periods of a group 2 and 7 to 12 groups in a periodic table, and organic ligands (I) of the metallic ions represented by a general formula (I), wherein R, R, R, R, R, R, R, R, R, Ridentically or differently are an alkyl group, 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 in the formula.

Description

  The present invention relates to a metal complex, and an adsorbent, an occlusion material, and a separation material comprising the same. More specifically, an anionic ligand, at least one metal ion selected from ions of metals belonging to Groups 2 and 5 to 12 in the periodic table, and bidentate to the metal ion. The present invention relates to a metal complex composed of a specific organic ligand capable of positioning. 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 due to an external stimulus have been developed as adsorbents that give better adsorption performance. 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 metal complex comprising a terephthalic acid derivative, a metal ion, and an organic ligand capable of bidentate coordination with the metal ion has been 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 the substituent of terephthalic acid and the organic ligand capable of bidentate coordination other than pyrazine are gases. No mention is made of the effect on the adsorption behavior.

  A polymer metal complex comprising a terephthalic acid derivative, a metal ion, and an organic ligand capable of bidentate coordination with the metal ion has been 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. -No mention is made of the effect of organic ligands capable of bidentate coordination other than diazabicyclo [2.2.2] octane on gas adsorption behavior.

  A polymer metal complex composed of terephthalic acid, a metal ion, and 4,4'-bipyridyl has been disclosed (see Patent Document 3). However, in the separation of the mixed gas, no mention is made of the effect that the substituents of terephthalic acid and organic ligands capable of bidentate coordination other than 4,4'-bipyridyl have on gas adsorption behavior.

JP 2000-109485 A JP 2001-348361 A JP 2003-342260 A

  Therefore, the 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 having excellent mixed gas separation performance. Is to provide.

  The present inventor has intensively studied, an anionic ligand, at least one metal ion selected from ions of metals belonging to Groups 2 and 7 to 12 in the periodic table, and the metal ion. It has been found that the above object can be achieved by a metal complex comprising an organic ligand capable of bidentate coordination to the present invention, and the present invention has been achieved.

That is, according to the present invention, the following is provided.
(1) An anionic ligand, at least one metal ion selected from ions of metals belonging to groups 2 to 5 and groups 2 to 5 of the periodic table, and the following general formula (I):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each may have a hydrogen atom or a substituent. A good alkyl group, alkoxy group, formyl group, acyloxy group, alkoxycarbonyl group, nitro group, cyano group, amino group, monoalkylamino group, dialkylamino group, acylamino group or halogen atom. A metal complex comprising an organic ligand (I) capable of bidentate coordination with ions.
(2) The bidentate organic ligand (I) is 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5-c ′] dipyrrole-1,3 The metal complex according to (1), which is 5,7 (2H, 6H) -tetron.
(3) An adsorbent comprising the metal complex according to (1) or (2).
(4) 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 (3), which is an adsorbent for adsorbing organic vapor.
(5) An occlusion material comprising the metal complex according to (1) or (2).
(6) The storage material is a storage material for storing 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 storage material according to (5).
(7) A separating material comprising the metal complex according to (1) or (2).
(8) 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 separating material according to (7), which is a separating material for separating organic vapor.
(9) The separator is methane and carbon dioxide, ethylene and carbon dioxide, hydrogen and carbon dioxide, nitrogen and carbon dioxide, air and methane, methane and ethane, ethane and ethylene, ethylene and acetylene, ethane and propane, propane The separation material according to (7), which is a separation material for separating propene or methane, ethane, and propane.
(10) An anionic ligand, at least one metal ion selected from ions of metals belonging to 2 to 5 periods of Groups 2 and 7-12 of the periodic table, and bidentate coordination to the metal ions The method for producing a metal complex according to (1), wherein a possible organic ligand (I) is reacted in a solvent to precipitate a metal complex.

  According to the present invention, an anionic ligand, at least one metal ion selected from ions of metals belonging to 2 to 5 periods of Groups 2 and 7 to 12 of the periodic table, and bidentate to the metal ions It is possible to provide a metal complex comprising a specific organic ligand (I) capable of being positioned.

  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 adsorbing substances, nitrogen oxides, siloxanes, water vapor, organic vapors and the like.

  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.

It is a schematic diagram of the structural change accompanying adsorption / desorption of the metal complex of this invention. 3 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 1. FIG. 4 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 2. FIG. 3 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 1. FIG. 4 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 2. FIG. 4 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 3. FIG. 6 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 4. FIG. 7 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 5. FIG. 2 is an adsorption isotherm of ethane at 195 K for the metal complexes obtained in Synthesis Example 1 and Comparative Synthesis Example 1. 2 is an adsorption / desorption isotherm of carbon dioxide at 195 K of the metal complexes obtained in Synthesis Example 1 and Comparative Synthesis Example 2. FIG. 2 is an adsorption / desorption isotherm of carbon dioxide and ethylene at 195 K of the metal complex obtained in Synthesis Example 1. FIG. 3 is an adsorption / desorption isotherm of carbon dioxide and ethylene at 195 K of the metal complex obtained in Synthesis Example 2. FIG. 3 is an adsorption / desorption isotherm of carbon dioxide and ethylene at 195 K of the metal complex obtained in Comparative Synthesis Example 2. FIG. 3 is an adsorption / desorption isotherm of carbon dioxide and ethylene at 195 K of the metal complex obtained in Comparative Synthesis Example 3. FIG. 2 is an adsorption / desorption isotherm of carbon dioxide and nitrogen at 195 K of the metal complex obtained in Synthesis Example 1. FIG. 2 is an adsorption / desorption isotherm of carbon dioxide and nitrogen at 195 K of the metal complex obtained in Synthesis Example 2. FIG. 6 is an adsorption / desorption isotherm of carbon dioxide and nitrogen at 195 K of the metal complex obtained in Comparative Synthesis Example 4. FIG. 2 is an adsorption / desorption isotherm of carbon dioxide and methane at 195 K of the metal complex obtained in Synthesis Example 1. FIG. 2 is an adsorption / desorption isotherm of carbon dioxide and methane at 195 K of the metal complex obtained in Synthesis Example 2. FIG. 6 is an adsorption / desorption isotherm of carbon dioxide and methane at 195 K of the metal complex obtained in Comparative Synthesis Example 4. FIG. 6 is an adsorption / desorption isotherm of carbon dioxide and methane at 195 K of the metal complex obtained in Comparative Synthesis Example 5. FIG.

  The metal complex used in the present invention includes an anionic ligand, at least one metal ion selected from the ions of metals belonging to Groups 2 and 7 to 12 in the periodic table, and the metal ion. And a specific organic ligand (I) capable of bidentate coordination.

  The metal complex includes an anionic ligand, at least one metal ion selected from ions of metals belonging to Groups 2 and 7 to 12 in the periodic table, and bidentate to the metal ion. It can be produced by reacting a specific organic ligand (I) capable of being reacted in a solvent under normal pressure for several hours to several days and depositing it. For example, an aqueous solution or organic solvent solution of a metal salt and an organic solvent solution containing an anionic ligand and an organic ligand (I) capable of bidentate coordination are mixed and reacted under normal pressure. Can be obtained.

  Examples of the anionic ligand used in the present invention include fluoride ion, chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, hexafluorosilicate ion, hexafluorophosphate ion, and hexafluoro. Arsenate ion, hexafluoroantimonate ion, formate ion, acetate ion, benzoate ion, 2,5-dihydroxybenzoate ion, 3,7-dihydroxy-2-naphthoate ion, 2,6-dihydroxy-1-naphthoate Acid ion, 4,4′-dihydroxy-3-biphenylcarboxylic acid ion, nicotinic acid ion, isonicotinic acid ion, trifluoroacetic acid ion, trifluoromethanesulfonic acid ion, benzenesulfonic acid ion, fumarate ion, 1,4- Cyclohexane dicarboxylate ion Pyrazine-2,3-dicarboxylate ion, pyridine-2,5-dicarboxylate ion, pyridine-3,5-dicarboxylate ion, 1,3-benzenedicarboxylate ion, 1,4-benzenedicarboxylate ion Rate ion, 2,5-thiophene dicarboxylate ion, 1,4-naphthalenedicarboxylate ion, 2,6-naphthalenedicarboxylate ion, 2,7-naphthalenedicarboxylate ion, 4,4′-biphenyldi Carboxylate ion, 2,2'-dithiophene dicarboxylate ion, 1,3,5-benzenetricarboxylate ion, 1,3,4-benzenetricarboxylate ion and 1,2,4,5-benzenetetra Carboxylate ions and the like can be used. An anionic ligand may mix and use 2 or more types of anionic ligands. Here, the anionic ligand means a ligand in which a site coordinated with a metal ion has an anionic property. When the above anionic ligand is an organic acid ligand such as carboxylate ion or sulfonate ion, the organic acid ligand is a non-ionizable substituent other than a substituent that can be an anion such as carboxylic acid or sulfonic acid. It may further have a group. For example, the 1,4-benzenedicarboxylate ion may be a 2-nitro-1,4-benzenedicarboxylate ion. The number of substituents may be 1, 2 or 3. Although it does not specifically limit as a substituent, For example, linear or branched, such as an alkyl group (Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, etc.). Having a C1-C5 alkyl group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, Isobutoxy group, tert-butoxy group, etc.), amino group, monoalkylamino group (methylamino group etc.), dialkylamino group (dimethylamino group etc.), formyl group, epoxy group, acyloxy group (acetoxy group, n-propanoyl) Oxy group, n-butanoyloxy group, pivaloyloxy group, benzoyloxy group, etc.), alcohol Aryloxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc. n- butoxycarbonyl group), a nitro group, a cyano group, a hydroxyl group, an acetyl group, and a trifluoromethyl group.

  Examples of the metal ions belonging to the 2nd to 5th periods of Groups 2 and 7-12 of the periodic table used in the present invention include beryllium ions, magnesium ions, calcium ions, strontium ions, barium ions, manganese ions, iron ions, Ruthenium ions, cobalt ions, rhodium ions, nickel ions, palladium ions, copper ions, silver ions, zinc ions or cadmium ions can be used. 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.

  Examples of the metal salt used for the production of the metal complex include beryllium salt, magnesium salt, calcium salt, strontium salt, barium salt, manganese salt, iron salt, ruthenium salt, cobalt salt, rhodium salt, nickel salt, palladium salt, copper Metal salts selected from salts, silver salts, zinc salts and cadmium salts can be used. 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 capable of bidentate coordination to the metal ion 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 , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each may have a hydrogen atom or a substituent. An alkyl group, 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 , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , the number of carbon atoms of the alkyl group or alkoxy group is 1-5 are preferable. 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, isoproxy 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 are examples of alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group are examples of monoalkylamino group, methylamino Examples of groups where the dialkylamino group is dimethylamino group are 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 anhydride group (—CO—OCO—R group) (R is carbon And an alkyl group having a number of 1 to 5). 1-3 are preferable and, as for the number of the substituents of an alkyl group, one is more preferable.

  As an organic ligand capable of bidentate coordination, for example, 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5-c ′] dipyrrole-1,3,5,7 (2H, 6H) -Tetron can be used. Here, the bidentate organic ligand means a neutral ligand having at least two sites capable of coordinating with a metal ion by a lone pair.

  The mixing ratio between the anionic ligand and the bidentate organic ligand (I) when producing the metal complex is as follows: anionic ligand: bidentate organic ligand (I ) = 1: 5 to 8: 1 molar ratio is preferable, and 1: 3 to 6: 1 molar ratio 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.

  When the metal complex is produced, the mixing ratio of the metal salt and the organic ligand (I) capable of bidentate coordination is as follows: metal salt: organic ligand capable of bidentate coordination (I) = 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 anionic ligand 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 (I) 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.

  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 does not adsorb gas molecules when solvent molecules are adsorbed. Therefore, when using it as an adsorbent, an occlusion material, and a separation material, it is necessary to vacuum-dry the metal complex obtained in advance to remove solvent molecules in the pores.

  The metal complex of the present invention obtained as described above can selectively adsorb and desorb gas molecules regardless of the type of anionic ligand used.

  The metal complex of the present invention can have a one-dimensional, two-dimensional, or three-dimensional integrated structure depending on the type of anionic ligand. When a carboxylate ion is used, a three-dimensional structure in which a jungle gym skeleton formed from a carboxylate ion, a metal ion, and an organic ligand (I) capable of bidentate coordination to the metal ion is interpenetrated multiple times. Can be built.

  In this specification, the “jungle gym skeleton” means that an organic ligand (I) capable of bidentate coordination with an axial position of a metal ion in a paddle wheel skeleton composed of a carboxylate ion and a metal ion is coordinated. It is defined as a jungle gym-like three-dimensional structure formed by connecting two-dimensional lattice-like sheets composed of carboxylate ions 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 two or more jungle gym skeletons penetrate each other so as to fill the pores of each other.

  It can be confirmed by, for example, single crystal X-ray structural analysis, powder X-ray crystal structural analysis, and the like that the metal complex constructs a structure in which the jungle gym skeleton is interpenetrated multiple times.

  Since the integrated 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. FIG. 1 shows a schematic diagram of a structural change accompanying adsorption / desorption when the metal complex of the present invention constructs the three-dimensional structure. In the present invention, the charge density of the pore shape and the pore surface is controlled by using the anionic ligand and the organic ligand (I) capable of bidentate coordination represented by the general formula (I). 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 said adsorption mechanism is presumption, even if it does not follow the said mechanism, if the requirements prescribed | regulated by this invention are satisfied, it will be included in the technical scope of this 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, hydrocarbon having 1 to 4 carbon atoms (methane, ethane, ethylene, acetylene, propane, Propene, methylacetylene, propadiene, etc.), noble gases (helium, neon, argon, krypton, xenon, etc.), hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane (hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane) Etc.), and is preferable as an adsorbent for adsorbing water vapor or organic vapor. 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 and triethylamine; aldehydes such as acetaldehyde; aliphatic hydrocarbons having 5 to 16 carbon atoms; aromatic hydrocarbons such as benzene and toluene. Ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as methyl chloride, methylene chloride and chloroform;

  In addition, 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 (methane, ethane, ethylene, acetylene, Propane, propene, methylacetylene, propadiene, etc.), noble gases (helium, neon, argon, krypton, xenon, etc.), hydrogen sulfide, ammonia, water vapor, or organic vapor are also preferred as occlusion materials. 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 can selectively adsorb various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, C 1-4 hydrocarbons (methane, ethane, ethylene, Acetylene, propane, propene, methylacetylene, propadiene, etc.), noble gases (helium, neon, argon, krypton, xenon, etc.), hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane (hexamethylcyclotrisiloxane, octane) Methylcyclotetrasiloxane, etc.), and is also preferable as a separating material for separating water vapor or organic vapor, and in particular, carbon dioxide in methane, carbon dioxide in ethylene, carbon dioxide in hydrogen, carbon dioxide in nitrogen, air Methane in methane, ethane in methane, ethylene in ethane, acetylene in ethylene, Propane in Tan, propene in propane or ethane and propane in methane, is suitable for separation by pressure swing adsorption or temperature swing adsorption. 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) Measurement of powder X-ray diffraction pattern Using a powder 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 analysis 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 °

(2) Creation of adsorption / desorption isotherm
A gas adsorption amount was measured by a capacity method (based on JIS Z8831-2) using a gas adsorption amount measuring device, and an adsorption / desorption isotherm was created. At this time, prior to the measurement, the sample was dried at 373 K and 50 Pa for 8 hours to remove adsorbed water and the like. Details of the measurement conditions are shown below.
<Analysis conditions>
Device: Nippon Bell Co., Ltd. BELSORP-18PLUS
Equilibrium waiting time: 500 seconds

<Synthesis Example 1>
Under a nitrogen atmosphere, zinc nitrate hexahydrate 2.81 g (9.5 mmol), 2-nitro-1,4-benzenedicarboxylic acid 2.00 g (9.5 mmol) and 2,6-di (4-pyridyl)- Benzo [1,2-c: 4,5-c ′] dipyrrole-1,3,5,7 (2H, 6H) -tetron 1.75 g (4.7 mmol) in a volume ratio of N, N-dimethylformamide: It was dissolved in 800 mL of a mixed solvent of N, N-dimethylformamide and ethanol consisting of ethanol = 1: 1 and stirred at 363 K for 24 hours. 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 4.13g (yield 95%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Synthesis Example 2>
Under a nitrogen atmosphere, zinc nitrate hexahydrate 2.81 g (9.5 mmol), 1,4-benzenedicarboxylic acid 1.57 g (9.5 mmol) and 2,6-di (4-pyridyl) -benzo [1, 2-c: 4,5-c ′] dipyrrole-1,3,5,7 (2H, 6H) -tetron 1.75 g (4.7 mmol) in a volume ratio of N, N-dimethylformamide: ethanol = 1: This was dissolved in 800 mL of a mixed solvent of N, N-dimethylformamide and ethanol consisting of 1 and stirred at 363 K for 48 hours. 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 objective metal complex 3.72g (yield 95%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Comparative Synthesis Example 1>
In a nitrogen atmosphere, zinc nitrate hexahydrate 5.03 g (17 mmol), 2-nitro-1,4-benzenedicarboxylic acid 3.57 g (17 mmol) and trans-1,2-bis (4-pyridyl) ethene 55 g (8.5 mmol) was dissolved in 690 mL of N, N-dimethylformamide and stirred at 393 K for 24 hours. The precipitated metal complex was collected by suction filtration, and then washed with ethanol three times. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex 4.05g (yield 65%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Comparative Synthesis Example 2>
Under a nitrogen atmosphere, zinc nitrate hexahydrate 2.81 g (9.5 mmol), 2-nitro-1,4-benzenedicarboxylic acid 2.00 g (9.5 mmol) and 4,4′-bipyridyl 0.739 g (4 0.7 mmol) 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 24 hours. 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 2.89g (yield 87%). FIG. 5 shows a powder X-ray diffraction pattern of the obtained metal complex.

<Comparative Synthesis Example 3>
Under a nitrogen atmosphere, 2.81 g (9.5 mmol) of zinc nitrate hexahydrate, 1.57 g (9.5 mmol) of 1,4-benzenedicarboxylic 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 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 2.75 g (yield 95%) of the target metal complex. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Comparative Synthesis Example 4>
Under nitrogen atmosphere, zinc nitrate hexahydrate 1.78 g (6.0 mmol), 2-nitro-1,4-benzenedicarboxylic acid 1.27 g (6.0 mmol) and N, N′-di (4-pyridyl) A mixed solvent of N, N-dimethylformamide and ethanol comprising 1.26 g (3.0 mmol) of 1,4,5,8-naphthalenetetracarboxydiimide in a volume ratio of N, N-dimethylformamide: ethanol = 1: 1 Dissolve in 540 mL and stir at 363 K for 24 hours. 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 2.66 g (yield 91%) of the target metal complex. FIG. 7 shows a powder X-ray diffraction pattern of the obtained metal complex.

<Comparative Synthesis Example 5>
Under nitrogen atmosphere, zinc nitrate hexahydrate 5.35 g (18 mmol), 1,4-benzenedicarboxylic acid 0.598 g (3.6 mmol) and N, N′-di (4-pyridyl) -1,4,5 , 8-Naphthalenetetracarboxydiimide (1.51 g, 3.6 mmol) was dissolved in 1800 mL of N, N-dimethylformamide and stirred at 353 K for 72 hours. 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 0.648g (yield 41%). 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 amount of ethane adsorbed at 195 K was measured by the volumetric method, and an adsorption isotherm was prepared. The results are shown in FIG.

<Comparative Example 1>
For the metal complex obtained in Comparative Synthesis Example 1, the amount of ethane adsorbed at 195 K was measured by the volumetric method, and an adsorption isotherm was prepared. The results are shown in FIG.

  FIG. 9 shows that the metal complex of the present invention is excellent as an adsorbent for ethane because it has a large amount of ethane adsorbed.

<Example 2>
For the metal complex obtained in Synthesis Example 1, the adsorption / desorption amount of carbon dioxide at 195 K was measured by the volume method, and an adsorption / desorption isotherm was prepared. The results are shown in FIG.

<Comparative example 2>
For the metal complex obtained in Comparative Synthesis Example 2, the adsorption / desorption amount of carbon dioxide at 195 K was measured by the volume method, and an adsorption / desorption isotherm was prepared. The results are shown in FIG.

  From FIG. 10, it can be seen that the metal complex of the present invention is excellent as a storage material for carbon dioxide because it has a large effective adsorption amount of carbon dioxide.

<Example 3>
For the metal complex obtained in Synthesis Example 1, the adsorption and desorption amounts of carbon dioxide and ethylene at 195 K were measured by the volume method, and adsorption and desorption isotherms were created. The results are shown in FIG. Table 1 shows the adsorption amount ratio of carbon dioxide and ethylene at 10 kPa, 50 kPa, and 90 kPa.

<Example 4>
For the metal complex obtained in Synthesis Example 2, the adsorption and desorption amount of carbon dioxide and ethylene at 195 K was measured by the volume method, and an adsorption and desorption isotherm was created. The results are shown in FIG. Table 1 shows the adsorption amount ratio of carbon dioxide and ethylene at 10 kPa, 50 kPa, and 90 kPa.

<Comparative Example 3>
For the metal complex obtained in Comparative Synthesis Example 2, the adsorption and desorption amounts of carbon dioxide and ethylene at 195 K were measured by the volume method, and an adsorption and desorption isotherm was created. The results are shown in FIG. Table 1 shows the adsorption amount ratio of carbon dioxide and ethylene at 10 kPa, 50 kPa, and 90 kPa.

<Comparative example 4>
For the metal complex obtained in Comparative Synthesis Example 3, the adsorption and desorption amounts of carbon dioxide and ethylene at 195 K were measured by the volume method, and an adsorption and desorption isotherm was created. The results are shown in FIG. Table 1 shows the adsorption amount ratio of carbon dioxide and ethylene at 10 kPa, 50 kPa, and 90 kPa.

  From Table 1, it can be seen that the metal complex of the present invention has a large adsorption ratio of carbon dioxide with respect to ethylene and has a high carbon dioxide selective adsorption ability, and thus is excellent as a separator for ethylene and carbon dioxide.

<Example 5>
For the metal complex obtained in Synthesis Example 1, the adsorption and desorption amounts of carbon dioxide and nitrogen at 195 K were measured by the volume method, and an adsorption and desorption isotherm was created. The results are shown in FIG. Table 2 shows the adsorption amount ratio of carbon dioxide and nitrogen at 10 kPa, 50 kPa, and 90 kPa.

<Example 6>
For the metal complex obtained in Synthesis Example 2, the adsorption and desorption amounts of carbon dioxide and nitrogen at 195 K were measured by the volume method, and an adsorption and desorption isotherm was created. The results are shown in FIG. Table 2 shows the adsorption amount ratio of carbon dioxide and nitrogen at 10 kPa, 50 kPa, and 90 kPa.

<Comparative Example 5>
For the metal complex obtained in Comparative Synthesis Example 4, the adsorption and desorption amounts of carbon dioxide and nitrogen at 195 K were measured by the volume method, and an adsorption and desorption isotherm was created. The results are shown in FIG. Table 2 shows the adsorption amount ratio of carbon dioxide and nitrogen at 10 kPa, 50 kPa, and 90 kPa.

  From Table 2, it can be seen that the metal complex of the present invention has a large adsorption ratio of carbon dioxide with respect to nitrogen and has a high carbon dioxide selective adsorption ability, and thus is excellent as a separator for nitrogen and carbon dioxide.

<Example 7>
For the metal complex obtained in Synthesis Example 1, the adsorption and desorption amounts of carbon dioxide and methane at 195 K were measured by the volume method, and adsorption and desorption isotherms were created. The results are shown in FIG. Table 3 shows the adsorption ratio of carbon dioxide and methane at 10 kPa, 50 kPa, and 90 kPa.

<Example 8>
For the metal complex obtained in Synthesis Example 2, the adsorption and desorption amounts of carbon dioxide and methane at 195 K were measured by the volume method, and adsorption and desorption isotherms were created. The results are shown in FIG. Table 3 shows the adsorption ratio of carbon dioxide and methane at 10 kPa, 50 kPa, and 90 kPa.

<Comparative Example 6>
For the metal complex obtained in Comparative Synthesis Example 4, the adsorption and desorption amounts of carbon dioxide and methane at 195 K were measured by the volume method, and an adsorption and desorption isotherm was created. The results are shown in FIG. Table 3 shows the adsorption ratio of carbon dioxide and methane at 10 kPa, 50 kPa, and 90 kPa.

<Comparative Example 7>
For the metal complex obtained in Comparative Synthesis Example 5, the adsorption and desorption amounts of carbon dioxide and methane at 195 K were measured by the volume method, and an adsorption and desorption isotherm was created. The results are shown in FIG. Table 3 shows the adsorption ratio of carbon dioxide and methane at 10 kPa, 50 kPa, and 90 kPa.

  From Table 3, it can be seen that the metal complex of the present invention has a large adsorption ratio of carbon dioxide with respect to methane and has a high carbon dioxide selective adsorption ability, and thus is excellent as a separator for methane and carbon dioxide.

  From the results of Examples 1 to 8 and Comparative Examples 1 to 7, the metal complexes obtained in Synthesis Examples 1 and 2 that satisfy the constituent requirements of the present invention are obtained in Comparative Synthesis Examples 1 to 5 that do not satisfy the constituent requirements of the present invention. It is clear that the adsorption performance, occlusion performance, and separation performance of various gases are superior to those of the above metal complexes. The reason why such a difference occurs is not necessarily clear, but by using the constituent ligand of the metal complex of the present invention, the interaction between the gas molecules and the pore surface is increased, so that excellent gas adsorption performance, This is thought to be due to the development of excellent gas storage performance and gas separation performance.

Claims (10)

An anionic ligand, at least one metal ion selected from ions of metals belonging to groups 2 to 5 and groups 2 to 5 of Groups 7 to 12, and the following general formula (I);
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each may have a hydrogen atom or a substituent. A good alkyl group, alkoxy group, formyl group, acyloxy group, alkoxycarbonyl group, nitro group, cyano group, amino group, monoalkylamino group, dialkylamino group, acylamino group or halogen atom. A metal complex comprising an organic ligand (I) capable of bidentate coordination with ions. The bidentate organic ligand (I) is 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5-c ′] dipyrrole-1,3,5,7. The metal complex according to claim 1, which is (2H, 6H) -tetron. 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 3, which is an adsorbent for adsorbing. An occlusion material comprising the metal complex according to claim 1. 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. 5. The occlusion material according to 5. A separating material comprising the metal complex according to claim 1. 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 7, which is a separation material for separation. The separator is methane and carbon dioxide, ethylene and carbon dioxide, hydrogen and carbon dioxide, nitrogen and carbon dioxide, air and methane, methane and ethane, ethane and ethylene, ethylene and acetylene, ethane and propane, propane and propene, or The separation material according to claim 7, which is a separation material for separating methane, ethane and propane. An anionic ligand, at least one metal ion selected from ions of metals belonging to groups 2 to 5 and groups 2 to 5 of groups 7 to 12, and an organic compound capable of bidentate coordination with the metal ion The method for producing a metal complex according to claim 1, wherein the ligand (I) is reacted in a solvent to precipitate a metal complex.