JP5725784B2 - Metal complex and separation material comprising the same - Google Patents

Description

  The present invention relates to a metal complex, a method for producing the same, and a separating material comprising the metal complex. More specifically, the present invention relates to a metal complex comprising a specific dicarboxylic acid compound, at least one metal ion, and an organic ligand capable of bidentate coordination with the metal ion. The metal complex of the present invention 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 It is preferable as an adsorbing material such as steam, an occlusion material, and a separating material, and particularly preferable as a separating material such as methane and carbon dioxide, hydrogen and carbon dioxide, nitrogen and carbon dioxide, methane and ethane, or air and methane.

  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 current situation is that cost reduction by further downsizing of the apparatus is required, and in order to achieve this, further improvement in adsorption performance, occlusion performance, or separation performance is required.

  A polymer metal complex consisting of 2,7-naphthalenedicarboxylic acid, zinc ion and 4,4'-bipyridyl shows an I-type adsorption profile in the IUPAC classification, but it is an adsorption test for a mixed gas of carbon dioxide, nitrogen and oxygen. Is known to selectively adsorb carbon dioxide (see Non-Patent Document 3). However, when the present inventors evaluated the separation performance of carbon dioxide and methane for the disclosed metal complexes, the separation performance was not satisfactory.

A polymer metal complex composed of an isophthalic acid derivative, a 2,7-naphthalenedicarboxylic acid derivative or a 4,4′-benzophenone dicarboxylic acid derivative, a metal ion, and an organic ligand capable of bidentate coordination with the metal ion, It has an affinity for unsaturated organic molecules, and is known to be effective for separating unsaturated organic molecules (see Patent Document 1). However, when the present inventors evaluated the separation performance of carbon dioxide and methane for the disclosed metal complexes, the separation performance was not satisfactory. Complexes such as 4,4′-dicarbonylbiphenylsulfone (H ₂ dbsf) and Cu (Non-Patent Document 4), Cd, Ni or Mn (Non-Patent Documents 5, 6, 7, 8) are known. These are different metal ions or organic ligands capable of bidentate coordination, and the gas adsorption, occlusion and separation properties of these complexes are not described.

JP 2008-24784A

Kazuhiro Uemura, Susumu Kitagawa, Future Materials, Volume 2, 44-51 (2002) Ryotaro Matsuda, Susumu Kitagawa, Petrotech, Vol. 26, 97-104 (2003) Hiroshi Nakagawa, Daisuke Tanaka, Satoru Shimomura, Susumu Kitagawa, 61st Annual Meeting on Colloid and Interface Chemistry, 462 (2008) Polyhedron 26 (2007) 1123-1132 Inorg. Chem. 2007, 46, 4158-4166 Inorganica Chimica Acta 362 (2009) 543-550 CrystEngComm, 2008, 10, 905-914 Solid State Sciences, 11 (2009) 364-367

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

  The present inventors have intensively studied and achieve the above object with a metal complex comprising a specific dicarboxylic acid compound, at least one metal ion, and an organic ligand capable of bidentate coordination with the metal ion. The present inventors have found that it is possible to achieve the present invention.

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

（式中、Ｘは窒素、ケイ素、リン、硫黄、ゲルマニウム、ヒ素、セレンから選ばれ、他原子と結合していてもよいヘテロ原子であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ同一または異なって水素原子、置換基を有していてもよいアルキル基もしくはハロゲン原子を示すか、Ｒ^１とＲ^２、或いはＲ^５とＲ^６が一緒になって置換基を有していてもよいアルキレン基、オキシアルキレン基またはアルケニレン基である。）で表されるジカルボン酸化合物（Ｉ）と、マグネシウムイオン、アルミニウムイオン、カルシウムイオン、クロムイオン、モリブデンイオン、タングステンイオン、鉄イオン、ルテニウムイオン、ロジウムイオン、パラジウムイオン及び亜鉛イオンから選択される少なくとも１種の金属イオンと、１つの金属イオンに対してキレート配位し得ない構造を有する該金属イオンに二座配位可能な有機配位子とからなる金属錯体。
（２）該二座配位可能な有機配位子が１，４−ジアザビシクロ［２．２．２］オクタン、ピラジン、２，５−ジメチルピラジン、４，４’−ビピリジル、２，２’−ジメチル−４，４’−ビピリジン、１，２−ビス（４−ピリジル）エチン、１，４−ビス（４−ピリジル）ブタジイン、１，４−ビス（４−ピリジル）ベンゼン、３，６−ジ（４−ピリジル）−１，２，４，５−テトラジン、２，２’−ビ−１，６−ナフチリジン、フェナジン、ジアザピレン、トランス−１，２−ビス（４−ピリジル）エテン、４，４’−アゾピリジン、１，２−ビス（４−ピリジル）エタン、１，２−ビス（４−ピリジル）−グリコール、Ｎ−（４−ピリジル）イソニコチンアミド、１，２−ビス（４−ピリジル）プロパン、４，４’−ビス（４−ピリジル）ビフェニル、Ｎ，Ｎ’−ジ（４−ピリジル）−１，４，５，８−ナフタレンテトラカルボキシジイミド、２，６−ジ（４−ピリジル）−ベンゾ［１，２−ｃ：４，５−ｃ’］ジピロール−１，３，５，７（２Ｈ，６Ｈ）−テトロン及びＮ，Ｎ’−ジ（４−ピリジル）−１，４，５，８−ナフタレンテトラカルボキシジイミドから選択される少なくとも１種である（１）に記載の金属錯体。
（３）該金属イオンが亜鉛イオンである（１）または（２）に記載の金属錯体。
（４）（１）〜（３）のいずれかに記載の金属錯体からなる吸着材。
（５）該吸着材が、二酸化炭素、水素、一酸化炭素、酸素、窒素、炭素数１〜４の炭化水素、希ガス、硫化水素、アンモニア、硫黄酸化物、窒素酸化物、シロキサン、水蒸気または有機蒸気を吸着するための吸着材である（４）に記載の吸着材。
（６）（１）〜（３）のいずれかに記載の金属錯体からなる吸蔵材。
（７）該吸蔵材が、二酸化炭素、水素、一酸化炭素、酸素、窒素、炭素数１〜４の炭化水素、希ガス、硫化水素、アンモニア、水蒸気または有機蒸気を吸蔵するための吸蔵材である（６）に記載の吸蔵材。
（８）（１）〜（３）のいずれかに記載の金属錯体からなる分離材。
（９）該分離材が、二酸化炭素、水素、一酸化炭素、酸素、窒素、炭素数１〜４の炭化水素、希ガス、硫化水素、アンモニア、硫黄酸化物、窒素酸化物、シロキサン、水蒸気または有機蒸気を分離するための分離材である（８）に記載の分離材。
（１０）該分離材が、メタンと二酸化炭素、水素と二酸化炭素、窒素と二酸化炭素、メタンとエタンまたは空気とメタンを分離するための分離材である（８）に記載の分離材。
（１１）ジカルボン酸化合物（Ｉ）と、マグネシウムイオン、アルミニウムイオン、カルシウムイオン、クロムイオン、モリブデンイオン、タングステンイオン、鉄イオン、ルテニウムイオン、ロジウムイオン、パラジウムイオン及び亜鉛イオンの塩から選択される少なくとも１種の金属塩と、１つの金属イオンに対してキレート配位し得ない構造を有する該金属イオンに二座配位可能な有機配位子とを溶媒中で反応させ、析出させる、（１）に記載の金属錯体の製造方法。

(In the formula, X is selected from nitrogen, silicon, phosphorus, sulfur, germanium, arsenic, and selenium, and is a heteroatom that may be bonded to other atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group or a halogen atom, or R ¹ and R ² , or R ⁵ and R ⁶ together represent a substituent. An alkylene group, an oxyalkylene group, or an alkenylene group, which may have an organic group.) And a magnesium ion, an aluminum ion, a calcium ion, a chromium ion, a molybdenum ion, a tungsten ion, At least one metal ion selected from iron ion, ruthenium ion, rhodium ion, palladium ion and zinc ion, and one Metal complexes consisting of a bidentate coordination acceptable organic ligands to the metal ions having a structure which can not chelate ligand against metal ions.
(2) The bidentate organic ligand is 1,4-diazabicyclo [2.2.2] octane, pyrazine, 2,5-dimethylpyrazine, 4,4'-bipyridyl, 2,2'- Dimethyl-4,4′-bipyridine, 1,2-bis (4-pyridyl) ethyne, 1,4-bis (4-pyridyl) butadiyne, 1,4-bis (4-pyridyl) benzene, 3,6-di (4-pyridyl) -1,2,4,5-tetrazine, 2,2′-bi-1,6-naphthyridine, phenazine, diazapyrene, trans-1,2-bis (4-pyridyl) ethene, 4,4 '-Azopyridine, 1,2-bis (4-pyridyl) ethane, 1,2-bis (4-pyridyl) -glycol, N- (4-pyridyl) isonicotinamide, 1,2-bis (4-pyridyl) Propane, 4,4'-bis (4-pyridyl) biphe N, N′-di (4-pyridyl) -1,4,5,8-naphthalenetetracarboxydiimide, 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5- c ′] at least one selected from dipyrrole-1,3,5,7 (2H, 6H) -tetron and N, N′-di (4-pyridyl) -1,4,5,8-naphthalenetetracarboxydiimide. The metal complex according to (1), which is a seed.
(3) The metal complex according to (1) or (2), wherein the metal ion is a zinc ion.
(4) An adsorbent comprising the metal complex according to any one of (1) to (3).
(5) 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 (4), which is an adsorbent for adsorbing organic vapor.
(6) An occlusion material comprising the metal complex according to any one of (1) to (3).
(7) 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 (6).
(8) A separating material comprising the metal complex according to any one of (1) to (3).
(9) 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.
(10) The separation material 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, or air and methane.
(11) At least selected from a salt of dicarboxylic acid compound (I) and magnesium ion, aluminum ion, calcium ion, chromium ion, molybdenum ion, tungsten ion, iron ion, ruthenium ion, rhodium ion, palladium ion and zinc ion Reacting and depositing one kind of metal salt and an organic ligand capable of bidentate coordination with the metal ion having a structure incapable of chelating with one metal ion in a solvent (1 The manufacturing method of the metal complex as described in).

  According to the present invention, a specific dicarboxylic acid compound and at least one selected from magnesium ion, aluminum ion, calcium ion, chromium ion, molybdenum ion, tungsten ion, iron ion, ruthenium ion, rhodium ion, palladium ion and zinc ion And a metal complex having a structure incapable of chelate coordination with one metal ion and an organic ligand capable of bidentate coordination with the metal ion.

  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.

3 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 1. 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. It is the result of measuring the adsorption-desorption isotherm of carbon dioxide and methane at 273 K by the volumetric method for the metal complex obtained in Synthesis Example 1. It is the result of having measured the adsorption-desorption isotherm of carbon dioxide and methane at 273K by the volume method for 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 3. FIG. It is the result of measuring the adsorption-desorption isotherm of carbon dioxide and nitrogen at 273 K by the capacitance method for the metal complex obtained in Synthesis Example 1. It is the result of having measured the adsorption-desorption isotherm in carbon dioxide and nitrogen at 273K 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 carbon dioxide and nitrogen at 273 K by the volumetric method for the metal complex obtained in Comparative Synthesis Example 3. 4 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 2. 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. It is the result of having measured the adsorption isotherm of the carbon dioxide in 273K by the capacitance method about the metal complex obtained by the synthesis example 2, the comparative synthesis example 4, and the comparative synthesis example 5. FIG. It is the result of having measured the adsorption-desorption isotherm of the carbon dioxide in 273K by the capacitance method about the metal complex obtained by the synthesis example 2, the comparative synthesis example 4, and the comparative synthesis example 5. FIG. 3 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 3. FIG. 7 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 6. FIG. It is the result of having measured the adsorption isotherm of the carbon dioxide in 273K by the capacitance method about the metal complex obtained by the synthesis example 3 and the comparative synthesis example 6. FIG. It is the result of having measured the adsorption-desorption isotherm of the carbon dioxide in 273K by the capacitance method about the metal complex obtained by the synthesis example 3 and the comparative synthesis example 6. FIG. 6 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 4. FIG. 7 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 7. FIG. It is the result of having measured the adsorption isotherm of the carbon dioxide in 273K by the capacitance method about the metal complex obtained by the synthesis example 4 and the comparative synthesis example 7. FIG. It is the result of having measured the adsorption-desorption isotherm of the carbon dioxide in 273K by the capacitance method about the metal complex obtained by the synthesis example 4 and the comparative synthesis example 7. FIG.

  The metal complex of the present invention is selected from dicarboxylic acid compound (I) and magnesium ion, aluminum ion, calcium ion, chromium ion, molybdenum ion, tungsten ion, iron ion, ruthenium ion, rhodium ion, palladium ion and zinc ion. At least one kind of metal ion and an organic ligand capable of bidentate coordination with the metal ion having a structure incapable of chelate coordination with one metal ion.

  The metal complex is selected from a salt of dicarboxylic acid compound (I) and magnesium ion, aluminum ion, calcium ion, chromium ion, molybdenum ion, tungsten ion, iron ion, ruthenium ion, rhodium ion, palladium ion and zinc ion. At least one metal salt and an organic ligand capable of bidentate coordination to the metal ion having a structure that cannot be chelate-coordinated to one metal ion, from a few hours in a solvent under normal pressure It can be produced by reacting and precipitating for several days. For example, an organic solvent containing an aqueous solution or an organic solvent solution of a metal salt and a dicarboxylic acid compound (I) and an organic ligand capable of bidentate coordination having a structure that cannot be chelated to one metal ion The solution can be obtained by mixing and reacting under normal pressure.

で表される。式中、Ｘは窒素、ケイ素、リン、硫黄、ゲルマニウム、ヒ素、セレンから選ばれ、他原子と結合していてもよいヘテロ原子であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ同一または異なって水素原子、置換基を有していてもよいアルキル基もしくはハロゲン原子であるか、Ｒ^１とＲ^２、或いはＲ^５とＲ^６が一緒になって置換基を有していてもよいアルキレン基、オキシアルキレン基またはアルケニレン基である。 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, X is selected from nitrogen, silicon, phosphorus, sulfur, germanium, arsenic, and selenium, and is a heteroatom that may be bonded to another atom. R ¹ , R ² , R ³ , R ⁴ , R ⁵ And R ⁶ are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group or a halogen atom, or R ¹ and R ² , or R ⁵ and R ⁶ together form a substituent. An alkylene group, an oxyalkylene group or an alkenylene group which may be present.

Examples of X include an amino group, a monoalkylamino group (methylamino group, ethylamino group, etc.), a dialkylsilanediyl group (dimethylsilanediyl group (—Si (CH ₃ ) ₂ —), a diethylsilanediyl group ( _{-Si (CH 2 CH 3) 2} -) , etc.), hydroxy phosphoryl group (-P (O) (OH) -), a sulfur atom, a sulfonyl group, a dialkyl germanium group (the dimethyl germane diyl group (-Ge (CH ₃ ) _2- ), diethylgermandiyl group (-Ge (CH ₂ CH ₃ ) _2- ), etc.), arsandiyl group (-AsH-), alkylarsantolyl group (methylarsantolyl group (-As (CH ₃ )) -), ethyl Al San tolyl _{(-As (CH 2 CH 3)} -) , etc.), a selenium atom, Serenoniru group (-SeO ₂ -) and the like It is.

Among the substituents that can constitute R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , 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, 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 anhydride group (—CO—O—CO—R group) (R is an alkyl group having 1 to 5 carbon atoms) and the like. 1-3 are preferable and, as for the number of the substituents of an alkyl group, one is more preferable.

3-6 are preferable and, as for carbon number of the said alkylene group, 3-4 are more preferable. When the alkylene group has 3 to 6 carbon atoms, R ¹ and R ² , or R ⁵ and R ⁶ , together with the carbon atoms to which they are bonded, form a 5- to 8-membered ring (cyclopentane ring, cyclohexane ring). , Cycloheptane ring, cyclooctane ring).

3-6 are preferable and, as for the total number of atoms of carbon of the said oxyalkylene group and oxygen, 3-4 are more preferable. When the total number of atoms of carbon and oxygen in the alkylene group is 3 to 6, as the oxyalkylene group, —O—CH ₂ —O—, —CH ₂ —O—CH ₂ —, —O—CH ₂ —CH _{2 -O -, - O-CH 2} -CH 2 -CH 2 -, - CH 2 -O-CH 2 -CH 2 -, - O-CH 2 -CH 2 -CH 2 -CH 2 -, - O-CH _{2 -CH 2 -CH 2 -CH 2 -CH} 2 - and the like.

3-6 are preferable and, as for carbon number of the said alkenylene group, 3-4 are more preferable. When the alkylene group has 3 to 6 carbon atoms, R ¹ and R ² , or R ⁵ and R ⁶ together with the carbon atoms to which they are bonded are 5- to 8-membered rings (cyclopentene ring, cyclohexene ring ( Or a benzene ring (when it has two double bonds), a cycloheptene ring or a cyclooctene ring).

  Examples of the substituent that the alkylene group, oxyalkylene group, and alkenylene group may have include an alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group). Group, tert-butoxy group, etc.), amino 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 anhydride group (—CO—O—CO—R group) (R is an alkyl group having 1 to 5 carbon atoms) and the like. It is done.

The dicarboxylic acid compound (I) used in the present invention is preferably a symmetrical compound in which R ¹ = R ⁶ , R ² = R ⁵ and R ³ = R ⁴ .

  As the dicarboxylic acid compound (I), 4,4′-dicarboxydiphenyl sulfone is preferable.

  Magnesium, aluminum, calcium, chromium, molybdenum, tungsten, iron, ruthenium, rhodium, palladium, and zinc salts may be used as metal ion salts for the production of metal complexes. Zinc salts are preferred. The metal salt is preferably a single metal salt, but two or more metal salts may be mixed and used. 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. 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.

  Examples of the organic ligand capable of bidentate coordination having a structure that cannot be chelated to one metal ion used in the present invention include 1,4-diazabicyclo [2.2.2] octane, Pyrazine, 2,5-dimethylpyrazine, 4,4′-bipyridyl, 2,2′-dimethyl-4,4′-bipyridine, 1,2-bis (4-pyridyl) ethyne, 1,4-bis (4- Pyridyl) butadiyne, 1,4-bis (4-pyridyl) benzene, 3,6-di (4-pyridyl) -1,2,4,5-tetrazine, 2,2′-bi-1,6-naphthyridine, Phenazine, diazapyrene, trans-1,2-bis (4-pyridyl) ethene, 4,4′-azopyridine, 1,2-bis (4-pyridyl) ethane, 1,2-bis (4-pyridyl) -glycol, N- (4-pyridyl) iso Cotinamide, 1,2-bis (4-pyridyl) propane, 4,4′-bis (4-pyridyl) biphenyl, N, N′-di (4-pyridyl) -1,4,5,8-naphthalenetetracarboxyl Diimide, 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5-c ′] dipyrrole-1,3,5,7 (2H, 6H) -tetron and N, N′- Examples include di (4-pyridyl) -1,4,5,8-naphthalenetetracarboxydiimide, among which 4,4′-bipyridyl, 1,2-bis (4-pyridyl) ethyne, 1,4- Bis (4-pyridyl) benzene and 3,6-di (4-pyridyl) -1,2,4,5-tetrazine are preferred. Here, the bidentate organic ligand having a structure incapable of chelate coordination with one metal ion means two or more sites coordinated to the metal ion with a lone pair of electrons. It means a neutral ligand which has a chelate coordination to one metal ion. Examples of the organic ligand having a structure capable of chelate coordination with one metal ion include ethylenediamine, 2,2′-bipyridyl, 1,10-phenanthroline, and the like. An organic ligand capable of coordination is exemplified. When an organic ligand having a structure capable of chelate coordination is used, the central metal ion has a pentacoordinate tetragonal shape, and a water molecule fills one coordination site, so that the metal complex has a three-dimensional integrated structure. Form. Therefore, when a pretreatment for gas adsorption is performed, the water molecules are desorbed, and the metal complex cannot maintain an integrated structure.

  The mixing ratio of the dicarboxylic acid compound (I) to the bidentate organic ligand when producing the metal complex is as follows: dicarboxylic acid compound (I): bidentate organic ligand = 1: A molar ratio in the range of 5-8: 1 is preferred, and a molar ratio in the range of 1: 3-6: 1 is more preferred. 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 and the bidentate organic ligand when producing the metal complex is as follows: metal salt: bidentate organic ligand = 3: 1 to 1: 3 molar ratio Within the range, the molar ratio of 2: 1 to 1: 2 is more preferable. 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 solvent for producing the metal complex is preferably from 0.01 to 5.0 mol / L, more preferably from 0.05 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 solvent for producing the metal complex is preferably from 0.01 to 5.0 mol / L, more preferably from 0.05 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 organic ligand capable of bidentate coordination in the solvent for producing the metal complex is preferably from 0.01 to 5.0 mol / L, more preferably from 0.05 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.

  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 has an organic configuration capable of bidentate coordination in the axial position of the metal in the one-dimensional chain composed of the dicarboxylic acid compound (I) and a metal ion (for example, zinc ion). A ligand is coordinated, and a one-dimensional chain composed of the dicarboxylic acid compound (I) and a metal ion is connected to form a layered two-dimensional structure. This two-dimensional structure is a structure in which the two-dimensional structure penetrates each other, and has pores (one-dimensional channels).

  A metal complex having pores has high gas adsorption performance, high occlusion performance, and high selectivity due to 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). To express. In the present invention, high gas adsorption performance, high occlusion performance, and high selectivity are exhibited by controlling the charge density on the pore surface using the dicarboxylic acid compound represented by the general formula (I).

  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 the carbon dioxide in methane, carbon dioxide in hydrogen, carbon dioxide in nitrogen, ethane in methane, methane in air, etc. Suitable for separation by 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) 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 °

(2) Measurement of adsorption / desorption isotherm The measurement was performed by a volume method using a high-pressure 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>
Apparatus: BELSORP-HP manufactured by Nippon Bell Co., Ltd.
Equilibrium waiting time: 500 seconds

(3) Measurement of gas adsorption rate at 0.1 MPa A glass 10 mL two-necked flask equipped with a three-way cock and a septum is prepared, and a 100-mL syringe is connected to one end of the three-way cock via another three-way cock with a tube. did. For measurement, put the sample in a two-necked flask, dry at 373 K, 4.0 × 10 ⁻³ Pa for 3 hours, remove adsorbed water, etc., then close the three-way cock attached to the flask, and then three-way on the syringe side 100 mL of the mixed gas was introduced into the syringe through the cock, and finally, the three-way cock attached to the flask was opened to adsorb the mixed gas to the sample. At this time, the adsorption amount was calculated from the decrease in the scale of the syringe (the dead volume was measured in advance using helium).

<Synthesis Example 1>
Under a nitrogen atmosphere, 5.00 g (17 mmol) of zinc nitrate hexahydrate, 5.18 g (17 mmol) of 4,4′-dicarboxydiphenylsulfone and 2.65 g (17 mmol) of 4,4′-bipyridyl were added to N, N— Dissolved in 200 mL of 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 373 K and 50 Pa for 8 hours, and obtained the target metal complex 6.95g (yield 99%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Comparative Synthesis Example 1>
Under a nitrogen atmosphere, 5.00 g (17 mmol) of zinc nitrate hexahydrate, 4.36 g (17 mmol) of 4,4′-dicarboxydiphenyl ether and 2.65 g (17 mmol) of 4,4′-bipyridyl were converted to N, N-dimethyl. It was dissolved in 200 mL of formamide 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 373 K and 50 Pa for 8 hours, and obtained the target metal complex 6.01g (yield 74%). 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 rates of carbon dioxide and methane at 273 K and 0.1 MPa were measured. Table 1 shows the ratio of the adsorption amount of carbon dioxide and methane 10 minutes after the start of adsorption.

<Comparative Example 1>
For the metal complex obtained in Comparative Synthesis Example 1, the adsorption rate of carbon dioxide and methane at 273 K and 0.1 MPa was measured. Table 1 shows the ratio of the adsorption amount of carbon dioxide and methane 10 minutes after the start of adsorption.

表１より、本発明の金属錯体は高い二酸化炭素選択吸着能を有するので、メタンと二酸化炭素の分離材として優れていることは明らかである。

From Table 1, it is clear that the metal complex of the present invention is excellent as a separator for methane and carbon dioxide because it has a high carbon dioxide selective adsorption ability.

<Comparative Synthesis Example 2>
Under a nitrogen atmosphere, 5.00 g (17 mmol) of zinc nitrate hexahydrate, 3.68 g (17 mmol) of 2,7-naphthalenedicarboxylic acid and 2.65 g (17 mmol) of 4,4′-bipyridyl were added to N, N-dimethylformamide. Dissolve in 200 mL and stir 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 373 K and 50 Pa for 8 hours, and obtained the target metal complex 7.02g (yield 95%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Example 2>
For the metal complex obtained in Synthesis Example 1, the adsorption and desorption isotherms of carbon dioxide and methane at 273K were measured. The results are shown in FIG.

<Comparative Example 2>
For the metal complex obtained in Comparative Synthesis Example 2, adsorption and desorption isotherms of carbon dioxide and methane at 273K were measured. The results are shown in FIG.

  From FIG. 4 and FIG. 5, it is clear that the metal complex of the present invention is excellent as a separator for methane and carbon dioxide because it has a high carbon dioxide selective adsorption ability.

<Comparative Synthesis Example 3>
Under a nitrogen atmosphere, 5.00 g (17 mmol) of zinc nitrate hexahydrate, 2.80 g (17 mmol) of isophthalic acid and 2.65 g (17 mmol) of 4,4′-bipyridyl were dissolved in 200 mL of N, N-dimethylformamide, Stir 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 373 K and 50 Pa for 8 hours, and obtained 6.35 g (yield 98%) of the target metal complex. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Example 3>
For the metal complex obtained in Synthesis Example 1, the adsorption and desorption isotherms of carbon dioxide and nitrogen at 273K were measured. The results are shown in FIG. Table 2 shows the adsorption ratio of carbon dioxide and nitrogen at 0.2, 0.4 and 0.6 MPa.

<Comparative Example 3>
For the metal complex obtained in Comparative Synthesis Example 2, adsorption and desorption isotherms of carbon dioxide and nitrogen at 273K were measured. The results are shown in FIG. Table 2 shows the adsorption ratio of carbon dioxide and nitrogen at 0.2, 0.4 and 0.6 MPa.

<Comparative Example 4>
For the metal complex obtained in Comparative Synthesis Example 3, adsorption and desorption isotherms of carbon dioxide and nitrogen at 273K were measured. The results are shown in FIG. Table 2 shows the adsorption ratio of carbon dioxide and nitrogen at 0.2, 0.4 and 0.6 MPa.

表２より、本発明の金属錯体は高い二酸化炭素選択吸着能を有するので、窒素と二酸化炭素の分離材として優れていることは明らかである。

From Table 2, it is clear that the metal complex of the present invention is excellent as a separator for nitrogen and carbon dioxide because it has a high carbon dioxide selective adsorption ability.

<Synthesis Example 2>
Under a nitrogen atmosphere, zinc nitrate hexahydrate 3.21 g (11 mmol), 4,4′-dicarboxydiphenylsulfone 3.31 g (11 mmol) and 1,2-bis (4-pyridyl) ethine 0.97 g (5. 4 mmol) was dissolved in 130 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 4.09g (yield 82%). 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 5.00 g (17 mmol), isophthalic acid 2.80 g (17 mmol) and 1,2-bis (4-pyridyl) ethine 3.03 g (17 mmol) were added to N, N-dimethylformamide. Dissolve in 200 mL and stir at 393 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 3.50g (yield 51%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Comparative Synthesis Example 5>
Under a nitrogen atmosphere, 2.81 g (9.5 mmol) of zinc nitrate hexahydrate, 1.57 g (9.5 mmol) of terephthalic acid and 0.852 g (4.7 mmol) of 1,2-bis (4-pyridyl) ethyne were added. It was dissolved in 800 mL of a mixed solvent of N, N-dimethylformamide and ethanol consisting 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 2.65 g (yield 88%) of the target metal complex. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Example 4>
For the metal complex obtained in Synthesis Example 2, the adsorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

<Comparative Example 5>
For the metal complex obtained in Comparative Synthesis Example 4, the adsorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

<Comparative Example 6>
With respect to the metal complex obtained in Comparative Synthesis Example 5, the adsorption isotherm of carbon dioxide at 273K 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 a carbon dioxide adsorbent because it has a large amount of effective carbon dioxide adsorption.

<Example 5>
With respect to the metal complex obtained in Synthesis Example 2, the adsorption and desorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

<Comparative Example 7>
For the metal complex obtained in Comparative Synthesis Example 4, the adsorption and desorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

<Comparative Example 8>
For the metal complex obtained in Comparative Synthesis Example 5, the adsorption and desorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

  From FIG. 14, it is clear that the metal complex of the present invention is excellent as a storage material for carbon dioxide because it has a large effective storage amount of carbon dioxide.

<Synthesis Example 3>
Under nitrogen atmosphere, zinc nitrate hexahydrate 1.94 g (6.5 mmol), 4,4′-dicarboxydiphenylsulfone 2.00 g (6.5 mmol) and 1,4-bis (4-pyridyl) benzene 0.8. 76 g (3.3 mmol) was dissolved in 80 mL of N, N-dimethylformamide and stirred at 393 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 2.82g (yield 89%). FIG. 15 shows a powder X-ray diffraction pattern of the obtained metal complex.

<Comparative Synthesis Example 6>
Under a nitrogen atmosphere, 2.81 g (9.5 mmol) of zinc nitrate hexahydrate, 1.57 g (9.5 mmol) of terephthalic acid and 1.10 g (4.7 mmol) of 1,4-bis (4-pyridyl) benzene were added. It was dissolved in 800 mL of a mixed solvent of N, N-dimethylformamide and ethanol consisting 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 373 K and 50 Pa for 8 hours, and obtained the target metal complex 3.01g (yield 92%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Example 6>
For the metal complex obtained in Synthesis Example 3, the adsorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

<Comparative Example 9>
With respect to the metal complex obtained in Comparative Synthesis Example 6, the adsorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

  From FIG. 17, it is clear that the metal complex of the present invention is excellent as an adsorbent for carbon dioxide because it has a large effective adsorption amount of carbon dioxide.

<Example 7>
For the metal complex obtained in Synthesis Example 3, the adsorption and desorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

<Comparative Example 10>
For the metal complex obtained in Comparative Synthesis Example 6, the adsorption and desorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

  From FIG. 18, it is clear that the metal complex of the present invention is excellent as a storage material for carbon dioxide because it has a large effective storage amount of carbon dioxide.

<Synthesis Example 4>
Under a nitrogen atmosphere, 3.21 g (11 mmol) of zinc nitrate hexahydrate, 3.31 g (11 mmol) of 4,4′-dicarboxydiphenylsulfone, and 3,6-di (4-pyridyl) -1,2,4, 1.28 g (5.4 mmol) of 5-tetrazine was dissolved in 130 mL of N, N-dimethylformamide and stirred at 393 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 2.70g (yield 51%). FIG. 19 shows a powder X-ray diffraction pattern of the obtained metal complex.

<Comparative Synthesis Example 7>
Under nitrogen atmosphere, zinc nitrate hexahydrate 5.00 g (17 mmol), isophthalic acid 2.80 g (17 mmol) and 3,6-di (4-pyridyl) -1,2,4,5-tetrazine 3.97 g ( 17 mmol) was dissolved in 200 mL of N, N-dimethylformamide and stirred at 393 K for 24 hours. After suction filtration, it was washed with ethanol three times and dried at 373 K and 50 Pa for 8 hours to obtain 4.18 g (yield 53%) of the target metal complex. A powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Example 8>
For the metal complex obtained in Synthesis Example 4, the adsorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

<Comparative Example 11>
For the metal complex obtained in Comparative Synthesis Example 7, the adsorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

  From FIG. 21, it is clear that the metal complex of the present invention is excellent as an adsorbent for carbon dioxide because it has a large amount of effective adsorption of carbon dioxide.

<Example 9>
For the metal complex obtained in Synthesis Example 4, the adsorption and desorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

<Comparative Example 12>
For the metal complex obtained in Comparative Synthesis Example 7, the adsorption and desorption isotherm of carbon dioxide at 273K was measured. The results are shown in FIG.

  FIG. 22 clearly shows that the metal complex of the present invention is excellent as a storage material for carbon dioxide because it has a large effective storage amount for carbon dioxide.

Claims (10)

The following general formula (I);

(In the formula, X represents a sulfonyl group , and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group or a halogen which may have a substituent. Or an alkylene group, an oxyalkylene group or an alkenylene group which may have a substituent by combining R ¹ and R ² , R ⁵ and R ⁶ together. (I),
At least one metal ion selected from magnesium ion, calcium ion, palladium ion and zinc ion ;
1,4-diazabicyclo [2.2.2] octane, pyrazine, 2,5-dimethylpyrazine, 4,4′-bipyridyl, 2,2′-dimethyl-4,4′-bipyridine, 1,2-bis ( 4-pyridyl) ethyne, 1,4-bis (4-pyridyl) butadiyne, 1,4-bis (4-pyridyl) benzene, 3,6-di (4-pyridyl) -1,2,4,5-tetrazine 2,2′-bi-1,6-naphthyridine, phenazine, diazapyrene, trans-1,2-bis (4-pyridyl) ethene, 4,4′-azopyridine, 1,2-bis (4-pyridyl) ethane 1,2-bis (4-pyridyl) -glycol, N- (4-pyridyl) isonicotinamide, 1,2-bis (4-pyridyl) propane, 4,4′-bis (4-pyridyl) biphenyl, N, N′-di (4-pyridyl)- 1,4,5,8-naphthalenetetracarboxydiimide and 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5-c ′] dipyrrole-1,3,5,7 (2H , 6H) -a metal complex comprising an organic ligand capable of bidentate coordination to the metal ion having a structure that cannot be chelated to at least one metal ion selected from tetron . The metal complex according to claim 1 , wherein the metal ion is a zinc ion. An adsorbent comprising the metal complex according to claim 1 or 2 . 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. 6. The occlusion material according to 6. 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 separation material according to claim 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, or air and methane. The following general formula (I);

(In the formula, X represents a sulfonyl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group or a halogen which may have a substituent. Or an alkylene group, an oxyalkylene group or an alkenylene group which may have a substituent by combining R ¹ and R ² , R ⁵ and R ⁶ together. (I),
At least one metal salt selected from a salt of at least one metal ion selected from magnesium ion, calcium ion, palladium ion and zinc ion ;
1,4-diazabicyclo [2.2.2] octane, pyrazine, 2,5-dimethylpyrazine, 4,4′-bipyridyl, 2,2′-dimethyl-4,4′-bipyridine, 1,2-bis ( 4-pyridyl) ethyne, 1,4-bis (4-pyridyl) butadiyne, 1,4-bis (4-pyridyl) benzene, 3,6-di (4-pyridyl) -1,2,4,5-tetrazine 2,2′-bi-1,6-naphthyridine, phenazine, diazapyrene, trans-1,2-bis (4-pyridyl) ethene, 4,4′-azopyridine, 1,2-bis (4-pyridyl) ethane 1,2-bis (4-pyridyl) -glycol, N- (4-pyridyl) isonicotinamide, 1,2-bis (4-pyridyl) propane, 4,4′-bis (4-pyridyl) biphenyl, N, N′-di (4-pyridyl)- 1,4,5,8-naphthalenetetracarboxydiimide, 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5-c ′] dipyrrole-1,3,5,7 (2H , 6H) -Tetron and N, N′-di (4-pyridyl) -1,4,5,8-naphthalenetetracarboxydiimide, an organic compound capable of bidentate coordination with at least one of the metal ions. The method for producing a metal complex according to claim 1, wherein the ligand is reacted and precipitated in a solvent.

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