JP2015202469A - porous metal complex composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having excellent gas adsorption performance, gas occlusion performance and gas separation performance.SOLUTION: The problem is solved by a composition that comprises a porous metal complex, and a thermoplastic resin having a density of 1 g/cmor less. The composition has excellent gas adsorption, occlusion and separation performance.

Description

The present invention relates to a porous metal complex composition. More specifically, the present invention relates to a composition comprising a porous metal complex capable of changing its structure with adsorption and a thermoplastic resin having a density of 1 g / cm ³ or less. The composition of the present invention is an adsorbent for adsorbing carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, noble 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, porous metal complexes have been developed as adsorbents that give better adsorption performance. Porous metal complexes are characterized by (1) a large surface area and high porosity, (2) high designability, and (3) dynamic structural changes due to external stimuli, which are not found in existing adsorbents. Expected characteristics.

  In particular, when a porous metal complex that generates a dynamic structural change due to external stimuli is used as a gas adsorbent, it does not adsorb gas up to a certain pressure. Observed. 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.

  When the porous metal complex is used as the adsorbent, it is preferably used after being molded rather than in powder form. For example, pelletization by tableting is known as a method for forming a porous metal complex (see Patent Document 1 and Patent Document 2). However, there is no description about the effect of the resin used for the binder on the strength of the pellet.

WO2003 / 102000 publication WO2006 / 050898

  Accordingly, an object of the present invention is to provide an adsorbent, occlusion material, or separation material having a high crushing strength, which contains a porous metal complex that can change its structure with adsorption as a constituent component.

The present inventors have intensively studied and found that the above object can be achieved by a composition comprising a porous metal complex capable of changing its structure with adsorption and a thermoplastic resin having a density of 1 g / cm ³ or less. Invented.

That is, according to the present invention, the following is provided.
(1) A composition comprising a porous metal complex (A) capable of changing its structure with adsorption and a thermoplastic resin (B) having a density of 1 g / cm ³ or less.
(2) The composition according to (1), wherein the thermoplastic resin (B) is an α-olefin polymer.
(3) The composition as described in (1) or (2) whose mass ratio of a porous metal complex (A) and a thermoplastic resin (B) exists in the range of 1: 99-99: 1.
(4) The composition is in any shape selected from pellets, films, sheets, plates, pipes, tubes, rods, granules, heterogeneous shapes, fibers, hollow fibers, woven fabrics, knitted fabrics and non-woven fabrics. The composition according to any one of (1) to (3).
(5) An adsorbent comprising the composition according to any one of (1) to (4).
(6) The adsorbent is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or The adsorbent according to (5), which is an adsorbent for adsorbing organic vapor.
(7) An occlusion material comprising the composition according to any one of (1) to (4).
(8) The storage material is a storage material for storing carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, water vapor or organic vapor. The occlusion material according to (7).
(9) A separating material comprising the composition according to any one of (1) to (4).
(10) The separator is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or The separation material according to (9), which is a separation material for separating organic vapor.
(11) The separation method using the separation material according to (9), including a step of bringing the separation material and the mixed gas into contact with each other in a pressure range of 0.01 to 10 MPa.
(12) The separation method according to (11), wherein the separation method is a pressure swing adsorption method or a temperature swing adsorption method.
(13) A porous metal complex capable of changing its structure with adsorption, characterized by being molded in a state of being heated to a Vicat softening point or higher of a thermoplastic resin (B) having a density of 1 g / cm ³ or less (A) And a method for producing a molded body comprising a thermoplastic resin (B) having a density of 1 g / cm ³ or less.

According to the present invention, it is possible to provide a composition comprising a porous metal complex (A) capable of changing its structure with adsorption and a thermoplastic resin (B) having a density of 1 g / cm ³ or less.

  Since the composition of the present invention is excellent in 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.

  In addition, since the composition 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 composition 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 a jungle gym skeleton formed by coordination of 4,4'-bipyridyl at an axial position of a zinc ion in a paddle wheel skeleton composed of a carboxylate ion and a zinc ion of terephthalic acid. It is a schematic diagram of a three-dimensional structure in which the jungle gym skeleton is double interpenetrated. It is a schematic diagram of the structural change accompanying the adsorption / desorption of the gas of a porous metal complex. 3 is a powder X-ray diffraction pattern in which methanol of the metal complex obtained in Synthesis Example 1 is adsorbed. It is a crystal structure in a state where methanol of the metal complex obtained in Synthesis Example 1 is adsorbed. It is a powder X-ray diffraction pattern of the dried state of the metal complex obtained in Synthesis Example 1. It is the crystal structure of the dried state of the metal complex obtained in Synthesis Example 1. 2 is a ¹ H-NMR spectrum measured by dissolving the metal complex obtained in Synthesis Example 1 in an aqueous heavy ammonia solution. 2 is an adsorption / desorption isotherm of carbon dioxide at 293 K of the composition obtained in Synthesis Example 2. FIG. 2 is an adsorption / desorption isotherm of carbon dioxide at 293 K of the composition obtained in Synthesis Example 3. FIG. 2 is an adsorption / desorption isotherm of carbon dioxide at 293 K of the metal complex obtained in Synthesis Example 1. FIG.

The composition of the present invention contains a porous metal complex (A) capable of changing its structure with adsorption and a thermoplastic resin (B) having a density of 1 g / cm ³ or less.

  The porous metal complex (A) used in the present invention contains at least one metal ion selected from ions of metals belonging to Groups 1 to 13 of the periodic table and an anionic ligand.

  The metal ion contained in the porous metal complex (A) is at least one metal ion selected from ions of metals belonging to Groups 1 to 13 of the periodic table. Metal ions belonging to Group 1 of the periodic table are lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, and francium ions. Metal ions belonging to Group 2 of the periodic table are beryllium ions, magnesium ions, calcium ions, strontium ions, barium ions, and radium ions. Metal ions belonging to Group 3 of the periodic table are scandium ions, yttrium ions, lanthanoid ions, and actinide ions. Metal ions belonging to Group 4 of the periodic table are titanium ions, zirconium ions, hafnium ions, and rutherfordium ions. Metal ions belonging to Group 5 of the periodic table are vanadium ions, niobium ions, tantalum ions, and dobnium ions. Metal ions belonging to Group 6 of the periodic table are chromium ions, molybdenum ions, tungsten ions, and seaborgium ions. Metal ions belonging to Group 7 of the periodic table are manganese ions, technetium ions, rhenium ions, and bolium ions. Metal ions belonging to Group 8 of the periodic table are iron ions, ruthenium ions, osmium ions, and hash ions. Metal ions belonging to Group 9 of the periodic table are cobalt ions, rhodium ions, iridium ions, and mitnerium ions. Metal ions belonging to Group 10 of the periodic table are nickel ions, palladium ions, platinum ions, and dermisstatium ions. Metal ions belonging to Group 11 of the periodic table are copper ions, silver ions, gold ions, and roentgenium ions. Metal ions belonging to Group 12 of the periodic table are zinc ions, cadmium ions, mercury ions, and ununbium ions. The metal ions belonging to Group 13 of the periodic table are boron ions, aluminum ions, gallium ions, indium ions, thallium ions, and unium ions.

  Examples of the metal ions belonging to Groups 1 to 13 of the periodic table used for the porous metal complex (A) include lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, scandium ions, lanthanoid ions (lanthanum ions). , Terbium ions, lutetium ions, etc.), actinoid ions (actinium ions, lauren ions, etc.), zirconium ions, vanadium ions, chromium ions, molybdenum ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions, Cadmium ions and aluminum ions can be used, among which manganese ions, cobalt ions, nickel ions, copper ions and zinc ions are preferable, and copper ions are more preferable.

  The metal ion used for the porous metal complex (A) may be a single metal ion or may contain two or more kinds of metal ions. Moreover, the porous metal complex (A) used for this invention can also mix and use 2 or more types of metal complexes which consist of a single metal ion.

  In the production of the porous metal complex (A), a metal salt containing the metal ion can be used. Examples of metal salts include lithium salts, sodium salts, potassium salts, magnesium salts, calcium salts, scandium salts, lanthanoid salts (such as lanthanum salts, terbium salts, and lutetium salts), actinoid salts (such as actinium salts and lauren salts), Zirconium salt, vanadium salt, chromium salt, molybdenum salt, manganese salt, iron salt, cobalt salt, nickel salt, copper salt, zinc salt, cadmium salt and aluminum salt can be used, among which manganese salt, cobalt salt, Nickel salts, copper salts and zinc salts are preferred, and copper salts are more preferred.

  The metal salt may be a single metal salt or a mixture of two or more metal salts. Further, as these metal salts, organic acid salts such as acetates and formates, inorganic acid salts such as sulfates, nitrates, hydrochlorides, hydrobromides and carbonates can be used.

  Examples of the anionic ligand used in the porous metal complex (A) include halide ions such as fluoride ion, chloride ion, bromide ion and iodide ion; tetrafluoroborate ion and hexafluorosilicate Ions, hexafluorophosphate ions, hexafluoroarsenate ions, hexafluoroantimonate ions, etc .; sulfonate ions such as trifluoromethanesulfonate ions, benzenesulfonate ions; formate ions, acetate ions, trifluoroacetic acid ions Ion, propionate ion, butyrate ion, isobutyrate ion, valerate ion, caproate ion, enanthate ion, cyclohexanecarboxylate ion, caprylate ion, octylate ion, pelargonate ion, caprate ion, laurate ion, Listinoic acid ion, pentadecylic acid ion, palmitic acid ion, margaric acid ion, stearic acid ion, tuberculostearic acid ion, arachidic acid ion, behenic acid ion, lignoceric acid ion, α-linolenic acid ion, eicosapentaenoic acid ion, docosahexaene Aliphatic monocarboxylic acid ions such as acid ion, linoleic acid ion, oleic acid ion; benzoic acid ion, 2,5-dihydroxybenzoic acid ion, 3,7-dihydroxy-2-naphthoic acid ion, 2,6-dihydroxy- Aromatic monocarboxylic acid ions such as 1-naphthoic acid ion and 4,4′-dihydroxy-3-biphenylcarboxylic acid ion; heteroaromatic monocarboxylic acid ions such as nicotinic acid ion and isonicotinic acid ion; 1,4- Cyclohexane dicarbo Aliphatic dicarboxylate ions such as xylate ion and fumarate ion; 1,3-benzenedicarboxylate ion, 1,4-benzenedicarboxylate ion, 1,4-naphthalenedicarboxylate ion, 2,6-naphthalene Aromatic dicarboxylate ions such as dicarboxylate ion, 2,7-naphthalene dicarboxylate ion, 4,4′-biphenyl dicarboxylate ion; 2,5-thiophene dicarboxylate, 2,2′-dithiophene di Heteroaromatic dicarboxylate ions such as carboxylate ion, 2,3-pyrazine dicarboxylate ion, 2,5-pyridinedicarboxylate ion, 3,5-pyridinedicarboxylate ion; 1,3,5-benzenetri Carboxylate ion, 1,3,4-be Aromatic tricarboxylate ions such as zentricarboxylate ions, biphenyl-3,4 ', 5-tricarboxylate ions; 1,2,4,5-benzenetetracarboxylate ions, [1,1': 4 ', 1 ″] aromatic tetracarboxylate ions such as terphenyl-3,3 ″, 5,5 ″ -tetracarboxylate ion, 5,5 ′-(9,10-anthracenediyl) diisophthalate ion; Ions of heterocyclic compounds such as imidazolate ions, 2-methylimidazolate ions, and benzoimidazolate ions can be used. Here, the anionic ligand means a ligand in which a site coordinated with a metal ion has an anionic property.

  Among these, as the anionic ligand, those having a carboxylate group are preferable. That is, aliphatic monocarboxylate ion, aromatic monocarboxylate ion, heteroaromatic monocarboxylate ion, aliphatic dicarboxylate ion, aromatic dicarboxylate ion, heteroaromatic dicarboxylate ion, aromatic tricarboxylate ion and aromatic It is preferably any one selected from group tetracarboxylate ions.

  When the above anionic ligand has a carboxylate group, a sulfonate group or the like, the anionic ligand further has a non-ionizable substituent other than a substituent that can be an anion such as a carboxyl group and a sulfo group. May be. Specifically, 2-nitro-1,4-benzenedicarboxylate ion, 2-fluoro-1,4-benzenedicarboxylate ion, 2,3,5,6-tetrafluoro-1,4-benzenedi It may be a polyvalent carboxylate ion having a substituent such as a carboxylate ion or 2,4,6-trifluoro-1,3,5-benzenetricarboxylate ion.

  The anionic ligand used in the porous metal complex (A) may be a single anionic ligand or may contain two or more types of anionic ligands. Moreover, 2 or more types of metal complexes which consist of a single anionic ligand can also be mixed and used for a porous metal complex (A).

  In the production of the porous metal complex (A), a salt containing the anionic ligand can be used. As the salt, for example, lithium salt, sodium salt, potassium salt, ammonium salt and the like can be used. The salt is preferably a single salt, but two or more salts may be mixed and used.

  Moreover, the anionic ligand used for a porous metal complex (A) may use the counter anion of the metal salt used as a metal ion source as it is.

  Furthermore, in the production of the porous metal complex (A), a conjugated acid containing the anionic ligand or an acid anhydride thereof can be used. The acid is preferably a single acid, but two or more acids may be mixed and used.

  Since the porous metal complex (A) used in the present invention is a porous body and can adsorb and desorb low molecules such as gas in its pores, various gas adsorbents, occlusion materials and It can be used as a separating material.

  The porous metal complex (A) used in the present invention may contain a neutral organic ligand capable of multidentate coordination with the above metal ion.

  The neutral organic ligand capable of multidentate coordination is not particularly limited, but a bidentate organic ligand, a tridentate organic ligand, a tetradentate organic ligand, or the like can be used. . Here, the neutral organic ligand capable of multidentate coordination means a neutral ligand having at least two sites coordinated to a metal ion by an unshared electron pair. A bidentate organic ligand is a neutral organic ligand that has two sites coordinated to a metal ion with an unshared electron pair; a tridentate organic ligand is an unshared electron pair with respect to a metal ion. A neutral organic ligand having three sites to coordinate with each other; a tetradentate organic ligand is a neutral organic ligand having four sites to coordinate to a metal ion with an unshared electron pair.

  As a neutral organic ligand (bidentate ligand) capable of bidentate coordination, for example, 1,4-diazabicyclo [2.2.2] octane, pyrazine, 4,4′-bipyridyl, 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, 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5-c ′] dipyrrole-1 , 3,5,7 (2H, 6H) -tetron, N, N′-di (4-pyridyl) -1,4,5,8-naphthalenetetracarboxydiimide, trans-1,2-bis (4-pyridyl) ) Ethene, 4,4′-azopyridine, 1,2-bis (4-pyridyl) 4,4′-dipyridyl sulfide, 1,3-bis (4-pyridyl) propane, 1,2-bis (4-pyridyl) -glycol, N- (4-pyridyl) isonicotinamide, 1,2- Bis (1-imidazolyl) ethane, 1,2-bis (1,2,4-triazolyl) ethane, 1,2-bis (1,2,3,4-tetrazolyl) ethane, 1,3-bis (1- Imidazolyl) propane, 1,3-bis (1,2,4-triazolyl) propane, 1,3-bis (1,2,3,4-tetrazolyl) propane, 1,4-bis (4-pyridyl) butane, 1,4-bis (1-imidazolyl) butane, 1,4-bis (1,2,4-triazolyl) butane, 1,4-bis (1,2,3,4-tetrazolyl) butane, 1,4- Bis (benzimidazol-1-ylmethy ) -2,4,5,6-tetramethylbenzene, 1,4-bis (4-pyridylmethyl) -2,3,5,6-tetramethylbenzene, 1,3-bis (imidazol-1-ylmethyl) Examples include -2,4,6-trimethylbenzene and 1,3-bis (4-pyridylmethyl) -2,4,6-trimethylbenzene. Examples of neutral organic ligands (tridentate ligands) capable of tridentate coordination include 1,3,5-tris (2-pyridyl) benzene and 1,3,5-tris (3-pyridyl). Benzene, 1,3,5-tris (4-pyridyl) benzene, 1,3,5-tris (1-imidazolyl) benzene, 2,4,6-tris (2-pyridyl) -1,3,5-triazine 2,4,6-tris (3-pyridyl) -1,3,5-triazine, 2,4,6-tri (4-pyridyl) -1,3,5-triazine, 2,4,6-tris (1-imidazolyl) -1,3,5-triazine and the like. Examples of the neutral organic ligand capable of tetradentate coordination (tetradentate ligand) include 1,2,4,5-tetrakis (2-pyridyl) benzene, 1,2,4,5-tetrakis (3- Pyridyl) benzene, 1,2,4,5-tetrakis (4-pyridyl) benzene, 1,2,4,5-tetrakis (1-imidazolyl) benzene, tetrakis (3-pyridyloxymethylene) methane and tetrakis (4- Pyridyloxymethylene) methane, tetrakis (1-imidazolylmethyl) methane and the like. Among these, an organic ligand capable of bidentate coordination is preferable.

  The neutral organic ligand capable of multidentate coordination may have a substituent. Specific examples include neutral organic ligands capable of multidentate coordination having a substituent such as 2-methylpyrazine, 2,5-dimethylpyrazine, and 2,2′-dimethyl-4,4′-bipyridine. It is done.

  The neutral organic ligand capable of multidentate coordination used in the porous metal complex (A) may be a single type or two or more types. In addition, the metal complex (A) may be used by mixing two or more metal complexes composed of a single multidentate neutral organic ligand.

  The porous metal complex (A) may further contain a monodentate organic ligand as long as the effects of the present invention are not impaired. The monodentate organic ligand means a neutral ligand having one site coordinated to a metal ion by an unshared electron pair. As monodentate organic ligands, for example, substituted or unsubstituted furan, thiophene, pyridine, quinoline, isoquinoline, acridine, triphenylphosphine, triphenylphosphite, methylisocyanide, etc. can be used, and pyridine is particularly preferred. preferable. The monodentate organic ligand may have a hydrocarbon group having 1 to 23 carbon atoms as a substituent.

  When the porous metal complex (A) contains a monodentate organic ligand, the ratio is not particularly limited as long as the effect of the present invention is not impaired, but the multidentate organic ligand and the monodentate organic are not limited. The composition ratio with the ligand is preferably in the range of 1:20 to 5,000: 1, more preferably in the range of 20: 1 to 5,000: 1 in terms of molar ratio, Is particularly preferably within the range of 1 to 2,500: 1. The composition ratio can be determined by analyzing the porous metal complex (A) by using, for example, gas chromatography, high performance liquid chromatography, NMR, etc. after decomposing the porous metal complex (A) into a uniform solution. It is not limited to these.

  The porous metal complex (A) used in the present invention includes a metal salt containing at least one metal ion selected from ions of metals belonging to Groups 1 to 13 of the periodic table, an anionic ligand, and Accordingly, it can be produced by reacting a neutral organic ligand capable of multidentate coordination with the metal ion in a gas phase, a liquid phase or a solid phase. Among them, it is preferable to produce by precipitation by reacting in a solvent for several hours to several days under normal pressure. At this time, the reaction may be performed under ultrasonic wave or microwave irradiation. For example, an aqueous solution or an organic solvent solution of a metal salt and an organic solvent solution containing an anionic ligand and a neutral organic ligand capable of multidentate coordination are mixed and reacted under normal pressure to react. A porous metal complex (A) used in the invention can be obtained (for example, see JP-A-2010-70545).

  The mixing ratio of the metal salt and the anionic ligand when producing the porous metal complex (A) is preferably within the range of the molar ratio of metal salt: anionic ligand = 1: 10 to 10: 1. More preferably, the molar ratio is in the range of 1: 5 to 5: 1. 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 increased.

  When the porous metal complex (A) contains a neutral organic ligand capable of multidentate coordination, the mixing ratio when the metal complex (A) is produced is an anionic ligand: polydentate. The neutral organic ligand capable of coordination is preferably within a range of a molar ratio of 1: 5 to 8: 1, and more preferably within a range of a molar ratio of 1: 3 to 6: 1. Further, the neutral organic ligand capable of multidentate coordination: preferably within a molar ratio range of 3: 1 to 1: 3, and more preferably within a molar ratio range of 2: 1 to 1: 2. .

  The porous metal complex (A) used in the present invention has a one-dimensional or two-dimensional structure depending on the type of anionic ligand to be used and the type of neutral organic ligand capable of multidentate coordination. Or a three-dimensional integrated structure.

  The integrated structure of the porous metal complex (A) can be confirmed by, for example, single crystal X-ray structure analysis, powder X-ray crystal structure analysis, single crystal neutron structure analysis, powder neutron crystal structure analysis, etc., but is not limited thereto. It is not a thing.

  As an example of the porous metal complex (A) whose volume changes with adsorption, a porous metal complex (A-1) having a three-dimensional structure in which a jungle gym skeleton is double-interpenetrated is exemplified. As a specific example, zinc ion as a metal ion, 1,4-benzenedicarboxylate (terephthalate ion) as an anionic ligand, and 4,4′- as a neutral organic ligand capable of multidentate coordination. The porous metal complex having bipyridyl will be described in detail. This porous metal complex is formed by coordination of 4,4′-bipyridyl at the axial position of the zinc ion in the paddle wheel skeleton composed of the carboxylate ion of 1,4-benzenedicarboxylate and the zinc ion. The jungle gym skeleton has a three-dimensional structure (A-1) in which a double interpenetration occurs. A schematic diagram of the jungle gym skeleton is shown in FIG. 1, and a schematic diagram of a three-dimensional structure in which the jungle gym skeleton is double-interpenetrated is shown in FIG.

  The above “jungle gym skeleton” refers to a multiplicity such as 4,4′-bipyridyl at the axial position of a metal ion in a paddle wheel skeleton composed of an anionic ligand such as 1,4-benzenedicarboxylate and a metal ion. It means a jungle-gym-like three-dimensional structure formed by coordination between neutral organic ligands that can be coordinated and connecting two-dimensional lattice sheets composed of anionic ligands and metal ions. To do. “A structure in which multiple jungle gym skeletons interpenetrate” is a three-dimensional integrated structure in which a plurality of jungle gym skeletons penetrate each other so as to fill the pores.

  In this specification, “a porous metal complex whose volume changes with adsorption” means that the pores in the skeleton are chemically stimulated by a substance (for example, gas) adsorbed in the pores of the porous metal complex. It means a porous metal complex whose structure and size change. In addition to chemical stimulation, the metal complex can change in volume by physical stimulation such as temperature, pressure, and electric field.

  Changes in the pore structure and size of the porous metal complex (A) depend on the type of substance to be adsorbed, the adsorption pressure, and the adsorption temperature. That is, in addition to the difference in the interaction between the pore surface and the substance (the strength of the interaction is proportional to the magnitude of the Lennard-Jones potential of the substance), the degree of structural change differs depending on the adsorbed substance. As an example, FIG. 3 shows a schematic diagram of the structural change accompanying adsorption / desorption when the porous metal complex (A) has a three-dimensional structure in which the jungle gym skeleton is double interpenetrated.

  Other examples of the porous metal complex (A) that can change in volume with gas adsorption include, for example, copper ions as metal ions, tetrafluoroborate ions as anionic ligands, and multidentate coordination. A porous metal complex (A-2) obtained by using 1,2-bis (4-pyridyl) ethane as a possible neutral organic ligand and having a three-dimensional structure in which one-dimensional chain skeletons are accumulated; For example, a copper ion as a metal ion, a tetrafluoroborate ion as an anionic ligand, and 4,4′-bipyridyl as a neutral organic ligand capable of multidentate coordination are obtained. Porous metal complex (A-3) having a three-dimensional structure in which a three-dimensional lattice skeleton is laminated; for example, copper ions as metal ions, 2,5-dihydroxybenzoate ions as anionic ligands, multidentate Can rank Obtained when using 4,4'-bipyridyl as organic ligand, a porous metal complex having a three-dimensional structure two-dimensional seat frame is fitted mutually (A-4) and the like.

  The fact that the porous metal complex (A) used in the present invention can change in volume with adsorption is, for example, comparison of single crystal X-ray structural analysis results, change in powder X-ray diffraction pattern, change in absorption wavelength, Although it can confirm by the change of a magnetic susceptibility etc., it is not limited to these.

The thermoplastic resin (B) used in the present invention has a density of 1 g / cm ³ or less. In a preferred embodiment of the present invention, the density is in the range of 0.90~1g / cm ^3, and more preferably in a range of 0.90~0.950g / cm ^3.

  The density can be determined by measuring according to JIS K7112: 1999.

  The thermoplastic resin (B) is preferably an α-olefin polymer.

  As the α-olefin, for example, ethylene, propylene, 1-butene, 1-heptene, 1-hexene, 1-octene and the like can be used, and among them, ethylene and propylene are preferable.

  The α-olefin may be a single α-olefin or two or more α-olefins.

Examples of the thermoplastic resin (B) used in the present invention include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and polypropylene as long as the density is 1 g / cm ³ or less. Among them, low density polyethylene, linear low density polyethylene, and polypropylene are preferable, and linear low density polyethylene is more preferable.

  The mixing ratio of the porous metal complex (A) and the thermoplastic resin (B) is such that the mass ratio of the porous metal complex (A) and the thermoplastic resin (B) is in the range of 1:99 to 99: 1. It is preferable that it is in the range of 10:90 to 90:10. Outside this range, the gas adsorption performance may decrease and / or the composition may not be maintained in the form. In one embodiment, when the composition is formed into pellets, A: B can be from 80:20 to 99: 1.

  The total proportion of the porous metal complex (A) and the thermoplastic resin (B) in the composition of the present invention is preferably 30% by mass or more, more preferably 50% by mass or more, and 80% by mass. The above is particularly preferable.

Between the crystalline particles of the porous metal complex (A) in the molded article made of the composition of the present invention are bound by the thermoplastic resin (B), and the density is 1 g / cm ³ or less. Since the thermoplastic resin (B) occupying in the unit volume increases, the obtained molded body has a high crushing strength.

The crushing strength can be determined by measuring according to JIS Z8841. in this case,
In the preferable aspect of this invention, it is preferable that the crushing strength of the molded object obtained is 200 N or more, It is more preferable in the range of 200-400N, It is especially preferable in the range of 300-360N.

  The crushing strength mechanism is an estimate, but 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.

  A method for mixing the porous metal complex (A) and the thermoplastic resin (B) is not particularly limited, but a specific method for mixing is preferably a melt-kneading method from the viewpoint of simplicity of process and cost. At this time, using a device capable of achieving a high degree of kneading and dispersing each component finely and uniformly improves the gas adsorption performance, gas storage performance and gas separation performance, and the gel in the composition. It is preferable at the point which can prevent generation | occurrence | production and mixing of a crack.

  Examples of apparatuses that can achieve a high degree of kneading include continuous kneaders such as continuous intensive mixers, kneading type twin screw extruders, mixing rolls, and kneaders; high-speed mixers, Banbury mixers, intensive mixers, pressure kneaders, etc. Batch type kneaders; Equipment using a rotating disk with a grinding mechanism such as a stone mill; Equipment provided with a kneading part (Dalmage, CTM, etc.) on a single screw extruder; Simple such as ribbon blender, Brabender mixer, etc. A mold kneader or the like can be used, but is not limited thereto.

  The kneading temperature is usually in the range of 300 to 600K. In order to prevent oxidative deterioration of the porous metal complex (A) and the thermoplastic resin (B), it is preferable that the hopper port is sealed with nitrogen and extruded at a low temperature. The kneading time is usually from 10 to 1,800 seconds, preferably from 15 to 1,000 seconds, from the viewpoint of preventing oxidation deterioration of the porous metal complex (A) and the thermoplastic resin (B) and producing efficiency.

  The usage form of the composition of the present invention is not particularly limited, and any form may be used as long as it can be produced using a composition containing the porous metal complex (A) and the thermoplastic resin (B). Examples of usage modes include pellets, films, sheets, plates, pipes, tubes, rods, granules, powders, various deformed shapes, fibers, hollow fibers, woven fabrics, knitted fabrics, and nonwoven fabrics. . Moreover, as long as the effects of the present invention are not impaired, natural or synthetic fibers, or inorganic fibers such as glass may be included as necessary to form a composite.

  Although the manufacturing method of the molded object containing a porous metal complex (A) and a thermoplastic resin (B) is not specifically limited, It is preferable to shape | mold in the state heated more than the Vicat softening point of a thermoplastic resin (B).

  The Vicat softening point can be determined by measuring according to JIS K7206: 1999.

  There is no limitation in particular as a preparation method of the pellet containing the composition of this invention, Any of the conventionally known pelletization methods can be employ | adopted. The compression molding method is preferable from the viewpoint that the density of the pellet can be increased. Usually, at the time of compression molding, a composition of a porous metal complex (A) and a thermoplastic resin (B) is prepared in advance, and this is solidified into a certain shape under pressure using a commercially available tablet molding machine. . At this time, if necessary, a lubricant such as graphite and magnesium stearate may be added to the preparation.

  When using the composition of this invention as a pellet, it is preferable that a diameter exists in the range of 0.5 mm-5.0 mm, and length exists in the range of 1.0 mm-10.0 mm.

  The method for producing the film containing the composition of the present invention is not particularly limited, and a liquid composition is prepared by dispersing or dissolving the porous metal complex (A) and the thermoplastic resin (B) in an appropriate solvent. And after applying the said liquid composition on a peelable base material or a support body, the method of drying and removing a solvent etc. is employable. As a solvent for dispersing or dissolving the porous metal complex (A) and the thermoplastic resin (B), for example, toluene, tetrahydrofuran and the like can be used, but the solvent is not limited thereto.

  The method for applying the composition of the present invention to a releasable substrate or support is not particularly limited, and any of the conventionally known coating methods using a liquid coating material can be employed. For example, dip coating method, spray coating method, spinner coating method, bead coating method, wire bar coating method, blade coating method, roller coating method, curtain coating method, slit die coater method, gravure coater method, slit reverse coater method, micro A gravure method, a comma coater method, etc. can be used.

  The method for producing a sheet containing the composition of the present invention is not particularly limited, and any conventionally known sheeting method can be adopted. The wet papermaking method is preferable from the viewpoint that the sheet can be densified. The wet papermaking method is a manufacturing method in which raw materials are dispersed in water, filtered through a net, and dried.

  A honeycomb shape can be given as an example of the deformed shape. Any conventionally known processing method can be adopted as a method for forming a sheet containing the composition of the present invention into a honeycomb shape. In addition, in the present invention, the honeycomb shape refers to a continuous hollow column body such as a square, sinusoidal, or roll-shaped hollow polygonal column or a cylinder in addition to a hexagonal cross section. For example, in order to obtain a sinusoidal honeycomb shape, first, the sheet is passed through a shaping roll and shaped into a corrugated shape, and a flat sheet is bonded to one or both sides of the corrugated sheet. This is laminated to form a sinusoidal honeycomb filter. Here, it is common to attach and fix the top of the corrugation with an adhesive, but when the corrugated sheet containing the composition of the present invention or the like is laminated, the flat sheet in between is necessarily fixed. It is not always necessary to apply an adhesive. In addition, when attaching an adhesive agent, it is necessary to use what does not impair the adsorption | suction ability of a sheet | seat. As the adhesive, for example, corn starch, vinyl acetate resin, acrylic resin, or the like can be used. In order to improve the gas adsorption performance, it is preferable to reduce the adhesion pitch of the corrugated sheet and reduce the peak height. The pitch is preferably 0.5 to 8 mm, and the peak height is preferably 0.4 to 5 mm.

  As long as the composition of the present invention is within a range that does not impair the effects of the present invention, an antioxidant, an antifreeze agent, a pH adjuster, a concealing agent, a colorant, an oil agent, a flame retardant, a near-infrared absorption, if necessary. 1 type (s) or 2 or more types of an agent, a ultraviolet absorber, a color tone correction agent, dye, antioxidant, and another special function agent can be contained.

  The composition of the present invention is excellent in various gas adsorption performance, occlusion performance, and separation performance. Therefore, the composition of the present invention is useful as an adsorbent, adsorbent and separator for various gases, and these are also included in the scope of the present invention.

  Examples of the adsorbent, occlusion material, and separation material of the present invention include carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, and hydrocarbons having 1 to 4 carbon atoms (methane, ethane, ethylene, acetylene, propane, propene, methyl Acetylene, propadiene, butane, 1-butene, isobutene, 1-butyne, 2-butyne, 1,3-butadiene, methylallene, etc.), noble gases (helium, neon, argon, krypton, xenon, etc.), hydrogen sulfide, ammonia , Sulfur oxides, nitrogen oxides, siloxanes (hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, etc.), water vapor or organic vapor can be suitably used to adsorb, occlude, and separate gases. In the separation material of the present invention, in particular, methane and carbon dioxide, hydrogen and carbon dioxide, nitrogen and carbon dioxide, ethylene and carbon dioxide, methane and ethane, ethylene and ethane, nitrogen and oxygen, oxygen and argon, nitrogen and It is suitable for separating methane, air and methane by pressure swing adsorption method or temperature swing adsorption method.

  The organic vapor means a vaporized organic substance that is liquid at normal temperature and pressure. Examples of such organic substances include alcohols such as methanol and ethanol; amines such as trimethylamine; aldehydes such as formaldehyde and acetaldehyde; pentane, isoprene, hexane, cyclohexane, heptane, methylcyclohexane, octane, 1-octene, cyclohexane C5-C16 hydrocarbons such as octane, cyclooctene, 1,5-cyclooctadiene, 4-vinyl-1-cyclohexene, 1,5,9-cyclododecatriene; aromatic hydrocarbons such as benzene and toluene Ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; halogenated hydrocarbons such as methyl chloride and chloroform.

  The composition of the present invention (or the adsorbent of the present invention) can also be used in a canister by taking advantage of its adsorption performance. A canister is widely used as a device for preventing fuel evaporated in a fuel tank in a vehicle from diffusing into the atmosphere. The canister adsorbs the fuel vapor in contact with the surface and includes an adsorbent having a property of releasing the fuel vapor by the flow of air. The adsorbent comprising the composition of the present invention includes the adsorbent. It can be suitably used as a material. A canister including an adsorbent made of the composition of the present invention exhibits superior adsorption performance and can improve the amount of fuel vapor adsorbed as compared to a canister including conventional activated carbon as an adsorbent. Therefore, the present invention is particularly useful as a canister for a hybrid vehicle that requires a canister with higher adsorption performance.

  The composition of the present invention (or the storage material of the present invention) can also be used in a gas storage device taking advantage of its storage performance. As an example of the gas storage device, there is a gas storage device in which a gas storage space is provided inside a pressure-resistant container that can be kept airtight and has a gas inlet / outlet, and the storage space is provided with a storage material made of the composition of the present invention. . By press-fitting a desired gas into the gas storage device, the gas can be adsorbed and stored in the internal storage material. When taking out the gas from the gas storage device, the gas can be desorbed by opening the pressure valve and reducing the internal pressure in the pressure vessel. In installing the occlusion material in the gas storage space, the composition of the present invention may be powdered, but from the viewpoint of handleability, etc., a pellet-shaped product obtained by molding the composition of the present invention is used. May be.

  Such a gas storage device can store fuel gas in a storage space, and can be suitably used as a fuel tank for a gas vehicle or the like. Since the occlusion material made of the composition of the present invention is incorporated, the fuel tank can increase the gas compressibility against the apparent pressure as compared with the fuel tank not filled with the occlusion material. It is possible to reduce the thickness of the gas storage device and to reduce the weight of the entire gas storage device. This fuel tank is normally in a normal temperature state, and is not particularly cooled. The temperature of the fuel tank is relatively high in summer, for example, when the temperature rises. Even under such a high temperature range (about 298 to 333 K), the occlusion material of the present invention can keep its occlusion ability high and is useful.

  The gas separation method using the composition of the present invention (or the separation material of the present invention) is a method of separating the mixed gas and the composition of the present invention (or the separation material of the present invention) under conditions that allow the mixed gas to be adsorbed on the composition. A step of contacting. The adsorption pressure and adsorption temperature, which are conditions under which the gas can be adsorbed to the composition, can be set as appropriate according to the type of substance to be adsorbed. For example, the adsorption pressure is preferably 0.01 to 10 MPa, and more preferably 0.1 to 3.5 MPa. Further, the adsorption temperature is preferably 195K to 343K, and more preferably 273 to 313K.

  The separation method can be a pressure swing adsorption method or a temperature swing adsorption method. When the separation method is a pressure swing adsorption method, the separation method further includes a step of increasing the pressure from the adsorption pressure to a pressure at which gas can be desorbed from the metal complex. The desorption pressure can be appropriately set according to the type of substance to be adsorbed. For example, the desorption pressure is preferably 0.005 to 2 MPa, and more preferably 0.01 to 0.1 MPa. When the separation method is a temperature swing adsorption method, the separation method further includes a step of raising the temperature from the adsorption temperature to a temperature at which the gas can be desorbed from the metal complex. The desorption temperature can be appropriately set according to the type of substance to be adsorbed. For example, the desorption temperature is preferably 303 to 473K, and more preferably 313 to 373K.

  When the separation method is a pressure swing adsorption method or a temperature swing adsorption method, the step of bringing the gas into contact with the metal complex and the step of changing the pressure to a temperature or a temperature at which the gas can be desorbed from the metal complex are repeated as appropriate. Can do.

  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 analysis conditions are shown below.
<Analysis conditions>
Apparatus: SmartLab, manufactured by Rigaku Corporation
X-ray source: CuKα (λ = 1.5418Å) 45 kV 200 mA
Goniometer: Horizontal goniometer Detector: D / teX Ultra
Step width: 0.02 °
Slit: Divergent slit = 2/3 °
Receiving slit = 0.3mm
Scattering slit = 2/3 °

(2) Quantification of acetic acid contained in metal complex ¹ H-NMR measurement was performed on a sample in which the metal complex was dissolved in an aqueous heavy ammonia solution, and the obtained spectrum was calculated from the integral ratio of the obtained spectrum. Details of the analysis conditions are described below.
<Analysis conditions>
Device: JNM-LA500 manufactured by JEOL Ltd.
Resonance frequency: 500 MHz
Solvent: 25 wt% heavy ammonia aqueous solution Reference material: sodium 3- (trimethylsilyl) propanoate-d ₄
Temperature: 298K
Integration count: 2,048 times

(3) Measurement of adsorption / desorption isotherm Using a high-pressure gas adsorption amount measuring device, the gas adsorption / desorption amount was measured by the volume method to create an adsorption / desorption isotherm (conforming to JIS Z8831-2). At this time, the sample was dried at 373 K and 0.5 Pa for 5 hours prior to measurement to remove adsorbed water and the like. Details of the analysis conditions are shown below.
<Analysis conditions>
Apparatus: BELSORP-HP manufactured by Nippon Bell Co., Ltd.
Equilibrium waiting time: 500 seconds

(4) Measurement of crushing strength The cylindrical pellets were installed in a uniaxial press machine in the horizontal direction, and uniaxially pressed at a loading speed of 9 mm / min at 298K. The applied pressure (N) when stress relaxation occurred was measured, and this value was taken as the crushing strength (based on JIS Z8841). Details of the analysis conditions are shown below.
<Analysis conditions>
Equipment: Autograph AGS-10kNG manufactured by Shimadzu Corporation
Load cell 5BL-1kN
Measurement mode: Compression / Tension mode

<Synthesis Example 1>
[First step]
Under a nitrogen atmosphere, 21.8 g (109 mmol) of copper acetate monohydrate, 18.2 g (109 mmol) of terephthalic acid and 19.7 g (328 mmol) of acetic acid were dispersed in 200 mL of methanol and stirred at 333 K for 18 hours in a suspended state. . The precipitated metal complex intermediate was collected by suction filtration and then washed three times with methanol to isolate the intermediate.

[Second step]
Under a nitrogen atmosphere, the isolated intermediate was dispersed in 133 mL of methanol, 8.54 g (54.7 mmol) of 4,4′-bipyridyl was added, and the mixture was stirred at 298 K for 3 hours. At this time, the reaction solution remained suspended. The metal complex was recovered by suction filtration, and then washed with methanol three times. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the comparison with the simulation pattern obtained from the structural analysis result of a separately synthesized single crystal, it was found that the obtained metal complex had a structure in which the jungle gym skeleton was double interpenetrated. The single crystal structure analysis results are shown below. The crystal structure is shown in FIG.

Triclinic (P-1)
a = 10.8195 (18) Å
b = 14.004 (3) Å
c = 21.682 (4) Å
α = 87.570 (4) °
β = 866.577 (5) °
γ = 88.083 (5) °
V = 3274.9 (10) ^{３ 3}
R = 0.0458R _w = 0.1187

  Subsequently, the obtained metal complex was dried at 373 K and 50 Pa for 8 hours to obtain 26.3 g of the target metal complex. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the comparison with the simulation pattern obtained from the structural analysis result of a separately synthesized single crystal, it was found that the obtained metal complex had a structure in which the jungle gym skeleton was double interpenetrated. The single crystal structure analysis results are shown below. The crystal structure is shown in FIG.

Triclinic (P-1)
a = 7.898 (3) Å
b = 8.930 (3) Å
c = 10.818 (3) Å
α = 67.509 (12) °
β = 80.401 (14) °
γ = 79.566 (13) °
V = 689.3 (4) Å ³
R = 0.0330R _w = 0.0905

From a comparison between FIG. 4 and FIG. 6, it can be seen that the structure of this complex changes dynamically with the adsorption and desorption because the structure is different before and after the adsorption and desorption of methanol. The volume change rate at this time is such that the volume of the structural unit of the metal complex before vacuum drying (methanol adsorption state) is 3274.9 (10) ^{３ 3} , and the volume of the structural unit of the metal complex after vacuum drying is 689.3 ( 4) since it is Å ^3, it is calculated to be 27.1 percent according to the following equation.
Volume change rate = {3274.9 / (689.3 × 4) −1} × 100 = 27.1%

10 mg of the obtained metal complex was dissolved in 700 mg of 25 wt% heavy ammonia water (containing 0.4 wt% of sodium 3- (trimethylsilyl) propanoate-d ₄ as a reference substance), and ¹ H-NMR measurement was performed. The obtained spectrum is shown in FIG. As a result of analyzing the spectrum, the integrated value of the peak at 7.917 ppm (s, 4H) attributed to protons at the 2nd, 3rd, 5th and 6th positions of terephthalic acid was 2.037, whereas acetic acid was Since the integrated value of the peak at 1.928 ppm (s, 3H) attributed to the proton of the methyl group of 0.030 was 0.030, the molar ratio of terephthalic acid and acetic acid contained in the metal complex was terephthalic acid: acetic acid. = 104: 1. In FIG. 8, the broad signal around 3.9 ppm is due to water.

From the results of single crystal X-ray structural analysis and ¹ H-NMR measurement, the composition formula of the obtained metal complex is [Cu ₂ (C ₈ H ₄ O ₄ ) _2-x (C ₁₀ H ₈ N ₂ ) (CH ₃ COO) _x ] _n (x = 0.1.9). Since the value of x is small, the theoretical yield is [Cu ₂ (C ₈ H ₄ O ₄ ) ₂ (C ₁₀ H ₈ N ₂ )] _n (copper: terephthalic acid: 4,4′-bipyridyl = 2: 2: 1). ) Was calculated from the molecular weight of the compound represented. As a result, the yield of the obtained metal complex was 81%.

<Synthesis Example 2>
A linear low density polyethylene made of a copolymer of ethylene and 1-hexene manufactured by Prime Polymer Co., Ltd. <Ultzex (registered trademark)> (brand: 1020 L, density 0.909 g / cm ³ ) 1.00 g in toluene It was added to 56.3 mL and dissolved by stirring at 383K. To the obtained solution, 9.01 g of the metal complex obtained in Synthesis Example 1 was added, and the mixture was stirred at 383 K for 5 minutes. Subsequently, toluene was distilled off under reduced pressure, followed by drying at 443 K and 50 Pa for 15 hours to obtain 9.43 g (yield 94%) of the desired metal complex composition.

453 mg of the obtained metal complex composition was put into a mortar having an inner diameter of 3.0 mm and a length of 15 mm, and 5 at a tableting pressure of 610 kgf / cm ² and a temperature of 473 K using a simple tablet molding machine HANDTAB-100 manufactured by Ichihashi Seiki Co., Ltd. Compressed for 5 minutes, 6 cylindrical pellets (455 mg) having a diameter of 3.0 mm and a length of 8.8 mm were obtained.

<Synthesis Example 3>
Toluene is a linear low density polyethylene made of a copolymer of ethylene and 1-hexene manufactured by Prime Polymer Co., Ltd. <Ultzex (registered trademark)> (brand: 4020 L, density 0.937 g / cm ³ ). It was added to 56.3 mL and dissolved by stirring at 383K. To the obtained solution, 9.00 g of the metal complex obtained in Synthesis Example 1 was added, and the mixture was stirred at 383 K for 5 minutes. Subsequently, toluene was distilled off under reduced pressure, followed by drying at 443 K and 50 Pa for 15 hours to obtain 9.30 g (yield 93%) of the target metal complex composition.

453 mg of the obtained metal complex composition was put into a mortar having an inner diameter of 3.0 mm and a length of 15 mm, and 5 at a tableting pressure of 610 kgf / cm ² and a temperature of 473 K using a simple tablet molding machine HANDTAB-100 manufactured by Ichihashi Seiki Co., Ltd. Compressed for 5 minutes, 6 cylindrical pellets (452 mg) having a diameter of 3.0 mm and a length of 8.7 mm were obtained.

<Comparative Synthesis Example 1>
<Klarity (registered trademark)> manufactured by Kuraray Co., Ltd. (brand: 2140e, density 1.18 g / cm), which is an acrylic thermoplastic elastomer comprising a triblock copolymer of methyl methacrylate, n-butyl acrylate and methyl methacrylate ³ ) 2.80 g was added to 160 mL of chloroform and dissolved by stirring at 298K. 25.2 g of the metal complex obtained in Synthesis Example 1 was added to the obtained solution, and the mixture was stirred at 298K for 5 minutes. Then, after distilling chloroform off under reduced pressure, it was dried at 373 K and 50 Pa for 8 hours to obtain 24.5 g (yield 85%) of the target metal complex composition.

452 mg of the obtained metal complex composition was put into a mortar having an inner diameter of 3.0 mm and a length of 15 mm, and a tableting pressure of 610 kgf / cm ² and a temperature of 473 K was used using a simple tablet molding machine HANDTAB-100 manufactured by Ichihashi Seiki Co., Ltd. Compressed for minutes, 6 cylindrical pellets (445 mg) having a diameter of 3.0 mm and a length of 8.6 mm were obtained.

<Example 1>
The crushing strength of the composition molded into the pellet shape obtained in Synthesis Example 2 was measured and found to be 308N (n = 6 average value).

<Example 2>
It was 353N (n = 6 average value) as a result of measuring crushing strength about the composition shape | molded by the pellet shape obtained in the synthesis example 3. FIG.

<Comparative Example 1>
It was 199N (n = 6 average value) as a result of measuring crushing strength about the composition shape | molded by the pellet shape obtained in the comparative synthesis example 1. FIG.

  From the comparison between Example 1 and Example 2 and Comparative Example 1, the pellets composed of the compositions obtained in Synthesis Example 1 and Synthesis Example 2 that satisfy the constituent requirements of the present invention are not compared to satisfy the constituent requirements of the present invention. It is clear that the strength is stronger than the pellet made of the composition obtained in Synthesis Example 1.

<Example 3>
About the composition shape | molded by the pellet shape obtained in the synthesis example 2, the adsorption amount of the carbon dioxide in 293K was measured by the volume method, and the adsorption / desorption isotherm was created. The results are shown in FIG.

<Example 4>
About the composition shape | molded by the pellet shape obtained in the synthesis example 3, the adsorption amount of the carbon dioxide in 293K was measured by the volume method, and the adsorption / desorption isotherm was created. The results are shown in FIG.

  From FIG. 9 and FIG. 10, it is clear that the pellet made of the composition satisfying the constituent requirements of the present invention can adsorb carbon dioxide with increasing pressure. Therefore, it is clear that a molded body containing the composition of the present invention can also be used as an adsorbent such as carbon dioxide, an occlusion material, and a separation material.

<Reference Example 1>
With respect to the green metal complex obtained in Synthesis Example 1, the adsorption amount of carbon dioxide at 293K was measured by the volume method, and an adsorption / desorption isotherm was prepared. The adsorption / desorption isotherm is shown in FIG.

Claims (13)

A composition comprising a porous metal complex (A) capable of changing its structure upon adsorption and a thermoplastic resin (B) having a density of 1 g / cm ³ or less.   The composition according to claim 1, wherein the thermoplastic resin (B) is an α-olefin polymer.   The composition according to claim 1 or 2, wherein the mass ratio of the porous metal complex (A) to the thermoplastic resin (B) is in the range of 1:99 to 99: 1.   The composition is in any shape selected from pellets, films, sheets, plates, pipes, tubes, rods, granules, heteromorphs, fibers, hollow fibers, woven fabrics, knitted fabrics and non-woven fabrics. The composition as described in any one of 1-3.   The adsorbent which consists of a composition as described in any one of Claims 1-4.   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 organic vapor. The adsorbent according to claim 5, which is an adsorbent for adsorbing.   The occlusion material which consists of a composition as described in any one of Claims 1-4.   The occlusion material is an occlusion material for occluding carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, water vapor or organic vapor. The occlusion material according to 7.   The separating material which consists of a composition as described in any one of Claims 1-4.   The separation material is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or organic vapor. The separation material according to claim 9, which is a separation material for separation.   The separation method using the separation material according to claim 9, comprising a step of bringing the separation material and the mixed gas into contact with each other in a pressure range of 0.01 to 10 MPa.   The separation method according to claim 11, wherein the separation method is a pressure swing adsorption method or a temperature swing adsorption method. A porous metal complex (A) capable of changing its structure with adsorption, characterized by being molded in a state heated to a Vicat softening point or higher of a thermoplastic resin (B) having a density of 1 g / cm ³ or less. The manufacturing method of a molded object containing 1 g / cm < ³ > or less thermoplastic resin (B).