JP6522397B2 - Method of producing porous metal complex pellet - Google Patents

Description

  The present invention relates to a method of producing pellets. More specifically, the present invention relates to a method for producing a pellet comprising a composition comprising a porous metal complex and a thermoplastic resin.

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

  When separating mixed gas by pressure swing adsorption method or temperature swing adsorption method, generally, molecular sieve carbon, zeolite, etc. are used as separation adsorbents, and separation is performed by the difference of their equilibrium adsorption amount or adsorption rate. . However, in the case of separating the mixed gas by the difference in the equilibrium adsorption amount, the separation coefficient becomes small because the conventional adsorbent can not selectively adsorb only the gas to be removed, and the enlargement of the apparatus is inevitable. . Also, when separating the mixed gas by the difference in adsorption rate, depending on the type of gas, it is possible to adsorb only the gas to be removed, but it is necessary to alternate adsorption and desorption, and in this case also the device still becomes large. I did not get it.

  On the other hand, porous metal complexes have been developed as adsorbents that provide better adsorption performance. Porous metal complexes have features such as (1) large surface area and high porosity, (2) high designability, and (3) dynamic structural change due to external stimuli, and adsorption not found in existing adsorbents Characteristics are expected.

  When using a porous metal complex as an adsorbent, it is preferable to use it after forming it, not as powder. For example, pelletization by tableting is known as a method of forming a porous metal complex (see Patent Document 1 and Patent Document 2). However, no mention is made of the influence of the lubricant at the time of tableting on the strength of the pellet.

WO 2003/102000 Publication WO 2006/050898 gazette

  Therefore, an object of the present invention is to provide a method for producing a pellet comprising a porous metal complex having a high crushing strength.

  The inventors of the present invention have intensively studied and, in a method for producing a pellet comprising a composition comprising a porous metal complex and an elastomer, the mass ratio of the porous metal complex (A) to the elastomer (B) is 1:99 to 99. It has been found that the above object can be achieved by adding a lubricant within the range of 1: 1 and performing tableting by adding a lubricant at the time of molding, and the present invention has been achieved.

That is, according to the present invention, the following is provided.
(1) A method for producing a pellet comprising a composition comprising a porous metal complex (A) and an elastomer (B) in a mass ratio of 1:99 to 99: 1, the porous metal complex (A) and the porous metal complex (A) A lubricant having a saturated solubility of 30 mg / mL or less is added to the elastomer (B), and a tablet manufacturing method is characterized by tableting and molding.
(2) The method for producing a pellet according to (1), wherein the porous metal complex (A) changes its volume with adsorption.
(3) The manufacturing method of the pellet as described in (1) or (2) whose volume change rate accompanying adsorption of a porous metal complex (A) is 0.5 to 50%.
(4) Pellets manufactured by the manufacturing method according to any one of (1) to (3).

  According to the present invention, it is possible to provide a method for producing a pellet comprising a composition comprising a porous metal complex and a thermoplastic resin.

It is a schematic diagram of a jungle gym skeleton formed by 4,4'-bipyridyl coordinating at the axial position of the metal ion in the paddle wheel skeleton consisting of the carboxylate ion of terephthalic acid and the metal ion. It is a schematic diagram of a three-dimensional structure in which a jungle gym skeleton interpenetrates doubly. It is a powder X-ray-diffraction pattern of the state which adsorb | sucked methanol of the metal complex obtained by the synthesis example 1. FIG. It is the crystal structure of the state which adsorb | sucked the methanol of the metal complex obtained by the synthesis example 1. FIG. It is a powder X-ray-diffraction pattern of the dried state of the metal complex obtained by the synthesis example 1. FIG. It is a crystal structure of the dried state of the metal complex obtained in Synthesis Example 1. It is a < ¹ > H NMR spectrum which was made to melt | dissolve the metal complex obtained by the synthesis example 1 in the heavy ammonia aqueous solution, and was measured.

  The present invention is a method for producing a pellet comprising a composition comprising a porous metal complex (A) and an elastomer (B).

  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.

  Examples of ions of metals belonging to Groups 1 to 13 of the periodic table used for the porous metal complex (A) include lithium, sodium, potassium, magnesium ions, calcium ions, scandium ions, lanthanoid ions (lanthanum ions, terbium ions) , Lutetium ions, etc., actinide ions (actinium ions, laurenzium ions, etc.), zirconium ions, vanadium ions, chromium ions, molybdenum ions, manganese ions, iron ions, cobalt ions, cobalt ions, nickel ions, copper ions, zinc ions, cadmium ions, 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 types of metal ions. Moreover, the metal complex (A) used for this invention can also be used in mixture of 2 or more types of metal complexes which consist of a single metal ion.

  Examples of the anionic ligand used for the porous metal complex (A) include halide ions such as fluoride ion, chloride ion, bromide ion and iodide ion; tetrafluoroborate ion, hexafluorosilicic acid Inorganic acid ion such as ion, hexafluorophosphate ion, hexafluoroarsenate ion, hexafluoroantimonate ion; sulfonate ion such as trifluoromethanesulfonate ion, benzenesulfonate ion; formate ion, acetate ion, trifluoroacetic acid Ion, propionate ion, butyrate ion, isobutyrate ion, valerate ion, caproate ion, enanthate ion, cyclohexane carboxylate ion, caprylate ion, octylate ion, pelargonate ion, caprate ion, laurate ion, Lystic acid ion, pentadecyl acid ion, palmitate ion, margaric acid ion, stearic acid ion, tubercurostearic acid ion, arachidic acid ion, behenic acid ion, lignoceric acid ion, α-linolenic acid ion, eicosapentaenoic acid ion, docosahexaene ion Aliphatic monocarboxylic acid ions such as acid ion, linoleic acid ion and 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-naphthoate ion and 4,4'-dihydroxy-3-biphenyl carboxylate ion; heteroaromatic monocarboxylic acid ions such as nicotinate ion and isonicotinate ion; 1,4- Cyclohexane dicarb Aliphatic dicarboxylic acid ions such as sylate ion and fumarate ion; 1,3-benzenedicarboxylate ion, 1,4-benzenedicarboxylate ion, 1,4-naphthalenedicarboxylate ion, 2,6-naphthalene Aromatic dicarboxylic acid ions such as dicarboxylate ion, 2,7-naphthalene dicarboxylate ion, 4,4'-biphenyl dicarboxylate ion; 2,5-thiophene dicarboxylate, 2,2'-dithiophene di Heteroaromatic dicarboxylic acid ions such as carboxylate ion, 2,3-pyrazine dicarboxylate ion, 2,5-pyridine dicarboxylate ion, 3,5-pyridine dicarboxylate ion; 1,3,5-benzenetriol Carboxylate ion, 1,3,4-benze Aromatic tricarboxylate ions such as tricarboxylate ion, biphenyl-3,4 ', 5-tricarboxylate ion; 1,2,4,5-benzenetetracarboxylate ion, [1,1': 4 ', 1 '' Terphenyl-3,3 '', 5,5 ''-tetracarboxylate ion, 5,5 '-(9,10-anthracenediyl) diisophthalate ion and other aromatic tetracarboxylate ions; imidazo Ions of heterocyclic compounds such as rate ions, 2-methyl imidazolate ions, benzimidazole ions, and the like can be used. Here, the anionic ligand means a ligand in which the site coordinated to the metal ion has an anionic property.

  Among the above, as the anionic ligand, those having a carboxylate group are preferable. That is, aliphatic monocarboxylic acid ion, aromatic monocarboxylic acid ion, heteroaromatic monocarboxylic acid ion, aliphatic dicarboxylic acid ion, aromatic dicarboxylic acid ion, heteroaromatic dicarboxylic acid ion, aromatic tricarboxylic acid ion and aromatic It is preferable that it is any one selected from group tetracarboxylic acid ions.

  When the above anionic ligand is an organic ligand having a carboxylate group, a sulfonate group or the like, the organic ligand is a substituent that does not ionize other than a substituent that can be an anion such as a carboxyl group or a sulfo group. You may have further. Specifically, 2-nitro-1,4-benzenedicarboxylate ion, 2-fluoro-1,4-benzenedicarboxylate ion, 2,3,5,6-tetrafluoro-1,4-benzenediyl It may be a polyvalent carboxylate ion having a substituent such as a carboxylate ion or a 2,4,6-trifluoro-1,3,5-benzene tricarboxylate ion.

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

  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, and therefore, it can be used as an adsorbent, storage material, and a variety of gases. It can be used as a separating material.

  The porous metal complex (A) used in the present invention preferably has a volume change rate of 0.5% to 50% due to the adsorption of a substance such as gas or liquid. Here, the volume change rate is defined as the volume ratio of the structural unit of the porous metal complex (A) before and after adsorption. The volume of the structural unit of the porous metal complex (A) can be determined by 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 limited thereto It is not something to be done.

  The volume change rate was, for example, immersed in the solvent used when synthesizing the porous metal complex (A), with the volume obtained when the porous metal complex (A) was allowed to dry under vacuum and then allowed to stand under normal temperature and normal pressure. Sometimes, it can be determined by comparing with the volume that has increased from the reference volume. As the solvent, methanol, ethanol, propanol, diethyl ether, dimethoxyethane, tetrahydrofuran, hexane, cyclohexane, heptane, benzene, benzene, toluene, methylene chloride, chloroform, acetone, ethyl acetate, acetonitrile, N, N-dimethylformamide, water or these Mixed solvents can be used. As immersion temperature, 253-423K is preferable.

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

  The organic ligand capable of multidentate coordination is not particularly limited, however, it is an organic ligand capable of bidentate coordination with metal ions, and an organic ligand capable of tridentate coordination with metal ions, Organic ligands capable of tetradentate coordination to metal ions can be used. Here, the neutral organic ligand capable of multidentate coordination means a neutral ligand having at least two or more sites coordinated to a metal ion by a noncovalent electron pair. A bidentate organic ligand is a multidentate neutral organic ligand having two sites coordinating to a metal ion with a noncovalent electron pair; a tridentate organic ligand has a noncovalent electron A multidentate neutral organic ligand that has three coordination sites for metal ions in pairs; a tetradentate organic ligand has a noncovalent electron pair that coordinates sites for metal ions It is a neutral organic ligand capable of multidentate coordination at four points.

  Examples of the bidentate organic ligand (bidentate ligand) include, for example, 1,4-diazabicyclo [2.2.2] octane, pyrazine, 4,4′-bipyridyl, and 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) ethane, 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 (benzimidazole) 1-ylmethyl) -2,4 5,6-Tetramethylbenzene, 1,4-bis (4-pyridylmethyl) -2,3,5,6-tetramethylbenzene, 1,3-bis (imidazol-1-ylmethyl) -2,4,6 -Trimethylbenzene, 1,3-bis (4-pyridylmethyl) -2,4,6-trimethylbenzene and the like. Examples of the organic ligand capable of tridentate coordination (tridentate ligand) include, for example, 1,3,5-tris (2-pyridyl) benzene, 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 1,4,6-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 organic ligand capable of tetradentate coordination (tetradentate ligand) include, for example, 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-pyridyloxy) Methylene) methane, tetrakis (1-imidazolylmethyl) methane and the like can be mentioned. Among these, an organic ligand capable of bidentate coordination is preferred.

  The organic ligand capable of multidentate coordination may have a substituent. Specifically, polydentate capable organic ligands having substituents such as 2-methylpyrazine, 2,5-dimethylpyrazine, 2,2'-dimethyl-4,4'-bipyridine and the like can be mentioned.

  The multidentate organic ligand capable of being used in the porous metal complex (A) is a single multidentate organic ligand, or an organic coordination capable of two or more types of multidentate coordinates. It may contain children. Moreover, porous metal complex (A) can also be used in mixture of 2 or more types of metal complexes which consist of a single multidentate-coordinateable 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 a noncovalent electron pair. As the monodentate organic ligand, for example, furan, thiophene, pyridine, quinoline, isoquinoline, acridine, triphenyl phosphine, triphenyl phosphite, methyl isocyanide and the like can be used, and among them, pyridine is preferable. The monodentate organic ligand may have a hydrocarbon group having 1 to 23 carbon atoms as a substituent.

  The porous metal complex (A) used in the present invention comprises a metal salt containing at least one metal ion selected from ions of metals belonging to Groups 1 to 13 of the periodic table, and a compound containing an anionic ligand And an organic ligand capable of multidentate coordination with the metal ion, if necessary, by reacting either in the gas phase, liquid phase or solid phase. Among them, the reaction is preferably carried out by reacting for several hours to several days in a solvent under normal pressure, for precipitation. At this time, the reaction may be performed under ultrasonic or microwave irradiation. For example, the present invention can be carried out by mixing and reacting an aqueous solution of a metal salt or an organic solvent solution and an organic solvent solution containing an anionic ligand and an organic ligand capable of multidentate coordination under normal pressure. The porous metal complex (A) used can be obtained (for example, refer Unexamined-Japanese-Patent No. 2010-70545).

  The mixing ratio of the metal salt to the anionic ligand when producing the porous metal complex (A) is preferably in the range of a molar ratio of metal salt: anionic ligand = 1: 10 to 10: 1. The molar ratio of 1: 5 to 5: 1 is more preferable. Even if the reaction is carried out in a range other than this range, the target metal complex can be obtained, but this is not preferable because the yield decreases and side reactions also increase.

  When the porous metal complex (A) contains an organic ligand capable of multidentate coordination, the mixing ratio when producing the metal complex (A) is an anionic ligand: multidentate coordination Possible organic ligands are preferably in the range of molar ratio of 1: 5 to 8: 1, and more preferably in the range of molar ratio of 1: 3 to 6: 1. Moreover, the inside of the range of the molar ratio of metal salt: organic ligand which can be polydentated to 3: 1 to 1: 3 is preferable, and the inside of the range of the molar ratio of 2: 1 to 1: 2 is more preferable.

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

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

  As an example of porous metal complex (A) whose volume changes with adsorption, zinc ion as metal ion, 1,4-benzenedicarboxylate (terephthalic acid ion) as anionic ligand, multidentate coordination The porous metal complex (A-1) having 4,4′-bipyridyl as a possible organic ligand is described in detail. In the porous metal complex (A-1), 4,4′-bipyridyl is coordinated to the axial position of the metal ion in the paddle wheel skeleton consisting of carboxylate ion of 1,4-benzenedicarboxylate and metal ion It has a three-dimensional structure in which the jungle gym skeleton formed is doubly interpenetrated. 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 interpenetrates doubly is shown in FIG.

  The above-mentioned "jungle gym skeleton" refers to a polymer such as 4,4'-bipyridyl at the axial position of the metal ion in the paddle wheel skeleton consisting of an anionic ligand such as 1,4-benzenedicarboxylate and the metal ion. It means a jungle gym-like three-dimensional structure formed by coordination between organic ligands capable of coordination and coordination between two-dimensional lattice-like sheets consisting of anionic ligands and metal ions. The “structure in which jungle gym skeletons interpenetrate each other” is a three-dimensional integrated structure in which a plurality of jungle gym skeletons interpenetrate each other in the form of filling in pores.

  In the present specification, “a porous metal complex whose volume changes with adsorption” refers to a change in the structure or size of pores in a skeleton by chemical stimulation in which a substance is adsorbed in the pores of a porous metal complex Mean a porous metal complex. The metal complex can also change in volume by physical stimuli such as temperature, pressure, electric field, etc. in addition to chemical stimuli.

  Changes in the structure and size of the pores 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 in proportion to the magnitude of the Lennard-Jones potential of the substance), the degree of structural change varies depending on the substance to be adsorbed.

  As another example of the porous metal complex (A) which can change its volume with adsorption, for example, it is possible to polydentate copper ions as metal ions and tetrafluoroborate ions as anionic ligands Metal complex (A-2) having a three-dimensional structure in which one-dimensional chain skeletons are accumulated obtained when 1,2-bis (4-pyridyl) ethane is used as an organic ligand; copper as a metal ion Three-dimensional layered two-dimensional lattice-like skeleton obtained when using tetrafluoroborate ion as an anionic ligand and 4,4'-bipyridyl as an organic ligand capable of multidentate coordination Porous metal complex having structure (A-3); copper ion as metal ion, 2,5-dihydroxybenzoic acid ion as anionic ligand, 4,4 as organic ligand capable of multidentate coordination '-Bipyridyl Two-dimensional seat frame obtained by use can be exemplified such as a porous metal complex having a interdigitated three-dimensional structure (A-4).

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

  The elastomer (B) used in the present invention is not particularly limited, and any one can be used. Among them, olefin (co) polymers or thermoplastic elastomers are preferred. As the olefin (co) polymer, a copolymer of ethylene or propylene and another monomer such as vinyl acetate can be used. As a thermoplastic elastomer, a block copolymer having at least one polymer block (rubber phase) having a glass transition temperature of 273 K or less (for example, a glass transition temperature of 173 K to 273 K) in part of a polymer chain Coalescing can be used. In particular, a polymer block (rubber phase) having a glass transition temperature of 273 K or less and a polymer having a glass transition temperature of 310 K or more (for example, a glass transition temperature of 310 K to 393 K) Thermoplastic elastomers which are block copolymers having a block (restricting phase) are preferred.

  Examples of the thermoplastic elastomer used in the present invention include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, nitrile-based elastomers, amide-based elastomers, polybutadiene-based elastomers, acrylic-based elastomers, and vinyl chloride-based thermoplastics. An elastomer or the like can be used. Among them, styrenic elastomers, olefinic elastomers and acrylic elastomers can be particularly preferably used.

  The mixing ratio of the metal complex (A) to the elastomer (B) is preferably such that the mass ratio of the metal complex (A) to the elastomer (B) is in the range of 1:99 to 99: 1, and 10:90 to More preferably, it is in the range of 90:10. Outside this range, the gas adsorption performance may be lowered and / or the form may not be maintained as a composition.

  The composition used in the present invention is an antioxidant, an antifreeze agent, a pH adjuster, a hiding agent, a coloring agent, an oil agent, a flame retardant, a near agent, if necessary, as long as the effects of the present invention are not impaired. The infrared absorber, the ultraviolet absorber, the color tone corrector, the dye, the antioxidant, and other special functional agents can be contained alone or in combination of two or more.

  The method for producing pellets according to the present invention is characterized in that a lubricant is added and tableting is performed when the composition is formed. By using a lubricant, pellets excellent in crush strength can be produced for the following reasons.

  When the composition is tableted and formed, if the frictional force between the mold wall and the composition is large, the composition in the vicinity of the mold wall may not be sufficiently compressed. This problem may be solved by the addition of suitable lubricants. That is, by adding a lubricant, the frictional force between the mold wall and the composition can be reduced, and sufficient compression pressure can be transmitted even in the vicinity of the mold wall. As a result, pellets of excellent crushing strength can be obtained. It is presumed that the cause of the decrease in the friction force between the mold wall and the composition is that the lubricant intervenes between them to reduce the contact area between the mold wall and the composition.

  The lubricant used in the present invention means a substance that reduces the friction between the composition containing the porous metal complex (A) and the elastomer (B) and the wall of the mold of the tablet forming machine. Do. As the lubricant, a lubricant which has a small saturation solubility of the elastomer and which is liquid at 25 ° C. is preferable. In the present invention, the lubricant needs to have a saturated solubility of 30 mg / mL or less, preferably 10 mg / mL or less, more preferably 5 mg / mL or less. When a lubricant that dissolves the elastomer is used, the elastomer in the vicinity of the mold wall is mixed with the lubricant, so that the effect of reducing the contact area between the mold wall and the composition may not be obtained. Also, during molding, friction heat is generated due to the friction between the mold wall and the composition. When the boiling point of the lubricant is 45 ° C. or less, the lubricant in the vicinity of the mold wall may be vaporized during compression, which may cause a buffer layer to be sufficiently compressed.

  Specific examples of the lubricant used in the present invention include, for example, alcohols such as methanol, ethanol, propanol, butanol, isopropyl alcohol, heptanol and hexanol; polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; dimethyl ether, ethyl methyl Ethers such as ether, 1,4-dioxane and tetrahydrofuran; cellosolve such as methyl cellosolve and ethyl cellosolve; methyl acetate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, isopentyl acetate, methyl salicylate and other esters; water; dimethylformamide And acetonitrile. These lubricants can be used alone or in combination of two or more. When using alcohol or polyhydric alcohol as a lubricant, a C2-C8 thing is preferable and a C2-C3 thing is more preferable. When a polyhydric alcohol is used as the lubricant, a mono- to tri-alcohol is preferable, and a di- to tri-alcohol is more preferable.

  In the present invention, the saturated solubility means a value measured at 25 ° C. according to the method described in the examples.

  Although the compounding ratio of a lubricant is not specifically limited, For example, 1-50 mass parts with respect to the total mass 100 mass parts of a metal complex (A) and an elastomer (B), Preferably it is 3-30 mass parts. It can be set appropriately.

  In the present invention, the crushing strength of the obtained pellet can be increased by compounding a lubricant and performing tablet forming. Therefore, in the present invention, the lubricant can be reworded as being used as a strength enhancing agent. Therefore, according to the present invention, in a composition containing a porous metal complex (A) and an elastomer (B) in a mass ratio of 1:99 to 99: 1, the saturation solubility of the elastomer (B) is 30 mg / mL or less There is also provided a method for enhancing the crush strength of pellets, which is characterized by adding a lubricant and tableting and forming.

  In the method of the present invention, the step of drying the obtained pellet may be performed after the tableting and forming step. If a lubricant remains in the pellet after the tableting and forming step, the lubricant can be removed by the drying step. Although the temperature of a drying process is not specifically limited, For example, 300 degrees C or less, Preferably it can set suitably in 80-250 degreeC. Further, the time of the drying step is also not particularly limited, but can be suitably set in the range of, for example, 10 to 3000 minutes, preferably 60 to 600 minutes. The drying step may be carried out without adjusting the pressure or under reduced pressure.

  The size of the pellet obtained by the present invention is not particularly limited because it varies depending on the use conditions, but the diameter is in the range of 0.5 mm to 5.0 mm and the length is 1.0 mm to 10 mm. It is preferable to be within the range of .0 mm.

  The crushing strength of the pellet obtained according to the present invention is not particularly limited because it varies depending on the size of the pellet and the conditions of use, but it is preferably 90 N or more, more preferably 100 N or more.

  Pellets obtained by the production method of the present invention are carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms (methane, ethane, ethylene, acetylene, propane, propene, methylacetylene, propadiene, Butane, 1-butene, isobutene, 1-butyne, 2-butyne, 1,3-butadiene, methyl allene etc., rare gases (helium, neon, argon, krypton, xenon etc), hydrogen sulfide, ammonia, sulfur oxide , Adsorption performance and storage performance of various gases such as nitrogen oxides, siloxanes (hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane etc.), water vapor or organic vapor (vaporized gas of organic substances liquid at normal temperature and pressure) And excellent in separation performance. Therefore, the pellet of the present invention is useful as an adsorbent, storage material and separation material for various gases, which are also included in the scope of the present invention.

  The organic vapor means vaporized gas of an organic substance which is liquid at normal temperature and pressure. 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, cyclocyclopentadiene Hydrocarbons having 5 to 16 carbon atoms such as octane, cyclooctene, 1,5-cyclooctadiene, 4-vinyl-1-cyclohexene and 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.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. 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 ° / minute and measured by a symmetrical reflection method. Details of the analysis conditions are shown below.
<Analytical conditions>
Device: Rigaku Corporation SmartLab
X-ray source: CuKα (λ = 1.5418 Å) 45 kV 200 mA
Goniometer: Horizontal goniometer detector: D / teX Ultra
Step width: 0.02 °
Slit: Divergence slit = 2/3 °
Light receiving slit = 0.3 mm
Scattering slit = 2/3 °.

(2) Determination of Acetic Acid Contained in Metal Complex The ¹ H NMR measurement was performed on a sample in which the metal complex was dissolved in an aqueous heavy ammonia solution, and calculated from the integral ratio of the obtained spectrum. The details of the analysis conditions are described below.
<Analytical conditions>
Device: JNM-LA500 manufactured by Nippon Denshi Co., Ltd.
Resonance frequency: 500 MHz
Solvent: 25 wt% deuterium aqueous ammonia reference material: sodium 3- (trimethylsilyl) propanoate-d4
Temperature: 298 K
Integration count: 2,048 times.

(3) Measurement of crushing strength The pellet was placed in a uniaxial press and uniaxially pressurized at a loading rate of 9 mm / min at 298K. The pressing force (N) at the time of stress relaxation occurred was measured, and this value was taken as the crushing strength (in accordance with JIS Z8841). Details of the analysis conditions are shown below.
<Analytical conditions>
Device: Autograph AGS-10kNG manufactured by Shimadzu Corporation
Load cell 5BL-1kN
Measurement mode: Compression / tension mode.

(4) Measurement of Saturated Solubility In a 50 mL eggplant flask, 50 mg, 300 mg, or 500 mg of the elastomer and 10 mL of a solvent were added, and stirring was performed at an internal temperature of 25 ° C. for 5 hours. Next, the contents of the eggplant flask were taken out and filtered using a PTFE filter. After the obtained residual solid was recovered, drying under reduced pressure was performed at 150 ° C. for 5 hours, and the mass of the solid was measured. The saturated solubility of the elastomer was calculated from the solid mass and the mass of the charged elastomer.

Synthesis Example 1
[First step]
Under 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 suspension . The precipitated metal complex was collected by suction filtration and then washed three times with methanol to isolate an intermediate.

[Second step]
Under 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 stirred at 298 K for 3 hours. At this time, the reaction solution remained suspended. The metal complex was collected by suction filtration and washed three times with methanol. 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 the separately synthesized single crystal, it was found that the obtained metal complex has a structure in which the jungle gym skeleton interpenetrates double. The results of single crystal structure analysis 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 = 86.577 (5) °
γ = 88.083 (5) °
V = 3274.9 (10) Å ³
R = 0.0458
R _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 the separately synthesized single crystal, it was found that the obtained metal complex has a structure in which the jungle gym skeleton interpenetrates double. The results of single crystal structure analysis 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 = 0.0330
R _w = 0.0905.

From the comparison between FIG. 3 and FIG. 5, since the structure is different before and after the adsorption and desorption of methanol, it is understood that the structure of the present complex changes dynamically with the adsorption and desorption. The volume change rate at this time is as follows: the volume of the structural unit of the metal complex before vacuum drying (in the methanol adsorption state) is 3274.9 (10) Å 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 as 27.1% according to the following equation.
Volume change rate = {3274.9 / (689.3 x 4)-1} x 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-d4 as a reference substance), and ¹ H NMR measurement was performed. The spectrum obtained is shown in FIG. As a result of analyzing the spectrum, the integral value of the 7.917 ppm (s, 4 H) peak which is assigned to the protons of the 2-, 3-, 5- and 6-positions of terephthalic acid is 2.037, while the integrated value is 2.037 Since the integral value of the peak of 1.928 ppm (s, 3H) attributed to the proton of the methyl group was 0.030, the molar ratio of terephthalic acid to acetic acid contained in the metal complex was terephthalic acid: acetic acid It turned out that it is = 104: 1. The broad signal near 3.9 ppm in FIG. 7 is due to water.

From the results of powder X-ray crystal structure 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 ₂ ) It turned out that it is ₃ COO) _x ] _n (x = 0.019). 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 It calculated from the molecular weight of the compound represented by these. As a result, the yield of the obtained metal complex was 81%.

Synthesis Example 2
2.60 g of <Evaflex (registered trademark)> (brand: EV45LX) manufactured by Mitsui-Dupont Polychemicals Co., Ltd., which is a random copolymer of ethylene and vinyl acetate, was added to 160 mL of chloroform and dissolved by stirring at 298K. To the resulting solution, 25.2 g of the metal complex obtained in Synthesis Example 1 was added, and stirred at 298 K for 5 minutes. Then, after distilling off chloroform under reduced pressure, it dried at 373 K and 50 Pa for 8 hours, and obtained 24.5 g (yield 85%) of a composition of a metal complex and an ethylene-vinyl acetate copolymer.

Example 1
450 mg of the composition of the metal complex and ethylene-vinyl acetate copolymer obtained in Synthesis Example 2 is mixed with 113 mg of water as a lubricant and placed in a die having an inner diameter of 3.0 mm and a length of 15 mm. Tablet using a simple tablet molding machine HANDTAB-100, tableting pressure 2,450 kgf / cm ² , temperature 473 K, holding time 0 minutes, 6 pellets of 3.0 mm in diameter and 7.8 mm in length ( 425 mg) was obtained.

  As a result of measuring the crushing strength of the obtained pellet, it was 137N (n = 5 average value).

Examples 2-3 and Comparative Examples 1-3
Pellets of Examples 2 to 3 and Comparative Examples 2 to 3 were produced in the same manner as in Example 1 except that lubricants of the type and amount described in Table 1 were used, and crushing strength was measured. A pellet of Comparative Example 1 was produced in the same manner as Example 1 except that no lubricant was added, and the crushing strength was measured. The results are shown in the following table.

  As shown in Table 1 above, by using a lubricant having a low saturation solubility of the elastomer (B), pellets of high crushing strength could be obtained. In Comparative Example 2, the elastomer was melted by toluene, and the wall of the tableting machine was soiled.

Claims (4)

A method for producing a pellet comprising a composition comprising a porous metal complex (A) and an elastomer (B) in a mass ratio of 1:99 to 99: 1, comprising the porous metal complex (A) and the elastomer (B). B) adding at least one lubricant selected from the group consisting of alcohol, polyhydric alcohol and water, the lubricant having a saturation solubility of 30 mg / mL or less of the elastomer (B), The manufacturing method of the pellet characterized by tableting.   The method for producing a pellet according to claim 1, wherein the porous metal complex (A) changes in volume as the substance is adsorbed.   The method for producing a pellet according to claim 1 or 2, wherein a volume change rate with adsorption of a substance of the porous metal complex (A) is 0.5 to 50%.   The pellet manufactured by the manufacturing method as described in any one of Claims 1-3.

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