JP6456075B2 - Coordination polymer complex containing fluorine, gas adsorbent, gas separation device and gas storage device using the same - Google Patents

Description

  The present invention relates to use as a porous polymer metal complex and a gas adsorbing material, and a gas separation device and a gas storage device using the same.

  The gas adsorbent has a characteristic of storing a large amount of gas at a low pressure as compared with pressurized storage and liquefied storage. For this reason, in recent years, development of a gas storage device and a gas separation device using a gas adsorbent has been active. As the gas adsorbent, activated carbon, zeolite and the like are known. Recently, a method of occluding gas in a porous polymer metal complex has also been proposed (see Patent Document 1 and Non-Patent Document 1).

  Porous polymer metal complexes are crystalline solids obtained from metal ions and organic ligands, and exhibit various gas adsorption properties due to the variety of metal ions, combinations of organic ligands and the variety of skeletal structures. It has potential. However, these conventionally proposed gas adsorbents are not sufficiently satisfactory in terms of the amount of gas adsorption and workability, and the development of gas adsorbents with better characteristics is desired. .

  One of the characteristics of the porous polymer metal complex is its network structure. There are known porous polymer metal complexes having various structures such as a one-dimensional chain aggregate, a two-dimensional square lattice laminate, and a jungle gym-shaped three-dimensional structure (Non-patent Document 2). These various porous polymer metal complexes exhibit various physical properties derived from the network structure, the metal ions constituting the network, the chemical properties of the ligand, and the physical shape.

  A PCP having a network structure of an interdigitated structure, commonly referred to as CID (hereinafter, a porous polymer metal complex may be referred to as “PCP”) is known. (See Non-Patent Documents 2 to 5)

  In order to control the gas adsorption characteristics of the porous material, attempts have been made to introduce fluorine atoms into the ligand (Non-Patent Documents 6-9). Sliding properties and water repellency are known as general effects on fluorine materials, but in the case of the porous polymer metal complex introduced with fluorine as described above, the hydrogen adsorption characteristics by fluorine atoms are improved. Is stated. These do not coincide with the physical properties caused by the above-mentioned fluorine atoms, and the principle by which the introduction of fluorine atoms improves the hydrogen adsorption characteristics is not described in detail. That is, the introduction of fluorine atoms is a porous polymer. It is not clear how it affects the gas adsorption properties of metal complexes.

  As described above, the PCP having the CID structure is known per se, but it is not known what characteristics are exhibited when a fluorine atom is introduced into the PCP having the CID structure of the present invention.

JP 2000-109493 A

Susumu Kitagawa, Integrated Metal Complex, Kodansha Scientific, 2001, pages 214-218 Kitagawa et al., Chem. Commun., 2010, 46, 4258-4260 Kitagawa et al., Chem. Commun., 2010, 46, 9229-9231 Kitagawa et al., Chem. Sci., 2012, 3, 116-120 Chen et al., Journal of Solid State Chemistry 170 (2003) 130-134 Omary et al., J. Am. Chem. Soc., 2007,129, 15454 Omary et al., Angew. Chem. Int. Ed. 2009, 48, 2500 Li et al., J. Am. Chem. Soc., 2004, 126, 1308 Ferey et al., J. Am. Chem. Soc., 2010, 132, 1127-1136

  The present invention is to provide a novel porous polymer metal complex having a CID structure formed from a ligand containing a fluorine atom, and a gas adsorbent having excellent characteristics using the same. . Another object of the present invention is to provide a gas storage device and a gas separation device that contain a gas adsorbent having the above-mentioned characteristics.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained isophthalic acid having a divalent transition metal ion and a perfluoroalkyl group having 1 to 10 carbon atoms in the 5-position (No. 1). (1 ligand) and a pyrazine, bipyridine, bipyridyl analog having a 4-pyridyl group at both ends of the molecule (second ligand) are reacted in a mixed solvent of a proton-based solvent and an amide-based solvent. It has been found that a porous polymer metal complex having a fluoroalkyl group and having a so-called CID structure can be produced. This porous polymer metal complex has been found to be usable as a gas storage and separation material, and the present invention has been completed. It was.

That is, the present invention is as follows.
(1) The following formula (1)
[MXY] _n (1)
(In the formula, M represents a divalent transition metal ion, X represents a first ligand, and is isophthalic acid having a C 1-10 perfluoroalkyl group at the 5-position. Y represents a second configuration. indicates ligand, a pyrazine, or 4,4'-bipyridine, 3,4'-bipyridine, or a bipyridine selected from 3,3'-bipyridine, or a 4-pyridyl group possess both ends of the molecule The following formula:
(In this formula, R is a C1-C4 alkylene group, a C2-C4 alkenylene group, a C2-C4 alkynylene group, an amide bond, an ether bond, an ester bond, a diazo bond,
X is —S—, —O— or —NH—, and Y is an arylene group. ) Is a bipyridine analogue you express by. n represents a characteristic that a large number of structural units composed of [MXY] are gathered, and the size of n is not particularly limited. )
The divalent transition metal ion is a six-coordinate structure that is coordinated with the first ligand and the second ligand, and has an interdigitated network structure called CID. Porous polymer metal complex.

  (2) The interdigitated network structure has one bidentate carboxyl group of the first ligand and two monodentate carboxyl groups coordinated to a divalent transition metal ion. The tetracoordinate divalent transition metal ion is used as a core, and the first ligand connects this to form a chain of a metal complex, which further forms the chain 2 A planar structure of a metal complex is formed by cross-linking of a valent transition metal ion by a second ligand, and this planar structure is obtained by stacking. The porous polymer metal complex according to the above (1), wherein core portions composed of valent transition metal ions are staggered between adjacent layers.

  (3) The porous polymer metal complex according to (1) or (2), wherein M is selected from zinc ion, copper ion, cobalt ion, and nickel ion.

  (4) The porous polymer metal complex according to the above (1) or (2), wherein M is a zinc ion.

(5) The perfluoroalkyl group is CF ₃ , C ₂ F ₅ , n-C ₃ F ₇ , n-C ₄ F ₉ , n-C ₅ F ₁₁ , n-C ₈ F ₁₇ , n-C ₁₀ F. The porous polymer metal complex according to (1) to (4), which is selected from ₂₁ .

  (6) Y is pyrazine, (E) -4,4 ′-(diazene-1,2-diyl) bipyridine, (E) -4,4 ′-(ethene-1,2-diyl) bipyridine, 4, 4 '-(thiophene-2,5-diylbicetin-2,1-diyl) bipyridine, 4,4'-(ethyne-1,2-diyl) bipyridine, 4,4 '-(9H-fluorene-2,7- Diyl) bis (ethyne-2,1-diyl) bipyridine, 4,4 ′-(naphthalene-1,4-diylbis (ethyne-2,1-diyl) bipyridine, 4,4 ′-(biphenyl-1,4- Diylbis (ethyne-2,1-diyl) bipyridine, 3,6-bi (pyridin-4-yl) -1,2,4,5-tetrazine, 4,4 ′-(ethylene-1,2-diyl) bipyridine , 4,4′-bipyridine, described in (1) to (5) above Porous polymer metal complex.

(7) The porous polymer metal complex contains water or an organic solvent, and has the following formula (2):
[MXY] _n (G) m (2)
(In the formula, M represents a divalent transition metal ion, X represents a first ligand, and is isophthalic acid having a C 1-10 perfluoroalkyl group at the 5-position. Y represents a second configuration. indicates ligand, a pyrazine, or 4,4'-bipyridine, 3,4'-bipyridine, or a bipyridine selected from 3,3'-bipyridine, or a 4-pyridyl group possess both ends of the molecule The following formula:
(In this formula, R is a C1-C4 alkylene group, a C2-C4 alkenylene group, a C2-C4 alkynylene group, an amide bond, an ether bond, an ester bond, a diazo bond,
X is —S—, —O— or —NH—, and Y is an arylene group. ) Is a bipyridine analogue you express by. G is water or a solvent molecule, and is a guest molecule. n represents a characteristic that a large number of structural units composed of [MXY] are gathered, and the size of n is not particularly limited. m is 0.2 to 6 with respect to the metal ion 1. )
The porous polymer metal complex according to any one of (1) to (6) above , which is in the form of a complex complex.

(8) A gas adsorbent comprising the porous polymer metal complex according to any one of (1) to (7) above.
(9) A gas separator using the gas adsorbent described in (8) above.
(10) A gas storage device using the gas adsorbent according to (8).

  The porous polymer metal complex of the present invention is capable of adsorbing and releasing a large amount of gas and selectively adsorbing gas. In addition, it is possible to manufacture a gas storage device and a gas separation device in which a gas adsorbing material comprising the porous polymer metal complex of the present invention is housed.

  When the porous polymer metal complex of the present invention is used, for example, as a gas separation device of a pressure swing adsorption method (hereinafter abbreviated as “PSA method”), very efficient gas separation is possible. In addition, the time required for pressure change can be shortened, contributing to energy saving. Furthermore, since it can contribute to the miniaturization of the gas separation device, it is possible to increase the cost competitiveness when selling high-purity gas as a product. 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.

  Another application of the porous polymer metal complex of the present invention is a gas storage device. When the gas adsorbent of the present invention is applied to a gas storage device (business gas tank, consumer gas tank, vehicle fuel tank, etc.), it is possible to dramatically reduce the pressure during transportation and storage. . As an effect resulting from the ability to reduce the gas pressure during transportation or storage, firstly, improvement in the degree of freedom of shape can be mentioned. In the conventional gas storage device, the gas adsorption amount cannot be maintained high unless the pressure during storage is maintained. However, in the gas storage device of the present invention, a sufficient gas adsorption amount can be maintained even if the pressure is lowered.

  When applied to a gas separation device or gas storage device, there is no need to use a special device for the shape of the container, the material of the container, the type of gas valve, etc., and those used in the gas separation device and gas storage device Can be used. However, the improvement of various devices is not excluded, and any device is included in the technical scope of the present invention as long as the porous polymer metal complex of the present invention is used. .

1 (a) and 2 (b) are diagrams for explaining the crystal structure of the porous polymer metal complex produced in Example 1. FIG. 2 (a) and 2 (b) are top views showing the crystal structure of the porous polymer metal complex produced in Example 1. FIG. 3 (a) and 3 (b) are side views showing the crystal structure of the porous polymer metal complex produced in Example 1. FIG.

The present invention provides the following formula (1):
[MXY] _n (1)
(In the formula, M represents a divalent transition metal ion, X represents a first ligand, and is isophthalic acid having a C 1-10 perfluoroalkyl group at the 5-position. Y represents a second configuration. A ligand, a pyrazine, bipyridine, and a bipyridyl analog having a 4-pyridyl group at both ends of the molecule, n is a characteristic that many structural units consisting of [MXY] are assembled, (The size is not particularly limited.)
The divalent transition metal ion is a six-coordinate structure that is coordinated with the first ligand and the second ligand, and has an interdigitated network structure called CID. A porous polymeric metal complex is provided.

  The porous polymer metal complex of the present invention is a PCP (porous coordination polymer) having a network structure of an interdigitated structure, commonly called CID (Coordination polymer with InterDigitated structure). A divalent transition metal ion has one bidentate carboxyl group and two monodentate carboxyl groups coordinated to a tetracoordinate divalent transition metal ion as a core. Derivatives (first ligands) are linked together to form a metal complex chain, and the divalent transition metal ion forming this chain has two coordination points. The planar structure of the metal complex is formed by cross-linking of pyrazine, bipyridine and bipyridyl analog (second ligand) having 4-pyridyl groups at both ends in the molecule, and the structure in which these are stacked is CID. Type network. During lamination, the core portion composed of carboxyl groups and divalent transition metal ions is staggered between adjacent layers, so it is called an interfitting type. This PCP contains a gas between the layers, and the layers are shifted at that time, so that a unique gas adsorption behavior called a gate type occurs.

The structure of the porous polymer metal complex of the present invention will be described with reference to FIGS. 1 to 3 showing the porous polymer metal complex produced in Example 1. FIG. FIG. 1 (a) shows a divalent transition metal ion (in this example, a zinc ion), 5-pentafluoroethylisophthalic acid (isophthalic acid in which C ₂ F ₅ is bonded to the 5-position, the first ligand), , (E) -4,4 ′-(diazene-1,2-diyl) bipyridine (a second ligand in which two pyridine rings are connected by an N═N bond) FIG. 5 is a capped stick diagram showing a coordinate bond of a polymer metal complex, where hydrogen atoms and fluorine atoms are omitted for simplicity. In FIG. 1 (a), two zinc ions (black) are respectively an oxygen atom (dark gray) of a bidentate carboxyl group of 5-pentafluoroethylisophthalic acid and 5-pentafluoroethylisophthalic acid. These are coordinated by two oxygen atoms of a monodentate carboxyl group and a total of four oxygen atoms to form a continuous chain structure. In contrast to this laterally continuous one-dimensional structure (chain structure), the nitrogen atoms (light gray) at both ends of the second ligand are coordinated in the vertical direction of the zinc ion in the vertical direction. The structure is cross-linked to form a two-dimensional structure. Carbon atoms are shown in white. As described above, although the fluorine atom of the 5-position pentafluoroethyl group of 5-pentafluoroethylisophthalic acid is omitted in FIG. 1 (a), the fluorine atom of the compound corresponding to FIG. 1 (b) is shown. In addition, FIGS. 1 to 3 show only a part of the porous polymer metal complex, which is actually infinitely spread in three dimensions.

  FIG. 2 (a) shows a state (plan view) of the structure shown in FIG. 1 as viewed from the direction perpendicular to the chain structure, that is, from the direction of the second ligand (bipyridyl type compound). Is the same as in FIG. A group of carbon atoms extending so as to be bundled with a zinc atom (black) portion is the second ligand bp. It can be seen that the one-dimensional structures formed from zinc ions and 5-pentafluoroethylisophthalic acid are laminated in an alternating manner. In order to show that the one-dimensional structures are alternately fitted, an alternating one-dimensional structure colored in dark gray and light gray is shown in FIG. 3A and 3B are views of the structure viewed from the side with respect to the plan view of FIGS. FIG. 3A shows the same atom color as in FIG. 1, and FIG. 3B shows an alternating one-dimensional structure colored in dark gray and light gray. In FIG. 3 (a), black to dark gray is a portion where zinc atoms and oxygen atoms are gathered, and it can be seen that the second ligand bp is bridged between the portions. Moreover, also in FIG.3 (b), a mutual fitting structure is seen.

  As described above, the porous polymer metal complex of the present invention is a bipyridyl analog having a divalent transition metal ion, an isophthalic acid derivative (first ligand), a pyrazine, a bipyridine, and a 4-pyridyl group at both molecular ends. (Second ligand) and a porous polymer metal complex forming an interdigitated network structure, and the 5-position of the isophthalic acid derivative (first ligand) is It is a perfluoroalkyl group having 1 to 10 carbon atoms, not an alkyl group containing no hydrogen atom or fluorine atom. Since the substituent at the 5-position of isophthalic acid is a perfluoroalkyl group, a fluorine atom is present between the network structures. Because of the specific interaction between fluorine atoms and gas molecules, it is considered that the characteristic of increasing the amount of adsorbed oxygen gas at room temperature and increasing the amount of adsorbed carbon dioxide at room temperature is obtained during the gas-like gas adsorption behavior. It is done.

Since the porous polymer metal complex of the present invention is a porous body, it contains a solvent used for synthesis, or when it comes into contact with water, alcohol, ether or other organic molecules present in the air, Contains an organic solvent, for example of formula (2)
[MXY] _n (G) m (2)
(In the formula, M represents a divalent transition metal ion, X represents a first ligand, and is isophthalic acid having a C 1-10 perfluoroalkyl group at the 5-position. Y represents a second configuration. A bipyridyl analog that represents a ligand and has a pyrazine, bipyridine, and 4-pyridyl group at both ends of the molecule, G is a solvent molecule used in the synthesis as described later, water in water or an organic molecule, and is usually a guest This is called a numerator, where n is a property that a large number of structural units composed of [MXY] are assembled, and the size of n is not particularly limited, and m is 0.2 to 6 relative to metal ion 1. is there.)
It may change to a complex complex such as

  However, the guest molecule represented by G in these complex complexes is only weakly bonded to the porous polymer metal complex, and is removed by pretreatment such as vacuum drying when used as a gas adsorbent. Return to the complex represented by the original formula (1). Therefore, even a complex represented by the formula (2) can be regarded as essentially the same as the porous polymer metal complex of the present invention.

The porous polymer metal complex of the present invention represented by the above formula (1) is a divalent transition metal salt, isophthalic acid having a C 1-10 perfluoroalkyl group at the 5-position (first coordination) ), Pyrazine, bipyridine, and bipyridyl analogs (second ligand) having 4-pyridyl groups at both ends of the molecule are dissolved in a mixed solvent of a proton solvent and an amide solvent and reacted in a solvent. .

  As the solvent, a mixed solvent of a proton solvent such as alcohols and an amide solvent such as dimethylformamide is used. Protonic solvents such as alcohols and amide solvents such as dimethylformamide and dimethylacetamide dissolve metal salts well and further stabilize and coordinate metal salts by coordinating and hydrogen bonding to metal ions and counter ions. By suppressing the rapid reaction with the child, side reactions are suppressed. Examples of alcohols include aliphatic monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol, and aliphatic dihydric alcohols such as ethylene glycol. Methanol, ethanol, 1-propanol, 2-propanol, and ethylene glycol are preferable because they are inexpensive and have high solubility of metal salts. Moreover, these alcohols may be used alone or in combination. Examples of amide solvents include dimethylformamide, diethylformamide, dibutylformamide, dimethylacetamide and the like. From the viewpoint of high solubility of the metal salt, dimethylformamide and diethylformamide are preferred.

  The mixing ratio of the alcohols and the amide solvent is arbitrary from 99: 1 to 1:99 (volume ratio). From the viewpoint that the solubility of both the ligand and the metal salt is increased and the generation of by-products can be suppressed, the mixing ratio is 90:10 to 10:90 (volume ratio), and the reaction can be accelerated. 20-20: 80 (volume ratio) is preferable.

  As the solvent, another kind of organic solvent can be mixed and used in a mixed solvent of the above alcohols and amide solvent. The mixing ratio of the mixed solvent composed of the alcohol and the amide solvent to another organic solvent is preferably 30% or more from the viewpoint of improving the solubility of the metal salt and the ligand.

  The divalent transition metal ion necessary for forming a novel porous polymer metal complex having an interdigitated network structure called CID of the present invention is preferably a zinc ion. Zinc ions form coordinate bonds with the ligand in a six-coordinate state.

  However, in the present invention, even with divalent transition metal ions other than zinc ions, it is possible to form a novel porous polymer metal complex having an interdigitated network structure called CID of the present invention. Examples thereof include copper, cobalt, and nickel bivalent and transition metal ions.

  The zinc salt used in the method of the present invention may be a salt containing a divalent zinc ion, and zinc nitrate, zinc acetate, zinc sulfate, formic acid in terms of high solubility in a solvent. Zinc, zinc chloride, and zinc bromide are preferable, and zinc nitrate and zinc sulfate are particularly preferable in terms of high reactivity.

  As the divalent transition metal salt other than the zinc salt used in the method of the present invention, any salt containing a divalent transition metal ion may be used, and in terms of high solubility in a solvent, a nitrate, Acetates, sulfates, formates, chlorides and bromides are preferred, and nitrates and sulfates are particularly preferred because of their high reactivity.

Hereinafter, the isophthalic acid which has a C1-C10 perfluoroalkyl group in 5-position is demonstrated .

The isophthalic acid having a C1-C10 perfluoroalkyl group at the 5-position used in the present invention is a compound represented by the following formula.
(In the formula, R is a perfluoroalkyl group having 1 to 10 carbon atoms.)

The substituent R of this ligand may be a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, but CF ₃ , C ₂ F ₅ , _{n-C 3 F 7, n} -C 4 F 9, n-C 5 F 11, n-C 8 F 17 or n-C ₁₀ F ₂₁ group is preferred. As a method for introducing a perfluoroalkyl group into the benzene ring, for example, Shibasaki et al., Chem. Asian J. 2006, 1, 314-321 can be referred to.

  Hereinafter, the second ligand will be described. The second ligand is a linear molecule and is a bidentate ligand having nitrogen atoms as coordination points at both ends, and a pyrazine, bipyridine, or 4-pyridyl group. Bipyridine analogs at both ends of the molecule.

  The bipyridine is preferably a bipyridine isomer such as 4,4'-bipyridine, 3,4'-bipyridine, or 3,3'-bipyridine.

Examples of the bipyridine analog having the above 4-pyridyl group at both ends of the molecule include compounds represented by the following general formula.
(In the formula, R is a C1-C4 alkylene group, a C2-C4 alkenylene group, a C2-C4 alkynylene group, an amide bond, an ether bond, an ester bond, a diazo bond,
X is —S—, —O— or —NH—, and Y is an arylene group. )
The second ligand is preferably pyrazine, 4,4′-bipyridine, or R is a diazene-1,2-diyl group, an ethylene group, a vinylene group, or an ethynylene group, because of the stability of the compound. Thiophene-2,5-diyl group, 9H-fluorene-2,7-diyl group, naphthalene-1,4-dii group, biphenyl-1,4-diyl group, phenylene group (more preferably p-phenylene group) It is a bipyridine-related compound which is a 1,2,4,5-tetrazine-1,4-diyl group or a 4,4′-biphenylene group.

Specifically, the second ligand is pyrazine, (E) -4,4 ′-(diazene-1,2-diyl) bipyridine, (E) -4,4 ′-(ethene-1,2- diyl) bipyridine, 4,4 '- (ethyne-1,2-diyl) bipyridine, 4, 4' - (9H-fluoren-2,7-diyl) bis (ethyne-2,1-diyl) bipyridine, 4, 4 ′-(naphthalene-1,4-diylbis (ethyne-2,1-diyl)) bipyridine, 4,4 ′-(biphenyl-1,4-diylbis (ethyne-2,1-diyl)) bipyridine, 3, 6-bi (pyridin-4-yl) -1,2,4,5-tetrazine, 4,4 ′-(ethylene-1,2-diyl) bipyridine, and 4,4′-bipyridine are more preferable. From the viewpoint of high heat resistance, pyrazine and 4,4′-bipyridine are particularly preferable.

The chemical formula of a typical second ligand used in the present invention is shown below.

  The second ligand may have a substituent on its aromatic ring, and the types of substituents include alkyl groups such as methyl, alkyl groups having polar functional groups such as hydroxymethyl groups, dimethylamino groups, etc. And the number of substituents is 1 to 4.

  In the method of the present invention, a base can be added as a reaction accelerator. The base is presumed to accelerate the reaction by converting the carboxyl group of the ligand isophthalic acid derivative into an anion. Examples of the base include, for example, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like as inorganic bases. Examples of the organic base include triethylamine, diethylisopropylamine, pyridine, 2,6-lutidine and the like. Lithium hydroxide, sodium carbonate, sodium hydroxide, and pyridine are preferred because of their high reaction acceleration. The addition amount is preferably 0.1 to 6.0 mol in terms of the effect of accelerating the reaction with respect to the total moles of isophthalic acid used, and more preferably 0.5 to less in terms of side reactions. 4.0 moles.

  In the method of the present invention, an organic acid can be added as a reaction control agent. It is considered that the organic acid controls the proper progress of the reaction by controlling the dissociation of the carboxyl group of the ligand as an acid. Aliphatic organic acids include monovalent acids such as acetic acid and propionic acid, divalent acids such as oxalic acid and malonic acid, and bicyclo [2,2,2] -octane-1,4-dicarboxylic acid. A cyclic carboxylic acid is mentioned. Examples of the aromatic organic acid include monovalent acids such as benzoic acid and 4-methylbenzoic acid. Of these, acetic acid, benzoic acid, and bicyclo [2,2,2] -octane-1,4-dicarboxylic acid, which have high solubility and do not have too strong coordination with metal ions, are preferable. The amount added is preferably 0.1 to 12.0 mol in terms of the effect of the reaction with respect to the total mol of the ligand used, and more preferably 0.5 in terms of few side reactions. To 8.0 moles.

  When the transition metal salt solution and the ligand are reacted, the transition metal salt and the ligand are separately prepared as solutions in addition to the method of adding the solvent after the transition metal salt and the ligand are charged into the container. Then, these solutions may be mixed. The method of mixing the solution may be adding the ligand solution to the transition metal salt solution or vice versa. Moreover, after laminating | stacking a metal salt solution and a ligand solution, you may mix by the method by natural diffusion. The mixing method does not necessarily need to be performed in a solution. For example, a method in which a solid ligand is added to a transition metal salt solution and a solvent is added at the same time. Various methods are possible as long as the reaction finally takes place substantially in a solvent, such as injecting a solid or solution of the above and a solution for dissolving the transition metal salt. However, the method of dropping and mixing the transition metal salt solution and the ligand solution is industrially the most convenient and preferable.

  The concentration of the solution is 10 μmol / L to 4 mol / L for the transition metal salt solution, preferably 100 μmol / L to 2 mol / L, and the organic solution of the ligand is 100 μmol / L to 3 mol / L, preferably 100 μmol / L. ~ 2 mol / L. Even if the reaction is carried out at a concentration lower than this, the desired product can be obtained, but this is not preferable because the production efficiency is lowered. On the other hand, a concentration higher than this is not preferable because the adsorption ability is lowered.

  The reaction temperature is -20 to 180 ° C, preferably 25 to 150 ° C. If it is performed at a lower temperature than this, the solubility of the raw material is lowered, which is not preferable. Although it is possible to carry out the reaction at a higher temperature using an autoclave or the like, there is no substantial meaning because the yield does not improve for the energy cost such as heating.

The mixing ratio of the transition metal salt used in the reaction of the present invention and the isophthalic acid (first ligand) having a C1-C10 perfluoroalkyl group at the 5-position is such that the ratio of transition metal salt: ligand is The molar ratio is in the range of 1: 5 to 5: 1, preferably 1: 3 to 3: 3. In other ranges, the yield of the target product decreases, and unreacted raw materials remain, making it difficult to take out the target product.

The transition metal salt used in the reaction of the present invention and the mixing ratio of isophthalic acid (first ligand) having a C1-C10 perfluoroalkyl group at the 5-position and the second ligand are transition metal salts: The total ratio of the two ligands (first ligand and second ligand) is in the range of a molar ratio of 1: 5 to 5: 1, preferably 1: 3 to 3: 3. It is. Furthermore, the ratio of the first ligand to the second ligand is in the range of a molar ratio of 1: 3 to 3: 1, preferably a molar ratio of 1: 2 to 2: 1. In other ranges, the yield of the target product decreases, and unreacted raw materials remain, making it difficult to take out the target product.

  The reaction can be carried out using an ordinary glass-lined SUS reaction vessel and a mechanical stirrer. After completion of the reaction, the target substance and raw material can be separated by filtration and drying to produce a target substance with high purity.

  Whether the porous polymer metal complex obtained by the above reaction has an intended interdigitated network structure called CID is determined by analyzing the reflection obtained by single crystal X-ray crystal analysis. It can be confirmed with. The gas adsorption ability of the porous polymer metal complex obtained by the above reaction can be measured using a commercially available gas adsorption apparatus.

The porous polymer metal complex of the present invention comprises a plurality of isophthalic acids (first ligands) having a C1-C10 perfluoroalkyl group used as a raw material at the 5-position, or a second ligand. By using a mixture of a plurality of types, it is possible to form a porous polymer metal complex containing a plurality of types of ligands used, that is, a so-called solid solution type porous polymer metal complex. The polymer metal complex includes such a so-called solid solution type porous polymer metal complex.

  The porous polymer metal complex of the present invention has an inter-fitting type network structure commonly called CID, and this network structure has a structure having a side chain containing fluorine. Originally known as CID, the interfitting type network structure causes a shift in the meshing structure when the gas is occluded inside, and develops a unique gas adsorption characteristic. However, the CID porous polymer containing the fluorine of the present invention In the metal complex, it is considered that a specific functional property is caused by the chain functional group containing fluorine affecting the mode of meshing structure shift. However, the present invention is not bound by theory, and the characteristics of the porous polymer metal complex of the present invention are not limited by this theory.

The preparation method of the porous polymer metal complex has various conditions and cannot be uniquely determined, but here, it will be described based on examples.
For powder X-ray diffraction measurement, a powder X-ray apparatus DISCOVER D8 with GADDS manufactured by Bruker AX Co., Ltd. was used.

Example 1
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position), (E) -4,4 ′-(diazene-1 , 2-diyl) bipyridine (0.01 mmol), ethanol (1 mL), and dimethylformamide (1 mL) were placed in a glass test tube having a diameter of 5 mm, capped, and heated in an aluminum block bath at 80 ° C. for 3 days. After coating the obtained single crystal with Palaton so as not to be exposed to the atmosphere, a single crystal measuring device manufactured by Rigaku Co., Ltd. (single crystal structure analysis device VariMax for ultrafine crystal, MoK line (λ = 0.70109Å) )) (Irradiation time 8 seconds, d = 45 mm, 2θ = −20, temperature = −180 ° C.), and the obtained diffraction image is analyzed with analysis software, analysis software “CrystalStructure” manufactured by Rigaku Corporation. As shown in FIGS. 1 to 3, it was confirmed that it has a so-called CID structure (a = 9.84410 (10), b = 10.008500 (10), c = 11 88420 (10); α = 79.790 (8), β = 74.551 (7), γ = 78.866 (8); space group = P1).

Example 2
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position), (E) -4,4 ′-(ethene-1) , 2-diyl) bipyridine (0.01 mmol), methanol (1 mL), and dimethylformamide (1 mL) were placed in a glass test tube having a diameter of 5 mm, capped, and heated in an aluminum block bath at 100 ° C. for 3 days. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 10.159 (9), b = 10.1086 (9) , c = 11.864 (9); α = 78.76 (5), β = 76.38 (4), γ = 78.39 (4); space group = P1).

Reference example 3
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position), 4,4 ′-(thiophene-2,5-diylbis) (Ethine-2,1-diyl)) 0.01 mmol of bipyridine, 1 mL of 1-propanol, and 1 mL of dimethylformamide are placed in a glass test tube having a diameter of 5 mm, covered, and 3 days at 80 ° C. in an aluminum block bath. Heated. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 10.09777 (14), b = 10.7557 (15)). , c = 13.1070 (18); α = 77.962 (5), β = 79.443 (5), γ = 78.375 (5); space group = P1).

Example 4
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position), 4,4 ′-(ethyne-1,2-diyl) ) 0.01 mmol of bipyridine, 1 mL of ethanol, and 1 mL of dimethylacetamide were placed in a glass test tube having a diameter of 5 mm, covered, and heated in an aluminum block bath at 80 ° C. for 3 days. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 10.0102 (2), b = 10.169 (2) , c = 23.448 (5); α = 96.673 (3), β = 99.635 (2), γ = 104.743 (2); space group = P1).

Example 5
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position), 4,4 ′-(9H-fluorene-2,7 -Diyl) bis (ethyne-2,1-diyl) bipyridine (0.01 mmol), ethanol (1 mL), dimethylformamide (1 mL) were placed in a glass test tube having a diameter of 5 mm, covered, and covered with an aluminum block bath at 120 ° C. Heated for days. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 10.119 (4), b = 23.943 (9) , c = 24.855 (10); α = 84.30 (2), β = 84.27 (2), γ = 79.253 (1)); space group = P1).

Example 6
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position), 4,4 ′-(naphthalene-1,4-diylbis) (Ethine-2,1-diyl) bipyridine (0.01 mmol), ethanol (1 mL), and dimethylformamide (1 mL) were placed in a glass test tube having a diameter of 5 mm, covered, and heated in an aluminum block bath at 60 ° C. for 3 days. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 10.145 (5), b = 11.084 (5) , c = 15.484 (7); α = 101.336 (9), β = 96.139 (7), γ = 102.356 (5); space group = P1).

Example 7
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position), 4,4 ′-(biphenyl-4,4′- Diylbis (ethyne-2,1-diyl) bipyridine (0.01 mmol), ethanol (1 mL), and dimethylformamide (1 mL) were placed in a 5 mm diameter glass test tube, covered, and heated at 80 ° C. for 3 days in an aluminum block bath. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 10.045, b = 18.345, c = 23. 335; α = 67.43, β = 80.38, γ = 84.77; space group = P1).

Example 8
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position), 3,6-bi (pyridin-4-yl)- 0.01 mmol of 1,2,4,5-tetrazine, 1 mL of ethanol and 1 mL of dimethylformamide were placed in a glass test tube having a diameter of 5 mm, capped, and heated at 80 ° C. for 3 days in an aluminum block bath. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 10.1361 (16), b = 10.5611 (18) , c = 12.861 (12); α = 81.278 (5), β = 85.563 (5), γ = 76.995 (4); space group = P1).

Example 9
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-heptafluoropropylisophthalic acid (isophthalic acid having a C ₃ F ₇ group at the 5-position), (E) -4,4′-ethene-1, 2-diyl) bipyridine (0.01 mmol), ethanol (1 mL), and dimethylformamide (1 mL) were placed in a glass test tube having a diameter of 5 mm, capped, and heated in an aluminum block bath at 80 ° C. for 3 days. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 18.949 (5), b = 13.641 (3) , c = 20.222 (5); α = 90, β = 108.592 (4), γ = 90); space group = Cc).

Example 10
Zinc nitrate trihydrate 0.01 mmol, 5-trifluoromethylisophthalic acid (isophthalic acid having a CF ₃ group at the 5-position) 0.01 mmol, 4,4′-bipyridine 0.01 mmol, ethanol 1 mL, dimethyl 1 mL of formamide was placed in a glass test tube having a diameter of 5 mm, capped, and heated in an aluminum block bath at 80 ° C. for 3 days. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 10.596 (4), b = 10.885 (4)). c = 21.346 (6); α = 96.254 (4), β = 99.242 (4), γ = 1034.245 (2); space group = P1).

Example 11
0.01 mmol of zinc nitrate trihydrate, 0.01 mmol of 5-heptadecafluorooctylisophthalic acid (isophthalic acid having a C ₈ F ₁₇ group at the 5-position), (E) -4,4 ′-(ethene- 1,2-Diyl) bipyridine (0.01 mmol), ethanol (1 mL), and dimethylformamide (1 mL) were placed in a glass test tube having a diameter of 5 mm, covered, and heated in an aluminum block bath at 80 ° C. for 3 days. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 18.375 (6), b = 13.299 (6)). , c = 19.3649 (5); α = 90, β = 107.467 (6), γ = 90; space group = Cc).

Example 12
Copper nitrate trihydrate 0.01 mmol, 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position) 0.01 mmol, 4,4′-bipyridine 0.01 mmol, ethanol 1 mL Then, 1 mL of dimethylformamide was put in a glass test tube having a diameter of 5 mm, covered, and heated in an aluminum lock bath at 120 ° C. for 3 days. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 16.649 (7), b = 13.749 (8)). , c = 19.269 (6); α = 90, β = 104.735 (7), γ = 90; space group = Cc).

Example 13
Nickel nitrate hexahydrate 0.01 mmol, 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position) 0.01 mmol, 4,4′-bipyridine 0.01 mmol, ethanol 1 mL Then, 1 mL of dimethylacetamide was placed in a glass test tube having a diameter of 5 mm, covered, and heated in an aluminum lock bath at 90 ° C. for 3 days. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 1.474 (8), b = 13.843 (8) , c = 19.821 (7); α = 90, β = 107.868 (9), γ = 90; space group = Cc).

Example 14
Cobalt nitrate hexahydrate 0.01 mmol, 5-pentafluoroethylisophthalic acid (isophthalic acid having a C ₂ F ₅ group at the 5-position) 0.01 mmol, 4,47′-bipyridine 0.01 mmol, 1- 0.4 mL of propanol and 1.6 mL of didibutylformamide were put in a glass test tube having a diameter of 5 mm, covered, and heated at 100 ° C. for 8 days in an aluminum lock bath. X-ray diffraction analysis of the obtained single crystal confirmed that it had a so-called CID structure as in Example 1 (a = 15.784 (4), b = 13.886 (8)). , c = 18.357 (7); α = 90, β = 107.946 (6), γ = 90); space group = Cc).

Comparative Example 1
CID-type PCP was synthesized in the same manner as in Example 1, using 5-nitroisophthalic acid as the isophthalic acid type ligand and 4,4′-bipyridine as the bipyridyl type ligand.

Comparative Example 2
CID-type PCP was synthesized in the same manner as in Example 1, using 5-methoxyisophthalic acid as the isophthalic acid-type ligand and 4,4′-bipyridine as the bipyridyl-type ligand.

<Results of gas adsorption>
Carbon dioxide adsorptivity and nitrogen adsorptivity of the obtained gas adsorbents were evaluated using a BET automatic adsorption device (Bell Mini II manufactured by Nippon Bell Co., Ltd.) (measurement temperatures: 195K and 273K for carbon dioxide, oxygen and nitrogen) 77K). Prior to the measurement, the sample was vacuum-dried at 423 K for 6 hours to remove solvent molecules that may remain in a trace amount.

  Table 1 shows the gas adsorption characteristics of the porous polymer metal complexes obtained in Examples 1 to 11. In both cases, gas-like gas adsorption behavior is observed, oxygen gas adsorption amount is particularly large, and carbon dioxide adsorption amount at room temperature is large. These are porous materials having an interdigitated network structure called CID. It is considered that the characteristics of fluorine atoms are reflected in the polymer metal complex.

  In the porous polymer metal complex of the present invention, a large number of micropores formed by alignment of ligands are present in the substance. Taking advantage of this porosity, specific adsorption of gas having affinity for fluorine atoms such as carbon dioxide and especially oxygen is possible, and it can be suitably used for separation and storage of these gases.

Claims (10)

Following formula (1)
[MXY] _n (1)
(In the formula, M represents a divalent transition metal ion, X represents a first ligand, and is isophthalic acid having a C 1-10 perfluoroalkyl group at the 5-position. Y represents a second configuration. Represents a ligand, is pyrazine, or is bipyridine selected from 4,4'-bipyridine, 3,4'-bipyridine, or 3,3'-bipyridine, or has 4-pyridyl groups at both ends of the molecule The following formula:
(In this formula, R is a C1-C4 alkylene group, a C2-C4 alkenylene group, a C2-C4 alkynylene group, an amide bond, an ether bond, an ester bond, a diazo bond,
X is —S—, —O— or —NH—, and Y is an arylene group. It is a bipyridine analog represented by n represents a characteristic that a large number of structural units composed of [MXY] are gathered, and the size of n is not particularly limited. )
The divalent transition metal ion is a six-coordinate structure that is coordinated with the first ligand and the second ligand, and has an interdigitated network structure called CID. Porous polymer metal complex.   The interdigitated network structure has one bidentate carboxyl group of the first ligand and two monodentate carboxyl groups coordinated to a divalent transition metal ion. A divalent transition metal ion having a coordinated divalent transition metal ion as a core, and a first ligand linking this to form a metal complex chain, and further forming the chain A metal ion is cross-linked by a second ligand to form a metal complex planar material, and this planar material is laminated to obtain a carboxyl group and a divalent transition during lamination. The porous polymer metal complex according to claim 1, wherein core portions composed of metal ions are staggered between adjacent layers.   The porous polymer metal complex according to claim 1 or 2, wherein M is selected from zinc ions, copper ions, cobalt ions, and nickel ions.   The porous polymer metal complex according to claim 1 or 2, wherein M is a zinc ion. The perfluoroalkyl group is selected from CF ₃ , C ₂ F ₅ , n-C ₃ F ₇ , n-C ₄ F ₉ , n-C ₅ F ₁₁ , n-C ₈ F ₁₇ , and n-C ₁₀ F _21. The porous polymer metal complex according to any one of claims 1 to 4. Y is, pyrazine, (E) -4,4 '- (diazene-1,2-diyl) bipyridine, (E) -4,4' - (ethene-1,2-diyl) bipyridine, 4, 4'- (Ethine-1,2-diyl) dipyridine, 4,4 ′-(9H-fluorene-2,7-diyl) bis (ethyne-2,1-diyl) bipyridine, 4,4 ′-(naphthalene-1,4 -Diylbis (ethyne-2,1-diyl)) dipyridine, 4,4 '-(biphenyl-1,4-diylbis (ethyne-2,1-diyl)) dipyridine, 3,6-bi (pyridin-4-yl) ) -1,2,4,5-tetrazine, 4,4 ′-(ethylene-1,2-diyl) bipyridine and 4,4′-bipyridine. Porous polymer metal complex. The porous polymer metal complex contains water or an organic solvent, and has the formula (2)
[MXY] _n (G) m (2)
(In the formula, M represents a divalent transition metal ion, X represents a first ligand, and is isophthalic acid having a C 1-10 perfluoroalkyl group at the 5-position. Y represents a second configuration. Represents a ligand, is pyrazine, or is bipyridine selected from 4,4'-bipyridine, 3,4'-bipyridine, or 3,3'-bipyridine, or has 4-pyridyl groups at both ends of the molecule The following formula:
(In this formula, R is a C1-C4 alkylene group, a C2-C4 alkenylene group, a C2-C4 alkynylene group, an amide bond, an ether bond, an ester bond, a diazo bond,
X is —S—, —O— or —NH—, and Y is an arylene group. It is a bipyridine analog represented by G is water or a solvent molecule, and is a guest molecule. n represents a characteristic that a large number of structural units composed of [MXY] are gathered, and the size of n is not particularly limited. m is 0.2 to 6 with respect to the metal ion 1. )
The porous polymer metal complex according to any one of claims 1 to 6, which is in the form of a complex complex.   A gas adsorbent comprising the porous polymer metal complex according to claim 1.   A gas separation apparatus using the gas adsorbent according to claim 8.   A gas storage device using the gas adsorbent according to claim 8.