Metal-organic framework production method

Abstract

To provide a metal-organic framework production method in which a step for removing an organic solvent is simplified or omitted, and in which productivity can be improved.SOLUTION: The present disclosure relates to a metal-organic framework production method in which a polycarboxylic acid and a metal compound are reacted in a solvent in the presence of one or more additives selected from ammonia, organic amines, and nitrogen-containing aromatic heterocyclic compounds, wherein the water content in 100 mass% of the solvent is greater than 80 mass%.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a metal-organic framework. [Background technology]

[0002] Metal organic frameworks, also known as porous coordination polymers, are a type of material that forms a porous structure through coordination bonds between metal ions and organic ligands. They are expected to be used for gas adsorption / desorption, as well as in catalysts, etc.

[0003] For example, Patent Document 1 discloses a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion, the at least one at least bidentate organic compound being derived from 2,5-furandicarboxylic acid or 2,5-thiophenedicarboxylic acid. As a method for producing such a metal-organic framework, for example, N,N-dimethylformamide, thiophenedicarboxylic acid, and aluminum chloride hexahydrate are stirred at room temperature, and the reaction mixture is heated and maintained to obtain the metal-organic framework. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2013-512223 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the above Patent Document 1, the metal organic framework is obtained using an organic solvent such as N,N-dimethylformamide, and a step for removing the organic solvent is required, which poses a problem in productivity.

[0006] Therefore, an object of the present invention is to provide a method for producing a metal organic framework that can omit or simplify the step of removing the organic solvent and improve productivity. [Means for solving the problem]

[0007] The present invention which achieves the above object is as follows. [1] A method for producing a metal organic framework, comprising reacting a polyvalent carboxylic acid with a metal compound in a solvent in the presence of one or more additives selected from ammonia, an organic amine, and a nitrogen-containing aromatic heterocyclic compound, 2. A method for producing a metal organic framework, wherein the content of water in 100 mass % of the solvent is more than 80 mass %. [2] The method according to [1], wherein the pressure during the reaction between the polyvalent carboxylic acid and the metal compound is 2.0 MPa or less. [3] A solution A1 in which the polycarboxylic acid and the additive are dissolved in a solvent a1 is mixed with a solution B in which the metal compound is dissolved in a solvent b to react the polycarboxylic acid with the metal compound; The method according to [1] or [2], wherein the water content in the total of the solvent a1 and the solvent b is 100% by mass is more than 80% by mass. [4] The method according to [3], wherein the pH of the solution A1 is 3.0 or higher. [5] The method according to any one of [1] to [4], wherein the pH of the liquid obtained after the reaction between the polyvalent carboxylic acid and the metal compound is 6.5 or less. [6] The process according to any one of [1] to [5], wherein the additive comprises at least one organic amine selected from secondary amines and tertiary amines. Effect of the Invention

[0008] According to the present invention, the metal organic framework can be produced while omitting or simplifying the step of removing the organic solvent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The method for producing a metal organic framework of the present invention is a method for producing a metal organic framework by reacting a polycarboxylic acid with a metal compound in a solvent in the presence of one or more additives selected from ammonia, an organic amine, and a nitrogen-containing aromatic heterocyclic compound, and is characterized in that the content of water in 100 mass% of the solvent is more than 80 mass%. The present inventors have conducted studies and found that it is difficult to obtain a metal organic framework when a polycarboxylic acid and a metal compound are reacted in a solvent containing a certain amount of water or more (hereinafter referred to as an aqueous solvent) in order to omit or simplify the step of removing the organic solvent, but that it is possible to obtain a metal organic framework even in an aqueous solvent when a polycarboxylic acid and a metal compound are reacted in the presence of one or more additives selected from ammonia, an organic amine, and a nitrogen-containing aromatic heterocyclic compound.

[0010] The aqueous solvent in the present invention has a water content of more than 80% by mass in 100% by mass of the solvent. As a solvent other than water, an organic solvent such as an alcohol solvent, an amide solvent, a ketone solvent, an ester solvent, or an ether solvent may be contained in a total amount of less than 20% by mass, but it is preferable that no organic solvent other than an alcohol solvent is contained. The amount of water in 100% by mass of the aqueous solvent is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. In any of these cases, it is preferable that the aqueous solvent is a mixed solvent of water and an alcohol solvent. It is most preferable that the aqueous solvent is a solvent of 100% by mass of water.

[0011] Of the additives, the organic amine is preferably at least one selected from secondary amines and tertiary amines. Examples of the secondary amine include aliphatic chain secondary amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, and methylethylamine; and heterocyclic aliphatic secondary amines such as piperidine and piperazine. These can be used alone or in combination of two or more. Examples of the tertiary amine include aliphatic chain tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, and triisobutylamine; heterocyclic aliphatic tertiary amines such as hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, morpholine, and 4-methylmorpholine; and nitrogen-containing aromatic ring-containing tertiary amines such as imidazole and 1-methylimidazole. These can be used alone or in combination of two or more.

[0012] Among the additives, examples of the nitrogen-containing aromatic heterocyclic compounds include monocyclic nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2-methylpyridine, and 4-methylpyridine, and these can be used alone or in combination of two or more.

[0013] The additive is preferably at least one of ammonia, diethylamine, diisopropylamine, trimethylamine, triethylamine, tri-n-propylamine, N,N-diisopropylethylamine, triisobutylamine, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, 1-methylimidazole, and pyridine, more preferably at least one of diisopropylamine, triethylamine, tri-n-propylamine, triisobutylamine, hexamethylenetetramine, and 1-methylimidazole, even more preferably at least one of triethylamine, tri-n-propylamine, and 1-methylimidazole, and most preferably triethylamine.

[0014] The molar ratio of the additive to the polyvalent carboxylic acid is preferably from 1.5 to 4.0, more preferably from 2.0 to 3.6, and further preferably from 2.2 to 3.1.

[0015] The ratio of the additive to the entire solvent is preferably from 0.05 to 2 mol / L, more preferably from 0.1 to 1.5 mol / L, and further preferably from 0.4 to 1.3 mol / L.

[0016] The order of mixing the polycarboxylic acid, the metal compound, the additive, and the solvent is not particularly limited, and (i) all may be mixed at the same time, (ii) a solution A1 in which the polycarboxylic acid and the additive are dissolved in a solvent a1 and a solution B in which the metal compound is dissolved in a solvent b are separately prepared, and solution A1 and solution B may be mixed, or (iii) a solution A2 in which the polycarboxylic acid and the metal compound are dissolved in a solvent a2 and a solution C in which the additive or the additive is dissolved in a solvent c are prepared, and solution A2 and the additive or solution C may be mixed. In particular, (ii) or (iii) are preferred, and (ii) is most preferred.

[0017] In the above embodiments (ii) and (iii), one or more kinds of solutions may be prepared for each of solution A1, solution B, solution A2, and solution C. When mixing solution A1 and solution B in embodiment (ii), it is preferable to drop one solution into the remaining solution in order, and in embodiment (iii), it is preferable to add (particularly dropwise) an additive or solution C to solution A2.

[0018] In the above embodiment (ii), the water content in the combined total of solvent a1 and solvent b is sufficient to be more than 80 mass%, and it is more preferable that the water content in 100 mass% of solvent a1 is more than 80 mass% (preferably 90 mass% or more, more preferably 95 mass% or more) and the water content in 100 mass% of solvent b is more than 80 mass% (preferably 90 mass% or more, more preferably 95 mass% or more), and it is preferable that both solvent a1 and solvent b are water (100 mass% water). In the embodiment (iii) above where solvent c is used, the water content in the combined total of solvent a2 and solvent c is sufficient to be greater than 80 mass%, and it is more preferable that the water content in 100 mass% of solvent a2 is greater than 80 mass% (preferably 90 mass% or more, more preferably 95 mass% or more) and that the water content in 100 mass% of solvent c is greater than 80 mass% (preferably 90 mass% or more, more preferably 95 mass% or more), and it is preferable that both solvent a2 and solvent c are water (100 mass% water).

[0019] It is also preferable to adjust the pH of solution A1 in the above embodiment (ii) and solution A2 in the above embodiment (iii), i.e., the pH of the liquid containing polyvalent carboxylic acid, to a predetermined range, and the pH is preferably 3.0 or more, more preferably 4.0 or more, even more preferably 6.0 or more, particularly preferably 8.0 or more, and most preferably 10.0 or more, with the upper limit being, for example, 11.5. In particular, it is preferable that the additive is triethylamine and the pH of solution A1 or solution A2 is 9.0 or more (particularly 10.0 or more). The pH of solution A1 or A2 described above is a value measured at about 17 to 25°C.

[0020] The pH of the liquid after the reaction of the polyvalent carboxylic acid with the metal compound is preferably 6.5 or less, more preferably 6.0 or less, even more preferably 5.5 or less, particularly preferably 5.0 or less, and most preferably 4.0 or less, with the lower limit being, but not particularly limited, for example, 2.0. The pH of the liquid after the reaction is a value measured at about 17 to 50°C.

[0021] The polycarboxylic acid, metal compound, additive, and solvent may be mixed at, for example, 15 to 70°C, and more preferably at 20 to 60°C. After mixing, the polycarboxylic acid and the metal compound are preferably reacted, for example, at 60 to 200°C (preferably 80 to 120°C) for about 5 to 60 hours (preferably 10 to 20 hours), while refluxing or leaving them to stand. The suspension after the reaction may be filtered under reduced pressure, washed, and then dried in a vacuum drying oven. The washing can be performed by immersing the obtained metal-organic framework in about 5 to 30 ml of water or alcohol for about 5 to 60 seconds. This operation is counted as one time, and washing with water or alcohol is preferably performed about 2 to 8 times in total, and more preferably washing with water and alcohol is performed at least once, and 2 to 8 times in total.

[0022] In the present invention, the reaction proceeds sufficiently if the pressure during the reaction of the polyvalent carboxylic acid with the metal compound is 2.0 MPa or less. The pressure may be 1.8 MPa or less, or 1.7 MPa or less, and the lower limit is, for example, 0.5 MPa.

[0023] Polycarboxylic acids include R(COOH) n (R is an n-valent group, n is an integer of 2 or more). The R is preferably an n-valent aliphatic chain hydrocarbon group, an aliphatic cyclic hydrocarbon group, an aliphatic heterocyclic hydrocarbon group (a group in which one or more carbon atoms of an aliphatic cyclic hydrocarbon group are replaced with heteroatoms), an aromatic hydrocarbon group, or an aromatic heterocyclic hydrocarbon group (a group in which one or more carbon atoms of an aromatic hydrocarbon group are replaced with heteroatoms). The aliphatic chain hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group. The heteroatom in the aliphatic heterocyclic hydrocarbon group or aromatic heterocyclic hydrocarbon group is preferably nitrogen or sulfur. n is preferably 2 or more and 4 or less, more preferably 2 or more and 3 or less, and most preferably 2. The number of carbon atoms in the R is preferably 3 or more, more preferably 6 or more, and preferably 30 or less, more preferably 24 or less, even more preferably 18 or less, even more preferably 12 or less, and most preferably 10 or less.

[0024] The above-mentioned aliphatic chain hydrocarbon group, aliphatic cyclic hydrocarbon group, aliphatic heterocyclic hydrocarbon group, aromatic hydrocarbon group and aromatic heterocyclic hydrocarbon group may further include a carboxylic anhydride group, -OH, -OR 12 , -NH2, -NHR 12 , -N(R 12 The R may contain a functional group Y which is one or more selected from the group consisting of -CN, a halogeno group, -C(=S)SH, -C(=O)SH and tautomers thereof, -SO3H, and -SS-, and the functional group Y is preferably -OH. 12 Each of these represents an alkyl group having 1 or 2 carbon atoms.

[0025] R is preferably an n-valent aromatic hydrocarbon group or aromatic heterocyclic hydrocarbon group, which may contain the functional group Y (particularly -OH).

[0026] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms which may contain a functional group Y (particularly -OH), more preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms which may contain a functional group Y (particularly -OH), and specific examples include groups obtained by removing n (preferably 2 or 3) hydrogen atoms from benzene, naphthalene, or biphenyl and which may contain a functional group Y (particularly -OH).

[0027] The aromatic heterocyclic hydrocarbon group is preferably a group in which one or two carbon atoms of an aromatic hydrocarbon group having 5 to 12 carbon atoms are replaced by nitrogen and / or sulfur, and more specific examples include groups in which n (preferably 2 or 3) hydrogen atoms have been removed from pyrrole, pyrazole, imidazole, thiophene, thiazole, pyridine, pyrimidine, pyridazine, pyrazine or bipyridine, and particularly preferred are groups in which 2 or 3 hydrogen atoms have been removed from thiophene or bipyridine.

[0028] The polyvalent carboxylic acid preferably contains a dicarboxylic acid, and examples of the dicarboxylic acid include succinic acid, fumaric acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid (phthalic acid), 1,3-benzenedicarboxylic acid (isophthalic acid), 2,3-pyridinedicarboxylic acid, and 1,3 -Butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid (terephthalic acid), 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, imidazole-2,4-dicarboxylic acid, 3,5-pyrazole dicarboxylic acid, 2,2-bipyridine-5,5-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid benzoic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, 2,2'-dithiodibenzoic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5 -Cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid, 4,4'-diamino-1,1'-biphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-binaphthyl dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran 250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-di Carboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, hydroxybenzophenone dicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, Pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid dicarboxylic acid, bis(4-aminophenyl)etherdiimide-dicarboxylic acid, 4,4'-diaminodiphenylmethanediimide-dicarboxylic acid, bis(4-aminophenyl)sulfonediimide-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene 2,3-dicarboxylic acid, 2',3'-diphenyl-p-terphenyl-4,4''-dicarboxylic acid, (diphenyl ether)-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-Benzenedicarboxylic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic acid, 4,4'-dihydroxy-diphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorbin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichloro Benzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazole dicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecane dicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, or camphor dicarboxylic acid. The dicarboxylic acid is preferably at least one of 1,3-benzenedicarboxylic acid (isophthalic acid), thiophene-2,5-dicarboxylic acid, 1,4-benzenedicarboxylic acid (terephthalic acid), 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid, 2,4-pyridinedicarboxylic acid, and 2,2-bipyridine-5,5-dicarboxylic acid, and more preferably at least one of 1,3-benzenedicarboxylic acid (isophthalic acid) and thiophene-2,5-dicarboxylic acid.

[0029] The metal in the metal compound preferably contains at least one metal selected from elements in periods 3 to 6 and groups 2 to 14 of the periodic table, more preferably contains at least one metal selected from the group consisting of Al, Ga, In, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr and Hf, still more preferably contains at least one metal selected from the group consisting of Al, In, Sc, Co, Cu and Zn, and particularly preferably contains Al. In this specification, the term "metal" is used to include semimetals such as Si and Ge.

[0030] The metal compound is preferably one or more of the nitrates, sulfates, acetates, halides, and alkoxides of the above-mentioned metals, and more preferably one or more of the nitrates, sulfates, and halides (chlorides or bromides).

[0031] In the present invention, it is preferable that the polyvalent carboxylic acid includes at least one of 1,3-benzenedicarboxylic acid (isophthalic acid), thiophene-2,5-dicarboxylic acid, 1,4-benzenedicarboxylic acid (terephthalic acid), 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid, 2,4-pyridinedicarboxylic acid, and 2,2-bipyridine-5,5-dicarboxylic acid, and that the metal compound includes at least one of nitrate, sulfate, or halide (chloride or bromide) of Al, In, Sc, Co, Cu, or Zn.

[0032] The molar ratio of the polycarboxylic acid to the metal compound (polycarboxylic acid / metal compound) is preferably 0.05 to 2.3, more preferably 0.1 to 2.0, and even more preferably 0.4 to 1.8. The molar ratio P (polycarboxylic acid / metal) of the polycarboxylic acid to the metal in the metal compound is preferably 0.01 to 2, more preferably 0.25 to 1.7, and even more preferably 0.3 to 1.5, relative to the theoretical molar ratio P0 (polycarboxylic acid / metal ion) at which the metal (metal ion) and the polycarboxylic acid are bonded to become electrically neutral (i.e., P / P0).

[0033] The metal organic framework obtained by the production method of the present invention has a structure in which an organic ligand derived from a polyvalent carboxylic acid is coordinately bonded to a metal ion of a metal compound. In particular, the metal organic framework is preferably SCM-5 or SCM-17, the organic ligand in SCM-5 is derived from isophthalic acid and the metal ion is an Al ion, and the organic ligand in SCM-17 is derived from 2,5-thiophenedicarboxylic acid and the metal ion is an Al ion.

[0034] According to the production method of the present invention, the yield of the metal-organic framework calculated by the procedure shown in the examples described later can be 50% or more, preferably 60% or more, more preferably 70% or more, and further preferably 80% or more, and the upper limit is, for example, 99%.

[0035] The BET specific surface area of ​​the metal organic framework obtained in the present invention, measured using nitrogen gas, is 3 cm 2 / g or more, and 2 / g or more is more preferable, and 2 / g or more is more preferable, 2 / g or more, 600cm 2 / g or more, 800cm 2 / g or more, 1000cm 2 / g or more, and the upper limit is, for example, 1350 cm 2 / g. EXAMPLES

[0036] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples, and can of course be modified within the scope of the above and below-mentioned aims, and all such modifications are within the technical scope of the present invention.

[0037] The following examples and comparative examples were evaluated according to the following methods.

[0038] (1) Measurement of pH of solution A1 or solution A2, and the suspension after the reaction The pH of the solution was measured using a HORIBA compact pH meter LAQUAtwin-pH-33B.

[0039] (2) Analysis of generated materials The product was measured using a powder X-ray diffraction (PXRD) device (Rigaku Corporation) under the following conditions. Source: Cu Measurement range: 2θ=3~40° Step size: 0.01° Scanning speed: 3° / min Measurement temperature: room temperature (25℃) The measurement results were evaluated as follows. ◎: A peak pattern derived from the metal-organic framework was obtained, and the structure of the metal-organic framework was identified from the peak pattern. ○: A peak pattern originating from the metal-organic framework and an impurity peak were obtained, and the structure of the metal-organic framework was identified from the peak pattern. △: A peak originating from the metal-organic framework and an impurity peak were obtained, and the structure of the metal-organic framework was not identified from the peak pattern. ×: No peak pattern derived from the metal-organic framework was obtained

[0040] (3) Evaluation of filterability The filterability when filtering using a Kiriyama funnel and a suction pump was judged under the following conditions. ◎: Good [filtrate flows continuously through the base of the funnel] 〇: Normal to good [Liquid is dripping continuously from the tip of the funnel (intervals between droplets are less than 1 second)] △: Normal [Liquid drips continuously from the tip of the funnel (intervals between droplets are 1 second or more)] ×: Poor [Liquid is dripping discontinuously from the tip of the funnel (intervals between droplets are 8 seconds or more)]

[0041] (4) Calculation of yield Based on the smaller amount of moles of metal salt or organic ligand (polycarboxylic acid) charged (the one contained in a molar ratio less than the molar ratio at which the two are combined to become electrically neutral. If the molar ratio is exactly neutral, either molar ratio can be used for calculation), the theoretical withdrawal weight was defined as A, and the actual withdrawal amount was defined as B, and the calculation was made as B / A x 100.

[0042] (5) Measurement of BET specific surface area Since the adsorption occupancy area of ​​nitrogen molecules was known in advance, the amount of gas molecules adsorbed only on the sample surface was measured, and the surface area of ​​the sample was measured using the BET adsorption isotherm. Sample preparation: In order to remove water from the sample, the sample was heated overnight at reduced pressure of 10 Pa or less and 200°C. Equipment: BELSORP-mini manufactured by Microtrack Bell Co., Ltd. Pretreatment conditions: (i) Place a glass rod (for standard sample tubes) to reduce the volume in the standard sample tube and plug it with a quick seal. Prepare the samples to be measured (up to 3 samples per measurement) with this sample tube set, connect it to the pretreatment device (BELPREP VACII), evacuate the air from inside the sample tube, and then introduce N2 gas (purity 99.999% or higher) up to atmospheric pressure. (ii) After that, remove the sample tube from the pretreatment machine and measure the weight three times on a precision balance (displayed to four or more decimal places) to obtain the average (W1). When using a precision balance, use an ionizer to eliminate the effects of static electricity. (iii) Weigh out approximately 50 mg of the sample to be measured onto a piece of packaging paper, and use a long-footed funnel to place the sample directly into the spherical bottom part of the standard sample tube. (iv) Place the glass rod back into the sample tube, plug the tube with a QuickSeal, and then measure the total weight once to provisionally confirm the amount of sample added. (v) The sample tube containing the sample is connected to the pretreatment device, and the inside of the sample tube is evacuated. (vi) After the pressure inside the sample tube has reached a sufficiently low level, heating begins (while continuing to draw a vacuum). Measurement conditions: (i) After the pretreatment (vacuum heating) is completed, the sample tube is cooled while being kept under reduced pressure, and after it has returned to room temperature, N2 gas is introduced up to atmospheric pressure and the tube is removed from the apparatus. (ii) After pretreatment, measure the weight of the sample tube containing the sample three times using a precision balance and obtain the average (W2). The weight of the sample is calculated by subtracting W1 from W2. (iii) Input the sample weight and N2 gas information (such as the second virial coefficient) at liquid nitrogen temperature into the measurement software, input the relative pressure to be measured, and press the measurement start button. Then, follow the instructions of the software to install the Dewar vessel filled with liquid nitrogen and the sample tube, and perform the measurement.

[0043] Example A1 Solution A1 was prepared by dissolving 5.22 mmol of isophthalic acid and 14.26 mmol of triethylamine in 7.52 ml of water (solvent a1). Separately, solution B was prepared by dissolving 2.92 mmol of Al2(SO4)3·nH2O (n is 14-18) in 7.52 ml of water (solvent b). Solution B was added dropwise to solution A1 over 30 minutes at 20-30°C. The mixture was then refluxed at 100°C for 12 hours to obtain a suspension. This was filtered under reduced pressure, and the resulting precipitated solid was washed three times with 20 ml of water and three times with 8 ml of methanol. The filter cake was dried in a vacuum oven at 80°C for 24 hours to obtain the product.

[0044] Example A2 The product was obtained in the same manner as in Example A1, except that the amount of triethylamine was 15.2 mmol.

[0045] Example A3 Solution A1 was prepared by dissolving 5.20 mmol of isophthalic acid and 14.44 mmol of triethylamine in 7.55 ml of water (solvent a1). Separately, solution B was prepared by dissolving 5.82 mmol of Al2(SO4)3·nH2O (n is 14-18) in 7.54 ml of water (solvent b). Solution B was added dropwise to solution A1 over 30 minutes at 20-30°C. The mixture was then refluxed at 100°C for 12 hours to obtain a suspension. This was filtered under reduced pressure, and the resulting precipitated solid was washed three times with 20 ml of water and three times with 8 ml of methanol. The filter cake was dried in a vacuum oven at 80°C for 24 hours to obtain the product.

[0046] Example A4 The product was obtained in the same manner as in Example A3, except that the amount of Al2(SO4)3·nH2O (n is 14 to 18) was 3.88 mol.

[0047] Example A5 The product was obtained in the same manner as in Example A3, except that the amount of Al2(SO4)3·nH2O (n is 14 to 18) was 4.85 mol.

[0048] Example A6 Solution A1 was prepared by dissolving 5.19 mmol of isophthalic acid and 14.15 mmol of triethylamine in 7.54 ml of water (solvent a1). Separately, solution B was prepared by dissolving 2.92 mmol of Al2(SO4)3·nH2O (n is 14-18) in 7.53 ml of water (solvent b). Solution B was added dropwise to solution A1 over 30 minutes at 20-30°C. The mixture was then refluxed at 100°C for 12 hours to obtain a suspension. This was filtered under reduced pressure, and the resulting precipitated solid was washed three times with 20 ml of water. The resulting filter cake was dried in a vacuum drying oven at 80°C for 24 hours to obtain the product.

[0049] Example A7 Solution A2 was prepared by dissolving 5.21 mmol of isophthalic acid and 2.92 mmol of Al2(SO4)3·nH2O (n is 14-18) in 7.53 ml of water (solvent a2). Separately, solution B was prepared by dissolving 14.31 mmol of triethylamine in 7.54 ml of water (solvent b). Solution B was added dropwise to solution A2 at 20-30°C over 30 minutes. The mixture was then refluxed at 100°C for 12 hours to obtain a suspension. This was filtered under reduced pressure, and the resulting precipitated solid was washed three times with 20 ml of water. The resulting filter cake was dried in a vacuum drying oven at 80°C for 24 hours to obtain the product.

[0050] Example A8 Solution A1 was prepared by dissolving 5.04 mmol of isophthalic acid and 14.09 mmol of triethylamine in 7.54 ml of water (solvent a1). Separately, solution B was prepared by dissolving 5.69 mmol of an aqueous solution of Al2(SO4)3 (27% by weight as Al2(SO4)3) in 2.23 ml of water (solvent b). Solution B was added dropwise to solution A over 30 minutes at 20-30°C. Then, the mixture was refluxed at 100°C for 12 hours to obtain a suspension. This was filtered under reduced pressure, and the obtained precipitated solid was washed three times with 20 ml of water, and the obtained filter cake was dried in a vacuum drying oven at 80°C for 24 hours to obtain a product.

[0051] Reference example A1 In a 1L eggplant flask, 3.233mmol of isophthalic acid and 75mL of DMF (dimethylformamide) were mixed at 25℃ and completely dissolved to obtain solution A. Separately, 92.43mmol of Al2(SO4)3·nH2O (n=14-18) was mixed with 301mL of ion-exchanged water to prepare solution B, which was completely dissolved, and added dropwise to solution A over 45 minutes at 25℃. The mixture was then refluxed at 125℃ for 24 hours to obtain a suspension. The suspension was decanted, and the precipitated solid was centrifuged and washed three times with 100mL of water. The obtained filter cake was dried in a vacuum drying oven at 80℃ for 24 hours, 100℃ for 24 hours, and then 120℃ for 48 hours to obtain 19.1g of the product (yield 96%).

[0052] Comparative Example A1 Solution A1 was prepared by dissolving 4.86 mmol of isophthalic acid and 10.17 mmol of sodium hydroxide in 3.52 ml of water. Separately, solution B was prepared by dissolving 4.60 mmol of Al2(SO4)3·nH2O (n is 14-18) in 15.18 ml of water. Solution B was added dropwise to solution A1 over 30 minutes at 20-30°C. The suspension was refluxed at 100°C for 24 hours to obtain a suspension. The suspension was decanted, and the precipitated solid was washed three times with 10 ml of water by centrifugation. The obtained filter cake was dried in a vacuum drying oven at 80°C for 24 hours to obtain the product.

[0053] Comparative example A2 Solution A1 was prepared by dissolving 25.47 mmol of isophthalic acid and 51.43 mmol of sodium hydroxide in a mixed solvent of 50.38 ml of water and 4.20 ml of ethanol. Separately, solution B was prepared by dissolving 9.67 mmol of Al2(SO4)3·nH2O (n is 14-18) and 9.67 mmol of sodium aluminate in 12.8 ml of water. Solution B was added dropwise to solution A1 over 50 minutes at 20-30°C. The mixture was then refluxed at 100°C for 10 hours to obtain a suspension. This was filtered under reduced pressure, and the resulting precipitated solid was washed three times with 30 ml of hot water and three times with 30 ml of water. The filter cake was dried in a vacuum drying oven at 80°C for 24 hours to obtain the product.

[0054] Comparative example A3 The product was obtained in the same manner as in Comparative Example A1, except that 12.98 mol of lithium hydroxide (LiOH) was used instead of sodium hydroxide as the base, and the reaction time was 16 hours (i.e., after the dropwise addition of solution B, the mixture was refluxed at 100°C for 16 hours).

[0055] Comparative example A4 A product substance was obtained in the same manner as in Comparative Example A1, except that 14.81 mol of potassium hydroxide (KOH) was used as the base instead of sodium hydroxide.

[0056] Comparative Example A5 A product was obtained in the same manner as in Comparative Example A1, except that 12.81 mol of sodium carbonate (Na2CO3) was used as the base instead of sodium hydroxide.

[0057] Comparative example A6 A product was obtained in the same manner as in Comparative Example A1, except that 12.65 mol of sodium hydrogen carbonate (NaHCO3) was used as the base instead of sodium hydroxide.

[0058] The results are shown in Table 1.

[0059] [Table 1]

[0060] According to Table 1, in Examples A1 to A8 in which a polycarboxylic acid and a metal compound were reacted in an aqueous solvent in the presence of an organic amine, a metal organic framework was produced, whereas in Comparative Examples A1 to A6 in which a polycarboxylic acid and a metal compound were reacted in an aqueous solvent in the presence of an organic amine and a base other than a nitrogen-containing aromatic heterocyclic compound, a metal organic framework could not be obtained.

[0061] Example B1 In a 100mL eggplant flask, 5.06mmol of 2,5-thiophenedicarboxylic acid and 10.22mmol of triethylamine were dissolved in 7.5ml of water (solvent a1) to prepare solution A1. Separately, 2.92mmol of Al2(SO4)3·nH2O (n is 14-18) was dissolved in 7.57ml of water (solvent b) to prepare solution B. At 20-30℃, solution B was added dropwise to solution A1 over 30 minutes. The mixture was then refluxed at 100℃ for 12 hours to obtain a suspension. This was filtered under reduced pressure, and the solid was washed three times with 20ml of water and 20ml of methanol. The obtained filter cake was dried in a vacuum oven at 80℃ for 24 hours to obtain the product.

[0062] Example B2 The product was obtained in the same manner as in Example B1, except that the amount of triethylamine was 12.95 mmol.

[0063] Example B3 The product was obtained in the same manner as in Example B1, except that the amount of triethylamine was 14.28 mmol.

[0064] Example B4 The product was obtained in the same manner as in Example B1, except that the amount of triethylamine was 15.32 mmol.

[0065] Example B5 The product was obtained in the same manner as in Example B1, except that the amount of triethylamine was 17.74 mmol.

[0066] Example B6 In a 100mL eggplant flask, 5.06mmol of 2,5-thiophenedicarboxylic acid and 2.92mmol of Al2(SO4)3·nH2O (n is 14-18) were dissolved in 7.5mL of water (solvent a2) to prepare solution A2. Separately, 10.22mmol of triethylamine was added. The mixture was then refluxed at 100℃ for 12 hours to obtain a suspension. This was filtered under reduced pressure, and the solid was washed three times with 20mL of water and 20mL of methanol. The obtained filter cake was dried in a vacuum drying oven at 80℃ for 24 hours to obtain the product.

[0067] Example B7 A product substance was obtained in the same manner as in Example B2, except that the temperature at which solution B was added dropwise to solution A1 was 40°C.

[0068] Example B8 A product substance was obtained in the same manner as in Example B2, except that the temperature at which solution B was added dropwise to solution A1 was 60°C.

[0069] Example B9 The product was obtained in the same manner as in Example B2, except that the amount of Al2(SO4)3·nH2O (n is 14 to 18) was 5.82 mmol.

[0070] Example B10 The product was obtained in the same manner as in Example B3, except that the amount of Al2(SO4)3·nH2O (n is 14 to 18) was 5.82 mmol.

[0071] Example B11 The product was obtained in the same manner as in Example B4, except that the amount of Al2(SO4)3·nH2O (n is 14 to 18) was 5.81 mmol.

[0072] Example B12 The product was obtained in the same manner as in Example B5, except that the amount of Al2(SO4)3·nH2O (n is 14 to 18) was 5.82 mmol.

[0073] Example B13 A product substance was obtained in the same manner as in Example B12, except that the temperature of solution B when dropwise added to solution A1 was 40°C.

[0074] Example B14 A product substance was obtained in the same manner as in Example B12, except that the temperature at which solution B was added dropwise to solution A1 was 60°C.

[0075] Reference example B1 In a 100mL eggplant flask, 5.07mmol of 2,5-thiophenedicarboxylic acid was dissolved in 8mL of dimethylformamide to prepare solution X. Separately, 5.81mmol of Al2(SO4)3·nH2O (n is 14-18) was dissolved in 32.02mL of water to prepare solution Y. Solution Y was added dropwise to solution X over 30 minutes at 20-30℃. The mixture was then refluxed at 135℃ for 24 hours to obtain a suspension. This was filtered under reduced pressure, and the solid was washed three times with 20mL of water and 20mL of methanol. The obtained filter cake was dried in a vacuum oven at 80℃ for 24 hours to obtain the product.

[0076] Comparative Example B1 The product was obtained in the same manner as in Example B1, except that 12.7 mmol of NaOH was used instead of triethylamine.

[0077] The results are shown in Table 2.

[0078] [Table 2]

[0079] According to Table 2, in Examples B1 to B14 in which a polycarboxylic acid and a metal compound were reacted in an aqueous solvent in the presence of an organic amine, a metal organic framework was produced, whereas in Comparative Example B1 in which a polycarboxylic acid and a metal compound were reacted in an aqueous solvent in the presence of an organic amine and a base other than a nitrogen-containing aromatic heterocyclic compound, a metal organic framework could not be obtained.

[0080] Furthermore, when the filterability was evaluated for Examples B1, and B9 to B13, Examples B1, and B9 to B12 were rated as ◯, and Example B13 was rated as △.

[0081] Example C1 In a 100mL eggplant flask, 5.09mmol of 2,5-thiophenedicarboxylic acid and 11.18mmol of hexamethylenetetramine (HMTA) were dissolved in 7.61ml of water (solvent a1) to prepare solution A1. Separately, 2.92mmol of Al2(SO4)3·nH2O (n is 14-18) was dissolved in 7.53ml of water (solvent b) to prepare solution B. At 20-30℃, solution B was added dropwise to solution A1 over 30 minutes. The mixture was then refluxed at 100℃ for 12 hours to obtain a suspension. This was filtered under reduced pressure, and the solid was washed three times with 20ml of water and 20ml of methanol. The obtained filter cake was dried in a vacuum oven at 80℃ for 24 hours to obtain the product.

[0082] Example C2 The product was obtained in the same manner as in Example C1, except that diethylamine was used instead of hexamethylenetetramine (HMTA).

[0083] Example C3 The product was obtained in the same manner as in Example C1, except that diisopropylamine was used instead of hexamethylenetetramine (HMTA).

[0084] Example C4 The product was obtained in the same manner as in Example C1, except that tri-n-propylamine was used instead of hexamethylenetetramine (HMTA).

[0085] Example C5 The product was obtained in the same manner as in Example C1, except that triisobutylamine was used instead of hexamethylenetetramine (HMTA).

[0086] Example C6 The product was obtained in the same manner as in Example C1, except that methylimidazole was used instead of hexamethylenetetramine (HMTA).

[0087] Example C7 The product was obtained in the same manner as in Example C1, except that N,N-diisopropylethylamine was used instead of hexamethylenetetramine (HMTA).

[0088] Example C8 The product was obtained in the same manner as in Example C1, except that 1,4-diazabicyclo[2.2.2]octane was used instead of hexamethylenetetramine (HMTA).

[0089] Example C9 The product was obtained in the same manner as in Example C1, except that pyridine was used instead of hexamethylenetetramine (HMTA).

[0090] Example C10 The product was obtained in the same manner as in Example C1, except that trimethylamine was used instead of hexamethylenetetramine (HMTA).

[0091] Example C11 The product was obtained in the same manner as in Example C1, except that ammonia was used instead of hexamethylenetetramine (HMTA).

[0092] The results are shown in Table 3.

[0093] [Table 3]

[0094] When the filterability of Examples C1, and C3 to C9 was evaluated, Examples C3 and C5 were rated as ⊚, Examples C1, C4 and C9 were rated as ◯, and Examples C6 to C8 were rated as △.

[0095] Reference example D1 In a 50mL vial, 2.49mmol of terephthalic acid and 2.65mmol of In(NO3)3·H2O were dissolved in 10mL of dimethylformamide to prepare solution X, which was then stirred at 20-30℃ for 30 minutes. Then, 2mL of ethanol was added to prepare solution Y. The solution was then left to stand at 120℃ for 48 hours to obtain a reaction solution. This was decanted, and the precipitated solid was washed three times with 20mL of dimethylformamide. The obtained filter cake was dried in a vacuum drying oven at 120℃ for 24 hours to obtain the product.

[0096] Example D1 In a 100mL eggplant flask, 4.86mmol of terephthalic acid and 10.60mmol of triethylamine were dissolved in 18.04ml of water (solvent a1) to prepare solution A1. Separately, 5.26mmol of In(NO3)3·H2O was dissolved in 6.03ml of water (solvent b) to prepare solution B. At 20-30℃, solution B was added dropwise to solution A1 over 30 minutes. The mixture was then refluxed at 100℃ for 16 hours to obtain a suspension. This was filtered under reduced pressure, and the resulting precipitated solid was washed three times with 20ml of water. The resulting filter cake was dried in a vacuum drying oven at 80℃ for 24 hours to obtain the product.

[0097] Reference example D2 In a 200mL three-neck flask, 2.03mmol of 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid was dissolved in 50ml of ethanol to prepare solution X. Separately, 6.75mmol of ZnBr2 was dissolved in 50ml of dimethylformamide to prepare solution Y. At 20-30°C, solution Y was added dropwise to solution X over 30 minutes. Then, the mixture was refluxed at 110°C for 12 hours to obtain a suspension. This was decanted, and the precipitated solid was washed three times with 50ml of dimethylformamide and three times with 50ml of methanol, and the obtained filter cake was dried in a vacuum drying oven at 180°C for 24 hours to obtain a product.

[0098] Example D2 In a 100 mL eggplant flask, 1.60 mmol of 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid and 3.61 mmol of triethylamine were dissolved in 12.5 ml of water (solvent a1) to prepare solution A1. Separately, 5.31 mmol of ZnBr2 was dissolved in 12.5 ml of water (solvent b) to prepare solution B. At 20-30°C, solution B was added dropwise to solution A1 over 30 minutes. Then, the mixture was refluxed at 100°C for 12 hours to obtain a suspension. This was filtered under reduced pressure, and the obtained precipitated solid was washed three times with 20 ml of water, and the obtained filter cake was dried in a vacuum drying oven at 60°C for 24 hours to obtain a product.

[0099] Reference example D3 In a 30mL vial, 0.58mmol of 2,2-bipyridine-5,5-dicarboxylic acid and 0.59mmol of Sc(NO3)2 were dissolved in 12.5ml of dimethylformamide to prepare solution X. Then, 0.05g of dilute hydrochloric acid was added at 20-30℃ and stirred for 30 minutes. Separately, 0.61mmol of CuCl2 was dissolved in 11ml of dimethylformamide to prepare solution Y. At 20-30℃, solution Y was added dropwise to solution X over 30 minutes. Then, the mixture was left to stand at 60℃ for 48 hours to obtain a suspension. This was decanted, and the precipitated solid was washed three times with 20ml of dimethylformamide, and the obtained filter cake was dried in a vacuum drying oven at 80℃ for 24 hours to obtain a product.

[0100] Example D3 In a 100 mL eggplant flask, 1.15 mmol of 2,2-bipyridine-5,5-dicarboxylic acid and 2.59 mmol of triethylamine were dissolved in 6.51 ml of water (solvent a1) to prepare solution A1. Separately, 1.20 mmol of Sc(NO3)2 was dissolved in 6.06 ml of water (solvent b1) to prepare solution B1. At 20 to 30 °C, solution B1 was dropped into solution A1 over 30 minutes. Then, 1.19 mmol of CuCl2 was dissolved in 11.07 ml of water (solvent b2) to prepare solution B2. At 20 to 30 °C, solution B2 was dropped into the mixture of solution A1 and solution B1 over 30 minutes. Then, the mixture was reacted at 60 °C for 48 hours to obtain a suspension. This was filtered under reduced pressure, and the obtained precipitated solid was washed three times with 20 ml of water, and the obtained filter cake was dried in a vacuum drying oven at 60 °C for 48 hours to obtain a product.

[0101] Reference example D4 In a pressure-resistant container of 100 mL, 0.50 mmol of terephthalic acid and 3.70 mmol of Al(NO3)2 were dissolved in 31.8 g of methanol to prepare solution A. Then, 1.57 g of a 2 M methanol solution of sodium hydroxide (0.2 g / 2.5 ml) was added to solution A. Then, the mixture was left to stand at 125°C for 20 hours to obtain a suspension. This was decanted, and the precipitated solid was washed three times with 20 ml of methanol, and the obtained filter cake was dried in a vacuum drying oven at 80°C for 24 hours to obtain a product. Note that the pressure at which terephthalic acid and aluminum nitrate react in this reference example is thought to be about 0.72 MPa.

[0102] Example D4 In a 100mL eggplant flask, 3.56mmol of terephthalic acid and 7.52mmol of triethylamine were dissolved in 22.5ml of water (solvent a1) to prepare solution A1. Separately, 27.59mmol of Al(NO3)2 was dissolved in 20.1ml of water (solvent b) to prepare solution B. At 20-30°C, solution B was added dropwise to solution A1 over 30 minutes. Then, the mixture was refluxed at 100°C for 16 hours to obtain a suspension. This was filtered under reduced pressure, and the obtained precipitated solid was washed three times with 30ml of water, and the obtained filter cake was dried in a vacuum drying oven at 60°C for 24 hours to obtain a product.

[0103] Comparative Example D1 In a 50 mL heat-resistant container, 1.47 mmol of CoCl2 was dissolved in 8 mL of water (solvent b) to prepare solution B. Separately, 2.09 mmol of 2,4-pyridinedicarboxylic acid and 6.15 mmol of potassium hydroxide were dissolved in 0.35 mL of water (solvent a1) to prepare solution A1. At 20 to 30 ° C, solution A1 was added dropwise to solution B over 30 minutes. Then, the mixture was left to stand at 200 ° C for 15 hours to obtain a suspension. This was decanted, and the precipitated solid was washed three times with 20 mL of water, and the obtained filter cake was dried in a vacuum drying oven at 80 ° C for 24 hours to obtain a product.

[0104] Example D5 In a pressure-resistant container of 50 mL, solution B was prepared by dissolving 4.59 mmol of CoCl2 in 9 ml of water (solvent b). Separately, solution A1 was prepared by dissolving 3.08 mmol of 2,4-pyridinedicarboxylic acid and 6.163 mmol of triethylamine in 12.02 ml of water (solvent a1). At 20 to 30 ° C, solution A1 was dropped into solution B over 30 minutes. Then, the mixture was left to stand at 200 ° C for 15 hours to obtain a suspension. This was decanted, and the precipitated solid was washed three times with 20 ml of water, and the obtained filter cake was dried in a vacuum drying oven at 80 ° C for 24 hours to obtain a product. In this example, the pressure at which 2,4-pyridinedicarboxylic acid and cobalt chloride react was about 1.55 MPa, in consideration of the saturated vapor pressure of water at a reaction temperature of 200 ° C.

[0105] The results are shown in Table 4.

[0106] [Table 4]

[0107] When the filterability of Examples D1 to D3 was evaluated, Examples D1 and D2 were rated as ⊚, and Example D3 was rated as ◯. [Industrial Applicability]

[0108] The metal-organic framework obtained by the present invention is useful because it can efficiently produce a metal-organic framework that is suitable for adsorption and removal of gases and organic molecules. Examples of the gas include water (water vapor), carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gases, hydrogen sulfide, ammonia, sulfur oxides, nitrogen oxides, and siloxanes. Examples of the organic molecules include hydrocarbons having 5 to 8 carbon atoms, alcohols having 1 to 8 carbon atoms, aldehydes having 1 to 8 carbon atoms, carboxylic acids having 1 to 8 carbon atoms, ketones having 1 to 8 carbon atoms, amines having 1 to 8 carbon atoms, esters having 1 to 8 carbon atoms, and amides having 1 to 8 carbon atoms. The organic molecules may contain an aromatic ring.

Claims

1. A method for producing a metal-organic structure, comprising reacting a polycarboxylic acid and a metal compound in a solvent at 60 to 200°C in the presence of one or more additives selected from ammonia, organic amines, and nitrogen-containing aromatic heterocyclic compounds, A method for producing a metal-organic structure, characterized in that the water content in 100% by mass of the solvent is more than 80% by mass.

2. The manufacturing method according to claim 1, wherein the pressure during the reaction between the polycarboxylic acid and the metal compound is 2.0 MPa or less.

3. The polycarboxylic acid and the additive are dissolved in solvent a1, and solution A1 is mixed with the metal compound in solvent b, and the polycarboxylic acid and the metal compound are reacted. The manufacturing method according to claim 1 or 2, wherein the water content in the total 100% by mass of solvent a1 and solvent b is more than 80% by mass.

4. The manufacturing method according to claim 3, wherein the pH of solution A1 is 3.0 or higher.

5. The manufacturing method according to claim 1 or 2, wherein the pH of the solution after the reaction of the polycarboxylic acid and the metal compound is 6.5 or less.

6. The manufacturing method according to claim 1 or 2, wherein the additive comprises an organic amine, which is at least one selected from secondary amines and tertiary amines.