JP2017066063A - Porous aluminum compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel porous aluminum compound having gas adsorbing and desorbing ability.SOLUTION: The present invention provides a porous aluminum compound comprising a basic skeleton represented by general formula (1) (n is an integer of 2-4; X is a monovalent anion; if n is 2, Reach independently represents H, a halogen atom, a C1-4 alkyl group, a C1-4 haloalkyl group or the like; Reach independently represents H, a C1-4 alkyl group, a C1-4 haloalkyl group, a C1-4 alkyloxy group, a C1-4 haloalkyloxy group or the like; if n is 3, Ris H, a halogen atom, a C1-4 alkyl group, a C1-4 haloalkyl group, a C1-4 alkyloxy group or the like, Reach independently represents H, a C1-4 alkyl group, a C1-4 haloalkyl group, a C1-4 alkyloxy group, a C1-4 haloalkyloxy group or the like; if n is 4, Reach independently represents H, a C1-4 alkyl group, a C1-4 haloalkyl group, a C1-4 alkyloxy group, a C1-4 haloalkyloxy group or the like).SELECTED DRAWING: None

Description

  The present invention relates to a porous coordination polymer having an amino group. More specifically, the present invention relates to a porous aluminum compound comprising diaminoterephthalic acid and a method for producing the same.

  A porous coordination polymer composed of a metal ion and an organic bridging ligand has been studied for its gas adsorption ability. Porous coordination coordination composed of amino group-containing aromatic dicarboxylic acid ligands and metal ions for the purpose of enhancing gas adsorption capacity by enhancing the interaction between porous coordination polymers and adsorbed molecules Molecules (hereinafter referred to as “nitrogen-containing porous coordination polymers”) have been studied (Non-patent Document 1). Catalytic reactions using a solid catalyst in which a catalytic metal is supported on the amino group of these nitrogen-containing porous coordination polymers have been studied. For example, in Non-Patent Documents 2 to 4, aminoterephthalic acid, aluminum, iron Alternatively, a nitrogen-containing porous coordination polymer made of titanium is disclosed. However, no synthesis of nitrogen-containing porous coordination polymer composed of metal and diaminoterephthalic acid has been reported so far.

Journal of the American Chemical Society, 131, 6326-6327, 2009. Chemistry of Materials, 23, 2565-2572, 2011. Inorganic Chemistry, 47, 7568-7576, 2008. Journal of the American Chemical Society, 135, 10942-10945, 2013.

Nitrogen-containing porous coordination polymers reported so far have a selective adsorption and desorption of carbon dioxide (hereinafter referred to as “CO ₂ ”) compared to porous coordination polymers having no amino group. Separation (hereinafter referred to as “adsorption / desorption”) is high. However, in order to use the conventional nitrogen-containing porous coordination polymer as a practical adsorption / desorption agent, it is necessary to further improve the adsorption / desorption ability.

  In view of the above-described problems, an object of the present invention is to provide a novel nitrogen-containing porous coordination polymer having a function that can also serve as an adsorption / desorption agent, as well as a separating agent and a gas storage material.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that a porous aluminum compound comprising an aluminum ion and a dicarboxylic acid having a specific amino group is a compound having performance capable of solving the above problems, and has completed the present invention.

That is, the present invention
(I) General formula (1)

(In the formula, n represents an integer of 2 to 4, X represents a monovalent anion. When n is 2, R ¹ is the same or different and is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 4 carbon atoms. represents an alkyl group, a haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group or haloalkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, R ² are the same or different and a hydrogen atom, a carbon number from 1 to 4 Alkyl group, haloalkyl group having 1 to 4 carbon atoms, alkyloxy group having 1 to 4 carbon atoms, haloalkyloxy group having 1 to 4 carbon atoms, acyl group having 2 to 5 carbon atoms or (alkyl having 1 to 4 carbon atoms) ) Represents an oxycarbonyl group, and when n is 3, R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or A haloalkyloxy group having 1 to 4 carbon atoms And, R ² are the same or different and a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, haloalkoxy group having 1 to 4 carbon atoms Represents an acyl group having 2 to 5 carbon atoms or an (oxyalkyl having 1 to 4 carbon atoms) oxycarbonyl group, and when n is 4, R ² is the same or different and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , A haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a haloalkyloxy group having 1 to 4 carbon atoms, an acyl group having 2 to 5 carbon atoms, or (alkyl having 1 to 4 carbon atoms) oxycarbonyl A porous aluminum compound comprising a basic skeleton represented by:
(Ii) The porous aluminum compound according to (i), which has a MIL-101 type crystal structure.
(Iii) The porous aluminum compound according to (i) or (ii), which has a BET specific surface area of 500 m ² / g or more and 3000 m ² / g or less.
(Iv) n is 2, R ¹ is a hydrogen atom, R ² is the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or 1 carbon atom. The porous aluminum compound according to any one of (i) to (iii), which is a haloalkyloxy group having 4 to 4 carbon atoms, an acyl group having 2 to 5 carbon atoms, or an (alkyl having 1 to 4 carbon atoms) oxycarbonyl group.
(V) The porous aluminum compound according to any one of (i) to (iv), wherein R ² is a hydrogen atom.
(Vi) The porous aluminum compound as described in any one of (i) to (v) above, wherein X is a chloride ion or a perchlorate ion.
(Vii) The method for producing a porous aluminum compound according to (i), wherein a trivalent aluminum salt and a dicarboxylic acid represented by the following general formula (2) are reacted in a solvent.

(In the formula, n represents an integer of 2 to 4. When n is 2, R ¹ is the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. Group, an alkyloxy group having 1 to 4 carbon atoms or a haloalkyloxy group having 1 to 4 carbon atoms, and R ² is the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. A haloalkyl group, an alkyloxy group having 1 to 4 carbon atoms, a haloalkyloxy group having 1 to 4 carbon atoms, an acyl group having 2 to 5 carbon atoms, or an (alkyl having 1 to 4 carbon atoms) oxycarbonyl group, where n is 3. In this case, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a haloalkyloxy group having 1 to 4 carbon atoms. R ² is the same or different A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a haloalkyloxy group having 1 to 4 carbon atoms, an acyl having 2 to 5 carbon atoms Group or (alkyl having 1 to 4 carbon atoms) oxycarbonyl group, when n is 4, R ² is the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. Group, a C1-C4 alkyloxy group, a C1-C4 haloalkyloxy group, a C2-C5 acyl group, or a (C1-C4 alkyl) oxycarbonyl group.)
(Viii) The method for producing a porous aluminum compound according to (vii), wherein the trivalent aluminum salt is aluminum chloride or aluminum perchlorate.
(Ix) The method for producing a porous aluminum compound according to (vii) or (viii), wherein the solvent is an amide compound.
(X) n is 2, R ¹ is a hydrogen atom, R ² is the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkylcarbonyl group having 1 to 4 carbon atoms, or 1 carbon atom. The method for producing a porous aluminum compound according to any one of (vii) to (ix) above, which is a haloalkylcarbonyl group having 4 to 4 or an (oxygen having 1 to 4 carbon) oxycarbonyl group.
(Xi) The method for producing a porous aluminum compound according to any one of (vii) to (x), wherein R ² is a hydrogen atom or a tert-butyloxycarbonyl group.
(Xii) The present invention relates to an adsorbent containing the porous aluminum compound according to any one of (i) to (vi).

  Hereinafter, the porous aluminum compound of the present invention will be described in more detail.

  The present invention is a porous aluminum compound including the basic skeleton represented by the general formula (1), and a porous aluminum compound having a metal-organic network formed by repeating this as a unit structure is also included in the present invention. . The metal-organic network that can be formed includes MIL-101 type. The MIL-101 type skeletal structure composed of trivalent chromium ions and terephthalic acid is shown in FIG. 1, and crystal data are listed in the following publications.

Science, 309, 2040-2042, 2005.

(In the formula, n, X, R ¹ and R ² represent the same meaning as described above.)
The definitions of R ¹ , R ² and X in the porous aluminum compound of the present invention will be described.

When R ¹ in the general formula (1) is a halogen atom, examples of the halogen atom include one or more selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group having 1 to 4 carbon atoms represented by R ¹ or R ^2, may be any of straight-chain alkyl group or branched alkyl group. Specific examples of the alkyl group include one or more selected from the group of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group. Furthermore, at least one of a methyl group and an ethyl group may be used in that the surface area of the porous aluminum compound of the present invention is increased.

When R ¹ or R ² is a haloalkyl group having 1 to 4 carbon atoms, the haloalkyl group may be a linear haloalkyl group or a branched haloalkyl group. Specific haloalkyl groups include fluoromethyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group, 2-chloroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2 -Trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-fluoropropyl group, 3-fluoropropyl group, 1,1-difluoropropyl group, 2,2-difluoropropyl group, 3,3 -Difluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 1,1-difluorobutyl group, 4,4,4-trifluorobutyl group, 2, 2,3,4,4,4-hexafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, and 1,1,2,2,3,3,4,4, - it can be exemplified one or more selected from the group of nonafluorobutyl group. Furthermore, what is necessary is just one or more types chosen from the group of a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group at the point which the surface area of the porous aluminum compound of this invention becomes large.

When R ¹ or R ² is an alkyloxy group having 1 to 4 carbon atoms, the alkyloxy group may be either a linear alkyloxy group or a branched alkyloxy group. Specific examples of the alkyloxy group include one or more selected from the group consisting of a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. can do. Furthermore, it may be a methyloxy group or an ethyloxy group in that the surface area of the porous aluminum compound of the present invention is increased.

When R ¹ or R ² is a haloalkyloxy group having 1 to 4 carbon atoms, the haloalkyloxy group may be either a linear haloalkyloxy group or a branched haloalkyloxy group. Specific haloalkyloxy groups include (fluoromethyl) oxy group, (chloromethyl) oxy group, (difluoromethyl) oxy group, (trifluoromethyl) oxy group, (trichloromethyl) oxy group, (bromodifluoromethyl) oxy Group, (2-fluoroethyl) oxy group, (2-chloroethyl) oxy group, (1,1-difluoroethyl) oxy group, (2,2-difluoroethyl) oxy group, (2,2,2-trifluoro) Ethyl) oxy group, (1,1,2,2-tetrafluoroethyl) oxy group, (pentafluoroethyl) oxy group, (2-fluoropropyl) oxy group, (3-fluoropropyl) oxy group, (2, 2-difluoropropyl) oxy group, (3,3-difluoropropyl) oxy group, (3,3,3-trifluoropropyl) Group, and (2,2,3,3-tetrafluoro propyl) one or more selected from the group of oxy group can be exemplified. Furthermore, the haloalkyloxy group may be at least one selected from the group consisting of a fluoromethyloxy group, a difluoromethyloxy group, and a trifluoromethyloxy group in that the surface area of the porous aluminum compound of the present invention is increased. .

When R ² is an acyl group having 2 to 5 carbon atoms, the acyl group may be either a linear acyl group or a branched acyl group. Specific examples of the acyl group include one or more selected from the group of acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, and pivaloyl group. Furthermore, the acyl group may be one or more selected from the group of acetyl group and propionitrile group in that the surface area of the porous aluminum compound of the present invention is increased.

When R ² is (alkyl having 1 to 4 carbons) oxycarbonyl, the alkyloxycarbonyl group may be either a linear alkyloxycarbonyl group or a branched alkyloxycarbonyl group. Specific examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, and a tert-butyloxycarbonyl group. 1 or more types selected from the group of etc. can be illustrated. Furthermore, the (C1-C4 alkyl) oxycarbonyl group should just be 1 or more types chosen from the group of an acetyl group and a tert- butyloxycarbonyl group.

In the general formula (1), when the porous aluminum compound of the present invention contains two R ^{1 s} , these R ^{1 s} may be different atoms or substituents. Since the surface area of the porous aluminum compound is increased, R ¹ in the general formula (1) is more preferably a hydrogen atom. When the porous aluminum compound of the present invention contains two or more R ^{2 s} , these R ^{2 s} may be different atoms or substituents. Since the surface area of the porous aluminum compound is increased, R ² in the general formula (1) is preferably a hydrogen atom.

  Monovalent anions represented by X include fluoride ions, chloride ions, bromide ions, iodide ions and other halide ions, hydroxide ions, perchlorate ions, nitrate ions, acetate ions, and lactic acid. Examples include one or more selected from the group of ions, hydrogen carbonate ions, hydrogen sulfate ions, dihydrogen phosphate ions, hydrogen oxalate ions, tetrafluoroborate ions, thiocyanate ions, cyanide ions, and phenoxide ions. it can. Since the surface area of the porous aluminum compound is increased, X may be at least one selected from the group of chloride ions and perchlorate ions.

  The porous aluminum compound of the present invention may contain any one or more selected from the group consisting of water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, and alcohols. In the present specification, the sulfoxide compound refers to di (alkyl having 1 to 4 carbons) sulfoxide, di (aryl having 6 to 12 carbons) sulfoxide, (alkyl having 1 to 4 carbons) (6 to 12 carbons). Aryl) sulfoxide, and examples thereof include dimethyl sulfoxide (hereinafter referred to as “DMSO”), di-n-butyl sulfoxide, and methylphenyl sulfoxide. In the present specification, the sulfone compound refers to di (alkyl having 1 to 4 carbon atoms) sulfone [two (alkyl having 1 to 4 carbon atoms) may be integrated], di (6 to 12 carbon atoms). Aryl) sulfone and (alkyl having 1 to 4 carbon atoms) (aryl having 6 to 12 carbon atoms) sulfoxide, and examples thereof include sulfolane, dipropylsulfone, and di-n-butylsulfone. In the present specification, an amide compound means a dialkyl carboxylate, for example, N, N-dimethylacetamide (hereinafter referred to as “DMAc”), N, N-dimethylformamide (hereinafter referred to as “DMF”). ), N, N-diethylformamide (hereinafter referred to as “DEF”), and N-methylpyrrolidone (hereinafter referred to as “NMP”). In the present specification, the nitrile compound means an alkyl nitrile having 1 to 4 carbon atoms (meaning an aryl nitrile having 6 to 12 carbon atoms, such as acetonitrile or propionitrile. In the present specification, an alcohol is used. Means a general organic alcohol compound, such as methanol, ethanol, 2-propanol, and butanol, etc. Since the surface area of the porous aluminum compound tends to increase, an amide compound or alcohol, and further DMAc , One or more selected from the group consisting of DMF, DEF, NMP, methanol, ethanol or 2-propanol is preferred.

  The porous aluminum compound of the present invention may contain a Bronsted acid. In this specification, the Bronsted acid means a compound that donates hydrogen ions, and includes inorganic acids such as hydrogen chloride, perchloric acid, sulfuric acid, and phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfone. Organic acids such as acid, acetic acid and benzoic acid can be mentioned. Since the yield of the porous aluminum compound tends to be high, any one or more selected from the group of hydrogen chloride, acetic acid, and benzoic acid is more preferable.

  The porous aluminum compound of the present invention may contain a trivalent aluminum salt and aluminum oxide.

  The porous aluminum compound of the present invention preferably has a MIL-101 type crystal structure. The MIL-101 type crystal structure is the same crystal structure as MIL-101 (Cr) described in Non-Patent Document 5. It can be confirmed by powder X-ray diffraction (hereinafter referred to as “XRD”) that the porous aluminum compound of the present invention has a MIL-101 type crystal structure. That is, the XRD pattern of the porous aluminum compound of the present invention can be identified by comparing with the XRD pattern described in FIG. S4 of Non-Patent Document 5, and at least the range of X-ray diffraction angle 2θ = 4 to 17 °. These peaks may be identified by comparing the peaks.

The porous aluminum compound of the present invention is a metal complex having a metal-organic framework, a so-called porous coordination polymer, and is measured using a surface area sufficient to function as an adsorption / desorption agent or a separating agent, for example, nitrogen molecules. A porous aluminum compound having a BET specific surface area of 500 m ² / g or more and 3000 m ² / g or less is preferable. The BET specific surface area of the porous aluminum compound of the present invention is preferably 1000 m ² / g or more, more preferably 1100 m ² / g, still more preferably 1300 m ² / g, particularly preferably 1500 m ² / g or more. . Thereby, the adsorption | suction characteristic of the porous aluminum compound of this invention improves more.

  Next, the production method of the present invention (hereinafter referred to as “the present production method”) will be described.

  The porous aluminum compound of the present invention is produced by reacting a trivalent aluminum salt with a dicarboxylic acid represented by the following general formula (2) in a solvent, and producing the porous aluminum compound of the present invention Is the method.

(In the formula, n, R ¹ and R ² represent the same meaning as described above.)
Aluminum salts that can be used in this production method include aluminum chloride (III), aluminum fluoride (III), aluminum bromide (III), aluminum iodide (III), aluminum acetate (III), aluminum nitrate (III ), Aluminum sulfate (III), aluminum sulfate (III) ammonium, aluminum carbonate (III), aluminum phosphate (III), aluminum dihydrogen phosphate (III), aluminum perchlorate (III), aluminum silicate (III ), Aluminum (III) tetrafluoroborate, aluminum (III) thiocyanate, aluminum (III) oxalate, aluminum (III) distearate, aluminum (III) acetylacetonate, aluminum (III) hexa Uroacetylacetonate, aluminum (III) cyanide, aluminum (III) (2,2,6,6-tetramethyl-3,5-heptanedionate), tris (8-hydroxyquinoline) aluminum (III), Aluminum (III) methoxide, Aluminum (III) ethoxide, Aluminum (III) tri (2-propoxide), Aluminum (III) tri (sec-butoxide), Aluminum (III) tri (tert-butoxide), Aluminum (III) Aluminum (III) alkoxide compounds such as tri (phenoxide), aluminum (III) hydrides such as lithium aluminum hydride and sodium aluminum hydride, triethylaluminum (III), trimethylaluminum (I Illustrative of any one or more selected from the group consisting of alkylaluminum compounds (III) such as I), diethylaluminum chloride (III) and dimethylaluminum chloride (III), aluminum (III) glycinate, and aluminum hydroxide (III) can do. The aluminum salt may be a hydrate of these. Aluminum (III) chloride or aluminum (III) perchlorate is preferable in that the yield of the porous aluminum compound is good.

Specific examples of ^{R 1} and ^{R 2} in the general formula (2), ^{R 1} and ^{R 2} in the general formula (1), as long as the same ^{R 1} and ^{R 2.}

In the general formula (2), when the dicarboxylic acid contains two R ^{1 s} , these R ^{1 s} may be different atoms or substituents. In terms of good yield of the porous aluminum compound of the present invention, R ¹ in the general formula (2) is preferably a hydrogen atom.

In the general formula (2), when the dicarboxylic acid contains two or more R ^{2 s} , these R ^{2 s} may be different atoms or substituents. In terms of good yield of the porous aluminum compound of the present invention, R ² in the general formula (2) is preferably a hydrogen atom or tert-butyloxycarbonyl. Furthermore, the dicarboxylic acid in the general formula (2) is 2,3-diaminoterephthalic acid or 2,6-bis (tert-butyloxycarbonyl) terephthalic acid in that the surface area of the porous aluminum compound of the present invention is increased. Is more preferable.

  The ratio of the aluminum salt and the dicarboxylic acid in this production method is arbitrary. In terms of good yield of the porous aluminum compound, the ratio of the aluminum salt to the dicarboxylic acid is preferably an arbitrary ratio in the range of 1: 4 to 10: 1 in terms of the molar ratio of the aluminum salt to the dicarboxylic acid. More preferably, the ratio is in the range of 1: 1 to 4: 1.

  This production method may be carried out in the presence of Bronsted acid. The Bronsted acid that can be used is not particularly limited as long as it does not harm the reaction, and specifically, hydrogen chloride, perchloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfone. One or more selected from the group consisting of acid, acetic acid and benzoic acid can be exemplified, and these can also be used in combination. The Bronsted acid may be a hydrate or an aqueous solution thereof. The Bronsted acid is preferably one or more selected from the group of concentrated hydrochloric acid, acetic acid, and benzoic acid in that the yield of the porous aluminum compound of the present invention is good. The amount of Bronsted acid used is arbitrary. From the viewpoint that a porous aluminum compound having a large surface area can be obtained in a higher yield, it is preferable to use 0.1 to 10 equivalents, more preferably 1 to 4 equivalents, of the Bronsted acid to the dicarboxylic acid.

  The solvent for this production method is at least one solvent selected from the group consisting of water, sulfoxide compounds, sulfone compounds, amide compounds, nitrile compounds, and alcohols. Any one or more selected from the group of DMSO, di-n-butyl sulfoxide, and methylphenyl sulfoxide as the sulfoxide compound, and any one selected from the group of sulfolane, dipropylsulfone, and di-n-butylsulfone as the sulfone compound One or more, as an amide compound, any one or more selected from the group of DMAc, DMF, DEF, and NMP, as a nitrile compound, at least one of acetonitrile or propionitrile, and as an alcohol, methanol, ethanol, Any 1 or more types chosen from the group of 2-propanol and butanol can be mentioned. Since the surface area of the porous aluminum compound tends to increase, the solvent is preferably an amide compound, and more preferably one or more selected from the group of DMAc, DMF, DEF and NMP.

  The reaction step in this production method may be performed at an arbitrary temperature of 20 ° C. or higher and 200 ° C. or lower, preferably 50 ° C. or higher and 150 ° C. or lower. The reaction time is not particularly limited as long as a porous aluminum compound can be obtained, but it is preferably 3 hours or more and 80 hours or less, more preferably 10 hours or more, and particularly preferably 20 hours or more in terms of good yield.

  In this manufacturing method, after a reaction process, post-processing processes, such as a separation process, an ion exchange process, a washing process, and a drying process, may be included. In the post-treatment process, those skilled in the art may appropriately select and use ordinary technical means for producing a coordination polymer. For example, in the separation step, the porous aluminum compound precipitated in the reaction step and the solvent are separated and recovered. The separation method is arbitrary as long as the porous aluminum compound can be separated, and examples thereof include filtration and further suction filtration. In the ion exchange step, monovalent anions in the porous aluminum compound recovered in the separation step are exchanged by ion exchange. The exchange method is arbitrary, but for example, it may be immersed in a solution containing a monovalent anion to be exchanged. In the washing step, the porous aluminum compound recovered in the separation step or ion exchange step is washed. The cleaning method is arbitrary, but for example, it may be cleaned with hot alcohol. As long as the porous aluminum compound can be dried in the drying step, the method is arbitrary. Although the porous aluminum compound can be dried at room temperature and under vacuum, it is preferable to carry out heat drying at 150 ° C. for 5 hours or more and 36 hours or less under vacuum because a larger surface area tends to be obtained.

  The porous aluminum compound of the present invention can be expected to be used as an adsorbent or adsorption / desorption agent for various gas adsorption / desorption. The adsorbent only needs to contain at least the porous aluminum compound of the present invention, and may contain other adsorbents.

  Examples of molecules that the porous aluminum compound of the present invention can adsorb / desorb include, for example, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, water vapor, Organic siloxane or organic vapor is mentioned. In the present specification, the organic vapor means a volatile organic compound, and includes hydrocarbons having 1 to 4 carbon atoms, alcohols, amines, aldehydes, aliphatic hydrocarbons having 5 to 16 carbon atoms, and aromatics. And low molecular weight organic compounds such as hydrocarbons, ketones, or halogenated hydrocarbons. In the present specification, the organosiloxane means a silicon compound in which a silicon atom and a carbon atom are bonded through oxygen, and examples thereof include hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane. Specific gases that the porous aluminum compound of the present invention can adsorb and desorb include hydrocarbons such as methane, ethane, ethylene, and acetylene, rare gases such as helium, neon, argon, krypton, and xenon, alcohols, and amines And organic vapors such as aldehydes, aliphatic hydrocarbons having 5 to 16 carbon atoms, aromatic hydrocarbons, ketones, or halogenated hydrocarbons, and mixtures thereof.

  The porous aluminum compound of the present invention can selectively adsorb gas depending on pressure and temperature. Therefore, the porous aluminum compound of the present invention can be expected to be used as a separating agent for separating a specific gas from the above mixture.

  The porous aluminum compound of the present invention has a high nitrogen adsorption amount. Therefore, the porous aluminum compound of the present invention can be used as an adsorbent for nitrogen, and can be specifically expected to be used as a material for separating, recovering and storing nitrogen.

  Furthermore, the porous aluminum compound of the present invention has a particularly high carbon dioxide adsorption amount. Therefore, the porous aluminum compound of the present invention can be expected to be used as a material for separating, recovering and storing carbon dioxide.

  INDUSTRIAL APPLICABILITY According to the present invention, a novel porous aluminum compound having a function that can be used as an adsorption / desorption agent, as well as a separating agent and a gas storage material can be provided.

It is a MIL-101 type skeleton structure composed of trivalent chromium ions and terephthalic acid. 2 is a powder X-ray diffraction pattern of porous aluminum compound 1 obtained in Example 1. FIG. It is the result of having measured the adsorption-and-desorption isotherm of nitrogen in 77K using the porous aluminum compound 1 obtained in Example 1. FIG. 4 is a powder X-ray diffraction pattern of porous aluminum compound 2 obtained in Example 2. FIG. It is the result of having measured the adsorption-and-desorption isotherm of nitrogen in 77K using the porous aluminum compound 2 obtained in Example 2. FIG. 3 is a powder X-ray diffraction pattern of porous aluminum compound 3 obtained in Example 3. FIG. It is the result of having measured the adsorption-and-desorption isotherm of nitrogen in 77K using the porous aluminum compound 3 obtained in Example 3. FIG. 4 is a powder X-ray diffraction pattern of porous aluminum compound 4 obtained in Example 4. FIG. It is the result of having measured the nitrogen adsorption-desorption isotherm in 77K using the porous aluminum compound 4 obtained in Example 4. FIG. 3 is a powder X-ray diffraction pattern of porous aluminum compound 5 obtained in Example 5. FIG. It is the result of having measured the adsorption-and-desorption isotherm of nitrogen in 77K using the porous aluminum compound 5 obtained in Example 5. FIG. 3 is a powder X-ray diffraction pattern of porous aluminum compound 6 obtained in Example 6. FIG. It is the result of having measured the adsorption-and-desorption isotherm of nitrogen in 77K using the porous aluminum compound 6 obtained in Example 6. FIG. It is the result of the test example 1 (the result of having measured the adsorption-desorption isotherm of the carbon dioxide in 298K using the porous aluminum compound 1).

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a test example are given and this invention is demonstrated further in detail, this invention is not limited to these.

  Identification of the dicarboxylic acid and the porous aluminum compound was performed using the following method.

(NMR)
^For measurement of ¹ H NMR, ¹⁹ F NMR, and ³⁵ Cl NMR, ULTRASHIELD PLUS AVANCE III (400 MHz, 376 MHz and 39 MHz) and ASCEND AVANCE III HD (400 MHz, 376 MHz and 39 MHz) manufactured by BRUKER were used.

¹ H NMR was measured using deuterated chloroform (CDCl ₃ ) and deuterated dimethyl sulfoxide (DMSO-d ₆ ) as measurement solvents and tetramethylsilane (TMS) as an internal standard substance.

¹⁹ F NMR was measured using deuterated chloroform (CDCl ₃ ) and deuterated dimethyl sulfoxide (DMSO-d ₆ ) as measurement solvents and trichlorofluoromethane (CFCl ₃ ) as an internal standard substance.

³⁵ Cl NMR was measured using heavy dimethyl sulfoxide (DMSO-d ₆ ) as a measurement solvent.

(Powder X-ray diffraction measurement)
The powder X-ray diffraction pattern was measured by a symmetrical reflection method using a Smart Lab apparatus manufactured by Rigaku Corporation, scanning a range of diffraction angle (2θ) = 2 to 50 ° at a scanning speed of 3 ° / min.

(Measurement of aluminum content)
The aluminum content of the complex was calculated by wet-decomposing a porous aluminum compound with sulfuric acid and nitric acid and measuring it using an ICP emission spectrometer (optima 3000 manufactured by PerkinElmer).

(Measurement of the content of each element in the complex)
The content of each element in the complex was calculated by quantifying the weights of carbon atoms, hydrogen atoms, and nitrogen atoms with an element analyzer (PerkinElmer 2400II).

(Measurement of BET specific surface area)
Using the obtained porous aluminum compound, the adsorption / desorption isotherm and the BET specific surface area of the obtained porous aluminum compound were measured by a measuring method according to JIS Z8831-2. The measurement was performed by measuring the adsorption / desorption of nitrogen by a volumetric method using a general gas adsorption device (BELSORP 28SA manufactured by Microtrack Bell). The obtained results are expressed as relative pressure P / P ₀ (P ₀ is the saturated vapor pressure of the adsorbate at the measurement temperature) on the horizontal axis and the adsorption amount [VNmL / g] was plotted. In addition, prior to measurement, it was dried at 150 ° C. for 300 minutes under a reduced pressure of 0.1 Pa to remove adsorbed water and the like.

(Measurement of CO ₂ adsorption isotherm)
Using the obtained porous aluminum compound, CO ₂ adsorption isotherm of the obtained porous aluminum compound was measured by a measuring method according to JIS Z8831-2. The measurement was performed using a general gas adsorption device (BELSORP 28SA manufactured by Microtrack Bell).

Synthesis example 1
2,3-Diaminoterephthalic acid was synthesized by the following method.

2,3-difluoroterephthalic acid (7.72 g, 38.2 mmol) was dissolved in ethanol (70 mL), concentrated sulfuric acid (2.2 mL, 40.6 mmol) was added, and the reaction was stirred for 66 hours under reflux with heating. A mixture was obtained. After stirring, the reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution (65 mL) cooled in an ice bath, ethyl acetate (40 mL) was added, and the mixture was concentrated under reduced pressure. After concentration, ethyl acetate (70 mL) was added, and after separation, the reaction product was extracted with ethyl acetate (70 mL × 2). The reaction product was washed with 7% aqueous sodium hydrogen carbonate solution (30 mL) and saturated brine (30 mL), and then the organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The crude product was purified by Yamazen's automatic medium pressure column chromatography [SiO ₂ 265 g, hexane: ethyl acetate (8: 1)] to give diethyl 2,3-difluoroterephthalate (7.18 g, yield 73). %) Was obtained as a white solid.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.74-7.67 (m, 2H), 4.43 (q, J = 7.1 Hz, 2H), 1.41 (t, J = 7. 1 Hz, 3H). ¹⁹ F NMR (376 MHz, Acetone-d ₆ ): δ = -133.5 (s, 2F).
Dissolve diethyl 2,3-difluoroterephthalate (3.00 g, 11.6 mmol) in anhydrous dimethyl sulfoxide (12 mL), add sodium azide (2.32 g, 35.7 mmol), and heat at 80 ° C. for 8 hours. Stir to give a reaction mixture. After stirring, water (40 mL) was added to the reaction mixture, and the reaction product was extracted with ethyl acetate (60 mL × 3). The reaction product was washed with water (40 mL × 2) and saturated brine (30 mL), dried over magnesium sulfate, and concentrated under reduced pressure to give diethyl 2,3-bisazidoterephthalate (2.31 g) as a dark brown oil. It was obtained as a product. This crude product was used in the next reaction without further purification.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.63 (s, 2H), 4.43 (q, J = 7.1 Hz, 2H), 1.42 (t, J = 7.1 Hz, 3H) .
Diethyl 2,3-bisazidoterephthalate (2.31 g) was dissolved in ethyl acetate (30 mL), 10 wt% Pd / C (231 mg) was added, and the mixture was stirred at room temperature for 19 hours under a hydrogen atmosphere. Obtained. The reaction mixture was filtered through a glass filter with celite, the residue was washed with ethyl acetate, and the filtrate was concentrated under reduced pressure. The reaction product was purified by Yamazen's automated medium pressure column chromatography [SiO ₂ 150 g, hexane: ethyl acetate (5: 1)] to give diethyl 2,3-diaminoterephthalate (1.37 g, total of 2 steps). Yield 47%) was obtained as a yellow solid.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.32 (s, 2H), 5.58 (brs, 4H), 4.36 (q, J = 7.1 Hz, 2H), 1.40 (t , J = 7.1 Hz, 3H).
Diethyl 2,3-diaminoterephthalate (1.37 g, 5.43 mmol) was dissolved in dioxane (36 mL) and water (18 mL), and lithium hydroxide monohydrate (1.15 g, 27.3 mmol) was added. The mixture was stirred at room temperature for 14 hours to obtain a reaction mixture. The reaction mixture was cooled to 0 ° C., 0.50 M hydrochloric acid (70 mL) was added, and the mixture was stirred at room temperature for 5 minutes. The precipitate was collected by filtration, washed with water and acetone, and dried under reduced pressure to obtain 2,3-diaminoterephthalic acid (804 mg, 81% yield) as a yellow powder.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ = 8.57 (brs, 6H), 7.04 (s, 2H).
Synthesis example 2
2,5-bis (tert-butoxycarbonylamino) terephthalic acid was synthesized by the following method.

To a solution of 2,5-diaminoterephthalic acid (949 mg, 4.79 mmol) in tetrahydrofuran (14 mL) was added 1.5M aqueous sodium hydroxide (14.0 mL, 21.0 mmol) and ditert-butyl dicarbonate (2.2 mL, 9 mL). .58 mmol) and stirred at room temperature for 30 hours. The reaction mixture was cooled to 0 ° C., 15% aqueous citric acid solution (10 mL) and ethyl acetate (20 mL) were added, the precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate (20 mL × 3). The combined organic layers were washed with water (20 mL) and saturated brine (20 mL), dried over magnesium sulfate, and concentrated under reduced pressure. Acetone was added to the resulting crude product, collected by filtration, and dried to obtain 2,5-bis (tert-butoxycarbonylamino) terephthalic acid (396 mg, yield 21%) as a yellow powder.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ = 9.96 (brs, 2H), 8.68 (s, 2H), 3.06 (brs, 2H), 1.55 (s, 18H) .
Example 1
(Synthesis of porous aluminum compound 1)
2,3-Diaminoterephthalic acid (79.2 mg, 0.40 mmol), concentrated hydrochloric acid (132 μL, 1.60 mmol) and aluminum chloride hexahydrate (260 mg, 1.08 mmol) were added to N, N-dimethylformamide (5. 8 ml) and irradiated with ultrasonic waves for 10 minutes. This was heated at 130 ° C. for 24 hours to obtain a reaction mixture. A solid was collected from the obtained reaction mixture by filtration, washed with acetone, and then dried at room temperature under vacuum to obtain a yellow-green powder (205 mg). The obtained yellow-green powder was suspended in ethanol (15 mL) and heated under reflux for 24 hours. After standing at room temperature, decantation was performed to obtain a reaction product, and this operation was further repeated twice. A solid was collected from the obtained reaction mixture by filtration, washed with ethanol, and dried under vacuum at room temperature to obtain porous aluminum compound 1 as a yellow-green powder. The porous aluminum compound 1 had a yield of 184 mg and an aluminum content of 24.1 mg, and the aluminum in the porous aluminum compound relative to the aluminum (III) ion in the raw material mixture was 82%. The weight ratio of each element contained in the porous aluminum compound 1 was calculated from elemental analysis. _{Theory: {Al 3 (O) [} OOCC 6 H 2 (NH 2) 2 COO] 3 (Cl)} · (H 2 O) 13 · (CH 3 CH 2 OH) 6.5 · (HCl) · ( Al ₂ O ₃ ) _2.2 : carbon: 29.4 wt%, hydrogen: 5.6 wt%, nitrogen: 5.6 wt%; measured values: carbon: 29.7 wt%, hydrogen: 5.3 wt% %, Nitrogen: 5.3% by weight. Porous aluminum compound 5 (10 mg) was decomposed with 0.02 mL of deuterated concentrated sulfuric acid, and ³⁵ Cl NMR was measured in deuterated DMSO solvent to observe a chloride ion signal (0 ppm).

The reaction formula of this example is shown below, and the powder X-ray diffraction pattern of the obtained porous aluminum compound 1 is shown in FIG. Moreover, the result of having measured the adsorption / desorption isotherm of nitrogen in 77K using the obtained porous aluminum compound 1 is shown in FIG. The resulting BET specific surface area was 1175 m ² / g.

Example 2
(Synthesis of porous aluminum compound 2)
2,3-diaminoterephthalic acid (79.2 mg, 0.40 mmol), acetic acid (48.0 mg, 0.80 mmol) and aluminum chloride hexahydrate (260 mg, 1.08 mmol) were added to N, N-dimethylformamide (5 8 mL) and irradiated with ultrasonic waves for 10 minutes. This was heated at 130 ° C. for 24 hours to obtain a reaction mixture. A solid was collected from the obtained reaction mixture by filtration, washed with acetone, and then dried at room temperature under vacuum to obtain a light green powder (216 mg). The obtained light green powder was suspended in ethanol (8.0 mL) and heated under reflux for 14 hours to obtain a reaction mixture. A solid was collected from the reaction mixture by filtration, washed with ethanol, and then dried at room temperature under vacuum to obtain porous aluminum compound 2 as a yellow-green powder. The obtained porous aluminum compound 2 had a yield of 238 mg and an aluminum content of 27.8 mg, and 97% of the aluminum in the porous aluminum compound with respect to aluminum (III) ions in the raw material mixture. The weight ratio of each element contained in the porous aluminum compound 2 was calculated from elemental analysis. Theoretical value: {Al ₃ (O) [OOCC ₆ H ₂ (NH ₂ ) ₂ COO] ₃ Cl} · (H ₂ O) _14.5 · (CH ₃ CH ₂ OH) _5.8 · [Al ₂ O _{3 2.3} · (CH ₃ COOH) _4.8 as carbon: 30.7 wt%, hydrogen: 5.8 wt%, nitrogen: 4.8 wt%; measured value: carbon: 30.4 wt%, hydrogen : 5.6% by weight, nitrogen: 4.9% by weight. Porous aluminum compound 2 (10 mg) was decomposed with 0.02 mL of deuterated concentrated sulfuric acid, and ³⁵ Cl NMR was measured in deuterated DMSO solvent to observe a chloride ion signal (0 ppm).

The reaction formula of this example is shown below, and the powder X-ray diffraction pattern of the obtained porous aluminum compound 2 is shown in FIG. Moreover, the result of having measured the nitrogen adsorption-and-desorption isotherm in 77K using the obtained porous aluminum compound 2 is shown in FIG. The resulting BET specific surface area was 1360 m ² / g.

Example 3
(Synthesis of porous aluminum compound 3)
2,3-Diaminoterephthalic acid (79.2 mg, 0.40 mmol), benzoic acid (97.6 mg, 0.80 mmol) and aluminum chloride hexahydrate (260 mg, 1.08 mmol) were added to N, N-dimethylformamide ( 5.8 mL) and irradiated with ultrasonic waves for 10 minutes. This was heated at 130 ° C. for 24 hours to obtain a reaction mixture. A solid was collected from the obtained reaction mixture by filtration, washed with acetone, and then dried at room temperature under vacuum to obtain a light green powder (241 mg). The obtained light green powder was suspended in ethanol (8.0 mL) and heated under reflux for 14 hours to obtain a reaction mixture. A solid was collected from the reaction mixture by filtration, washed with ethanol, and dried under vacuum at room temperature to obtain porous aluminum compound 3 as a yellow-green powder. The obtained porous aluminum compound 3 had a yield of 227 mg and an aluminum content of 28.6 mg, and the aluminum in the porous aluminum compound was 98% with respect to aluminum (III) ions in the raw material mixture. The weight ratio of each element contained in the porous aluminum compound 3 was calculated from elemental analysis. _{Theory: {Al 3 (O) [} OOCC 6 H 2 (NH 2) 2 COO] 3 Cl} · (H 2 O) 11 · (CH 3 CH 2 OH) 5 · (Al 2 O 3) 1.5 · _{(C 6} H 5 _COOH) carbon as _2.3: 38.2 wt%, hydrogen: 5.4% by weight, nitrogen: 5.3 wt%; Found: carbon: 37.9% by weight, hydrogen: 5 0.2% by weight, nitrogen: 5.0% by weight. Porous aluminum compound 3 (10 mg) was decomposed with 0.02 mL of deuterated concentrated sulfuric acid, and ³⁵ Cl NMR was measured in deuterated DMSO solvent to observe a chloride ion signal (0 ppm).

The reaction formula of this example is shown below, and the powder X-ray diffraction pattern of the obtained porous aluminum compound 3 is shown in FIG. Moreover, the result of having measured the adsorption-and-desorption isotherm of nitrogen in 77K using the obtained porous aluminum compound 3 is shown in FIG. The resulting BET specific surface area was 1190 m ² / g.

Example 4
(Synthesis of porous aluminum compound 4)
2,3-diaminoterephthalic acid (79.2 mg, 0.40 mmol) and aluminum perchlorate nonahydrate (526 mg, 1.08 mmol) were dissolved in N, N-dimethylformamide (5.8 mL) Was irradiated for 10 minutes. This was heated at 130 ° C. for 24 hours to obtain a reaction mixture. A solid was collected from the resulting reaction mixture by filtration, washed with acetone, and then dried at room temperature under vacuum to obtain a light green powder (257 mg). The obtained light green powder was suspended in ethanol (8.0 mL) and heated under reflux for 14 hours to obtain a reaction mixture. A solid was collected from the reaction mixture by filtration, washed with ethanol, and dried under vacuum at room temperature to obtain porous aluminum compound 4 as a yellow-green powder. The obtained porous aluminum compound 4 had a yield of 227 mg and an aluminum content of 26.8 mg, and the aluminum in the porous aluminum compound was 92% with respect to aluminum (III) ions in the raw material mixture. The weight ratio of each element contained in the porous aluminum compound 4 was calculated from elemental analysis. Theoretical value: {Al ₃ (O) [OOCC ₆ H ₂ (NH ₂ ) ₂ COO] ₃ (ClO ₄ )} · (H ₂ O) ₉ · (CH ₃ CH ₂ OH) _7.1 · (Al ₂ O ₃₎ carbon as _1.7: 31.8 wt%, hydrogen: 5.5% by weight, nitrogen: 5.8 wt%; Found: carbon: 31.6% by weight, hydrogen: 5.4% by weight, nitrogen : 5.6% by weight. In addition, the porous aluminum compound 4 (10 mg) was decomposed with 0.02 mL of deuterated concentrated sulfuric acid, and ³⁵ Cl NMR was measured in deuterated DMSO solvent, and a signal of perchlorate ion (1011 ppm) was observed. .

The reaction formula of this example is shown below, and the powder X-ray diffraction pattern of the obtained porous aluminum compound 4 is shown in FIG. Moreover, the result of having measured the adsorption / desorption isotherm of nitrogen in 77K using the obtained porous aluminum compound 4 is shown in FIG. The resulting BET specific surface area was 2000 m ² / g.

Example 5
(Synthesis of porous aluminum compound 5)
2,3-diaminoterephthalic acid (79.6 mg, 0.40 mmol) and aluminum chloride hexahydrate (145 mg, 0.60 mmol) were dissolved in N, N-dimethylformamide (5.8 mL), and ultrasonic waves were applied for 10 times. Irradiated for 1 minute. This was heated at 130 ° C. for 24 hours to obtain a reaction mixture. A solid was collected from the obtained reaction mixture by filtration, washed with DMF and ethanol, and dried under vacuum at room temperature to obtain a yellow-green powder (243 mg). The resulting yellow-green powder was suspended in ethanol (25 mL) and heated under reflux for 24 hours. After standing at room temperature, decantation was performed to obtain a reaction product, and this operation was further repeated twice. A solid was collected from the obtained reaction mixture by filtration, washed with ethanol, and then dried at room temperature under vacuum to obtain porous aluminum compound 5 as a yellow-green powder. The obtained porous aluminum compound 5 had a yield of 131 mg and an aluminum content of 12.6 mg, and the aluminum in the porous aluminum compound relative to the aluminum (III) ion in the raw material mixture was 78%. The weight ratio of each element contained in the porous aluminum compound 1 was calculated from elemental analysis. _{Theory: {Al 3 (O) [} OOCC 6 H 2 (NH 2) 2 COO] 3 Cl} · (H 2 O) 11 · (CH 3 CH 2 OH) 5.5 · (Al 2 O 3) 0 _.6 : carbon: 33.6% by weight, hydrogen: 5.7% by weight, nitrogen: 7.1% by weight; measured values: carbon: 33.8% by weight, hydrogen: 5.6% by weight, nitrogen: 6. 8% by weight. Porous aluminum compound 5 (10 mg) was decomposed with 0.02 mL of deuterated concentrated sulfuric acid, and ³⁵ Cl NMR was measured in deuterated DMSO solvent to observe a chloride ion signal (0 ppm).

The reaction formula of this example is shown below, and the powder X-ray diffraction pattern of the obtained porous aluminum compound 5 is shown in FIG. Moreover, the result of having measured the adsorption / desorption isotherm of nitrogen in 77K using the obtained porous aluminum compound 5 is shown in FIG. The resulting BET specific surface area was 1610 m ² / g.

Example 6
(Synthesis of porous aluminum compound 6)
2,5-bis (tert-butoxycarbonylamino) terephthalic acid (158 mg, 0.40 mmol) and aluminum perchlorate nonahydrate (526 mg, 1.08 mmol) in N, N-dimethylformamide (5.8 mL) Dissolved and irradiated with ultrasound for 10 minutes. This was heated at 130 ° C. for 12 hours to obtain a reaction mixture. A solid was collected from the resulting reaction mixture by filtration, washed with N, N-dimethylformamide and then with ethanol, and then dried at room temperature under vacuum to obtain an orange powder (173 mg). The resulting orange powder was suspended in ethanol (15 mL) and heated under reflux for 24 hours. After standing at room temperature, decantation was performed to obtain a reaction product, and this operation was further repeated twice. A solid was collected from the obtained reaction mixture by filtration, washed with ethanol, and then dried at room temperature under vacuum to obtain porous aluminum compound 6 as a green powder. The porous aluminum compound 6 had a yield of 82.9 mg and an aluminum content of 11.4 mg, and the aluminum in the porous aluminum compound relative to the aluminum (III) ion in the raw material mixture was 39%. The weight ratio of each element contained in the porous aluminum compound 6 was calculated from elemental analysis. _{Theory: {Al 3 (O) [} OOCC 6 H 2 (NH 2) 2 COO] 3 (ClO 4)} · (H 2 O) 13 · (CH 3 CH 2 OH) 4 · (Al 2 O 3) ₂ : carbon: 27.7 wt%, hydrogen: 4.6 wt%, nitrogen: 5.7 wt%; measured values: carbon: 27.7 wt%, hydrogen: 4.6 wt%, nitrogen: 5.7 weight%. In addition, the porous aluminum compound 6 (10 mg) was decomposed with 0.02 mL of deuterated concentrated sulfuric acid, and ³⁵ Cl NMR was measured in deuterated DMSO solvent to observe a perchlorate ion signal (1011 ppm). .

The reaction formula of this example is shown below, and the powder X-ray diffraction pattern of the obtained porous aluminum compound 6 is shown in FIG. Moreover, the result of having measured the nitrogen adsorption-desorption isotherm in 77K using the obtained porous aluminum compound 6 is shown in FIG. The resulting BET specific surface area was 1590 m ² / g.

  Table 1 shows the BET specific surface areas of the porous aluminum compounds obtained as a result of the above Examples 1 to 6.

As shown in Table 1, the porous aluminum compound of the present invention has a BET specific surface area of 1000 m ² / g or more and was confirmed to have a specific surface area that can be used as an adsorbent / desorbent. Moreover, it was confirmed that the porous aluminum compound of the present invention has nitrogen adsorption ability.

Test example 1
The porous aluminum compound 1 obtained in Example 1, using carbon dioxide were measured CO ₂ adsorption isotherm at the temperature 298K. At this time, prior to measurement, it was dried at 150 ° C. for 300 minutes under a reduced pressure of 0.1 Pa to remove adsorbed water and the like. The obtained adsorption isotherm is shown in FIG.
It was confirmed that the porous aluminum compound 1 (porous aluminum compound containing a dicarboxylic acid ligand having two amino groups) of the present invention has a CO ₂ adsorption ability.

  The porous aluminum compound of the present invention can be used as an adsorbent or adsorption / desorption agent for various gases, a separation agent, or an occlusion material. Furthermore, it can also be used as a shape-selective catalyst or a solid acid catalyst that can be used for separation and recovery of the catalyst by heterogeneity.

Claims (12)

General formula (1)

(In the formula, n represents an integer of 2 to 4, X represents a monovalent anion. When n is 2, R ¹ is the same or different and is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 4 carbon atoms. represents an alkyl group, a haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group or haloalkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, R ² are the same or different and a hydrogen atom, a carbon number from 1 to 4 Alkyl group, haloalkyl group having 1 to 4 carbon atoms, alkyloxy group having 1 to 4 carbon atoms, haloalkyloxy group having 1 to 4 carbon atoms, acyl group having 2 to 5 carbon atoms or (alkyl having 1 to 4 carbon atoms) ) Represents an oxycarbonyl group, and when n is 3, R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, C1-C4 haloalkyloxy group, charcoal Represents an alkyl group or a haloalkoxy group having 1 to 4 carbon atoms having 1 to 4, R ² are the same or different and a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, Represents an acyl group having 2 to 5 carbon atoms or (an alkyl having 1 to 4 carbon atoms) oxycarbonyl group, and when n is 4, R ² is the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, C1-C4 haloalkyl group, C1-C4 alkyloxy group, C1-C4 haloalkyloxy group, C2-C5 acyl group or (C1-C4 alkyl) oxycarbonyl group A porous aluminum compound containing a basic skeleton represented by:   The porous aluminum compound according to claim 1, which has a MIL-101 type crystal structure. The porous aluminum compound according to claim 1, which has a BET specific surface area of 500 m ² / g or more and 3000 m ² / g or less. n is 2, R ¹ is a hydrogen atom, R ² is the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The porous aluminum compound according to any one of claims 1 to 3, which is a haloalkyloxy group, an acyl group having 2 to 5 carbon atoms, or (alkyl having 1 to 4 carbon atoms) oxycarbonyl group. The porous aluminum compound according to any one of claims 1 to 4, wherein R ² is a hydrogen atom.   The porous aluminum compound according to any one of claims 1 to 5, wherein X is a chloride ion or a perchlorate ion. The method for producing a porous aluminum compound according to claim 1, wherein a trivalent aluminum salt and a dicarboxylic acid represented by the following general formula (2) are reacted in a solvent.

(In the formula, n represents an integer of 2 to 4. When n is 2, R ¹ is the same or different and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. Group, an alkyloxy group having 1 to 4 carbon atoms or a haloalkyloxy group having 1 to 4 carbon atoms, and R ² is the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. A haloalkyl group, an alkyloxy group having 1 to 4 carbon atoms, a haloalkyloxy group having 1 to 4 carbon atoms, an acyl group having 2 to 5 carbon atoms, or an (alkyl having 1 to 4 carbon atoms) oxycarbonyl group, where n is 3. In this case, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a haloalkyloxy group having 1 to 4 carbon atoms. R ² is the same or different A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a haloalkyloxy group having 1 to 4 carbon atoms, an acyl having 2 to 5 carbon atoms Group or (alkyl having 1 to 4 carbon atoms) oxycarbonyl group, when n is 4, R ² is the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. Group, a C1-C4 alkyloxy group, a C1-C4 haloalkyloxy group, a C2-C5 acyl group, or a (C1-C4 alkyl) oxycarbonyl group.)   The method for producing a porous aluminum compound according to claim 7, wherein the trivalent aluminum salt is aluminum chloride or aluminum perchlorate.   The method for producing a porous aluminum compound according to claim 7 or 8, wherein the solvent is an amide compound. n is 2, R ¹ is a hydrogen atom, R ² is the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkylcarbonyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The method for producing a porous aluminum compound according to any one of claims 7 to 9, which is a haloalkylcarbonyl group or a (C1-C4 alkyl) oxycarbonyl group. The method for producing a porous aluminum compound according to claim 10, wherein R ² is a hydrogen atom or a tert-butyloxycarbonyl group.   An adsorbent comprising the porous aluminum compound according to any one of claims 1 to 6.

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