WO2024048308A1

WO2024048308A1 - Metal-organic framework dispersion production method, metal-organic framework dispersion, and metal-organic framework composition including metal-organic framework dispersion

Info

Publication number: WO2024048308A1
Application number: PCT/JP2023/029742
Authority: WO
Inventors: 健吾脇田
Original assignee: 日産化学株式会社
Priority date: 2022-09-01
Filing date: 2023-08-17
Publication date: 2024-03-07

Abstract

[Problem] To provide a method for using a mechanical pulverization technique to produce a dispersion comprising a nm-size metal-organic framework which has good dispersion stability while maintaining a crystal structure. [Solution] A metal-organic framework dispersion production method comprising: a step (1) for mixing a component (a), which is a solid powder of a metal-organic framework that contains metal ions and organic ligands coordinated to the metal ions, said metal ions being at least one type selected from the group consisting of Zr ions, Al ions, and Zn ions, a component (b), which is a dispersant and which is an aliphatic amine compound that is a primary amine, a secondary amine, or a tertiary amine having one amino group in a molecule thereof, and which is soluble in a dispersion medium (c1), and a component (c1), which is said dispersion medium; and a step (2) for using the obtained mixture to produce a dispersion via a mechanical pulverization technique (wherein in the mechanical pulverization technique, the crystal structure of the metal-organic framework (a) does not change, and the crystal structure of the solid powder is maintained).

Description

Method for producing a metal-organic structure dispersion, metal-organic structure dispersion, and metal-organic structure composition containing the metal-organic structure dispersion

The present invention relates to a method for producing a metal-organic framework (MOF) dispersion having excellent dispersion stability, a metal-organic framework dispersion, and a metal-organic framework composition containing the metal-organic framework dispersion.

A metal-organic framework is a porous coordination compound obtained by self-assembly of a metal ion and an organic ligand having a site that coordinates with the metal ion. They are bonded by positional bonds and have both inorganic and organic parts.
Metal-organic frameworks have excellent porosity and excellent ability to adsorb and desorb molecules into pores, and are therefore being considered for a variety of applications such as gas separation membranes, gas storage, liquid adsorption, and catalysts.

Examples of practical applications of metal-organic structures include tablets formed from powder, and the range of practical applications is limited. The reason for this is that the metal-organic structure has a crystal size on the order of μm due to crystal growth due to rapid self-organization, and also has the property of easily agglomerating.

It is generally difficult to dissolve a metal-organic framework in a solvent or polymer while maintaining its crystal structure. Therefore, in recent years, studies have been made to prepare dispersions in which metal-organic structures are dispersed in solvents or polymers, and to use them as composite films. However, metal-organic structures on the order of μm tend to settle in dispersion liquids, and metal-organic structures also tend to aggregate easily, so the dispersion stability of metal-organic structures becomes an issue when composited. . If the dispersion stability is poor, the dispersion state of the metal-organic structure is not stable, resulting in difficulty in handling and unstable performance and film quality. Therefore, dispersion stability is a major issue and a very important factor in mass production. For example, in gas separation applications, when a polymer and gas molecules are combined, non-selective pores are created between the polymers due to agglomeration of the metal-organic framework, resulting in a decrease in gas selectivity (Patent Document 1) ). In addition, if the dispersion stability is poor, during the composition preparation process or film formation process, formation of coarse particles due to agglomeration of the metal-organic framework or deterioration of the degree of dispersion of the metal-organic framework may result in film defects or property deterioration. Variations occur.

In Patent Document 1 and Patent Document 2, when synthesizing a metal-organic structure by the solvothermal method, for the purpose of suppressing crystal growth, a large amount of a chemical regulator or surfactant is added to the nanometer level by adding a large amount of chemical regulator or surfactant that is about the same amount as the raw material. We have obtained powders of metal-organic structures that are down to an order of magnitude. However, there is no description in the above literature regarding the dispersion stability of the obtained powder. Therefore, it is unclear whether a good dispersion state is maintained even after a film forming process such as dispersion preparation, composition preparation, application of the composition, and drying by heating. In addition, in the solvothermal method, a large amount of additives and raw materials are present, so in order to create a dispersion, it is necessary to remove the raw materials and additives such as reprecipitation and filtration, and then redisperse them in a solvent etc. In many cases. Therefore, the law poses challenges to manufacturing process costs.

Patent Document 3 reports that a composite composition can be obtained by coexisting a polymer that serves as a matrix when producing a metal-organic structure by solid-phase synthesis, but there are no specific details regarding dispersion stability. Not shown.
As a method to obtain a metal-organic structure dispersion, metal-organic structure powder is mixed with a resin or solvent, and the metal-organic structure is agglomerated by mixing using an ultrasonic homogenizer, a rotational stirring degassing device, etc. There are methods to obtain a dispersion liquid by relaxing the state, and methods to obtain a dispersion liquid by relaxing the agglomerated state using a mechanical grinding method such as a ball mill or a bead mill. However, mechanical crushing methods such as ball mills and bead mills create conditions that generate strong physical force and shear stress, which causes the problem that the crystal structure of the metal-organic structure is broken (Patent Document 4).

Special Publication No. 2021-526962 Japanese Patent Application Publication No. 2018-118929 Special Publication No. 2021-523823 JP 2019-56055 Publication

In order to improve dispersion stability in a metal-organic structure dispersion, it is necessary to reduce the primary particle size of the metal-organic structure. In order to reduce the primary particle size by mechanical crushing, a stress stronger than that required to break up the agglomeration of the primary particles is required, and in this case, the crystal structure of the metal-organic framework changes. Challenges arise. Therefore, it is assumed that there is a trade-off between dispersion stability and maintenance of crystal structure.

An object of the present invention is to obtain a metal-organic structure dispersion having good dispersion stability and a metal-organic structure composition containing the metal-organic structure dispersion. In addition, when a solid powder of a metal-organic structure is reduced in crystal size by mechanical pulverization to produce a dispersion, it is necessary to maintain the crystal structure of the metal-organic structure in terms of properties. However, there is a problem in that mechanical crushing changes the crystal structure of the metal-organic framework.

In order to solve the above problems and obtain a dispersion liquid having good dispersion stability, the inventor focused on the crystal size of the metal-organic structure and attempted to increase the crystal size from μm to nm. However, mechanical crushing methods with weak shear stress do not reduce the crystal size, while mechanical crushing methods with strong shear stress, such as ball mills and bead mills, reduce the crystal size but change the crystal structure. . The inventor discovered that the crystal size of the metal-organic structure can be reduced without changing the crystal structure of the metal-organic structure by adding a suitable dispersant in a ball mill or bead mill. Furthermore, even after reducing the crystal size, the metal-organic structure can be aggregated by appropriately selecting and combining the metal ions and organic ligands that make up the metal-organic structure, as well as the dispersant and dispersion medium. I discovered that it is possible to avoid this. That is, the inventor found an appropriate mechanical crushing method, metal-organic structure, dispersant, and dispersion medium, and completed the invention.

That is, the present invention is a method for producing a metal-organic structure dispersion, comprising:
(a) Component: a metal-organic structure containing a metal ion and an organic ligand coordinated to the metal ion, where the metal ion is at least one selected from the group consisting of Zr ions, Al ions, and Zn ions. a solid powder of
(b) Component: As a dispersant, it is a primary amine, secondary amine, or tertiary amine having one amino group represented by the following formula (1) in the molecule, and (c1) a dispersion medium. an aliphatic amine compound having solubility in

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an aliphatic hydrocarbon group, and * represents a bond with a carbon atom.)
(c1) component: step (1) of mixing with a dispersion medium, and step (2) of preparing a dispersion liquid by a mechanical pulverization method using the resulting mixture (however, the mechanical pulverization method A method for producing a dispersion of a metal-organic structure, provided that the crystal structure of the metal-organic structure does not change and maintains the crystal structure of a solid powder.

The metal-organic structure dispersion liquid is such that the Z-average particle size of the solid powder of the metal-organic structure in the dispersion liquid is 10 nm or more and less than 1000 nm, and the metal-organic structure is A method for producing a metal-organic structure dispersion, wherein the sedimentation rate of solid powder particles is 100 μm/s or less.

A step (3) of mixing the metal-organic structure dispersion liquid with at least one of a dispersion medium (c2) component and an additive (d) component different from the dispersion medium (c1) component in the dispersion liquid. , a method for producing a metal-organic framework composition.

Production of a metal organic framework dispersion, wherein the organic ligand is at least one selected from the group consisting of fumaric acid, terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2-methylimidazole, and dicarboxypyrazole. Method.

A method for producing a metal-organic structure dispersion, wherein the metal-organic structure is MIL-53, CAU-10, ZIF-8, MOF-801, MOF-303, UiO-66, or UiO-NH2-66.

The method for producing a metal-organic structure dispersion, wherein the mechanical pulverization method is a pulverization method using a ball mill or a bead mill.

The ball mill or bead mill has a ball or bead diameter of 0.01 mm or more and 10 mm or less, and the material of the balls or beads is at least one selected from the group consisting of metal and glass, for producing a metal-organic structure dispersion. Method.

(a) Component: a metal-organic structure containing a metal ion and an organic ligand coordinated to the metal ion, where the metal ion is at least one selected from the group consisting of Zr ions, Al ions, and Zn ions. a solid powder of
(b) Component: As a dispersant, it is a primary amine, secondary amine, or tertiary amine having one amino group represented by the following formula (1) in the molecule, and (c1) a dispersion medium. an aliphatic amine compound having solubility in

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an aliphatic hydrocarbon group, and * represents a bond with a carbon atom.)
(c1) Component: A dispersion liquid containing a dispersion medium,
The Z-average particle size of the solid powder of the metal-organic structure in the dispersion is 10 nm or more and less than 1000 nm, and the sedimentation rate of the solid powder particles of the metal-organic structure in an environment with a centrifugal force of 470 G or less is 100 μm/ s or less.

A dispersion of a metal-organic structure, wherein the organic ligand is at least one selected from the group consisting of fumaric acid, terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2-methylimidazole, and dicarboxypyrazole.

A metal-organic framework dispersion, wherein the metal-organic framework is MIL-53, CAU-10, ZIF-8, MOF-801, MOF-303, UiO-66, or UiO-NH2-66.

A metal-organic structure composition comprising at least one of the metal-organic structure dispersion liquid, a dispersion medium (c2) component different from the dispersion medium (c1) component in the dispersion liquid, and an additive (d) component.

According to the method for producing a metal-organic structure dispersion of the present invention, it is possible to provide a method for producing a metal-organic structure dispersion with excellent dispersion stability without changing the crystal structure of the metal-organic structure. . According to the present invention, the metal-organic structure dispersion and the metal-organic structure composition containing the metal-organic structure dispersion have the effect of exhibiting excellent dispersion stability without changing the crystal structure of the metal-organic structure. .
According to the present invention, the metal-organic structure dispersion liquid has a Z-average particle size of the solid powder of the metal-organic structure of 10 nm or more and less than 1000 nm, and a solid powder of the metal-organic structure in an environment with a centrifugal force of 470 G or less. It has the effect of exhibiting excellent dispersion stability with a sedimentation rate of powder particles of 100 μm/s or less.

FIG. 1 is an X-ray diffraction pattern showing the crystal structure analysis results of the powder of Production Example 1, the powder obtained from the dispersion of Example 1, and the powder obtained from the dispersion of Comparative Example 1. FIG. 2 is a photograph of the SEM-EDX analysis results of the powder of Production Example 1, the powder obtained from the dispersion of Example 1, and the powder obtained from the dispersion of Comparative Example 1. FIG. 3 is an X-ray diffraction pattern showing the crystal structure analysis results of the powder of Production Example 2, the powder of Production Example 3, the powder obtained from the dispersion of Example 11, and the powder obtained from the dispersion of Example 15. It is.

The method for producing a metal-organic structure dispersion, the metal-organic structure dispersion, and the metal-organic structure composition containing the metal-organic structure dispersion according to the present invention will be described below.
<Metal-organic structure>
A metal-organic framework is a crystalline porous material consisting of metal ions and organic ligands coordinated to the metal ions. The metal ion is at least one selected from the group consisting of Mg, V, Cr, Nb, Mo, Zr, Hf, Mn, Fe, Co, Cu, Ni, Zn, Cd, Ru, Al, Ti, V, and Ga. It is an ion of two metals. Among these metal ions, Zr ions, Al ions and Zn ions are preferred, and from the viewpoint of structural stability against water, Zr ions and Al ions are more preferred.
Component (a) of the present invention is a solid powder of a metal-organic framework.

<Organic ligand>
The organic ligand is a compound having two or more functional groups (coordination functional groups) capable of coordinating with metal ions. Examples of coordinating functional groups include carboxyl groups, pyridinyl groups, cyano groups, amino groups, sulfonyl groups, porphyrinyl groups, acetylacetonate groups, hydroxyl groups, Schiff bases, amino acid residues, and the like. The coordination functional group is preferably one that can form a strong coordination bond with a metal ion. The organic ligand can preferably have two or more coordinating functional groups at any position on the organic ligand. An organic ligand having a coordinating functional group at the end of the organic ligand is preferable from the viewpoint of easily controlling the structure of the metal-organic structure and obtaining a metal-organic structure having relatively large pores.
Organic ligands include oxalic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, citric acid, trimesic acid, squaric acid, imidazole, pyrazole, diazole, triazole, tetrazole, and azole. and mixtures thereof.
Among these organic ligands, fumaric acid, terephthalic acid, isophthalic acid, -At least one selected from the group consisting of aminoterephthalic acid, 2-methylimidazole, and dicarboxypyrazole is preferable.

<Dispersant, component (b)>
Examples of the dispersant include aliphatic amine compounds such as primary amines, secondary amines, or tertiary amines having one amino group in the molecule. Note that the aliphatic amine compound shown in the present invention has solubility in component (c1) and component (c2).
Aliphatic amines include primary amines, secondary amines, and tertiary amines.
Examples of primary amines include propylamine, butylamine, hexylamine, pentylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine (aminundecane), dodecylamine, tridecylamine, tetradecylamine, and pentadecylamine. Examples include saturated aliphatic monoamines having a linear aliphatic hydrocarbon group such as decylamine, hexadecylamine, heptadecylamine, and octadecylamine. Examples of saturated aliphatic amines include, in addition to the above-mentioned straight-chain aliphatic amines, branched aliphatic amines such as isohexylamine, 2-ethylhexylamine, and tert-octylamine. Further examples include unsaturated aliphatic amines such as cyclohexylamine and oleylamine. Furthermore, in addition to these aliphatic amines, primary amines also include those in which hydrogen atoms are replaced with hydroxyl groups, such as propanolamine.
Examples of secondary amines include linear ones such as dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, octylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ethylmethylamine, Examples include dialkyl monoamines such as methylpropylamine, ethylpropylamine, and propylbutylamine. Examples of branched secondary amines include diisohexylamine and di(2-ethylhexyl)amine. Furthermore, in addition to these aliphatic amines, secondary amines include those in which hydrogen atoms are replaced with hydroxyl groups, such as methylaminoethanol.
Examples of the tertiary amine include tributylamine, tripentylamine, trihexylamine, and the like. Examples of branched tertiary amines include triisohexylamine, tri(2-ethylhexyl)amine, and tridodecylamine. In addition to these aliphatic amines, tertiary amines also include those in which hydrogen atoms are replaced with hydroxyl groups.
In order to suppress crystal structure changes suitable for ball mills and bead mills, the number of nitrogen atoms in the aliphatic amine (compound) is 1, and the group bonded to the nitrogen atom is a straight chain aliphatic amine having 1 to 15 carbon atoms. It is a hydrocarbon group, and a hydroxyl group is preferable as a substituent for the aliphatic hydrocarbon group.

<Dispersion medium, (c1) component>
The aliphatic amines including the primary amines, secondary amines, and tertiary amines have solubility in component (c1) of the dispersion medium of the present invention. (c1) Component types include solvents, crosslinkable monomers, and polymers. These can be used alone or in combination of two or more.
Specific examples of the component (c1) of the present invention are listed below, but the invention is not limited to these examples as long as the effects of the present invention are not lost. Specific examples of the solvent include methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl -1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3- Methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Those containing hydroxy groups such as butanediol and 1,5-pentanediol, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, ethylene glycol monomethyl ether, and ethylene glycol Monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, xylene, methyl ethyl ketone , methyl isobutyl ketone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxy acetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, 3 - Ethyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, butyl lactate, 2-heptanone, methoxycyclopentane, and anisole. These can be used alone or in combination of two or more. Moreover, a (meth)acrylate compound is mentioned as a specific example of a crosslinkable monomer. Examples of (meth)acrylate compounds include glycol-based compounds such as polyethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, and neopentyl glycol dimethacrylate. , tripropylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, and mixtures thereof. In addition, other (meth)acrylate compounds include, for example, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, Glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dimethylol-tricyclodecane diacrylate, 2-hydroxy-3-acryloyloxy Bifunctional (meth)acrylates such as propyl methacrylate, trifunctional (meth)acrylates such as pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol hexamethylene diisocyanate urethane prepolymer, pentaerythritol tetraacrylate Examples include tetrafunctional (meth)acrylates such as, hexafunctional (meth)acrylates such as dipentaerythritol hexaacrylate, and mixtures thereof.

<Dispersion medium, (c2) component>
Component (c2) of the present invention may be any compound as long as it dissolves aliphatic amines, and may be a compound different from component (c1). (c2) Component types include solvents, crosslinking monomers, and polymers, and are used when adjusting the solid content concentration, viscosity, coating properties, etc. of the resulting dispersion, and when forming a film from the dispersion. Can be added to adjust strength. Specific examples of component (c2) of the present invention include those described as specific examples of component (c1), but are not limited to these examples as long as the effects of the present invention are not lost.

<SP value>
The aliphatic amines including the primary amines, secondary amines, and tertiary amines have solubility in the components (c1) and (c2) of the dispersion medium of the present invention. Therefore, regarding this solubility, the present inventor confirmed that the solubility parameter SP value of the (c1) component and (c2) component of the dispersion medium serves as an index.
The SP value of the dispersion medium used in the examples of the present invention is shown in the column of component (c1) in the examples. As the dispersion medium used in the examples of the present invention, for example, methanol (MeOH) has an SP value of 30, and propylene glycol monomethyl ether acetate (PGMEA) has an SP value of 18. Regarding the SP value of the dispersion medium, it is not particularly limited as long as the effect of the present invention is not lost, but from the viewpoint of dispersion stability, the SP value should be in the range of 5 to 50, and preferably the SP value is 10. 40, more preferably an SP value of 15 to 35.

<(d) component>
Component (d) of the present invention includes additives that are generally added as necessary, such as inorganic fillers, leveling agents, polymerization initiators, polymerization inhibitors, photosensitizers, adhesion agents, and plasticizers. , ultraviolet absorbers, conductive agents, and pigments. As long as the effects of the present invention are not impaired, they may be used alone or in combination of two or more.

<Step (1), Step (2) and Step (3)>
Step (1) is a step of mixing component (a), component (b), and component (c1).
In step (2), the mixture mixed in step (1) is subjected to the condition that the crystal structure (crystalline state) of the metal-organic structure of component (a) does not change and maintains its crystal structure (crystalline state). This is a process of producing a metal-organic structure dispersion liquid by the mechanical pulverization method shown below.
Step (3) is a step of mixing the metal-organic structure dispersion prepared in step (2) with at least one of the components (c2) and (d) to produce a metal-organic structure composition.

<Mechanical crushing method>
In order to obtain a dispersion liquid in which the metal-organic structure in the dispersion medium is mechanically pulverized and the crystal size of the metal-organic structure is reduced from μm size to nm size, stirring blades, ultrasonic stirring, homogenizer, ultra Techniques such as sonic homogenizers, hammer mills, vibrating mills, high speed rotary mills, etc. can be used. However, when obtaining a dispersion liquid, in these methods, stirring methods that generate strong physical force or shearing force may change the crystals of the metal-organic structure, resulting in unfavorable results.
Here, one of the objects of the present invention is to obtain a nanometer-sized metal-organic structure while maintaining the crystal structure without changing the crystal of the metal-organic structure.
Therefore, in the present invention, it is possible to control the material, size, and number of media to be placed in the container, as well as the rotation speed and rotation time of the container, and it is possible to suppress changes in the crystals of the metal-organic structure. A ball mill and a bead mill were used. Furthermore, in the present invention, changes in the crystals of the metal-organic structure were suppressed by selecting an appropriate dispersant in addition to the metal-organic structure to be placed in the containers of the ball mill and bead mill.

<Crushing by ball mill/bead mill>
One of the mechanical grinding techniques used in the present invention is a ball mill and a bead mill. The difference between a ball mill and a bead mill is the mechanism of rotational movement: in a ball mill, the container rotates, whereas in a bead mill, a mixer inside the container rotates. The media placed in both containers is the same, and the rotation speed and rotation time can be adjusted. Therefore, similar effects can be expected no matter which method is used.
Media materials for ball mills and bead mills include (high) alumina, natural silica, silicon carbide, silicon nitride, glass, iron-cored nylon, zirconia, stainless steel, steel, carbon steel, and chrome steel. From the viewpoint of not changing the crystal structure of the metal-organic structure even when mechanically pulverized, a media having a diameter of 0.01 mm or more and 10 mm or less can be used. From the above point of view, preferred sizes include diameters of 0.03 mm to 5.0 mm, more preferably diameters of 0.1 mm to 2.0 mm.

<Crushing by ultrasonic wave>
One of the mechanical crushing techniques used in the present invention is ultrasonication. The apparatus, processing conditions, etc. used in the present invention are shown.
Ultrasonic generator: Ultrasonic cleaner (US CLEANER) manufactured by As One Co., Ltd.
Frequency: 40kHz

<Z average particle diameter>
In the present invention, the Z-average particle diameter of the solid powder of the metal-organic framework can be calculated, for example, by a dynamic light scattering method. Specifically, for example, the metal-organic structure dispersion can be placed in a measurement cell, irradiated with light, and the Z average particle diameter can be calculated from the solution viscosity and temperature based on the principle of Brownian motion.
In order to obtain good dispersion stability, the Z average particle diameter is preferably less than 1000 nm, more preferably 800 nm or less, and more preferably 600 nm or less. The apparatus used in the present invention, measurement conditions, etc. are shown.
Equipment: Spectris Co., Ltd. Malvern Zetasizer NanoZS
Measurement conditions: Backscatter (angle 173°)
Measurement temperature: 25℃
Measured concentration: 0.005% by mass
Measurement position: 4.2mm
Viscosity parameter: Use the viscosity of each dispersion medium at 25°C

<Sedimentation velocity>
In the present invention, the sedimentation velocity of the solid powder particles of the metal-organic framework was measured using a centrifugal sedimentation type device. The sedimentation velocity of the particles was calculated by forcibly causing the particles to sediment using the centrifugal force of the device, and by optically capturing and analyzing the changes. As for the analysis conditions, the sedimentation rate was calculated using the time change of the cell position at which the transmittance was 50%. The apparatus used in the present invention, measurement conditions, etc. are shown.
Equipment: LUMISIZER manufactured by LUM
Maximum radius of rotation: 105mm
Rotation speed: 2000rpm
Centrifugal force: 470G (calculated according to the formula below)
Centrifugal force = (rotation speed/1000) ² x maximum radius of rotation (mm) x 1.118
Measurement cell: Polyamide cell optical path length 2mm
Measurement temperature: 25℃
Analysis mode: Front Tracking

<Dispersion stability>
Dispersion stability indicates that the lower the sedimentation rate, the better the dispersibility. From the viewpoint of handling properties and quality stabilization, it can be said that dispersion stability is good if the sedimentation velocity is 100 μm/s or less in an environment with a centrifugal force of 470 G or less. For better dispersion stability, the sedimentation rate is preferably 90 μm/s or less, preferably 80 μm/s or less, and more preferably 70 μm/s or less.

<Crystal structure analysis>
In the present invention, an X-ray diffraction device (XRD) was used for crystal structure analysis. The measurement principle of an X-ray diffractometer is to analyze the diffraction that occurs as a result of X-rays scattering and interfering with electrons around atoms when a sample is irradiated with X-rays. Generally, by using this diffraction information, it is possible to identify and quantify the crystal phase of a sample, analyze the degree of crystallinity, crystal size and strain, and molecular structure. The apparatus used in the present invention is shown.
Equipment: Rigaku MiniFlex 600

<SEM and SEM/EDX>
In the present invention, scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (SEM/EDX) were used for crystal state observation and elemental analysis. SEM is a method that can obtain contrast based on the unevenness of the sample and differences in composition based on information on the electrons emitted from the sample when the sample is irradiated with an electron beam. This is a method of performing elemental and compositional analysis by detecting characteristic X-rays and performing spectroscopy based on energy. EDX is attached to SEM. The apparatus used in the present invention is a high-performance field emission scanning electron microscope that can obtain high resolution at an extremely low accelerating voltage of 1 kV or less in order to observe information on the surface of a sample. The apparatus used in the present invention, measurement conditions, etc. are shown.
Equipment: JEOL Ltd. JSM-7400F
Acceleration voltage: SEM 1.0kV, SEM-EDX 5.0kV
Emission current: 10μA

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
<Solid powder of metal-organic structure>
The solid powder of the metal-organic structure used in the present invention is shown together with abbreviations.
[Production Example 1] Production of MOF-801 In a 500 ml four-necked flask, 11.1 g (34.5 mmol) of zirconium chloride octahydrate as a metal component and 4.00 g (34.5 mmol) of fumaric acid as an organic ligand were added. ), 38.9 ml of formic acid as a catalyst, and 110.1 ml of dimethylformamide as a solvent were charged. After dissolving zirconium chloride octahydrate and fumaric acid in a solvent, the reaction solution was heated to 130°C using an oil bath, and reacted at 130°C for 24 hours. A white powder formed and precipitated in the reaction solution was collected on a filter paper by Kiriyama filtration, and after washing with 300 ml of DMF and 300 ml of MeOH, the obtained metal-organic framework powder was vacuum-dried at 150° C. for 5 hours. When the obtained powder was observed using a SEM, it was found to have a polyhedral shape close to a sphere with a primary particle size of about 1 μm, and secondary agglomeration to a size of about 5 to 50 μm.

[Production Example 2] Production of MOF powder UiO-NH2-66 In a 500 ml four-neck flask, 1.88 g (8.1 mmol) of zirconium chloride as a metal component and 2-amino-1,4-benzene as an organic ligand were placed in a 500 ml four-necked flask. 2.04 g (11.3 mmol) of dicarboxylic acid, 7.5 ml of hydrochloric acid as a catalyst, and 150 ml of dimethylformamide as a solvent were charged. After dissolving zirconium chloride and 2-amino-1,4-benzenedicarboxylic acid in a solvent, the reaction solution was heated to 120°C using an oil bath and reacted at 120°C for 6 hours. A yellowish white powder formed and precipitated in the reaction solution was collected on a filter paper by Kiriyama filtration, and after washing with 300 ml of MeOH and 300 ml of acetone, the obtained metal organic framework powder was vacuum dried at 120° C. for 5 hours. When the obtained powder was observed using a SEM, it was found to be spherical with a primary particle size of about 0.6 to 1.0 μm, and secondary agglomeration to a size of about 20 to 50 μm.

[Production Example 3] Production of MOF powder MOF-303 In a 1000 ml eggplant flask, 10.4 g (43.1 mmol) of aluminum chloride hexahydrate was added as a metal component, and 3,5-pyrazoledicarboxylic acid was added as an organic ligand. 7.50 g (43.1 mmol) of monohydrate and 720 mL of water as a solvent were charged, and aluminum chloride hexahydrate and 3,5-pyrazoledicarboxylic acid monohydrate were dissolved at room temperature. . Then, while stirring the reaction solution, a sodium hydroxide solution prepared by diluting 2.60 g of sodium hydroxide with 30 ml of water was added dropwise into the reaction solution, and the temperature of the reaction solution was raised to 100°C using an oil bath for 24 hours. The reaction was carried out at 100°C. The white powder produced and precipitated in the reaction solution was collected on a filter paper by filtration, washed with 500 ml of water and 500 ml of methanol, and the obtained metal-organic framework powder was vacuum-dried at 70° C. for 9 hours. It was vacuum dried at ℃ for 9 hours. When the obtained powder was observed using a SEM, it was found that quadrangular prism-shaped crystals with a primary particle size of about 50 to 150 nm were secondary agglomerated to form a spherical shape of about 2 μm.

Other metal-organic structures used in the present invention are shown with abbreviations.
・MIL-53: Basolite (registered trademark) A100 (metal species: Al, organic ligand: terephthalic acid) [Sigma-Aldrich] From SEM observation, the primary particle size is approximately 1.0 to 1.5 μm in length and approximately 1.5 μm in width. It is acicular with a size of 15 to 30 nm, and the secondary aggregate is spherical with a size of about 20 to 40 μm. CAU-10: Aluminum isophthalic acid hydroxide MOF (metal species: Al, organic ligand: isophthalic acid) [Fujifilm Wa Hikari Pure Chemical Industries, Ltd.] From SEM observation, the primary particle size was cubic with a side of approximately 3.0 to 7.0 μm. ZIF-8: Zinc 2-methylimidazole MOF (metal species: Zn, organic ligand: 2- Methylimidazole) [Fujifilm Wako Pure Chemical Industries, Ltd.] From SEM observation, the primary particle size is spherical with a size of about 0.2 to 0.3 μm, and the secondary aggregate is elliptical with a size of about 10 μm. UiO-66 : Zirconium 1,4-dicarboxybenzene MOF (metal type: Zr, organic ligand: 1,4-dicarboxybenzene) [Fujifilm Wako Pure Chemical Industries, Ltd.]

<Dispersant, component (b)>
The dispersants used in the present invention are shown together with abbreviations.
・AM-1: Tripentylamine [Tokyo Kasei Kogyo Co., Ltd.]
・AM-2: Propanolamine [Tokyo Kasei Kogyo Co., Ltd.]
・AM-3: Methylaminoethanol [Tokyo Kasei Kogyo Co., Ltd.]
・AM-4:1-Aminoundecane [Tokyo Kasei Kogyo Co., Ltd.]
・AM-5: Tridodecylamine [Tokyo Kasei Kogyo Co., Ltd.]
・AM-6: Trimethylstearylammonium chloride [Tokyo Kasei Kogyo Co., Ltd.]
・AM-7: N,N-bis(3-aminopropyl)ethylenediamine [Tokyo Kasei Kogyo Co., Ltd.]
・AM-8: 1,6-diaminohexane [Tokyo Kasei Kogyo Co., Ltd.]
・AM-9: N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine [Tokyo Kasei Kogyo Co., Ltd.]
・AM-10: Pyrrole [Tokyo Kasei Kogyo Co., Ltd.]
・AM-11: Pyridine [Tokyo Kasei Kogyo Co., Ltd.]
・AM-12: Aniline [Tokyo Kasei Kogyo Co., Ltd.]
・AC-1: Formic acid [Tokyo Chemical Industry Co., Ltd.]
・AC-2: Stearic acid [Tokyo Kasei Kogyo Co., Ltd.]
・AC-3: Phosphanol RS-710 (polyoxyethylene alkyl (12-15) ether phosphoric acid) [Toho Chemical Industry Co., Ltd.]

<(c1) component>
The component (c1) used in the present invention is shown together with abbreviations.
・DMF: N,N-dimethylformamide [Kanto Kagaku Co., Ltd.], viscosity (25°C): 0.8 mPa・s, refractive index (25°C): 1.428, SP value: 25 (Winmostar (registered trademark) )
・MeOH: methanol [Kanto Kagaku Co., Ltd.], viscosity (25°C): 0.5 mPa・s, refractive index (25°C): 1.329, SP value: 30 (calculated using Winmostar (registered trademark))
・PGME: Propylene glycol monomethyl ether [Tokyo Kasei Kogyo Co., Ltd.], viscosity (25°C): 1.9 mPa・s, refractive index (25°C): 1.404, SP value: 20 (Winmostar (registered trademark)) (calculated using)
・PGMEA: Propylene glycol monomethyl ether acetate [Tokyo Kasei Kogyo Co., Ltd.], viscosity (25°C): 1.1 mPa・s, refractive index (25°C): 1.404, SP value: 18 (Winmostar (registered trademark)) )
・D-1: Polyethylene glycol diacrylate [Shin Nakamura Chemical Co., Ltd. A-200], viscosity (25°C): 25 mPa・s, refractive index (25°C): 1.463, SP value: 19 (Winmostar ( Calculated using registered trademark)
・D-2: 1,6-hexanediol diacrylate [Osaka Organic Chemical Industry Co., Ltd. Viscoat #230], viscosity (25°C): 7 mPa・s, refractive index (25°C): 1.456, SP value: 18 (calculated using Winmostar (registered trademark))

<Mechanical crushing process>
・Method: The components listed in Table 1 were charged into a ball mill screw tube in a predetermined ratio. Thereafter, balls as media were added to the screw tube until the volume became about half of the liquid volume. Thereafter, the screw tube was stirred with a mixing rotor at a rotation speed of 70 rpm for a predetermined period of time to carry out pulverization. The media types used are hereinafter expressed using the abbreviations below.
M-1: Zirconia ball YTZ-1 manufactured by Nikkato Co., Ltd. (Size: φ1mm)
M-2: Zirconia ball YTZ-0.2 (size: φ0.2mm) manufactured by Nikkato Co., Ltd.
M-3: As One Co., Ltd. Glass beads BZ-1 (Size: φ0.99-1.40mm)
M-4: AS ONE Co., Ltd. High purity alumina ball AL9-1 (Size: φ1mm)

- Method: Ultrasonic treatment In the present invention, the above-mentioned ultrasonic treatment was also carried out as a method other than the above-mentioned ball mill. For the ultrasonic treatment, the components listed in Table 1 were charged into a screw tube in a predetermined ratio, and the treatment was carried out for the time listed in Table 1.

<Homogeneity>
The appearance of the prepared dispersion liquid was visually confirmed and evaluated according to the criteria shown below. It is preferable to use "A" as the dispersion liquid.
A: No aggregated particles can be visually confirmed in the solution, and a colloidal color is observed. C: Agglomerated particles are visible, but no colloidal color is observed.

As shown in Table 1, in the dispersions of Examples 1 to 9 and 11, the metal species constituting the metal-organic structure was Zr, and the dispersant was a polymer having one amino group in the molecule. It includes aliphatic amine compounds that are primary amines, secondary amines, or tertiary amines. As shown in Table 2, compared to Comparative Example 1 which does not contain a dispersant, in Examples 1 to 9 and 11, the metal-organic framework is dispersed in a small size on the order of nm. , and a dispersion liquid exhibiting excellent dispersion stability was obtained.

As shown in Table 1, in the dispersion liquid of Comparative Example 2, the metal species constituting the metal-organic structure was Zr, and the dispersant was a quaternary aliphatic amine compound having one amino group in the molecule. It includes. As shown in Table 2, compared to Examples 1 to 9, the metal-organic structures were aggregated in a large size on the μm order, and the dispersion stability was inferior.

As shown in Table 1, in the dispersions of Comparative Examples 3 to 5, the metal species constituting the metal-organic structure was Zr, and the dispersant was a primary amine having a plurality of amino groups in the molecule, It includes an aliphatic amine compound that is a secondary amine or a tertiary amine. As shown in Table 2, compared to Examples 1 to 9, the metal-organic structures were aggregated in a large size on the μm order, and the dispersion stability was inferior.

As shown in Table 1, in the dispersions of Comparative Examples 6 to 8, the metal species constituting the metal-organic structure was Zr, and the dispersant was a primary amine having one amino group in the molecule; It contains aromatic amine compounds that are secondary amines or tertiary amines. As shown in Table 2, compared to Examples 1 to 9, the metal-organic structures were aggregated in a large size on the μm order, and the dispersion stability was inferior.

As shown in Table 1, in the dispersions of Comparative Examples 9 to 12, the metal species constituting the metal-organic structure was Zr, and the dispersant contained monocarboxylic acid or phosphonic acid. As shown in Table 2, compared to Examples 1 to 9, the metal-organic structures were aggregated in a large size on the μm order, and the dispersion stability was inferior.

As shown in Table 1, in the dispersions of Examples 10, 12, 13, and 15, the metal species constituting the metal-organic framework was Al, and the dispersant contained one amino acid in the molecule. It contains an aliphatic amine compound which is a tertiary amine having a group. As shown in Table 2, in comparison with Comparative Example 13 in which the dispersant contains a monocarboxylic acid, in Examples 10, 12, 13, and 15, the metal-organic framework is on the order of nm. A dispersion liquid was obtained which was dispersed in a small size and showed excellent dispersion stability.

As shown in Table 1, in the dispersion of Example 14, the metal species constituting the metal-organic structure was Zn, and the dispersant was an aliphatic amine, which was a tertiary amine having one amino group in the molecule. It contains compounds. As shown in Table 2, a dispersion liquid was obtained in which the metal-organic framework was dispersed in a small size on the nanometer order and had excellent dispersion stability.

As shown in Table 1, in the dispersions of Example 1 and Examples 16 to 18, the metal species constituting the metal-organic framework was Zr, and the dispersant had one nitrogen atom in the molecule. It contains an aliphatic amine compound which is a tertiary amine. As shown in Table 2, dispersions were obtained in which the metal-organic structures were dispersed in small sizes on the order of nanometers, and showed excellent dispersion stability, although the media types and sizes were different. .

As shown in Table 1, in the dispersion of Comparative Example 14, the metal species constituting the metal-organic structure was Zr, and the dispersant was an aliphatic amine, which was a tertiary amine having one amino group in the molecule. Although it contains a compound, the processing method was ultrasonic treatment, and compared to the one that was mechanically pulverized in a ball mill in Example 1, the metal organic structure was aggregated in a large size on the μm order, It also showed that the dispersion stability was poor.

As shown in Table 1, in the dispersions of Examples 19 and 20, the metal species constituting the metal-organic framework was Zr, and the dispersant was a tertiary amine having one nitrogen atom in the molecule. It contains a certain aliphatic amine compound, and the dispersion medium is crosslinking monomers D-1 and D-2. As shown in Table 2, compared to Comparative Example 1 which does not contain a dispersant, Examples 19 and 20 have metal-organic structures dispersed in a small size on the order of nm, and have excellent A dispersion exhibiting dispersion stability was obtained.

As shown in Table 1, in the dispersion of Example 21, the metal species constituting the metal-organic structure was Al, and the dispersant was an aliphatic amine, which was a tertiary amine having one nitrogen atom in the molecule. It contains a compound, and the solid content concentration is higher than that of Examples 1 to 20 (15% by mass). As shown in Table 2, a dispersion liquid was obtained in which the metal-organic framework was dispersed in a small size on the nanometer order and had excellent dispersion stability.

[Effect on crystal structure due to ball milling]
By diluting the dispersions obtained in Example 1 and Comparative Example 1 10 times with toluene, the precipitated metal-organic framework white powder was collected on a filter paper by Kiriyama filtration, and washed with DMF and MeOH. Thereafter, the obtained metal-organic structure powder was vacuum-dried at 150° C. for 5 hours to obtain a white powder.

In order to confirm the influence of the ball milling treatment on the crystal structure, the crystal structure of the white powder obtained by the above treatment and the powder obtained in Production Example 1 before the ball milling treatment was analyzed using XRD. As shown in Figure 1, the diffraction peak of the powder obtained from Comparative Example 1, which did not contain a dispersant and was subjected to ball milling, is different from the diffraction peak of the powder obtained from Production Example 1 and Example 1. It was suggested that the crystal structure had changed. From this result, in order to form a dispersion liquid while maintaining the crystal structure through mechanical pulverization, it is necessary to use a primary amine, secondary amine, or tertiary amine that has one amino group in the molecule as a dispersant. It was suggested that inclusion of aliphatic amine compounds is important.

In order to confirm the influence of the ball mill treatment on the crystal structure, the white powder obtained by the above treatment and the powder obtained in Production Example 1 before the ball mill treatment were analyzed by SEM-EDX. As shown in Figure 2, the elemental composition of the powder obtained from Comparative Example 1, which did not contain a dispersant and was subjected to ball milling, was different from the elemental composition of the powder obtained from Production Example 1 and Example 1. It was suggested that the structure had changed. From this result, in order to form a dispersion liquid while maintaining the crystal structure through mechanical pulverization, it is necessary to use a primary amine, secondary amine, or tertiary amine that has one amino group in the molecule as a dispersant. It was suggested that it is important to include aliphatic amine compounds.

Similarly, by diluting the dispersion liquid obtained in Example 11 and Example 15 10 times with toluene, the precipitated metal-organic framework white powder was collected on a filter paper by Kiriyama filtration, and DMF and MeOH were collected. After washing, the obtained metal-organic structure powder was vacuum-dried at 150° C. for 5 hours to obtain a powder. The crystal structures of the obtained powder and the powders obtained in Production Example 2 and Production Example 3 before ball milling were analyzed using XRD. As shown in FIG. 3, it was suggested that the crystal structure was maintained before and after the ball milling treatment.

Claims

A method for producing a metal-organic structure dispersion, the method comprising:
(a) Component: a metal-organic structure containing a metal ion and an organic ligand coordinated to the metal ion, where the metal ion is at least one selected from the group consisting of Zr ions, Al ions, and Zn ions. a solid powder of
(b) Component: As a dispersant, it is a primary amine, secondary amine, or tertiary amine having one amino group represented by the following formula (1) in the molecule, and (c1) a dispersion medium. an aliphatic amine compound having solubility in

(In the formula, R 1 and R 2 each independently represent a hydrogen atom or an aliphatic hydrocarbon group, and * represents a bond with a carbon atom.)
(c1) component: step (1) of mixing with a dispersion medium, and step (2) of preparing a dispersion liquid by a mechanical pulverization method using the resulting mixture (however, the mechanical pulverization method A method for producing a dispersion of a metal-organic structure, provided that the crystal structure of the metal-organic structure does not change and maintains the crystal structure of a solid powder.
The metal-organic structure dispersion liquid is such that the Z-average particle size of the solid powder of the metal-organic structure in the dispersion liquid is 10 nm or more and less than 1000 nm, and the metal-organic structure is The method for producing a metal-organic structure dispersion according to claim 1, wherein the solid powder particles have a sedimentation rate of 100 μm/s or less.
A metal-organic structure dispersion produced by the method according to claim 1 or 2, and a dispersion medium (c2) component and an additive (d) component different from the dispersion medium (c1) component in the dispersion. A method for producing a metal-organic framework composition, comprising a step (3) of mixing at least one of the following.
Claim 1 or Claim 2, wherein the organic ligand is at least one selected from the group consisting of fumaric acid, terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2-methylimidazole, and dicarboxypyrazole. A method for producing the metal-organic framework dispersion described above.
3. The metal-organic framework according to claim 1 or 2, wherein the metal-organic framework is MIL-53, CAU-10, ZIF-8, MOF-801, MOF-303, UiO-66, or UiO-NH2-66. A method for producing a metal-organic framework dispersion.
3. The method for producing a metal-organic structure dispersion according to claim 1, wherein the mechanical pulverization method is a pulverization method using a ball mill or a bead mill.
The metal organic according to claim 6, wherein the ball mill or bead mill has a ball diameter or bead diameter of 0.01 mm or more and 10 mm or less, and the material of the balls or beads is at least one selected from the group consisting of metal and glass. Method for producing a structure dispersion.
(a) Component: a metal-organic structure containing a metal ion and an organic ligand coordinated to the metal ion, where the metal ion is at least one selected from the group consisting of Zr ions, Al ions, and Zn ions. a solid powder of
(b) Component: As a dispersant, it is a primary amine, secondary amine, or tertiary amine having one amino group represented by the following formula (1) in the molecule, and (c1) a dispersion medium. an aliphatic amine compound having solubility in

(In the formula, R 1 and R 2 each independently represent a hydrogen atom or an aliphatic hydrocarbon group, and * represents a bond with a carbon atom.)
(c1) Component: A dispersion liquid containing a dispersion medium,
The Z-average particle size of the solid powder of the metal-organic structure in the dispersion is 10 nm or more and less than 1000 nm, and the sedimentation rate of the solid powder particles of the metal-organic structure in an environment with a centrifugal force of 470 G or less is 100 μm/ A metal-organic structure dispersion liquid having a temperature of s or less.
The metal organic according to claim 8, wherein the organic ligand is at least one selected from the group consisting of fumaric acid, terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2-methylimidazole, and dicarboxypyrazole. Structure dispersion liquid.
10. The metal-organic framework according to claim 8 or 9, wherein the metal-organic framework is MIL-53, CAU-10, ZIF-8, MOF-801, MOF-303, UiO-66, or UiO-NH2-66. Metal-organic framework dispersion liquid.
At least one of the metal-organic structure dispersion liquid according to claim 8 or 9, and a dispersion medium (c2) component different from the dispersion medium (c1) component and an additive (d) component in the dispersion liquid. A metal-organic framework composition comprising: