JP2021116516A - Composite of cellulose and inorganic porous coordination polymer, and production method of the same, composite of cellulose and metal organic framework, and production method of the same - Google Patents

Abstract

To provide a composite carrying a large amount of inorganic porous coordination polymer which is scarcely eliminated and has sufficient hardness, and a production method of the same, and to provide a composite carrying a large amount of metal organic framework (MOF) which is scarcely eliminated and has sufficient hardness, and a production method of the same.SOLUTION: A composite which is a composite including cellulose and an inorganic porous coordination polymer and in which a carrying ratio of the inorganic porous coordination polymer after ultrasonic cleaning operation of the composite is 4-60 wt.%, and a production method of the composite are disclosed. A composite which is a composite including cellulose and a metal organic framework and in which a carrying ratio of the metal organic framework after ultrasonic cleaning operation of the composite is 4-60 wt.%, and a production method of the composite are disclosed.SELECTED DRAWING: Figure 5

Description

The present invention relates to a complex of cellulose and an inorganic porous coordination polymer, and a method for producing the complex.

The present invention relates to a complex of cellulose and a metal-organic framework, and a method for producing the same.

Cellulose has a structure represented by the molecular formula (C ₆ H ₁₀ O ₅ ) _n , and is a natural polymer in which a large number of β-glucose molecules are linearly polymerized by glycosidic bonds. Unlike synthetic polymers made from petroleum, it is naturally produced and is also biodegradable, making it a material that is friendly to the global environment. In addition, cellulose has various characteristics that synthetic polymers do not have. Specific examples of its characteristics are (i) it is chemically relatively stable and difficult to dissolve in various solvents, and (ii) it has heat resistance and does not decompose or melt even at a certain high temperature. iii) Not only hydrophilic but also lipophilic, (iv) less harmful substances are generated during combustion, (v) can be molded into various shapes by dissolving in a special solvent, (vi) It is possible to impart a function by carrying out a chemical reaction using a hydroxyl group, (vii) it is less toxic to the human body, (viii) it is difficult to interact with a substance such as a protein, and the like.

Further, cellulose obtained by dissolving and regenerating cellulose once is called regenerated cellulose, and not only can it be formed into an arbitrary shape, but also a void having a microporous structure can be provided inside the structure. Taking advantage of its characteristics, natural cellulose and regenerated cellulose are used for various purposes in various shapes such as various fibers, various non-woven fabrics, packaging films, excipients, artificial kidneys, filters, and cell culture substrates. Furthermore, in recent years, studies have been made on cellulose nanofibers. Furthermore, due to the microplastic problem, biodegradable cellulose has been regaining attention as an old and new material, and new utilization is expected.

Porous Coordination Polymer (hereinafter referred to as PCP) is a general term for compounds having a framework structure in which metal ions and ligands are crosslinked and having pores in the structure. Among PCPs, those in which a framework structure is formed by cross-linking metal ions with an organic ligand are generally called a metal-organic framework (hereinafter referred to as MOF). PCP not contained in MOF, that is, a ligand having a very simple structure with a metal ion (for example, oxide ion, sulfide ion, fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion) , Cyanate ion, thiocyanide ion, etc.) and compounds in which there is no organic ligand coordinated to the metal ion in the framework structure are referred to as inorganic PCP in the present specification. Call it. Examples of inorganic PCPs include Prussian blue (hereinafter referred to as PB) composed of iron and cyanide ions, and polyoxometallate which is an anionic cluster composed of metal ions and oxide ions. Examples thereof include a porous crystalline solid composed of cations (for example, metal ion, macrocation, alkylammonium ion, etc.).

PB, also called navy blue, has been used as a pigment for a long time, but in recent years it has been attracting attention from the aspect of being a functional material. Applications to adsorbents that utilize the pores of PB in the crystal structure, electrochromic materials that utilize changes in the valence of iron ions, electrode materials, and the like have been proposed. A series of compounds in which iron (II) ions and iron (III) ions constituting PB are replaced with other metal species are called Prussian Blue Analogues (hereinafter referred to as PBA). Like PB, PBA has pores in the crystal structure, and various physical properties such as color tone, stability, crystal structure, and electronic structure can be adjusted by combining metal species. Therefore, PBA is similar to PB. It is attracting attention as a functional material.

In addition to the method of mixing and synthesizing a solution in which metal ions are dissolved and a solution in which hexacyanometallate is dissolved at normal temperature and pressure, the method of synthesizing PBA is a method of synthesizing under high temperature and high pressure, and microwave or super in the solution. Examples include a method of synthesizing while applying sound waves, and a method of mixing raw materials in a solid state and synthesizing while applying a mechanical impact with a ball mill or the like. In either case, PBA is obtained in the form of powder, and after synthesis, it is recovered by membrane filtration, centrifugation, etc. after washing. When producing an inorganic PCP other than PBA, it is basically obtained in the form of powder. However, in the powder state, handling problems may occur depending on the application. In order to solve this problem, a method of using it as a complex in which an inorganic PCP is supported on some kind of support has been proposed.

In the following Patent Document 1, a cotton knit is used as a support, an acrylic acid ester resin is used as a binder, and HKUST-1 powder, which is a kind of metal-organic framework, is supported, thereby carrying a composite knit of cellulose and HKUST-1. The method of obtaining is reported.

In Patent Document 2 below, a solution obtained by mixing a first solution, an aqueous solution of potassium hexacyanoferrate (II) and a cellulose fiber, and a second solution, an aqueous solution of iron (III) chloride, are mixed with cellulose fibers as a support. A method of obtaining a complex in which PB is fixed on the surface of cellulose has been reported.

The following Patent Document 3 reports a method of obtaining a composite of cellulose and PBA by using a regenerated cellulose non-woven fabric as a support, impregnating it with a dispersion liquid of PBA synthesized in advance, and drying it.

In the following Patent Document 4, a cellulose oxide nanofiber is used as a support, and zinc ion is introduced as a counterion of a carboxyl group by treating with an aqueous solution of zinc nitrate for washing, and a DMF solution of 2-imidazole carbaldehyde is further prepared. By adding, a method of obtaining a complex of MOF-90, which is a kind of metal-organic framework, and cellulose has been reported.

In the following Patent Document 5, zinc oxide fine particles are dispersed in a DMAc solution in which a polyether sulfone is dissolved, coated with an applicator and dried by heating to prepare a film in which zinc oxide particles are dispersed, and further 2-methylimidazole. A method of obtaining a complex of ZIF-8, which is a kind of metal-organic framework, and a polyether sulfone by adding a DMAc solution of the above has been reported.

Cellulose has a structure represented by the molecular formula (C ₆ H ₁₀ O ₅ ) _n , and is a natural polymer in which a large number of β-glucose molecules are linearly polymerized by glycosidic bonds. Unlike synthetic polymers made from petroleum, it is naturally produced and is also biodegradable, making it a material that is friendly to the global environment. In addition, cellulose has various characteristics that synthetic polymers do not have. Specific examples of its characteristics are (i) it is chemically relatively stable and difficult to dissolve in various solvents, and (ii) it has heat resistance and does not decompose or melt even at a certain high temperature. iii) Not only hydrophilic but also lipophilic, (iv) less harmful substances are generated during combustion, (v) can be molded into various shapes by dissolving in a special solvent, (vi) It is possible to impart a function by carrying out a chemical reaction using a hydroxyl group, (vii) it is less toxic to the human body, (viii) it is difficult to interact with a substance such as a protein, and the like.

Further, cellulose obtained by dissolving and regenerating cellulose once is called regenerated cellulose, and not only can it be formed into an arbitrary shape, but also a void having a microporous structure can be provided inside the structure. Taking advantage of its characteristics, natural cellulose and regenerated cellulose are used for various purposes in various shapes such as various fibers, various non-woven fabrics, packaging films, excipients, artificial kidneys, filters, and cell culture substrates. Furthermore, in recent years, studies have been made on cellulose nanofibers. Furthermore, due to the microplastic problem, biodegradable cellulose has been regaining attention as an old and new material, and new utilization is expected.

On the other hand, in recent years, studies on metal-organic frameworks (MOFs) have been actively conducted, and new utilization is expected. MOF is a material obtained by self-assembly of metal ions and organic ligands, and is a crystalline porous material in which a framework structure is formed by cross-linking metal ions serving as nodes with organic ligands. Is. Examples of MOFs include HKUST-1, which is composed of copper and trimesic acid, MOF-5, which is composed of zinc and terephthalic acid, ZIF-8, which is composed of zinc and 2-methylimidazole, and MIL-53 (Fe), which is composed of iron and terephthalic acid. , MOF-74 (Fe) composed of iron and 2,5-dihydroxyterephthalic acid and the like. There are innumerable types of MOFs depending on the combination of metal ions and organic ligands. A ligand having an extremely simple structure with a metal ion (for example, oxide ion, sulfide ion, fluoride ion, chloride ion, bromide ion, iodide ion, cyanate ion, cyanate ion, thiocyanide ion) The MOF does not include a compound composed only of (such as) or a compound in which an organic ligand coordinated with a metal ion does not exist in the framework structure. For example, Prussian blue (PB), which consists of iron and cyanide ions, is not included in the MOF. As another example, it is composed of polyoxometallate, which is an anionic cluster consisting of metal ions and oxide ions, and an arbitrary cation (for example, metal ion, macrocation, alkylammonium ion, etc.) and is coordinated with the metal ion. The porous crystalline solid in which no organic ligand is present is not included in the MOF.

The pores of the MOF are the same size and are arranged periodically as compared with silica gel, zeolite, and activated carbon, which are also known as porous bodies. By selecting metal ions and ligands, physical properties such as pore size and arrangement, specific surface area, and surface polarity can be controlled. Recently, various uses such as gas storage such as hydrogen storage and gas separation for the purpose of suppressing carbon dioxide emission have been studied by taking advantage of the characteristics of the pores.

For the synthesis of MOF, in addition to the method of mixing and synthesizing a solution in which metal ions are dissolved and a solution in which a ligand is dissolved at normal temperature and pressure, a method of mixing and synthesizing under high temperature and high pressure, microwaves and ultrasonic waves in the solution Examples include a method of synthesizing while applying ultrasonic waves, and a method of mixing raw materials in a solid state and synthesizing while applying a mechanical impact with a ball mill or the like. In either case, MOF is obtained in the form of powder or crystal particles, and after synthesis, it is recovered by washing, membrane filtration, centrifugation, or the like. However, in the state of powder or particles, handling problems may occur depending on the application. In order to solve this problem, a method of using it as a complex in which MOF is supported on some kind of support has been proposed.

The following Patent Document 1 reports a method of obtaining a composite knit of cellulose and HKUST-1 by supporting HKUST-1 powder using a cotton knit as a support and an acrylic acid ester resin as a binder. ..

In Patent Document 2 below, a solution obtained by mixing a first solution, an aqueous solution of potassium hexacyanoferrate (II) and a cellulose fiber, and a second solution, an aqueous solution of iron (III) chloride, are mixed with cellulose fibers as a support. A method of obtaining a complex in which PB is fixed on the surface of cellulose has been reported.

The following Patent Document 3 reports a method of obtaining a composite of cellulose and PBA by impregnating a dispersion liquid of a pre-synthesized Prussian blue analog (PBA) with a regenerated cellulose non-woven fabric as a support and drying the mixture. ing.

In the following Patent Document 4, a cellulose oxide nanofiber is used as a support, and zinc ion is introduced as a counterion of a carboxyl group by treating with an aqueous solution of zinc nitrate for washing, and a DMF solution of 2-imidazole carbaldehyde is further prepared. A method of obtaining a complex of MOF-90 and cellulose by addition has been reported.

In Patent Document 5 below, zinc oxide fine particles are dispersed in a DMAc solution in which a polyether sulfone is dissolved, coated with an applicator, and dried by heating to prepare a film in which zinc oxide particles are dispersed, and further 2-methylimidazole. A method of obtaining a complex of ZIF-8 and a polyether sulfone by adding a DMAc solution of ZIF-8 has been reported.

Japanese Unexamined Patent Publication No. 2019-88499 JP-A-2019-49063 Japanese Patent No. 6345774 Japanese Patent No. 65664663 Special Table 2019-523701

When the inorganic PCP is used as a complex supported on a support, it is required that the inorganic PCP is not easily detached and that the pores of the inorganic PCP are not damaged. Further, when the inorganic PCP is used for storage or separation, it is desirable that a large amount of the inorganic PCP can be supported. Further, although it depends on the method of using the complex, if the strength of the complex is low, the handling becomes poor, so a supporting method that does not reduce the strength of the complex is desirable.

A composite can be easily obtained by using a binder as in Patent Document 1, but there is a possibility that the pores of the inorganic PCP may be blocked by the binder and the original performance may not be obtained, or the binder may be deteriorated or dissolved. It is conceivable that the inorganic PCP may be desorbed. Patent Document 2 describes that PB is difficult to desorb and has a high ash yield, and that the treatment is performed in the presence of cavitation bubbles. However, there is no ash yield data in the examples, and the presence of cavitation bubbles is present. There is no description of an example of processing by cavitation. In the method of Patent Document 3, since the inorganic PCP is only physically adsorbed on the surface of the cellulose, the inorganic PCP is easily desorbed. It is known that the introduction of a carboxyl group by TEMPO-oxidized cellulose described in Patent Document 4 proceeds selectively on the fiber surface and does not react inside. That is, even in this method, since the inorganic PCP is supported on the fiber surface, there is a risk of desorption. In addition, since cellulose is oxidized, the strength is lowered, particularly in water, which may limit the applications in which it can be used. Since the method of Patent Document 5 can support the inorganic PCP inside the support, there is a possibility that the risk of the inorganic PCP being detached is low. However, as can be seen from the XRD pattern described in Patent Document 5, not all zinc reacts with 2-methylimidazole and is converted into a metal-organic framework. That is, it is difficult to increase the amount of inorganic PCP supported by this method. Further, in this method, the types of supports, the solvent, and the fine particles that can be used as precursors are limited, and the complex that can be produced is limited.

As described above, the inventors of the present application have found that the complex obtained by the existing technology has room for study on various performances required for practical use. The problem to be solved by the present invention is to provide a complex having a large amount of inorganic PCP supported, difficult to be detached, and having sufficient strength in view of the level of the above background technology, and further, it is necessary for the application to be used. It is to provide a complex of various shapes to be made.

When the MOF is used as a complex supported on a support, it is required that the MOF is not easily detached and that the pores of the MOF are not damaged. Further, when MOF is used for storage or separation, it is desirable that a large amount of MOF can be supported. Further, although it depends on the method of using the complex, if the strength of the complex is low, the handling becomes poor, so a supporting method that does not reduce the strength of the complex is desirable.

A complex can be easily obtained by using a binder as in Patent Document 1, but there is a possibility that the pores of the MOF may be blocked by the binder and the original performance may not be obtained, or the MOF may be deteriorated or dissolved due to deterioration or dissolution of the binder. May be detached. Patent Document 2 describes that PB is difficult to desorb and has a high ash yield, and that the treatment is performed in the presence of cavitation bubbles. However, there is no ash yield data in the examples, and the presence of cavitation bubbles is present. There is no description of an example of processing by cavitation. In the method of Patent Document 3, since the MOF is only physically adsorbed on the surface of the cellulose, the MOF is easily desorbed. It is known that the introduction of a carboxyl group by TEMPO-oxidized cellulose described in Patent Document 4 proceeds selectively on the fiber surface and does not react inside. That is, even in this method, the MOF is supported on the fiber surface, so there is a risk of desorption. In addition, since cellulose is oxidized, the strength is lowered, particularly in water, which may limit the applications in which it can be used. Since the MOF can be supported inside the support by the method of Patent Document 5, the risk of MOF detachment may be low. However, as can be seen from the XRD pattern described in Patent Document 5, not all zinc reacts with 2-methylimidazole and is converted to MOF. That is, it is difficult to increase the amount of MOF supported by this method. Further, in this method, the types of supports, the solvent, and the fine particles that can be used as precursors are limited, and the complex that can be produced is limited.

As described above, the inventors of the present application have found that the complex obtained by the existing technology has room for study on various performances required for practical use. The problem to be solved by the present invention is to provide a complex having a large amount of MOF supported, difficult to be detached, and having sufficient strength in view of the level of the above background technology, and further required for use. It is to provide complexes of various shapes.

As a result of diligent studies and repeated experiments in order to solve the above problems, the inventors of the present application dissolved cellulose in a solvent containing metal ions, and formed a complex containing metal ions with the ligand solution. It was unexpectedly found that by reacting, an inorganic PCP can be synthesized inside the cellulose structure, and a complex having a large amount of the inorganic PCP carried and which is difficult to be detached can be provided. Further, the inventors of the present application can arbitrarily change the shape of the complex by such a method, can provide the shape of the complex according to the application, and surprisingly, the complex of the present invention. We also found that the strength was improved compared to cellulose alone.

That is, the present invention is as follows.
[1] A composite containing cellulose and an inorganic porous coordination polymer, wherein the carrying ratio of the inorganic porous coordination polymer after the ultrasonic cleaning operation of the composite is 4% by weight to 60% by weight. Is a complex.
[2] The ultrasonic cleaning operation uses a dual-frequency switching type ultrasonic cleaning machine in which pure water is placed in the cleaning tank, and the following operations are performed:
(1) A glass container containing a solvent and a composite that does not dissolve or decompose the inorganic porous coordination polymer is placed in an ultrasonic cleaner for 5 minutes.
(2) Replace the solvent in the glass container.
The complex according to the above [1], which is an operation of performing the above three times in total.
[3] The complex according to the above [1] or [2], wherein the inorganic porous coordination polymer is a Prussian blue analog.
[4] The complex according to any one of [1] to [3] above, wherein the cellulose is regenerated cellulose.
[5] The composite according to any one of [1] to [4] above, which has the shape of any of short fibers, long fibers, woven fabrics, knitted fabrics, non-woven fabrics, films, porous membranes, hollow fibers, particles, or fine particles. body.
[6] The following steps:
Step of preparing a cellulose solution in which cellulose is dissolved as a complex containing metal ions;
A step of molding a structure containing cellulose and metal ions from the cellulose solution; and a solution containing an anion species that reacts the obtained structure with the metal ions to form an inorganic porous coordination polymer. , A step of contacting to obtain a complex containing cellulose and an inorganic porous coordination polymer;
The method for producing a complex according to any one of the above [1] to [5], which comprises.
[7] The method according to the above [6], wherein the metal ion is any one of copper, zinc, calcium, cadmium, cobalt, nickel, iron, palladium, magnesium, or a combination thereof.

As a result of diligent studies and experiments in order to solve the above problems, the inventors of the present application react with a ligand in a state where cellulose forms a complex containing a metal ion, thereby causing MOF inside the cellulose structure. We have unexpectedly found that we can provide a complex that carries a large amount of MOF and is difficult to detach. Further, the inventors of the present application can arbitrarily change the shape of the complex by such a method, can provide the shape of the complex according to the application, and surprisingly, the complex of the present invention. We also found that the strength was improved compared to cellulose alone.

That is, the present invention is as follows.
[1] A complex containing cellulose and a metal-organic framework, wherein the support ratio of the metal-organic structure after the ultrasonic cleaning operation of the complex is 4% by weight to 60% by weight.
[2] The ultrasonic cleaning operation uses a dual-frequency switching type ultrasonic cleaning machine in which pure water is placed in a cleaning tank, and the following operation:
(1) A glass container containing the solvent that does not dissolve or decompose the metal-organic framework and the complex is placed in an ultrasonic cleaner for 5 minutes.
(2) Replace the solvent in the glass container.
The complex according to the above [1], which is an operation of performing the above three times in total.
[3] The complex according to the above [1] or [2], wherein the cellulose is regenerated cellulose.
[4] The composite according to any one of [1] to [3] above, which has the shape of any of short fibers, long fibers, woven fabrics, knitted fabrics, non-woven fabrics, films, porous membranes, hollow fibers, particles, or fine particles. body.
[5] The following steps:
A step of preparing a cellulose solution in which cellulose is dissolved as a complex containing metal ions; a step of forming a structure containing cellulose and metal ions from the cellulose solution; and a step of obtaining the obtained structure as an organic ligand. The step of contacting with a solution to obtain a complex containing cellulose and a metallic organic structure;
The method for producing a complex according to any one of the above [1] to [4], which comprises.
[6] The method according to the above [5], wherein the metal ion is any one of copper, zinc, calcium, cadmium, cobalt, nickel, iron, palladium, magnesium, or a combination thereof.

According to the present invention, a composite having a large amount of inorganic PCP supported, difficult to be detached, good handling, and having an arbitrary shape can be obtained, and a storage material, an adsorption material, a separation material, a sustained release material, It can be used for various purposes such as electronic materials.

According to the present invention, a complex having a large amount of MOF supported, difficult to be detached, good handling, and having an arbitrary shape can be obtained, and various materials such as a storage material, an adsorption material, a separation material, and a sustained release material can be obtained. It can be used for various purposes.

It is the X-ray diffraction data of the cellulose-PBA (Cu, Fe) complex obtained in Example 5. 6 is a surface SEM photograph of the cellulose-PBA (Cu, Fe) complex obtained in Example 5. 5 is a cross-sectional TEM photograph of the cellulose-PBA (Cu, Fe) complex obtained in Example 5.

It is the X-ray diffraction data of the cellulose-HKUST-1 composite film obtained in Example 1. It is a surface SEM photograph of the cellulose-HKUST-1 composite film obtained in Example 1. 3 is a cross-sectional TEM photograph of the cellulose-HKUST-1 composite film obtained in Example 1. It is an optical photograph of the cellulose-HKUST-1 composite long fiber non-woven fabric obtained in Example 7. It is a cross-sectional TEM photograph of the cellulose-MOF-2 composite film obtained in Example 12.

Hereinafter, embodiments of the present invention will be described in detail.
One embodiment of the present invention is a composite containing cellulose and an inorganic porous coordination polymer, and the carrying ratio of the inorganic porous coordination polymer after the ultrasonic cleaning operation of the composite is 4 It is a complex having a weight of% to 60% by weight.

In the specification of the present application, the term "inorganic porous coordination polymer (inorganic PCP)" refers to a ligand (for example, oxide ion, sulfide ion) having an extremely simple structure with a metal ion among PCPs. , Fluoride ion, chloride ion, bromide ion, iodide ion, cyanate ion, cyanate ion, thiocyanate ion, etc.) Refers to a compound that does not have a ligand. Examples of inorganic PCPs are Prussian blue (PB), which consists of iron and cyanide ions, polyoxometallate, which is an anionic cluster consisting of metal ions and oxide ions, and arbitrary cations (eg, metal ions, macro). Examples include a porous crystalline solid composed of cations, alkylammonium ions, etc.).

The PBA in the present invention, a cyano bridged metal complex was constructed element hexacyano metal ion, the general _{formula: A x M y [M '} (CN) 6] has a composition represented by _z · nH ₂ O It is a compound having a structure in which two kinds of metal ions M and M'are crosslinked with cyanide ions. In the above general formula, A is an alkali metal ion, M is a first metal ion, M'is a second metal ion, and M and M'can be arbitrarily selected from any metal species. Therefore, the PBA of the present embodiment may be rephrased as a metal salt of hexacyanometallic acid. There are various types of PBA depending on the combination of M and M'. Depending on the valences of M and M'and the synthetic conditions, PBA may contain alkali metal ion A derived from a raw material. The PBA of the present embodiment may be used alone or in combination of two or more.

Various metal ions can be used as the first metal ion constituting the PBA of the present embodiment. In order to support PBA inside the cellulose, it is preferable that the metal ion used for dissolving the cellulose is the first metal ion. Of these, copper ion, zinc ion, calcium ion, cadmium ion, cobalt ion, nickel ion, iron ion, palladium ion, and magnesium ion are more preferable because of the ease of dissolving cellulose. Further, copper ions in which the obtained cellulose has voids are particularly preferable. Only one type of the first metal ion may be used, or two or more types may be mixed and used.

The second metal ion constituting the PBA of the present embodiment may be any metal species capable of having a hexacoordination structure with the cyanide ion, and can be freely selected according to the purpose. Only one type of the second metal ion may be used, or two or more types may be mixed and used.

As the cellulose constituting the complex of the present embodiment, various celluloses can be used. Cellulose has both hydrophilicity and lipophilicity and is insoluble in most common solvents. Therefore, various solvents are used for adsorption separation to separate the target substance from the liquid, catalysts for controlling the reaction, etc. Can be used. In addition, since cellulose has a certain degree of heat resistance and does not melt, it can be used in a wide temperature range. Further, when recovering the object adsorbed by the inorganic PCP, various solvents can be used, and the recovery can be performed in a certain degree of thermal environment. As the cellulose constituting the complex of the present embodiment, regenerated cellulose is preferable because it can be molded into an arbitrary shape as a complex. Of these, regenerated cellulose obtained from a cellulosic solution such as copper ammonia, cadmium, cooxene, nioxene, zincoxene, and EWNN, which are metal complex solvents, is more preferable. These regenerated celluloses have a structure in which the obtained cellulose has voids, and as a result, the molecules can easily access the inorganic PCP existing inside the complex, and can be easily used for storage, adsorption, separation, sustained release, and the like. Further, cuprammonium-ray regenerated cellulose is particularly preferable from the viewpoint of ease of molding and control of voids.

In the composite of the present embodiment, the carrying ratio (ratio) of the inorganic PCP after the ultrasonic cleaning operation is 4% by weight to 60% by weight. If the proportion of inorganic PCP is low, functions such as storage, adsorption, separation, and sustained release may be insufficient. If the ratio exceeds 60% by weight, the toughness of the composite becomes low, and handling problems may occur depending on the usage. From the viewpoint of performance, the ratio is preferably 10% by weight or more, more preferably 20% by weight or more, and further preferably 30% by weight or more. From the viewpoint of handling, the ratio is preferably 50% by weight or less, more preferably 40% by weight or less.

For the ultrasonic cleaning operation, a dual-frequency switching ultrasonic cleaner containing pure water in a cleaning tank is used, and a glass container containing a solvent and a complex that does not dissolve or decompose inorganic PCP is ultrasonically cleaned for 5 minutes. After cleaning with a washing machine, the solvent in the glass container is replaced with a new one, and the operation of cleaning again is performed a total of three times.
The reason for selecting ultrasonic cleaning as the method for cleaning the complex of the present embodiment is that composites of various shapes can be easily cleaned. When performing ultrasonic cleaning, it is necessary to select a solvent in which the inorganic PCP does not dissolve or decompose. For example, in the case of PB, pure water can be used as the solvent.
In the complex of the present embodiment, it is preferable that a certain amount of inorganic PCP is present inside the cellulose. It is considered that the inorganic PCP existing inside is not only less likely to be desorbed, but also contributes to the improvement of the mechanical properties of the complex.

The shape of the complex of the present embodiment can be arbitrarily selected depending on the intended use. For example, short fibers, long fibers, woven fabrics, knitted fabrics, non-woven fabrics, films, porous membranes, hollow fibers, particles, fine particles and the like can be mentioned. These may be used alone or in combination. It can also be used in combination with another material, or it can be used by incorporating it into some module. Furthermore, the size and shape of the void can be arbitrarily selected according to the intended use. For example, when gas separation is performed, a dense structure can prevent non-selective gas permeation, and when adsorption separation is performed, a sparse structure can be used to increase the specific surface area and increase the adsorption efficiency. can.

Other embodiments of the present invention include the following steps:
Step of preparing a cellulose solution in which cellulose is dissolved as a complex containing metal ions;
A step of molding a structure containing cellulose and metal ions from the cellulose solution; and a solution containing an anion species that reacts the obtained structure with the metal ions to form an inorganic porous coordination polymer. , A step of contacting to obtain a complex containing cellulose and an inorganic porous coordination polymer;
The method for producing a complex according to any one of [1] to [5] above, which comprises. The method for producing the complex of the present embodiment is not particularly limited, and any method can be used. However, a cellulose solution in which cellulose is dissolved as a complex containing metal ions is prepared, and the above-mentioned cellulose solution is prepared. A method of synthesizing an inorganic PCP inside the cellulose structure by producing a structure containing cellulose and metal ions from the cellulose structure and bringing the structure into contact with a solution containing an anion species is preferable. Since the metal ions form a complex with cellulose in advance, the structure obtained by molding from the cellulose solution is in a state where the metal ions are immobilized inside the structure, and when a solution containing anionic species is brought into contact with the structure, it is inorganic. The system PCP can be precipitated inside the cellulose structure. Since one metal ion can be coordinated to one glucose ring constituting cellulose, many metal ions can be immobilized inside the structure, and a large amount of inorganic PCP can be supported. For example, it has been reported that when a cuprammonium solution is used as a solvent, copper ions are coordinated with the hydroxyl groups of C2 and C3. In this method, the structure obtained by molding from the cellulose solution can be treated with a solution containing anionic species in a state where the structure is not coagulated, so that the structure can be coagulated and the inorganic PCP can be synthesized at the same time. The structure obtained by molding from the solution is first coagulated in a poor solvent that does not break the coordination of cellulose and metal ions, and then treated with a solution containing anionic species to synthesize an inorganic PCP. You can also. Further, if necessary, a treatment for cutting the coordination between the cellulose and the metal ion may be performed thereafter. Further, when the complex of the present embodiment is prepared by a method of treating with a solution containing an anion species in a state where cellulose forms a complex containing metal ions, the mechanical properties are surprisingly higher than those of cellulose alone. improves. The exact principle is unknown, but the inorganic PCP existing inside the cellulose structure may contribute as a reinforcing material, it may form a hydrogen bond with cellulose and contribute as a cross-linking agent, and it is inorganic at the time of structure formation. It is conceivable that the crystal structure of cellulose itself may have changed due to the presence of the system PCP. Improving the mechanical properties of the complex leads to advantages such as improved handling in actual use.

In the method of the present embodiment, in that the amount of the inorganic PCP carried can be increased, the structure obtained by molding from the cellulose solution is treated with a solution containing anionic species in a state where it is not solidified. A method in which coagulation and synthesis of an inorganic PCP (or an intermediate thereof) are carried out at the same time is preferable. On the other hand, in terms of controlling the shape and voids of cellulose, a method of first coagulating the structure with a poor solvent such that the bond between cellulose and metal ions is not broken and then treating with a solution containing an anion species is preferable. Further, the carrier rate of the inorganic PCP can be adjusted by changing the conditions such as the concentration, temperature, and reaction time of the solution containing the anionic species. Further, for example, when a cuprammonium solution is used as the solvent for cellulose, the pH becomes alkaline due to the presence of ammonia, so that it may not precipitate depending on the type of inorganic PCP. Even in such a case, a method is preferable in which deammonia is performed with a poor solvent such that the bond between cellulose and the metal ion is not broken to solidify the structure, and then the structure is treated with a solution containing an anion species. Further, depending on the type of inorganic PCP, the reaction may be insufficient or an intermediate may be formed only by treating with a solution containing an anionic species. In such a case, if necessary, high-pressure treatment, high-temperature treatment, treatment with an acidic solution, treatment with an alkaline solution, ultrasonic treatment, microwave treatment, or the like may be performed.

After synthesizing the inorganic PCP inside the cellulose of the present embodiment, a washing treatment can be performed if necessary. If unreacted metal ions or anionic species remain in the complex, they can be dissolved and washed with a solvent that does not decompose the synthesized inorganic PCP. For example, in the case of a cellulose-PB complex, pure water can be used as the solvent.

The complex of the present embodiment may be used after being dried, if necessary, may be used as it is without being dried, or may be used after being replaced with a solvent. When the synthesized inorganic PCP is solvated and has low activity, drying or activation treatment may be required. Further, when it is desired to maintain the void of cellulose, solvent replacement drying can be performed, or the cellulose can be used as it is without drying.

Hereinafter, embodiments of the present invention will be described in detail.
One embodiment of the present invention is a complex containing cellulose and a metal-organic framework, and the support ratio of the metal-organic structure after the ultrasonic cleaning operation of the complex is 4% by weight to 60% by weight. , A complex.

The MOF of the present embodiment is a porous material having a structure in which metal ions are crosslinked with each other by an organic ligand. By changing the types of metal ions and organic ligands according to the purpose, the size and chemical properties of the pores can be adjusted. As the MOF, a known MOF or a MOF that can be manufactured in the future can be used. Examples of MOFs include HKUST-1, MOF-2, MOF-4, CPL-1, CPL-2, Cu-BTTri, ELM-11, MOF-505, PCN-6, MOF-5, MOF-74, Examples thereof include MOF-177, ZIF-8, ZIF-zni, Zn-BTB, ZIF-67, MIL-100, MIL-53, MIL-89, UiO-66 and PCN-111. In order to support MOF inside cellulose, HKUST-1, MOF-2, MOF-4, CPL-1, CPL-2, Cu-BTTri, ELM-11, which contain metal species used for dissolving cellulose, MOF-505, PCN-6, MOF-5, MOF-74, MOF-177, ZIF-8, ZIF-zni, Zn-BTB, ZIF-67, MIL-100, MIL-53, MIL-89 are preferable. The MOF of the present embodiment may be used alone or in combination of two or more.

Any metal species can be used as the metal species constituting the MOF of the present embodiment. For example, lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, etc. Iron, cobalt, nickel, copper, zinc, gallium, rubidium, strontium, ittrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, cesium, barium, lantern, cerium, placeodium, Neogym, Prometium, Samalium, Europium, Gadolinium, Terbium, Disprosium, Holmium, Elbium, Thulium, Itterbium, Rutethium, Hafnium, Tantal, Tungsten, Renium, Osmium, Iridium, Platinum, Gold, Mercury, Talium, Lead, Bismus, Francium, Examples include radium, actinium, thulium, protactinium and uranium. The MOF may contain one or more metal species. In particular, in order to support MOF inside the cellulose, it is preferable to contain a metal species used for dissolving the cellulose. Above all, it is more preferable to contain copper, zinc, calcium, cadmium, cobalt, nickel, iron, palladium and magnesium because of the ease of dissolving cellulose. Further, it is particularly preferable that the resulting cellulose contains copper having voids.

The organic ligand constituting the MOF of the present embodiment may be any as long as it can coordinate with a metal ion to form a framework structure, and a known organic ligand or an organic ligand that can be produced in the future is used. It can be done and is not particularly limited. Examples of the organic ligand include a carboxylic acid-based ligand, a ketone-based ligand, an aldehyde-based ligand, an ether-based ligand, an amine-based ligand, an imine-based ligand, and an amino acid-based coordination. Child, nitrile-based ligand, phosphate-based ligand, phosphine-based ligand, sulfonic acid-based ligand, thiol-based ligand, sulfide-based ligand, fluoride-based ligand, chloride-based Examples thereof include ligands, brominated ligands, and iodide-based ligands. The MOF may contain one kind or two or more kinds of organic ligands, and can be freely selected according to the purpose. Further, depending on the combination of the metal ion and the organic ligand, the skeleton of the organic metal structure may be positively or negatively charged, and an anion or cation may be contained in the MOF in order to maintain electrical neutrality. A ligand having an extremely simple structure with a metal ion (for example, oxide ion, sulfide ion, fluoride ion, chloride ion, bromide ion, iodide ion, cyanate ion, cyanate ion, thiocyanide ion) The MOF does not include a compound composed only of (such as) or a compound in which an organic ligand coordinated with a metal ion does not exist in the framework structure. For example, Prussian blue (PB) consisting of iron and cyanide ions, polyoxometallate which is an anionic cluster consisting of metal ions and oxide ions, and arbitrary cations (for example, metal ions, macrocations, alkylammonium ions, etc.) ), And the porous crystalline solid in which the organic ligand coordinated to the metal ion does not exist is not included in the MOF.

As the cellulose constituting the complex of the present embodiment, various celluloses can be used. Cellulose has both hydrophilicity and lipophilicity and is insoluble in most common solvents. Therefore, various solvents are used for adsorption separation to separate the target substance from the liquid, catalysts for controlling the reaction, etc. Can be used. In addition, since cellulose has a certain degree of heat resistance and does not melt, it can be used in a wide temperature range. Further, when recovering the object adsorbed by MOF, various solvents can be used, and recovery can be performed in a certain degree of thermal environment. As the cellulose constituting the complex of the present embodiment, regenerated cellulose is preferable because it can be molded into an arbitrary shape as a complex. Of these, regenerated cellulose obtained from a cellulosic solution such as copper ammonia, cadmium, cooxene, nioxene, zincoxene, and EWNN, which are metal complex solvents, is more preferable. These regenerated celluloses have a structure in which the obtained cellulose has voids, and as a result, the molecules can easily access the MOF existing inside the complex, and can be easily used for storage, adsorption, separation, sustained release, and the like. Further, cuprammonium-ray regenerated cellulose is particularly preferable from the viewpoint of ease of molding and control of voids.

The composite of the present embodiment has a MOF loading ratio (ratio) of 4% by weight to 60% by weight after the ultrasonic cleaning operation. If the proportion of MOF is low, functions such as storage, adsorption, separation, and sustained release may be inadequate. If the ratio exceeds 60% by weight, the toughness of the composite becomes low, and handling problems may occur depending on the usage. From the viewpoint of performance, the ratio is preferably 10% by weight or more, more preferably 20% by weight or more, and further preferably 30% by weight or more. From the viewpoint of handling, the ratio is preferably 50% by weight or less, more preferably 40% by weight or less.

For the ultrasonic cleaning operation, a dual frequency switching type ultrasonic cleaning machine containing pure water in a cleaning tank is used, and a glass container containing a solvent and a complex that does not dissolve or decompose MOF is ultrasonically cleaned for 5 minutes. After cleaning, the solvent in the glass container is replaced with a new one, and the operation of cleaning again is performed a total of three times.
The reason for selecting ultrasonic cleaning as the method for cleaning the complex of the present embodiment is that composites of various shapes can be easily cleaned. When performing ultrasonic cleaning, it is necessary to select a solvent that does not decompose MOF. As an example, DMF, ethanol, or the like can be used for ultrasonic cleaning of HKUST-1, which decomposes in the presence of water.

In the complex of the present embodiment, it is preferable that MOF is present in a certain amount inside the cellulose. It is considered that the MOF existing inside is not only less likely to be desorbed, but also contributes to the improvement of the mechanical properties of the complex.

The form of the complex of the present embodiment can be arbitrarily selected depending on the usage. For example, short fibers, long fibers, woven fabrics, knitted fabrics, non-woven fabrics, films, porous membranes, hollow fibers, particles, fine particles and the like can be mentioned. These may be used alone or in combination. It can also be used in combination with another material, or it can be used by incorporating it into some module. Furthermore, the size and shape of the void can be arbitrarily selected according to the intended use. For example, when gas separation is performed, a dense structure can prevent non-selective gas permeation, and when adsorption separation is performed, a sparse structure can be used to increase the specific surface area and increase the adsorption efficiency. can.

Other embodiments of the present invention include the following steps:
Step of preparing a cellulose solution in which cellulose is dissolved as a complex containing metal ions;
A step of forming a structure containing cellulose and metal ions from the cellulose solution; and a step of contacting the obtained structure with an organic ligand solution to obtain a complex containing cellulose and a metal-organic structure. ;
Is a method for producing the complex.
The method for producing the complex of the present embodiment is not particularly limited, and any method can be used. However, a cellulose solution in which cellulose is dissolved as a complex containing metal ions is prepared, and the above-mentioned cellulose solution is prepared. A method of synthesizing MOF inside the cellulose structure by producing a structure containing cellulose and metal ions from the cellulose structure and bringing the structure into contact with an organic ligand solution is preferable. Since the metal ions form a complex with cellulose in advance, the structure obtained by molding from the cellulose solution is in a state where the metal ions are immobilized inside the structure, and when the organic ligand solution is brought into contact with the structure, the MOF Can be precipitated inside the cellulose structure. Since one metal ion can be coordinated to one glucose ring constituting cellulose, many metal ions can be immobilized inside the structure, and a large amount of MOF can be supported. For example, it has been reported that when a cuprammonium solution is used as a solvent, copper ions are coordinated with the hydroxyl groups of C2 and C3. In this method, the structure obtained by molding from the cellulose solution can be treated with the organic ligand solution in a non-coagulated state to simultaneously perform the coagulation of the structure and the synthesis of MOF, or from the cellulose solution. MOF can also be synthesized by first coagulating the structure obtained by molding in a poor solvent such that the coordination between cellulose and metal ions is not broken, and then treating with an organic ligand solution. Further, if necessary, a treatment for cutting the coordination between the cellulose and the metal ion may be performed thereafter. Further, when the complex of the present embodiment is prepared by a method of treating with an organic ligand solution in a state where cellulose forms a complex containing a metal ion, the mechanical properties are surprisingly higher than those of cellulose alone. improves. The exact principle is unknown, but the MOF existing inside the cellulose structure may contribute as a reinforcing material, it may form a hydrogen bond with cellulose and contribute as a cross-linking agent, and the MOF at the time of structure formation. It is possible that the crystal structure of cellulose itself has changed due to the presence of. Improving the mechanical properties of the complex leads to advantages such as improved handling in actual use.

In the method of the present embodiment, the amount of MOF supported can be increased by treating the structure obtained by molding from the cellulose solution with an organic ligand solution in a state where the structure is not solidified. A method in which MOF (or an intermediate thereof) is synthesized at the same time is preferable. On the other hand, in terms of controlling the shape and voids of cellulose, a method of first coagulating the structure with a poor solvent that does not break the bond between cellulose and metal ions and then treating with an organic ligand solution is preferable. Further, the MOF loading ratio can be adjusted by changing the conditions such as the concentration, temperature, and reaction time of the organic ligand solution. Further, for example, when a copper-ammonia solution is used as the solvent for cellulose, the pH becomes alkaline due to the presence of ammonia, so that it may not precipitate depending on the type of MOF. Even in such a case, a method is preferable in which deammonia is performed with a poor solvent such that the bond between cellulose and the metal ion is not broken to solidify the structure, and then the structure is treated with an organic ligand solution. Further, depending on the type of MOF, the reaction may be insufficient or an intermediate may be formed only by treating with an organic ligand solution. In such a case, if necessary, high-pressure treatment, high-temperature treatment, treatment with an acidic solution, treatment with an alkaline solution, ultrasonic treatment, microwave treatment, or the like may be performed.

After synthesizing the MOF inside the cellulose of the present embodiment, a washing treatment can be performed if necessary. If unreacted metal ions or ligands remain in the complex, they can be dissolved and washed with a solvent that does not decompose the synthesized MOF.

The complex of the present embodiment may be used after being dried, if necessary, may be used as it is without being dried, or may be used after being replaced with a solvent. When the synthesized MOF is solvated and has low activity, drying or activation treatment may be required. Further, when it is desired to maintain the void of cellulose, solvent replacement drying can be performed, or the cellulose can be used as it is without drying.

First, the evaluation methods used in the following Examples and Comparative Examples will be described. As an example, the evaluation method of the cellulose-PB complex will be described, but the solvent and container used for cleaning take into consideration the solubility of metal ions and anion species forming the inorganic PCP and the stability of the inorganic PCP. You may choose.

<Measurement of inorganic PCP loading rate of complex>
The complex is dried by heating under reduced pressure at 105 ° C. for one day and night, and the absolute dry weight of the complex is measured. Subsequently, 3% by weight caustic soda and the complex are placed in a container that can be sealed and immersed for 1 hour to decompose and elute the inorganic PCP supported on the complex. Subsequently, the complex is taken out and immersed in 10 wt% sulfuric acid placed in another sealable container for 1 hour to elute the metal ions remaining in the complex. The above dipping treatment in 3% by weight caustic soda and dipping treatment in 10% by weight sulfuric acid are repeated once again. The remaining cellulose structure is collected and washed with pure water. The obtained cellulose structure is dried by heating under reduced pressure at 105 ° C. for 1 hour, and the absolute dry weight of the cellulose structure is measured. The inorganic PCP loading ratio of the complex is calculated from the measured absolute dry weight of the complex and the absolute dry weight of the cellulose structure by the following formula:
Inorganic PCP loading ratio (%) of complex = {(absolute dry weight of complex-absolute weight of cellulose structure) ÷ absolute dry weight of complex} × 100
Calculated by

<Complex cleaning operation>
As an ultrasonic cleaner, an AS ONE ultrasonic cleaner (ASU-6D, dual frequency switching type) is used, and pure water is put into the washing tank. Further, pure water and the composite are put in a glass container that can be sealed, and washed with an ultrasonic cleaner for 5 minutes. After cleaning for 5 minutes, the pure water in the glass container is replaced, and a series of ultrasonic cleaning operations are performed a total of 3 times.

<Measurement of carrier rate when inorganic PCP cannot be decomposed>
If the inorganic PCP cannot be decomposed, the cellulose is dissolved using a solvent that dissolves cellulose such as NMMO but does not decompose the inorganic PCP, and the absolute dry weight of the isolated inorganic PCP is measured and the measured complex. Based on the absolute dry weight of the inorganic PCP and the absolute dry weight of the inorganic PCP, the carrying ratio of the inorganic PCP of the composite is calculated by the following formula:
Inorganic PCP loading ratio (%) of complex = {(absolute dry weight of inorganic PCP) ÷ absolute dry weight of complex} × 100
Calculated by

<Calculation of desorption rate of inorganic PCP before and after cleaning operation>
The desorption rate of the inorganic PCP before and after the cleaning operation is calculated from the inorganic PCP carrying rate of the complex before and after the cleaning operation by the following formula:
Inorganic PCP desorption rate (%) of complex = {(supporting rate before washing-supporting rate after washing) ÷ loading rate before washing} × 100
Calculated by

<Example 1: Preparation of cellulose-PB composite film>
A cotton linter was dissolved in EWNN by a known method to prepare a stock solution having a cellulose concentration of 4.0% by weight, an iron concentration of 1.5% by weight, a tartaric acid concentration of 12.9% by weight, and a sodium hydroxide concentration of 18.7% by weight. .. The stock solution was cast with a film thickness of 300 μm on an 8 cm square glass substrate using an applicator. Subsequently, 50 ml of pure water was placed in a 10 cm square stainless steel container with a lid, and while heating at 40 ° C., the glass substrate was immersed for 10 minutes to solidify. Subsequently, 50 ml of a 2.5 wt% potassium hexacyanoferrate (II) acid aqueous solution was placed in a 10 cm square stainless steel lidded container and immersed for 30 minutes together with the glass substrate while heating at 40 ° C. to form a complex with the hydroxyl group of cellulose. The iron (III) ion and the hexacyanoferrate (II) acid ion were reacted. Subsequently, 50 ml of 2 wt% sulfuric acid was placed in a 10 cm square container with a stainless steel lid, and the glass substrate was immersed for 10 minutes. The film after immersion in sulfuric acid had a deep blue color peculiar to PB. Subsequently, the film is peeled off from the glass substrate, placed in a container with a 10 cm square stainless steel lid together with 50 ml of pure water, and the PB adhering to the surface is washed off by rinsing the film with tweezers, and then 5 in pure water. The sulfuric acid remaining in the membrane was washed off by allowing it to stand for a minute. A series of cleaning operations was repeated until no coloring due to desorption of PB into pure water was observed. The obtained washed film was sandwiched between 5 cm square stainless steel molds and dried by heating under reduced pressure at 50 ° C. for one day and night while suppressing drying shrinkage to obtain a dried film. When analyzed using an X-ray diffraction measuring device (X-ray diffractometer "Mini FlexII" manufactured by Rigaku Co., Ltd.), peaks of both cellulose and PB were confirmed. From the above results, it was confirmed that a cellulose-PB composite film was obtained.

<Example 2: Preparation of cellulose-PB composite film>
A cellulose-PB composite film was prepared in the same manner as in Example 1 except that the coagulating liquid used was not pure water but a 50% by weight aqueous acetone solution.

<Example 3: Preparation of cellulose-PB composite film>
The same method as in Example 1 was used except that the solidification step with pure water was omitted and the cast film was immersed in a 2.5 wt% potassium hexacyanoferrocyanate (II) aqueous solution to perform solidification and reaction at the same time. , Cellulose-PB composite film was prepared.

<Preparation of regenerated cellulose film>
A cotton linter was dissolved in a cuprammonium-rayon solution by a known method to prepare a cuprammonium-rayon cellulose solution having a cellulose concentration of 10% by weight, an ammonia concentration of 7% by weight, and a copper concentration of 3.6% by weight. Using an applicator, it was cast on an 8 cm square glass substrate with a film thickness of 300 μm. Subsequently, 50 ml of pure water was placed in a 10 cm square stainless steel container with a lid, and while heating at 40 ° C., the glass substrate was immersed for 10 minutes to solidify. Subsequently, 50 ml of 2 wt% sulfuric acid was placed in a 10 cm square container with a stainless steel lid, and the glass substrate was immersed for 10 minutes to perform a copper removal treatment. The decoppered film was taken out, placed in a 10 cm square stainless steel container with a lid, and immersed in 50 ml of pure water for 5 minutes to wash off sulfuric acid. The dipping operation in pure water was repeated a total of 3 times until the sulfuric acid was completely washed away. The obtained washed film was sandwiched between 5 cm square stainless steel molds and dried by heating under reduced pressure at 50 ° C. for one day and night while suppressing drying shrinkage to obtain a regenerated cellulose film.

<Comparative Example 1: Preparation of Cellulose-PB Composite Film by Post-Processing>
With reference to Patent Document 2, 50 ml of a 2.5 wt% potassium hexacyanoferrate (II) aqueous solution and a regenerated cellulose film were placed in a sealable glass container, mixed, and allowed to stand for 10 minutes. Subsequently, 50 ml of a 2.0 wt% iron (III) chloride aqueous solution was added, the lid of the container was closed, and the mixture was allowed to stand for 10 minutes. The obtained film was washed with pure water in the same manner as in Example 1, sandwiched between 8 cm square stainless steel molds, and dried under reduced pressure at 50 ° C. for one day and night while suppressing drying shrinkage to obtain a dried film. The obtained film had a deep blue color peculiar to PB.

<Comparative Example 2: Preparation of Cellulose-PB Composite Film by Post-Processing>
With reference to Patent Document 3, PB particles were synthesized by reacting potassium hexacyanoferrate (II) with iron (III) chloride in advance, and the particles were dispersed in pure water, applied to a regenerated cellulose film, and dried. A dried film was obtained in the same manner as in Comparative Example 1. The obtained film had a deep blue color peculiar to PB.

<Evaluation of physical properties of cellulose-PB composite film>
The carrying ratio of PB was measured using a part of the cellulose-PB composite films obtained in Examples 1 to 3 and Comparative Examples 1 and 2. Subsequently, a cleaning operation was performed, the loading rate of PB after cleaning was measured, and the desorption rate of PB before and after the cleaning operation was calculated. The results are shown in Tables 1 and 2 below.

As is clear from Table 1, the complexes obtained in Examples 1 to 3 had a high carrying rate of PB, and further, it was difficult for PB to be detached by a washing operation. On the other hand, as is clear from Table 2, the complex obtained by a method other than the present embodiment has a low carrying rate of PB and is likely to be detached by a washing operation. Further, when each film and the regenerated cellulose film not supporting PB were pulled and the handling was confirmed, the films obtained in Comparative Examples 1 and 2 broke with the same force as the regenerated cellulose film. On the other hand, the films obtained in Examples 1 to 3 were more difficult to break than the regenerated cellulose film.

_{<Example 4: Evaluation of NH 4} ⁺ ion adsorption performance in liquid of cellulose-PB composite film>
Ammonium chloride was dissolved in pure water to prepare an aqueous solution _{having an NH 4} ^{+ concentration of 200 ppm.} Subsequently the cellulose produced in Example 1 and -PB composite film 0.5g of (bone dry weight) was immersed in an aqueous solution 50 mL, it was adsorbed NH ₄ ⁺ and 24h standing at room temperature. The NH ₄ ⁺ concentration in the residual liquid was taken out of the film was measured by formalin method described in JIS K1441. The evaluation results are shown in Table 3 below.

As is clear from Table 3, the cellulose-PB composite film obtained in Example 1 _{showed NH 4} ⁺ adsorption performance.

<Example 5: Preparation of cellulose-PBA (Cu, Fe) composite film>
A cellulose-PBA (Cu, Fe) composite film was prepared in the same manner as in Example 1 except that a cellulose copper-aluminum solution was used as the cellulose solution. The film was green when reacted with an aqueous solution of potassium hexacyanoferrate (II), but when treated with 2% sulfuric acid, it became reddish brown peculiar to PBA (Cu, Fe). When analyzed using an X-ray analyzer, peaks of both cellulose and PBA (Cu, Fe) as shown in FIG. 1 were confirmed. Subsequently, the surface and cross section of the film obtained in Example 5 were observed by SEM and TEM, respectively. The photographs are shown in FIGS. 2 and 3.

<Example 6: Preparation of cellulose-PBA (Cu, Fe) composite film>
The coagulation liquid to be used was not pure water but a 2% by weight caustic soda aqueous solution, and after coagulation, the cellulose was immersed in 50 ml of pure water for 5 minutes to replace the pure water three times in the same manner as in Example 5. -PBA (Cu, Fe) composite film was prepared. The obtained film was reddish brown peculiar to PBA (Cu, Fe). When analyzed using an X-ray analyzer, peaks of both cellulose and PBA (Cu, Fe) were confirmed.

<Example 7: Preparation of cellulose-PBA (Cu, Fe) composite film>
A cellulose-PBA (Cu, Fe) composite film was prepared in the same manner as in Example 3 except that a cellulose copper-aluminum solution was used as the cellulose solution. The obtained film was reddish brown peculiar to PBA (Cu, Fe). When analyzed using an X-ray analyzer, peaks of both cellulose and PBA (Cu, Fe) were confirmed.

<Example 8: Preparation of cellulose-PBA (Zn, Fe) composite film>
Cellulose-PBA was used in the same manner as in Example 1 except that a zincoxene solution was used as a solution for dissolving the cotton linter and the cellulose concentration was 7% by weight, the zinc concentration was 4.5% by weight, and the ethylenediamine concentration was 13.5% by weight. A (Zn, Fe) composite film was prepared. The resulting film was white. When analyzed using an X-ray analyzer, peaks of both cellulose and PBA (Zn, Fe) were confirmed.

<Example 9: Preparation of cellulose-PBA (Cu, Co) composite film>
Cellulose-PBA (Cu, Co) A composite film was prepared. When analyzed using an X-ray analyzer, peaks of both cellulose and PBA (Cu, Co) were confirmed.

<Evaluation of physical properties of cellulose-PBA composite film>
The physical properties of the cellulose-PBA composite film obtained in Examples 5 to 9 were evaluated. The results are shown in Table 4 below.

As is clear from Table 4, in the methods of Examples 5 to 9, complexes carrying various PBAs could be obtained by changing the combination of the metal ion and the hexacyanometallic acid ion of the cellulose solution.

<Example 10: Preparation of cellulose-PBA (Cu, Fe) composite long fibers>
A gel-like long fiber containing cellulose and copper was obtained by flow-down tension spinning of a cellulose-copper-ammonia solution with pure water by a conventionally known method. Subsequently, 50 ml of a 2.5 wt% potassium hexacyanoferrate (II) acid aqueous solution was placed in a 10 cm square container with a stainless steel lid, and the long fibers were immersed for 30 minutes while heating at 40 ° C. to form a complex with the hydroxyl group of cellulose. The copper ion and hexacyanoferrate (II) acid ion were reacted. Subsequently, the long fibers were taken out, placed in a 10 cm square stainless steel lidded container containing 50 ml of 2 wt% sulfuric acid, and immersed for 10 minutes. Subsequently, the long fibers are taken out, placed in a 10 cm square stainless steel lidded container together with 50 ml of pure water, shaken to wash off PBA (Cu, Fe) adhering to the surface, and then immersed in pure water for 5 minutes. The unreacted hexacyanoferrate (II) acid ion and sulfuric acid were washed off by allowing to stand. A series of cleaning operations was repeated until no coloring due to desorption of PBA (Cu, Fe) into pure water was observed. The obtained washed long fibers were wound around a 5 cm square stainless steel mold and dried by heating under reduced pressure at 50 ° C. for one day and night while suppressing drying shrinkage to obtain dried long fibers.

<Example 11: Preparation of cellulose-PBA (Cu, Fe) composite knitted fabric>
The long fibers obtained in Example 10 were used for tubular knitting with a tubular knitting machine to obtain a cellulose-PBA (Cu, Fe) composite knitted fabric.

<Example 12: Preparation of cellulose-PBA (Cu, Fe) composite hollow fiber>
Using a conventionally known method, a cellulose copper ammonia solution is used as an external solution, a 2% by weight caustic soda solution is used as an internal solution, and the hollow fiber is spun by discharging it into a bath of a 2% by weight caustic soda solution. Cellulose-PBA (Cu, Fe) composite hollow fiber in the same manner as in Example 6 except that 2.5 g of the obtained hollow fiber was immersed in 50 ml of pure water for 5 minutes to replace the pure water three times. Was prepared.

<Example 13: Preparation of cellulose-PBA (Cu, Fe) composite long fiber non-woven fabric>
A cellulose-PBA (Cu, Fe) composite long fiber non-woven fabric was prepared in the same procedure as in Example 10 except that wet spunbond spinning of a cellulose copper ammonia solution was carried out by a conventionally known method.

<Example 14: Preparation of cellulose-PBA (Cu, Fe) composite particles>
Cellulose Copper Ammonia solution was diluted to adjust the viscosity to 60 mPa · s, spray-dried by a conventionally known method, and centrifuged for particle recovery after reaction and washing to contain cellulose and copper. Particles were made. Subsequently, 50 ml of a 2.5 wt% potassium hexacyanoferrate (II) acid aqueous solution was placed in a 10 cm square container with a stainless steel lid, and 0.5 g of the particles was immersed for 30 minutes while heating at 40 ° C. to form a complex with the hydroxyl group of cellulose. The copper ion and hexacyanoferrate (II) acid ion were reacted. After the reaction, the particles were collected by centrifugation and placed in a 10 cm square stainless steel lidded container containing 50 ml of 2 wt% sulfuric acid and immersed for 10 minutes. Subsequently, the particles are collected by centrifugation, placed in a centrifugation tube together with 50 ml of pure water, shaken to wash off PBA (Cu, Fe) adhering to the surface, and then allowed to stand in pure water for 5 minutes. By doing so, unreacted hexacyanoferrate (II) acid ions and sulfuric acid were washed away. A series of cleaning operations was repeated until no coloring due to desorption of PBA (Cu, Fe) into pure water was observed. The washed particles were collected by centrifugation and dried under reduced pressure at 50 ° C. for one day and night to obtain dried particles.

<Example 15: Preparation of cellulose-PBA (Cu, Fe) composite fine particles>
The cellulose copper ammonia solution was diluted to adjust the cellulose concentration to 0.37% by weight, the cellulose copper ammonia solution was coagulated with a 27% by weight aqueous acetone solution, and 2.5 g of particles recovered by centrifugation after coagulation. Cellulose-PBA (Cu, Fe) composite fine particles were prepared in the same manner as in Example 14 except that the mixture was immersed in 50 mL of pure water for 10 minutes to replace the pure water.

<Evaluation of physical properties of cellulose-PBA (Cu, Fe) complexes with different shapes>
The complexes obtained in Examples 10 to 15 were all reddish brown peculiar to PBA (Cu, Fe). Moreover, the physical characteristics were evaluated in the same manner as the composite film. The results are shown in Table 5 below.

As is clear from Table 5, the complex obtained by the method of this embodiment could be prepared into any shape.

<Comparative Example 3: Preparation of Cellulose-PB Composite Long Fiber by Post-Processing>
Cellulose-PB composite long fibers were prepared in the same manner as in Comparative Example 1 using regenerated cellulose long fibers obtained from a cellulose copper ammonia solution. The PB-supporting ratio of the obtained composite long fibers was 8.7% by weight, and the PB-supporting ratio after ultrasonic cleaning was 3.4% by weight.

<Example 16: Preparation of cellulose-PBA (Cu, Fe) composite film>
Cellulose-PBA (Cu, Fe) composite in the same manner as in Example 5 except that the composition of the cellulose copper ammonia solution was 10% by weight of cellulose, 8% by weight of ammonia concentration, and 4.3% by weight of copper concentration. A film was prepared.

<Example 17: Preparation of cellulose-PBA (Cu, Fe) composite film>
A cellulose-PBA (Cu, Fe) composite film was prepared in the same manner as in Example 5 except that the potassium hexacyanoferrate (II) concentration in the reaction solution was 1.0% by weight.

<Example 18: Preparation of cellulose-PBA (Cu, Fe) composite film>
A cellulose-PBA (Cu, Fe) composite film was prepared in the same manner as in Example 5 except that the potassium hexacyanoferrate (II) concentration in the reaction solution was 0.5% by weight.

<Example 19: Preparation of cellulose-PBA (Cu, Fe) composite film>
A cellulose-PBA (Cu, Fe) composite film was prepared in the same manner as in Example 5 except that the potassium hexacyanoferrate (II) concentration in the reaction solution was 0.1% by weight.

<Example 20: Preparation of cellulose-PBA (Cu, Fe) composite film>
A cellulose-PBA (Cu, Fe) composite film was prepared in the same manner as in Example 5 except that the film was air-dried instead of solidifying with pure water after casting.

<Evaluation of physical properties of cellulose-PBA (Cu, Fe) composite film>
The complexes obtained in Examples 16 to 20 were all reddish brown peculiar to PBA (Cu, Fe). Table 6 below shows the results of evaluating the physical characteristics of the complex film.

As is clear from Table 6, in Examples 16 to 20, the amount of PBA carried is controlled by adjusting the metal ion concentration in the cellulose solution, the hexacyanometallic acid ion concentration in the reaction solution, the coagulation method, and the like. I was able to.

First, the evaluation methods used in the following Examples and Comparative Examples will be described. As an example, the evaluation method when the MOF is HKUST-1 will be described, but the solvent and container used for cleaning take into consideration the solubility of the metal ions and ligands forming the MOF and the stability of the MOF. You may choose.

<Measurement of MOF loading rate of complex>
The complex is vacuum dried under reduced pressure at 105 ° C. for one day and night, and the absolute dry weight of the complex is measured. Subsequently, 10 wt% sulfuric acid and the complex are placed in a container that can be sealed and immersed for 1 hour to decompose the MOF supported on the complex. The remaining cellulose structure is collected and washed with pure water. This washing process of 10 wt% sulfuric acid and pure water is repeated once again. The obtained cellulose structure is vacuum dried under reduced pressure at 105 ° C. for 1 hour, and the absolute dry weight of the cellulose structure is measured. The MOF loading ratio of the complex is calculated from the measured absolute dry weight of the complex and the absolute dry weight of the cellulose structure by the following formula:
MOF loading ratio (%) of complex = {(absolute weight of complex-absolute weight of cellulose structure) ÷ absolute dry weight of complex} × 100
Calculated by

<Complex cleaning operation>
As an ultrasonic cleaner, an AS ONE ultrasonic cleaner (ASU-6D, dual frequency switching type) is used, and pure water is put into the washing tank. Further, put ethanol and the composite in a glass container that can be sealed, and wash with an ultrasonic cleaner for 5 minutes. After washing for 5 minutes, the ethanol in the container is replaced, and a series of ultrasonic cleaning operations are performed a total of 3 times.

<Measurement of MOF loading rate of complex after ultrasonic cleaning when MOF cannot be decomposed>
If the MOF cannot be decomposed, dissolve the cellulose using a solvent that dissolves cellulose such as NMMO but does not decompose the MOF, isolate the MOF, measure the absolute dry weight, and measure the absolute dry weight of the complex and the MOF. From the absolute dry weight, the MOF carrying ratio of the complex is calculated by the following formula:
MOF loading ratio (%) of complex = {(absolute weight of MOF) ÷ absolute dry weight of complex} × 100
Calculated by

<Calculation of MOF detachment rate before and after cleaning operation>
The MOF desorption rate before and after the cleaning operation is calculated from the support rate of the complex before and after the cleaning operation by the following formula:
MOF desorption rate (%) = {(supporting rate before cleaning-supporting rate after cleaning) ÷ loading rate before cleaning} x 100
Calculated by

<Example 1: Preparation of cellulose-HKUST-1 composite film>
A cotton linter was dissolved in a cuprammonium-rayon solution by a known method to prepare a cuprammonium-rayon cellulose solution having a cellulose concentration of 10% by weight, an ammonia concentration of 7% by weight, and a copper concentration of 3.6% by weight. Using an applicator, it was cast on an 8 cm square glass substrate with a film thickness of 300 μm. Subsequently, 50 ml of pure water was placed in a 10 cm square stainless steel container with a lid, and while heating at 40 ° C., the glass substrate was immersed for 10 minutes to solidify. Subsequently, 50 ml of DMF was placed in a 10 cm square stainless steel lidded container, and while heating at 40 ° C., the glass substrate was immersed for 10 minutes to perform DMF substitution. Subsequently, 50 ml of a DMF solution having a trimesic acid concentration of 5.0% by weight was placed in a 10 cm square container with a stainless steel lid, and while heating at 40 ° C., the glass substrate was immersed for 30 minutes to form a complex with the hydroxyl group of cellulose. The ion was reacted with trimesic acid. After the reaction, peel off the film from the glass substrate, put it in a container with a 10 cm square stainless steel lid together with 50 ml of ethanol, pinch the film with tweezers to wash off HKUST-1 adhering to the surface, and then put 5 in ethanol. The unreacted trimesic acid was washed off by allowing it to stand for a minute. A series of washing operations was repeated until no coloration due to HKUST-1 desorption into ethanol was observed. The obtained washed film was sandwiched between 5 cm square stainless steel molds and dried by heating under reduced pressure at 50 ° C. for one day and night while suppressing drying shrinkage to obtain a dried film. The obtained film had a blue color peculiar to HKUST-1. When analyzed using an X-ray diffraction measuring device (X-ray diffractometer "Mini FlexII" manufactured by Rigaku Co., Ltd.), peaks of both cellulose and HKUST-1 as shown in FIG. 1 were confirmed. From the above results, it was confirmed that a cellulose-HKUST-1 composite film was obtained.

<Example 2: Preparation of cellulose-HKUST-1 composite film>
A cellulose-HKUST-1 composite film was prepared in the same manner as in Example 1 except that the coagulating liquid used was not pure water but a 50% by weight aqueous acetone solution.

<Example 3: Preparation of cellulose-HKUST-1 composite film>
The coagulation liquid used was not pure water but a 2% by weight caustic soda aqueous solution, and after coagulation, it was immersed in 50 ml of pure water for 5 minutes to replace the pure water three times, and then DMF replacement was performed. A cellulose-HKUST-1 composite film was prepared in a similar manner.

<Preparation of regenerated cellulose film>
A regenerated cellulose film was prepared in the same manner as in Example 1 except that a DMF solution having a trimesic acid concentration of 5.0% by weight was not used and a 10% by weight aqueous sulfuric acid solution was used.

<Comparative Example 1: Preparation of Cellulose-HKUST-1 Composite Film by Post-Processing>
A cellulose-HKUST-1 composite film was prepared with reference to Patent Document 2. 50 ml of a 50 vol% ethanol aqueous solution having a trimesic acid concentration of 5.0% by weight and a regenerated cellulose film were placed in a sealable glass container, mixed, and allowed to stand for 10 minutes. Subsequently, 50 ml of a 50 vol% ethanol aqueous solution having a copper (II) nitrate trihydrate concentration of 3.7% by weight was added, the lid of the container was closed, and the mixture was heated to 105 ° C. for 60 minutes. The obtained film was washed with ethanol in the same manner as in Example 1, sandwiched between 8 cm square stainless steel molds, and vacuum dried under reduced pressure at 50 ° C. for one day and night while suppressing drying shrinkage to obtain a dried film. The obtained film had a blue color peculiar to HKUST-1.

<Comparative Example 2: Preparation of Cellulose-HKUST-1 Composite Film by Post-Processing>
With reference to Patent Document 3, except that trimesic acid and copper (II) nitrate trihydrate were first reacted to synthesize HKUST-1 particles, which were then dispersed in DMF and applied to a regenerated cellulose film and dried. , A dried film was obtained in the same manner as in Comparative Example 1. The obtained film had a blue color peculiar to HKUST-1.

<Evaluation of physical properties of cellulose-HKUST-1 composite film>
The carrier ratio of HKUST-1 was measured using a part of the cellulose-HKUST-1 composite films obtained in Examples 1 to 3 and Comparative Examples 1 and 2. Subsequently, a cleaning operation was performed, the loading rate of HKUST-1 after cleaning was measured, and the desorption rate of HKUST-1 before and after the cleaning operation was calculated. The results are shown in Tables 7 and 8 below.

As is clear from Table 7, the complexes obtained in Examples 1 to 3 had a high loading rate of MOF, and further, it was difficult for MOF to be detached by a washing operation. On the other hand, as is clear from Table 8, the complexes obtained by methods other than the present embodiment had a low MOF loading ratio at the time before washing, and were more likely to be detached by the washing operation. Subsequently, the surface and cross section of the film obtained in Example 1 were observed by SEM and TEM, respectively. The photographs are shown in FIGS. 2 and 3. It can be said that the complex obtained in Example 1 is difficult to detach because the MOF is also supported inside, whereas the complex obtained in Comparative Example is easy to detach MOF. Further, when each film and the regenerated cellulose film not supporting MOF were pulled and the handling was confirmed, the films obtained in Comparative Examples 1 and 2 broke with the same force as the regenerated cellulose film. On the other hand, the films obtained in Examples 1 to 3 were more difficult to break than the regenerated cellulose film.

<Example 4: Preparation of cellulose-HKUST-1 composite long fiber>
A gel-like long fiber containing cellulose and copper was obtained by flow-down tension spinning of a cellulose-copper-ammonia solution with pure water by a conventionally known method. Subsequently, 50 ml of DMF was placed in a 10 cm square stainless steel container with a lid, heated to 40 ° C., and 2.5 g of long fibers was immersed for 10 minutes to perform DMF substitution. Subsequently, 50 ml of a DMF solution having a trimesic acid concentration of 5.0% by weight was placed in a 10 cm square container with a stainless steel lid, and while heating at 40 ° C., the DMF-substituted long fibers were immersed for 30 minutes to form a complex with the hydroxyl group of cellulose. The copper ion was reacted with trimesic acid. After the reaction, the long fibers are taken out, placed in a 10 cm square stainless steel lidded container with 50 ml of ethanol, shaken to wash off HKUST-1 adhering to the surface, and then allowed to stand in ethanol for 5 minutes. The unreacted trimesic acid was washed off. A series of washing operations was repeated until no coloration due to HKUST-1 desorption into ethanol was observed. The obtained washed long fibers were wound around a 5 cm square stainless steel mold and dried by heating under reduced pressure at 50 ° C. for one day and night while suppressing drying shrinkage to obtain dried long fibers. The obtained long fibers had a blue color peculiar to HKUST-1.

<Example 5: Preparation of cellulose-HKUST-1 composite knitted fabric>
The long fibers obtained in Example 4 were used for tubular knitting with a tubular knitting machine to obtain a cellulose-HKUST-1 composite knitted fabric.

<Example 6: Preparation of cellulose-HKUST-1 composite hollow fiber>
Using a double concentric spun, a cellulose copper ammonia solution is used as an external solution, a 2% by weight caustic soda solution is used as an internal solution, and the hollow fiber is spun by discharging it into a bath of 2% by weight caustic soda solution. A cellulose-HKUST-1 composite hollow fiber was prepared in the same manner as in Example 4 except that 2.5 g of the obtained hollow fiber was immersed in 50 ml of pure water for 5 minutes to replace the pure water three times. did.

<Example 7: Preparation of cellulose-HKUST-1 composite long fiber non-woven fabric>
A cellulose-HKUST-1 composite long-fiber non-woven fabric as shown in FIG. 4 was prepared in the same procedure as in Example 4 except that wet spunbond spinning of a cellulose copper-ammonia solution was performed by a conventionally known method.

<Example 8: Preparation of cellulose-HKUST-1 composite particles>
Cellulose Copper Ammonia solution was diluted to adjust the viscosity to 60 mPa · s, and spray-dried by a conventionally known method to prepare particles containing cellulose and copper. Subsequently, 50 ml of a DMF solution having a trimesic acid concentration of 5.0% by weight was placed in a 10 cm square container with a stainless steel lid, and 0.5 g of particles were immersed for 30 minutes while heating at 40 ° C. to form a complex with a hydroxyl group of cellulose. The copper ion was reacted with trimesic acid. After the reaction, the particles are collected by centrifugation, placed in a centrifuge tube together with 50 ml of ethanol, shaken to wash off HKUST-1 adhering to the surface, and then allowed to stand in ethanol for 5 minutes to unreact. Trimesic acid was washed off. A series of washing operations was repeated until no coloration due to HKUST-1 desorption into ethanol was observed. The washed particles were collected by centrifugation and dried under reduced pressure at 50 ° C. for one day and night to obtain dried particles. The obtained particles had a blue color peculiar to HKUST-1.

<Example 9: Preparation of cellulose-HKUST-1 composite fine particles>
The cellulose copper ammonia solution was diluted to adjust the cellulose concentration to 0.37% by weight, the cellulose copper ammonia solution was put into a 27% by weight aqueous acetone solution to coagulate, and the particles recovered by centrifugation after coagulation. Cellulose-HKUST-1 composite fine particles were prepared in the same manner as in Example 8 except that 2.5 g was immersed in 50 mL of DMF heated to 40 ° C. for 10 minutes to replace DMF.

<Comparative Example 3: Preparation of Cellulose-HKUST-1 Composite Long Fiber by Post-Processing>
Cellulose-HKUST-1 composite long fibers were prepared using the regenerated cellulose long fibers obtained from the cuprammonium-rayon solution in the same manner as in Comparative Example 1. The HKUST-1 supporting ratio of the obtained composite long fibers was 8.1% by weight, and the HKUST-1 supporting ratio after ultrasonic cleaning was 2.6% by weight.

<Evaluation of physical properties of cellulose-HKUST-1 complex with different shape>
The complexes obtained in Examples 4 to 9 and Comparative Example 3 were all blue, which is peculiar to HKUST-1. Moreover, the physical characteristics were evaluated in the same manner as the composite film. The results are shown in Table 9 below.

As is clear from Table 9, the complex obtained by the method of this embodiment could be prepared into any shape.

<Evaluation of Ammonia Gas Adsorption Performance of Cellulose-HKUST-1 Composite Long Fiber>
The cellulose-HKUST-1 composite long fibers obtained in Example 4 were packed in a commercially available glass calcium tube, and both ends were sealed with absorbent cotton. A 0.5% by weight aqueous ammonia solution was placed in a commercially available glass beaker, and a calcium tube filled with cellulose-HKUST-1 composite long fibers was connected. Similarly, a calcium tube filled with the cellulose-HKUST-1 composite long fibers obtained in Comparative Example 3 was prepared. Ammonia gas concentration was measured using a commercially available gas sampler and a gas detector tube for ammonia in the open part of the calcium tube. When the calcium tube was not filled with cellulose-HKUST-1 composite long fibers, the ammonia concentration was 140 ppm, whereas when the composite long fibers obtained in Example 4 were packed, the ammonia concentration was below the detection limit ( (10 ppm or less), the ammonia concentration was 20 ppm when the composite long fibers obtained in Comparative Example 3 were packed. From the above results, it can be said that the complex of the present invention not only has the performance due to the high loading ratio of MOF, but also is easy to handle, and the shape can be selected according to various uses.

<Example 10: Preparation of cellulose-HKUST-1 composite film>
A cellulose-HKUST-1 composite film was prepared in the same manner as in Example 1 except that the composition of the cellulose-copper-ammonia solution was 10% by weight of cellulose, 8% by weight of ammonia, and 4.3% by weight of copper. did.

<Example 11: Preparation of cellulose-HKUST-1 composite film>
A cellulose-HKUST-1 composite film was prepared in the same procedure as in Example 1 except that the cellulose-copper-ammonia solution used in Example 10 was used and air-dried instead of solidifying with pure water.

<Evaluation of physical properties of cellulose-HKUST-1 composite film>
The physical properties of the cellulose-HKUST-1 composite films obtained in Examples 10 and 11 were evaluated. The results are shown in Table 10 below.

As is clear from Table 10, in the methods of Examples 10 and 11, the amount of MOF supported could be controlled by adjusting the amount of metal ions and the method of solidification.

<Example 12: Preparation of cellulose-MOF-2 composite film>
A cellulose-MOF-2 composite film was obtained in the same manner as in Example 1 except that the solution to be reacted after coagulation was a DMF solution having a terephthalic acid concentration of 4.0% by weight. The obtained film was light blue, and when analyzed using an X-ray analyzer, peaks of both cellulose and MOF-2 were confirmed. A cross-sectional TEM image of the cellulose-MOF-2 composite film is shown in FIG.

<Example 13: Preparation of cellulose-MOF-5 composite film>
A zincoxene solution is used as a solution for dissolving the cotton linter, the cellulose concentration is 7% by weight, the zinc concentration is 4.5% by weight, the ethylenediamine concentration is 13.5% by weight, and the solution to be reacted after coagulation is a terephthalic acid concentration of 4.0% by weight. A cellulose-MOF-5 composite film was obtained in the same manner as in Example 1 except that it was prepared as a DMF solution. The obtained film was white, and when analyzed using an X-ray analyzer, peaks of both cellulose and MOF-5 were confirmed.

<Example 14: Preparation of cellulose-ZIF-8 composite film>
A cellulose-ZIF-8 composite film was obtained in the same manner as in Example 18 except that the solution to be reacted after coagulation was a 50 vol% ethanol aqueous solution having a 2-methylimidazole concentration of 2.1%. The obtained film was white, and when analyzed using an X-ray analyzer, peaks of both cellulose and ZIF-8 were confirmed.

<Example 15: Preparation of cellulose-MIL-53 (Fe) composite film>
Using EWNN as a solution to dissolve the cotton linter, the cellulose concentration was 4.0% by weight, the iron concentration was 1.5% by weight, the tartrate acid concentration was 12.9% by weight, and the sodium hydroxide concentration was 18.7% by weight. Cellulose-MIL-53 in the same manner as in Example 1 except that the solution to be reacted after coagulation was a DMF solution having a terephthalic acid concentration of 4.0% by weight by performing DMF substitution after performing the washing operation according to 3 times. A (Fe) composite film was obtained. The obtained film was yellow, and when analyzed using an X-ray analyzer, peaks of both cellulose and MIL-53 (Fe) were confirmed.

<Cellulose-Performance evaluation of various MOF composite films>
The physical properties of the composite films obtained in Examples 12 to 15 were evaluated. The results are shown in Table 11 below.

As is clear from Table 11, the methods of Examples 12-15 were able to combine various metal ions and ligands.

The complex of the present invention is used for gas storage such as hydrogen storage, gas separation for the purpose of suppressing carbon dioxide emissions, a filter for removing chemical impurities in gas or liquid, and addition as a reaction field for polymer synthesis. Agents, catalysts that control reactions, adsorption separation that separates target substances from gases and liquids, recovery of valuable resources from liquids, dialysis membranes that remove waste products from blood, sustained release of substances trapped in voids It can be used as a sustained-release agent, an interior material for buildings and automobiles having deodorant, humidity control, and antibacterial properties, an ion conductive material, an electrode / separator for a secondary battery, an electrochromic material, and the like.

The complex of the present invention is used for gas storage such as hydrogen storage, gas separation for the purpose of suppressing carbon dioxide emissions, a filter for removing chemical impurities in gas or liquid, and addition as a reaction field for polymer synthesis. Agents, catalysts that control reactions, adsorption separation that separates target substances from gases and liquids, recovery of valuable resources from liquids, dialysis membranes that remove waste products from blood, sustained release of substances trapped in voids For sustained-release agents, interior materials for buildings and automobiles with deodorant, humidity control, and antibacterial properties, scaffolding materials using the crystalline sponge method, ion conductive materials, electrodes / separators for secondary batteries, electrochromic materials, etc. Can be used.

Claims (13)

A composite containing cellulose and an inorganic porous coordination polymer, wherein the carrying ratio of the inorganic porous coordination polymer after the ultrasonic cleaning operation of the composite is 4% by weight to 60% by weight. Complex. The ultrasonic cleaning operation uses a dual-frequency switching ultrasonic cleaning machine in which pure water is placed in the cleaning tank, and the following operations are performed:
(1) A glass container containing a solvent and a composite that does not dissolve or decompose the inorganic porous coordination polymer is placed in an ultrasonic cleaner for 5 minutes.
(2) Replace the solvent in the glass container.
The complex according to claim 1, wherein the operation is performed three times in total. The complex according to claim 1 or 2, wherein the inorganic porous coordination polymer is a Prussian blue analog. The complex according to any one of claims 1 to 3, wherein the cellulose is regenerated cellulose. The composite according to any one of claims 1 to 4, which has the shape of any of short fibers, long fibers, woven fabrics, knitted fabrics, non-woven fabrics, films, porous membranes, hollow fibers, particles, or fine particles. The following steps:
Step of preparing a cellulose solution in which cellulose is dissolved as a complex containing metal ions;
A step of molding a structure containing cellulose and metal ions from the cellulose solution; and a solution containing an anion species that reacts the obtained structure with the metal ions to form an inorganic porous coordination polymer. , A step of contacting to obtain a complex containing cellulose and an inorganic porous coordination polymer;
The method for producing a complex according to any one of claims 1 to 5, which comprises. The method according to claim 6, wherein the metal ion is any one of copper, zinc, calcium, cadmium, cobalt, nickel, iron, palladium, magnesium, or a combination thereof. A complex containing cellulose and a metal-organic framework, wherein the support ratio of the metal-organic structure after the ultrasonic cleaning operation of the complex is 4% by weight to 60% by weight. The ultrasonic cleaning operation uses a dual-frequency switching ultrasonic cleaning machine in which pure water is placed in the cleaning tank, and the following operations are performed:
(1) A glass container containing the solvent that does not dissolve or decompose the metal-organic framework and the complex is placed in an ultrasonic cleaner for 5 minutes.
(2) Replace the solvent in the glass container.
The complex according to claim 8, wherein the operation is performed three times in total. The complex according to claim 8 or 9, wherein the cellulose is regenerated cellulose. The composite according to any one of claims 8 to 10, which has the shape of any of short fibers, long fibers, woven fabrics, knitted fabrics, non-woven fabrics, films, porous membranes, hollow fibers, particles, or fine particles. The following steps:
A step of preparing a cellulose solution in which cellulose is dissolved as a complex containing metal ions; a step of forming a structure containing cellulose and metal ions from the cellulose solution; and a step of obtaining the obtained structure as an organic ligand. The step of contacting with a solution to obtain a complex containing cellulose and a metallic organic structure;
The method for producing a complex according to any one of claims 8 to 11, which comprises. The method according to claim 12, wherein the metal ion is any one of copper, zinc, calcium, cadmium, cobalt, nickel, iron, palladium, magnesium, or a combination thereof.

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