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WO2020022524A1 - Procédé de production de monolithe de cellulose, et monolithe de cellulose obtenu par ledit procédé de production - Google Patents

Procédé de production de monolithe de cellulose, et monolithe de cellulose obtenu par ledit procédé de production Download PDF

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Publication number
WO2020022524A1
WO2020022524A1 PCT/JP2019/030107 JP2019030107W WO2020022524A1 WO 2020022524 A1 WO2020022524 A1 WO 2020022524A1 JP 2019030107 W JP2019030107 W JP 2019030107W WO 2020022524 A1 WO2020022524 A1 WO 2020022524A1
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Prior art keywords
cellulose
monolith
water
solution
particles
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English (en)
Japanese (ja)
Inventor
信幸 原田
潤一 中村
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to JP2020532528A priority Critical patent/JP7223006B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum

Definitions

  • the present invention relates to a novel method for producing a cellulose monolith and a cellulose monolith obtained by the method.
  • Cellulose is one of the materials that have attracted attention as a resource.
  • Cellulose is a polymer material produced by living organisms with the highest production on the earth, and is a renewable polymer resource.
  • Cellulose is a compound that is hydrophilic and chemically and physically stable, and it is possible to add various functional groups to its surface by modification.
  • As one of the methods for utilizing cellulose many attempts have been made to increase the specific surface area while utilizing the properties of cellulose. One of them is to convert cellulose into a monolith, utilize its high specific surface area matrix, apply it to adsorbents, immobilize enzymes, and use it as a catalyst carrier.
  • the monolith in the present invention is a block of a porous body having a skeleton and a void each continuously, and has a high porosity (for example, the ratio of voids is 20% by volume or more) and a specific surface area (for example, 10 m 2 / g or more).
  • the monolith is a material having characteristics such as high air permeability, high liquid permeability, high strength, and light weight.
  • the cellulose monolith refers to a monolith having a skeleton forming the monolith (for example, 90% by mass or more of the skeleton) made of a cellulose material.
  • a method for producing a cellulose monolith containing porous spherical cellulose for example, (1) a method of dropping a cellulose acetate solution described in Non-Patent Documents 1 and 2 and Patent Documents 1 to 4 into an aqueous medium, followed by deacetylation, (2) a method of dropping a cellulose acetate solution to which water, an acid and / or an alkali have been added in advance into an aqueous medium, described in Non-Patent Document 3, Patent Documents 5 to 7, etc.
  • Patent Document 21 discloses a porous cellulose medium obtained by mixing a cellulose acetate solution, a deacetylating agent, and a catalyst at a low temperature. However, gelation of the medium itself is caused by deacetylation. Yes, a catalyst is required for that. In addition, in order to obtain particles in this method, there is a problem that a dispersion medium such as a surfactant or liquid paraffin is required, and the process becomes complicated.
  • a dispersion medium such as a surfactant or liquid paraffin
  • JP-A-57-38801 WO2016 / 159334 WO2016 / 012368 JP-A-63-83144 JP-B-63-62252 JP 2003-326145 A JP-A-2-84401 JP-A-9-132601 JP-A-6-145202 WO2015 / 029790 JP 2001-323095 A JP 2011-214003 A JP 2012-87202 A JP 2011-209221 A JP-A-2006-153449 JP 2012-206063 A WO2017 / 195888
  • the present invention has been made in view of the above circumstances, and provides an epoch-making production method in which a cellulose monolith having an arbitrary shape can be produced in one step from cellulose acylate. That is, in the method for producing a cellulose monolith of the present invention, the following inventions are provided. (1) The cellulose acylate solution is brought into contact with a medium containing water and a deacylating agent, and is deacylated while exchanging solvent with water, or the cellulose formate solution is mixed with water and a deformylating agent.
  • a method for producing a cellulose monolith which comprises contacting a medium containing a solvent with a solvent and exchanging the solvent with water to formylate.
  • the cellulose acylate solution is dropped into a medium containing water and a deacylating agent with stirring, and deacylation is performed while exchanging water with a solvent to obtain cellulose monolith particles.
  • a method for producing cellulose monolith characterized by dropping into a medium containing water and a deformylating agent under stirring, and performing deformylation while exchanging solvent with water to obtain cellulose monolith particles.
  • the molded cellulose acylate solution is brought into contact with a medium containing water and a deacylating agent and deacylated while exchanging solvent with water to obtain a molded cellulose monolith, or molded cellulose.
  • a process for producing a cellulose monolith comprising contacting a formate solution with a medium containing water and a deformylating agent, and performing a deformylation while exchanging a solvent with water to obtain a cellulose monolith molded article.
  • the cellulose acylate molded article formed by cooling the cellulose acylate solution to a temperature lower than its melting point is brought into contact with a medium containing water, or the cellulose formate solution is cooled to a temperature lower than its melting point.
  • a method for producing a cellulose monolith comprising contacting a molded cellulose formate molded article with a medium containing water.
  • a method for producing a cellulose monolith comprising subjecting the cellulose monolith to a heat treatment in the presence of urea and phosphoric acid (salt).
  • the cellulose monolith of the present invention provides the following inventions.
  • the cellulose monolith (iii) may further have a phosphate group.
  • the present invention further provides a fluid heterogeneous composition obtained by mixing a cellulose acylate solution or a cellulose formate solution with an aqueous sodium hydroxide solution.
  • the present invention further provides a molded article formed by cooling a cellulose acylate solution and / or a cellulose formate solution to a temperature lower than its melting point.
  • a monolith in which the skeleton forming the monolith is mainly made of a cellulose material (for example, 90% by mass or more), 2) an arbitrary shape, 3) one monolith At the stage, 4) at room temperature without the need for energy such as heating, 5) safely, and 6) it can be made simply.
  • a monolith composed of a 100% pure cellulose skeleton is preferable.
  • 1 is a scanning electron microscope (SEM) photograph of the particle surface of cellulose monolith particles of one embodiment of the present invention obtained in Example 1.
  • 1 is an SEM photograph of the inside of a cellulose monolith particle of one embodiment of the present invention obtained in Example 1.
  • 4 is an SEM photograph of the surface of the cellulose monolith particles obtained in Comparative Example 1.
  • 5 is an SEM photograph of the inside of the cellulose monolith particles obtained in Comparative Example 1.
  • 3 is an FT-IR chart of the cellulose monolith particles of one embodiment of the present invention obtained in Example 1 and the cellulose monolith particles obtained in Comparative Example 1.
  • 13 is an SEM photograph of the inside of the sheet-like cellulose monolith molded product obtained in Example 16.
  • 26 is a stereomicrograph of the appearance of the cellulose monolith particles (14) obtained in Example 25.
  • 31 is a stereomicrograph of a cross section of a cellulose monolith particle (14) obtained in Example 25 after water absorption.
  • 25 is a stereomicrograph of a cross section of another cellulose monolith particle (14) obtained in Example 25 and a cross section after dyeing with a Congo red aqueous solution.
  • 25 is a stereomicrograph of a cross section of another cellulose monolith particle (14) obtained in Example 25 and a cross section after dyeing with a Congo red aqueous solution.
  • 25 is a stereomicrograph of a cross section of cellulose monolith particles containing activated carbon and titanium oxide obtained in Example 26.
  • 21 is a stereomicrograph of a cellulose monolith molded product obtained in Example 28 and containing activated carbon therein and a cross section thereof.
  • 19 is a stereomicroscopic photograph of a cross section of the cellulose monolith molded article containing activated carbon obtained in Example 28, which is dyed with a dye.
  • 35 is a photograph of a butterfly-shaped cellulose monolith molded product obtained in Example 36.
  • 27 is an optical micrograph of activated carbon-encapsulated cellulose monolith particles obtained in Example 45.
  • 25 is an optical micrograph of a cross section of activated carbon-encapsulated cellulose monolith particles obtained in Example 45.
  • a method for producing a polymer monolith a method utilizing phase separation of a polymer solution is known.
  • a phase separation method a non-solvent induced phase separation method (NIPS method, Non-solvent Induced Phase Separation) for inducing phase separation by incorporation (solvent exchange) of a non-solvent (water), and inducing phase separation by cooling.
  • TIPS method Thermally induced phase separation method
  • PIPS polymerization (reaction) induced phase separation method
  • the monolith is prepared by a solvent exchange, so-called NIPS method, in which deacylation is carried out using water containing a deacylating agent (a medium containing water and a deacylating agent), or It is characterized in that the reaction is accompanied by reforming with water containing a reforming agent (a medium containing water and a reforming agent).
  • a deacylating agent a medium containing water and a deacylating agent
  • a reforming agent a medium containing water and a reforming agent
  • the cellulose acylate used as a raw material of the present invention may be any one as long as it forms a monolith by solvent exchange with water.
  • examples of such compounds include cellulose monoacetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate.
  • cellulose acetate which is industrially easily available, can be suitably used.
  • cellulose formate used as a raw material of the present invention examples include cellulose monoformate and cellulose diformate.
  • Typical physical properties of cellulose acetate or cellulose formate include the degree of polymerization and the degree of substitution.
  • the degree of polymerization is preferably 50 or more by mass average in the present invention from the viewpoint of increasing the mechanical strength of the obtained cellulose monolith and preventing elution into a solvent during use.
  • the upper limit any available one can be used.
  • the degree of substitution affects the solubility of cellulose acetate or cellulose formate.
  • the degree of substitution in acetylcellulose or cellulose formate is a numerical value indicating how many of the three hydroxyl groups per glucose repeating unit of cellulose are esterified (acetylated or formylated).
  • any cellulose acetate or cellulose formate may be used as long as it forms a monolith by solvent replacement with water.
  • the solvent that forms the cellulose acylate solution or the cellulose formate solution needs to be a solvent that has a high dissolving power for the cellulose acylate or the cellulose formate, and that forms a monolith by solvent exchange with water. . It is not preferable to add water to the cellulose acylate solution or the cellulose formate solution in advance because of the possibility of inducing phase separation and the storage stability of the cellulose acylate solution or the cellulose formate solution. Therefore, in the present invention, water must not be newly added during the preparation of a cellulose acylate solution or a cellulose formate solution, but the upper limit of water contained in a commercially available solvent is set, and water and a solvent are not included when the solution is prepared.
  • solvents can be used without purification, as long as they do not exchange to form a monolith.
  • aprotic polar solvents such as dimethylsulfoxide (DMSO), acetone, sulfolane, dimethylimidazolidinone, tetramethylurea, dimethylformamide (DMF), N-methylpyrrolidone, and dimethylacetamide (DMAc).
  • the cellulose acylate solution preferably contains the above-mentioned cellulose formate.
  • the concentration of cellulose acylate in the cellulose acylate solution in the present invention is in the range of 50% by mass to 0.1% by mass, and preferably in the range of 15% by mass to 1% by mass.
  • the concentration of cellulose formate in the cellulose formate solution is in the range of 50% by mass to 0.1% by mass, and preferably in the range of 15% by mass to 1% by mass.
  • the concentration exceeds 50% by mass the water absorption of the obtained monolith decreases, and when the concentration is lower than 0.1% by mass, the strength of the obtained monolith decreases, which is not preferable.
  • the cellulose acylate solution or cellulose formate solution of the present invention is preferably degassed in advance before solvent exchange with water. By degassing in advance, a monolith having uniform pores can be obtained.
  • a “water-containing medium” is brought into contact with the cellulose acylate solution.
  • a deacylating agent for example, a water-soluble acidic compound or basic compound can be used.
  • Such compounds include, for example, hydrochloric acid, sulfuric acid, nitric acid, ammonia, hydrazine and their alkyl-substituted products, guanidines and amidines and their substituted products, diamines, hydroxylamine, hydroxylamines such as ethanolamine, ethylamine, Alkylamines such as propylamine, metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and sodium hydrogen carbonate, quaternary ammonium hydroxide, metal alcoholates, and hydroxamic acids
  • examples include inorganic bases such as salts.
  • sodium hydroxide is preferred as the deacylating agent, and the ⁇ medium containing water and the deacylating agent '' as the deacylating agent.
  • Aqueous solutions are preferred, and aqueous sodium hydroxide solutions are preferred.
  • the concentration of the deacylating agent in the aqueous solution of the above deacylating agent is preferably in the range of 0.001% by mass to 1% by mass. If the concentration of the deacylating agent is lower than this, the rate of deacylation is slow, and the rate of solvent exchange with water cannot be balanced, which is not preferable. On the other hand, when the concentration is higher than this range, the deacylation rate is too high and a monolith having appropriate pores cannot be obtained, which is not preferable.
  • a more preferred concentration range of the deacylating agent is in the range of 0.005% by mass to 0.5% by mass.
  • the cellulose acylate solution is not particularly limited as a method for contacting with a ⁇ medium containing water and a deacylating agent '' and performing deacylation while exchanging solvent with water, even if water is in the form of a solution, Any form of mist or water vapor may be used as long as the cellulose acylate solution is deacylated while exchanging the solvent with water.
  • “Medium” includes a deformylating agent.
  • a deformylating agent for example, a water-soluble acidic compound or basic compound can be used.
  • a compound for example, the same compounds as those exemplified above as the deacylating agent can be exemplified.
  • the concentration of the deformylating agent in the aqueous solution of the above deformylating agent is preferably in the range of 0.001% by mass to 1% by mass. If the concentration of the deformylating agent is lower than this, the rate of deformylation is low, and the rate of solvent exchange with water cannot be balanced, which is not preferable. On the other hand, if the concentration is higher than this range, the rate of deformylation is too high, and a monolith having appropriate pores cannot be obtained, which is not preferable.
  • a more preferred concentration range of the deformylating agent is in the range of 0.005% by mass to 0.5% by mass.
  • Cellulose formate solution is not particularly limited as a method for performing a solvent exchange with water by contacting with a ⁇ medium containing water and a deformylating agent '' to formylate, even if water is in the form of a solution, Even if it is in the form of mist or water vapor, any form may be used as long as the cellulose formate solution is subjected to deformylation while exchanging the solvent with water.
  • the ratio of the cellulose acylate solution or the cellulose formate solution to water is not particularly limited as long as the solvent in the solution can be exchanged with water, but is usually used for the starting material, the cellulose acylate solution or the cellulose formate solution. It is preferred to use a larger amount of water than the solvent. When the amount of water is smaller than that of the solvent, the solvent exchange with water may be insufficient. Therefore, in the present invention, the amount of water and the solvent is preferably not less than the amount by which water becomes excessive in volume ratio, and is not particularly limited as long as it is not less than the amount. Preferably, the amount of water used is at least 5 times the volume of the solvent, more preferably at least 10 times the volume.
  • the temperature at which deacylation or deformylation is performed while exchanging the solvent with water can be selected from a temperature range in which water exists as a liquid. From the viewpoint, room temperature (for example, 25 ⁇ 5 ° C.) is more preferable.
  • the reaction time for deacylation or reformylation while exchanging the solvent with water also depends on the size and temperature of the monolith to be obtained, the required degree of deacylation or degree of reformylation. The time is in the range of minutes to 240 hours, preferably 2 minutes to 100 hours, more preferably 5 minutes to 50 hours, and still more preferably 10 minutes to 24 hours.
  • the cellulose monolith obtained in the present invention can be washed with water or ethanol, and preserved in a wet state by adding a preservative such as alcohol.
  • the water may be neutralized after the formation of the cellulose monolith in consideration of the waste water used. Thereafter, if necessary, further washing is performed with water or ethanol. After washing with water, a method of replacing water with a low boiling point solvent such as ethanol or hexane and drying under reduced pressure can also be adopted.
  • the drying method is not limited to reduced pressure, and a known drying method such as freeze drying, hot air drying or microwave drying can be employed.
  • cellulose monolith In the case of drying, for example, saccharides such as glycerin, sucrose, trehalose, and starch syrup, sugar alcohols, various amides, polar solvents such as DMSO, and urea can be added in appropriate amounts. By these additions, flexibility and the like can be imparted to the obtained cellulose monolith.
  • saccharides such as glycerin, sucrose, trehalose, and starch syrup
  • sugar alcohols various amides, polar solvents such as DMSO, and urea
  • flexibility and the like can be imparted to the obtained cellulose monolith.
  • the cellulose monolith obtained in the present invention contains no metal, it can be dried by a simple method such as microwave drying.
  • the size of cellulose monolith, pore diameter, specific surface area, water absorption, compression energy when wet for example, the degree of polymerization of cellulose acylate or cellulose formate, the degree of substitution of cellulose acylate or cellulose formate, cellulose
  • concentration of the acylate solution or the cellulose formate solution the solvent used for the cellulose acylate solution or the cellulose formate solution, the pH of water used for solvent exchange with the cellulose acylate solution or the cellulose formate solution, etc. It can be controlled by changing.
  • cellulose monolith particles the size of which is controlled by the viscosity and size of the cellulose acylate solution or cellulose formate solution to be dropped, the stirring efficiency, and the like. it can.
  • the viscosity of the cellulose acylate solution or the cellulose formate solution decreases as the concentration of the cellulose acylate or the cellulose formate solution in the cellulose acylate solution or the cellulose formate solution decreases. Therefore, for the same stirring rotation speed, the lower the concentration of cellulose acylate or cellulose formate, the better the stirring efficiency and the smaller the particle size.
  • stirring can be performed with a normal stirring blade or a stirrer, but if a cellulose acylate solution or a cellulose formate solution to be dropped can be stirred, a method such as ultrasonic vibration is also used. be able to.
  • particles can be obtained without using a surfactant.
  • surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants may be used.
  • anionic surfactant include sodium lauryl sulfate, N-acyl amino acid, and alkyl ether carboxylic acid.
  • cationic surfactant include compounds such as aliphatic amine salts and aliphatic quaternary ammonium salts.
  • the nonionic surfactant include polyoxyethylene sorbitan monolaurate, sorbitan sesquiolate, and a block copolymer having a polyoxypropylene chain and a polyoxyethylene chain.
  • the size of the cellulose monolith particles obtained in the present invention varies depending on the purpose of use, but is, for example, spherical, substantially spherical, or amorphous particles having a major axis in the range of 1 ⁇ m to 10,000 ⁇ m.
  • a molded article larger than this or produced from a molded cellulose acylate solution or a cellulose formate solution is referred to as a molded article.
  • a monolith having an arbitrary shape can be produced by using various casting methods such as a sheet, a film, a cube, a rectangular parallelepiped, a column, and a rod.
  • the cellulose acylate solution which has been formed in advance is deacylated while exchanging solvent with water.
  • Deacylation may be performed after solvent exchange with water.
  • a method in which the cellulose acylate solution is put into containers or castings having various shapes and the solvent is exchanged with water can be usually adopted. For example, it can be obtained by applying a cellulose acylate solution on a glass plate and immersing the solution in water containing a deacylating agent or in water.
  • a more preferable method is to put a cellulose acylate solution in a container or a casting having various shapes, cool the solution to a temperature lower than the melting point of the solution, take out a solidified molding solution (molded product), and include a deacetylating agent.
  • This is a method in which a solidified and molded cellulose acylate solution (molded article) is immersed in an aqueous solution or water and deacylated while exchanging the solvent with water, or deacylated after exchanging the solvent with water. According to this method, a monolith molded article having an arbitrary shape can be easily obtained without breaking its shape.
  • a freezer at about -10 ° C is used to quickly form a molded cellulose acylate.
  • Solution (cellulose acylate molded article) ".
  • a preformed cellulose formate solution is subjected to deformylation while exchanging a solvent with water.
  • Deformylation may be performed after solvent exchange with water.
  • a method in which a cellulose formate solution is put into containers or castings having various shapes and the solvent is exchanged with water can be usually adopted. For example, it can be obtained by applying a cellulose formate solution on a glass plate and immersing it in water containing a deformylating agent or in water.
  • a more preferable method is to put a cellulose formate solution into containers or castings having various shapes, cool the solution to a temperature lower than the melting point of the solution, take out a solidified molding solution (molded product), and include a deformylating agent.
  • This is a method in which a solidified and molded cellulose formate solution (molded product) is immersed in an aqueous solution or water and subjected to deformylation while exchanging the solvent with water, or deformylation after exchanging the solvent with water.
  • a monolith molded article having an arbitrary shape can be easily obtained without breaking its shape.
  • a freezer at about ⁇ 10 ° C. is used as a method of manufacturing a molded cellulose formate by cooling a cellulose formate solution to a temperature lower than the melting point of the solution.
  • Solution (cellulose formate molded product) ".
  • various functional substances may be added to a cellulose acylate solution or a cellulose formate solution as a starting material in order to impart further functions to the obtained cellulose monolith.
  • functional substances include PEG200, PEG600, polyacrylic acid (salt), gelatin, carboxymethylcellulose, polyvinyl alcohol, and water-soluble polymers such as polyvinylpyrrolidone.
  • Activated carbon as the functional substance; clay minerals such as kaolinite, smectite, montmorillonite, sericite, illite, glauconite, chlorite, talc, and zeolite; cellulose materials such as cellulose monolith, cellulose oxide, and pulp; Examples thereof include silicon compounds such as silicon, metal oxides such as titanium oxide, and nanoparticles such as titanium oxide nanoparticles.
  • the specific surface area can be 100 m 2 / g or more, preferably 300 m 2 / g or more, more preferably 500 m 2 / g or more, and still more preferably 1000 m 2 / g or more.
  • the upper limit of the specific surface area is not particularly limited, it is about 10,000 m 2 / g.
  • Other functional materials include carbon materials such as carbon nanotubes and carbon black, photocatalysts, fragrances, activated carbon, antibacterial agents, adsorbents, deodorants, defoamers, leveling agents, light stabilizers, ultraviolet absorbers, surfaces Colorants such as modifiers, pigments and dyes, polymer components for improving film properties and adhesion, water repellents, oil repellents, crosslinkers with chemical bonding, matting agents, silane coupling agents, filling Agents, lubricants, plasticizers, release agents, antioxidants, flame retardants, surfactants, pH adjusters, antistatic agents, weathering stabilizers, heat stabilizers, antislip agents, antiblocking agents, foaming agents, crystals Chemical auxiliaries, anti-fogging agents, (transparent) nucleating agents, anti-aging agents, hydrochloric acid absorbents, impact modifiers, crosslinking agents, co-crosslinking agents, crosslinking auxiliaries, adhesives, softeners, processing auxiliaries, etc
  • the amount of the functional substance to be added is, for example, 0 to 80 parts by mass, preferably 0 to 70 parts by mass, or 100 parts by mass of the cellulose acylate in the cellulose acylate solution, or the cellulose formate in the cellulose formate solution.
  • the amount can be, for example, 0 to 80 parts by mass, preferably 0 to 70 parts by mass with respect to 100 parts by mass of the mate.
  • a cellulose monolith having a functional substance dispersed therein can be simply and easily produced.
  • a cellulose monolith in which activated carbon is contained and dispersed can remove odors such as ammonia and methyl mercaptan, has excellent ink-adsorbing ability, and is excellent in purifying contaminated water.
  • the above-mentioned odor removal, contaminated water purification, etc. can exert their effects preferably within 1 minute, more preferably within 30 seconds, depending on the amount used. Even if the activated carbon is a fine powder, it can be easily handled while retaining functions such as deodorization by being included and dispersed in the cellulose monolith of the present invention.
  • the present invention provides a cellulose monolith (i) in which one or more other cellulose monolith layers are laminated on the cellulose monolith layer.
  • a cellulose monolith in which another one or more cellulose monolith layers are laminated on a cellulose monolith layer formed by adding the functional material can be provided.
  • the present invention provides a white cellulose monolith (ii) containing colored particles.
  • a functional substance having a large specific gravity such as activated carbon
  • a functional material such as activated carbon having a dark color is stored inside the stacked cellulose monolith. be able to.
  • a coloring agent or the like coloring and dyeing can be freely performed.
  • a cellulose monolith layer can be formed around the above-mentioned functional substance, and can be microencapsulated. Also in this case, it is possible to produce an almost white, preferably white, particulate white cellulose monolith having a functional substance such as activated carbon having a dark color. Further, by adding a coloring agent or the like, the particles can be colored or dyed to freely color.
  • a compound that reacts with water to generate carbon dioxide gas is added in advance to a cellulose acylate solution or a cellulose formate solution in a solid state, and the solvent is exchanged with water for deacylation or deformylation.
  • a monolith having a larger specific surface area can be formed by foaming.
  • the surface modification of the cellulose monolith may be performed by reacting the obtained cellulose monolith with a compound that reacts with a hydroxyl group of cellulose.
  • a compound that reacts with a hydroxyl group of cellulose are not particularly limited, and include compounds having a carboxyl group such as citric acid and polyacrylic acid, acid anhydrides, compounds having an acyl group such as an acyl halide group, compounds having an epoxy group, and isocyanate groups.
  • Compounds having a carboxyl group include aliphatic carboxylic acids, aromatic carboxylic acids, alicyclic carboxylic acids, and the like. Specifically, for example, in addition to citric acid and polyacrylic acid, it has a substituent such as acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, (meth) acrylic acid, cinnamic acid, and trifluoroacetic acid.
  • Aliphatic carboxylic acids 1-naphthylcarboxylic acid, 2-naphthylcarboxylic acid, m-methylbenzoic acid, p-methylbenzoic acid, m-methoxybenzoic acid, p-methoxybenzoic acid, 3,5- Dimethoxybenzoic acid, 3,4,5-trimethoxybenzoic acid, 2,4,6-trimethylbenzoic acid, m-cyanobenzoic acid, p-cyanobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, m- Fluorobenzoic acid, p-fluorobenzoic acid, 2,5-dichlorobenzoic acid, p-acetylbenzoic acid, p-phenylbenzoic acid, p-formylbenzoic acid, pt-butylbenzoic acid P-butoxybenzoic acid, m-acetoxybenzoic acid,
  • substituents examples include a halogen atom, a cyano group, a hydroxyl group, a nitro group, a silyl group, a silyloxy group, an alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, t-butyl group, etc.).
  • An alkoxy group having 1 to 12 carbon atoms (methoxy, ethoxy, propoxy group, etc.), an aryl group having 6 to 20 carbon atoms (phenyl, naphthyl group, etc.), an aryloxy group having 6 to 20 carbon atoms (phenyloxy, naphthyl) An oxy group), an acyl group having 1 to 20 carbon atoms (acetyl, propionyl, benzoyl group and the like), a substituted or unsubstituted carbamoyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbamoyloxy group having 1 to 20 carbon atoms, A sulfamoyl group having 1 to 20 carbon atoms, a sulfamoyloxy group having 1 to 20 carbon atoms, a phosphino group, a phosphinyl group, a phosphono group, Finyloxy group, phosphonooxy
  • Examples of the acid anhydride include a carboxylic anhydride corresponding to the above carboxylic acid.
  • Examples of the compound having an acyl group such as an acyl halide group include carboxylic acid chloride and carboxylic acid bromide corresponding to the above carboxylic acids.
  • the compound having an isocyanate group includes aromatic isocyanate, aliphatic isocyanate, alicyclic isocyanate and the like. Specifically, for example, phenyl isocyanate, 1-naphthyl isocyanate, 2-naphthyl isocyanate, 2-methylphenyl isocyanate, 3-methylphenyl isocyanate, 4-methylphenylisocyanate, 3,5-dimethylphenylisocyanate, 2-chlorophenylisocyanate And aromatic compounds such as 3-chlorophenyl isocyanate, 4-chlorophenyl isocyanate, 2-methoxyphenyl isocyanate, 3-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, 2-nitrophenyl isocyanate, 3-nitrophenyl isocyanate, and 4-nitrophenyl isocyanate Isocyanates; aliphatic isocyanates such as methyl isocyanate, ethy
  • Examples of the compound having a vinyl group include (meth) acrylic acid, ester compounds of (meth) acrylic acid, vinyl alcohol, vinylpyrrolidone, vinyl chloride, vinyl acetate, and vinylcyclohexane.
  • Examples of the compound having an epoxy group include halohydrins such as epichlorohydrin, epibromohydrin and dichlorohydrin; bifunctional bisepoxides (bisoxiranes); polyfunctional polyepoxides (polyoxiranes). it can.
  • Other compounds having an epoxy group that can be used in the present invention include resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenate bisphenol A diglycidyl ether, Glycerol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl terephthalate, diglycidyl orthophthalate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, Pentaerythritol polyglycidyl ether, diglycerol polyglycidyl Ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like.
  • Examples of the compound having an oxazoline group include Epocross K1010E, K1020E, K1030E, CX-K2010E, CX-K2020E, and CX-K2030E of Nippon Shokubai Co., Ltd.
  • the pH of the reaction solution in which the cellulose monolith is formed by deacylation is adjusted as necessary.
  • the reaction can be carried out by directly adding the oxirane compound while performing the reaction, followed by washing with water to obtain a surface-modified cellulose monolith.
  • the amount of the oxirane compound to be added is usually in the range of 0.01 to 10 times the volume of the obtained cellulose monolith. If the volume is less than 0.01 times the volume of the cellulose monolith, the desired increase in strength may not be achieved, and even if it is used more than 10 times, the effect corresponding to the cost cannot be obtained. By using in this range, the strength of the cellulose monolith can be improved, and when the above-mentioned cellulose monolith is used for the purpose of, for example, adsorption purification, the amount of the target substance to be purified can be increased.
  • the surface modification of the cellulose monolith may be carried out using proteins such as protein A, protein G and protein L and functional variants thereof.
  • proteins such as protein A, protein G and protein L and functional variants thereof.
  • the method described in Patent Document 21 can be applied.
  • exogenous pyrogens or pyrogens such as bacterial by-products and bacterial fragments
  • histidine, histamine, cytosine, adenine, compounds containing primary amino groups and secondary amino groups, and polymyxins are included.
  • the surface of the nitrogen compound may be modified.
  • the degree of deacylation and the concentration of cellulose acylate in the reaction the type and amount of the deacylating agent, or the degree of deformylation and the concentration of the cellulose formate in the reaction, the concentration of the deformylating agent
  • a water-absorbing cellulose monolith can be obtained.
  • the obtained water-absorbing agent can have an arbitrary shape such as a granular shape, a sheet shape, a strip shape, and a rod shape.
  • the water-absorbing cellulose monolith obtained in the present invention has continuous pores inside, a sheet-like, strip-like, or rod-like thing has a capability of vertically absorbing water. Therefore, it can be used for applications such as paper chromatography. Further, the water-absorbing cellulose monolith of the present invention can be made into a deodorizing water-absorbing cellulose monolith by inserting a material having a deodorizing function such as activated carbon or zeolite therein.
  • the composition obtained by deacylating the cellulose acylate solution while exchanging the solvent with water, or by subjecting the cellulose formate solution to deformylation while exchanging the solvent with water is a cellulose acylate solution or
  • the solvent exchange of the cellulose formate solution with water causes the cellulose acylate or the cellulose formate to form a monolith, thereby forming a non-uniform composition (including a gel) having fluidity. Therefore, another embodiment of the present invention also provides a fluid heterogeneous composition obtained by mixing a cellulose acylate solution or a cellulose formate solution with an aqueous sodium hydroxide solution.
  • the present invention also provides a method (5) for producing a cellulose monolith, which comprises subjecting the cellulose monolith to a heat treatment in the presence of urea and phosphoric acid (salt).
  • the amount of urea used is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, based on 100 parts by mass of the cellulose monolith.
  • the amount of phosphoric acid (salt) used is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass, per 100 parts by mass of the cellulose monolith.
  • the present invention provides a cellulose monolith (iii) having a carbamoyl group.
  • the cellulose monolith (iii) may further have a phosphate group.
  • This cellulose monolith (iii) is obtained by the above-mentioned production method (5).
  • Cellulose monolith having a carbamoyl group and a phosphate group (monolithic cellulose carbamate phosphate) has a nonion and an anion, and is excellent in water absorption capacity such as water and physiological saline. Also, since it is crosslinked with phosphoric acid (salt), it has excellent strength. The retained water absorption will be described later in detail.
  • the present invention provides a cellulose monolith (iv) having a retained water absorption with respect to physiological saline of at least 8 g / g.
  • This cellulose monolith (iv) is preferably the above-mentioned cellulose monolith (iii).
  • the cellulose monoliths (iii) and (iv) are excellent in water swellability.
  • the above-mentioned cellulose monoliths (iii) and (iv) may be referred to as a water-swellable cellulose monolith.
  • the retained water absorption with respect to the physiological saline is preferably 10 g / g or more, and more preferably 12 g / g or more.
  • Water absorption is the monolith weight (g / g) after immersing the monolith in water and removing the excess water on the monolith surface under no load and absorbing water (g). Divided by the amount of water absorption (unit: g / g).
  • the "retained water absorption” is obtained as the water absorption (unit: g / g) after the cellulose monolith is immersed in a medium to allow free swelling and then drained with a centrifuge (250G) for 3 minutes. Value.
  • the medium is preferably water or physiological saline.
  • the cellulose monolith of the present invention includes sanitary materials such as disposable diapers and sanitary napkins, cosmetics, freshness preserving agents, soil modifying agents, adsorbents, deodorants, water purifying agents, metal ion removal, gel filtration chromatography carriers,
  • sanitary materials such as disposable diapers and sanitary napkins, cosmetics, freshness preserving agents, soil modifying agents, adsorbents, deodorants, water purifying agents, metal ion removal, gel filtration chromatography carriers.
  • the present invention can be applied to various fields such as a drug release carrier, desalination of seawater, an ion exchange chromatography carrier, and an affinity chromatography carrier.
  • the cellulose acetate used in Examples and Comparative Examples was acetyl cellulose having a molecular weight of 50,000 and an acetyl content of 39.2 to 40.2% by mass purchased from Sigma-Aldrich unless otherwise specified.
  • the retained water absorption of the water-swellable cellulose monolith was measured according to the EDANA method (ERT441.2-02). Specifically, 0.2 g of water-swellable cellulose monolith is put into a non-woven bag, then immersed in a large excess of 0.9% by weight aqueous sodium chloride solution for 30 minutes to freely swell, and then centrifuged. The water absorption (unit: g / g) after draining at (250 G) for 3 minutes was obtained. The same operation was performed using deionized water instead of the 0.9% by weight aqueous sodium chloride solution, and the water absorption of the deionized water was also measured. The amount of the water-swellable cellulose monolith in the case of deionized water was 0.05 g.
  • Example 1 A DMSO solution of cellulose acetate (cellulose acetate concentration: 10.2% by mass) was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, deacetylated while exchanging the solvent with water, and stirring was continued for 18 hours. After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (1) of one embodiment of the present invention.
  • FIG. 1 shows a scanning electron microscope (SEM) photograph of the obtained cellulose monolith particles (1)
  • FIG. 2 shows the inside of the particles.
  • the water absorption of the cellulose monolith particles (1) was 5.2 g / g
  • the compression ratio (%) was 45%
  • the compression rigidity was 0.87
  • the specific surface area was 31.96 m 2 / g.
  • FIG. 5 shows an FT-IR chart of the cellulose monolith particles (1).
  • the cellulose monolithic particles (1) absorption of 1735 cm -1 from the ester groups in the starting acetylene chill cellulose disappeared and instead increase the absorption of hydroxyl groups derived from 3400 cm -1 and near 2900 cm -1 And the deacetylation was completed.
  • FIG. 5 shows an FT-IR chart of the comparative cellulose monolith particles (1) obtained in Comparative Example 1.
  • the comparative cellulose monolith particles (1) had 1,735 cm ⁇ 1 derived from the ester group of the raw material acetyl cellulose, and had a low water absorption.
  • the comparative cellulose monolith particles (1) have a monolith surface and an internal structure that are largely different from those of the cellulose monolith particles (1) (FIGS. 1 and 2) which are an embodiment of the present invention. Was different.
  • Example 2 A DMSO solution of cellulose acetate (concentration of cellulose acetate: 7.8% by mass) was dropped into 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 18 hours while deacetylating while exchanging the solvent with water. . After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (2) of one embodiment of the present invention. The water absorption of the cellulose monolith particles (2) was 8.3 g / g, and the specific surface area was 26.37 m 2 / g.
  • Example 3 A DMSO solution of cellulose acetate (cellulose acetate concentration: 10.2% by mass) was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 6 hours while deacetylating while exchanging the solvent with water. . After 6 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (3) of one embodiment of the present invention. The water absorption of the cellulose monolith particles (3) was 5.5 g / g, and the specific surface area was 25.01 m 2 / g.
  • Example 4 A DMSO solution of cellulose acetate (cellulose acetate concentration: 7.8% by mass) was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 4 hours while deacetylating while exchanging the solvent with water. . After 4 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (4) of one embodiment of the present invention. The water absorption of the cellulose monolith particles (4) was 8.1 g / g, the compression ratio (%) was 52%, and the compression rigidity was 0.76.
  • Example 5 A sheet-form monolith cellulose acetate DMSO solution (cellulose acetate concentration 10.2% by mass) was applied to a glass plate, and then dipped in 50 mL of a 0.1 mol / L sodium hydroxide aqueous solution to exchange solvent with water. Deacetylated and left for 18 hours. After 18 hours, the obtained cellulose monolith sheet was washed with water until the filtrate became neutral. After washing with water, the water in the cellulose monolith sheet was replaced with ethanol and dried under reduced pressure to obtain a cellulose monolith sheet (1) having a length of 40 mm and a width of 15 mm according to one embodiment of the present invention.
  • the water absorption of the cellulose monolith sheet (1) cut into strips along the long axis was 10.5 g / g.
  • a monolith sheet (length: 40 mm ⁇ width: 4 mm) cut in a strip shape was hung with the long axis direction up and down, and the lower end was immersed in a petri dish containing water, and water was sucked up to the upper end.
  • Example 6 A DMSO solution of cellulose acetate (cellulose acetate concentration: 7.8% by mass) was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 90 hours while deacetylating while exchanging the solvent with water. . After 90 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (5) of one embodiment of the present invention. The water absorption of the cellulose monolith particles (5) was 8.3 g / g, and the specific surface area was 25.41 m 2 / g.
  • Example 7 A DMSO solution of cellulose acetate (cellulose acetate concentration: 7.8% by mass) was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 90 hours while deacetylating while exchanging the solvent with water. . After 90 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol, and dried by heating in a microwave oven of 600 W for 1 minute to obtain cellulose monolith particles (6) of one embodiment of the present invention. The water absorption of the cellulose monolith particles (6) was 8.5 g / g.
  • Example 8 A DMSO solution of cellulose acetate (concentration of cellulose acetate: 5.4% by mass) was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 18 hours while deacetylating while exchanging the solvent with water. . After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (7) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith particles (7) was 15.5 g / g
  • the specific surface area was 23.61 m 2 / g
  • the compression ratio (%) was 81%
  • the compression rigidity was 0.34.
  • Example 9 A DMSO solution of cellulose acetate (concentration of cellulose acetate: 5.4% by mass) was dropped into 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 2 hours while deacetylation was performed while exchanging the solvent with water. . Two hours later, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (8) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith particles (8) was 15.5 g / g
  • the specific surface area was 25.51 m 2 / g
  • the compression ratio (%) was 80%
  • the compression rigidity was 0.30.
  • Example 10 Sodium carbonate powder and anhydrous sodium sulfate powder were added to a DMSO solution of cellulose acetate (cellulose acetate concentration: 7.8% by mass) in a mass ratio of 12% by mass and 50% by mass with respect to cellulose acetate, respectively, so that these particles were uniform.
  • This solution was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, followed by stirring for 4 hours. After 4 hours, the particles were suction filtered. After washing with water until the filtrate became neutral, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (9) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith particles (9) was 7.6 g / g, and the specific surface area was 27.03 m 2 / g.
  • the comparative cellulose monolith particles (5) had a water absorption of 7.8 g / g and a specific surface area of 12.22 m 2 / g.
  • Example 11 A DMSO solution of cellulose acetate (concentration of cellulose acetate: 7.8% by mass) was dropped into 30 mL of a 0.1 mol / L aqueous potassium hydroxide solution with stirring, and stirring was continued for 1 hour while deacetylating while exchanging the solvent with water. .
  • the obtained cellulose monolith particles were neutralized with a 0.1 mol / L aqueous hydrochloric acid solution and washed with water. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (10) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith particles (10) was 5.7 g / g.
  • Example 12 A DMSO solution of cellulose acetate (cellulose acetate concentration: 10.2% by mass) was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium carbonate solution with stirring, and stirring was continued for 18 hours while deacetylating while exchanging the solvent with water. After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (11) of one embodiment of the present invention. The water absorption of the cellulose monolith particles (11) was 4.8 g / g.
  • Example 13 0.825 g of a DMSO solution of cellulose acetate (cellulose acetate concentration: 7.8% by mass) was placed in a polyethylene container having a capacity of 6 mL (the container size was 18 mm ⁇ 18 mm at the bottom and 30 mm in height). This was put in a freezer together with the container for one hour, and was frozen and solidified. After one hour, the container is taken out of the freezer, and a sheet-like solidified cellulose acetate DMSO solution molded product is taken out of the container, immersed in 30 mL of 0.1 mol / L aqueous sodium hydroxide solution, and subjected to solvent exchange with water. The reaction was deacetylated for 190 hours.
  • the obtained sheet-shaped cellulose monolith molded article was washed with water until the filtrate became neutral. After washing with water, the water inside the molded cellulose monolith was replaced with ethanol, and dried under reduced pressure to obtain a molded cellulose monolith (2) of one embodiment of the present invention.
  • the water absorption of the formed cellulose monolith (2) was 10.5 g / g, and the specific surface area was 17.43 m 2 / g.
  • Example 14 0.799 g of a cellulose acetate DMSO solution (cellulose acetate concentration: 7.8% by mass) was placed inside a U-shaped polypropylene straw. This was put in a freezer together with the straw for one hour, and frozen and solidified. One hour later, the straw is taken out of the freezer, and a rod-shaped DMSO solution molded product of cellulose acetate solidified from the inside of the straw is taken out, immersed in 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution, and subjected to solvent exchange with water. The reaction was deacetylated for 190 hours.
  • a cellulose acetate DMSO solution cellulose acetate concentration: 7.8% by mass
  • the obtained rod-shaped cellulose monolith molding was washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith molded product was replaced with ethanol and dried under reduced pressure to obtain a rod-shaped cellulose monolith molded product (3) of one embodiment of the present invention.
  • the water absorption of the formed cellulose monolith (3) was 12.5 g / g, and the specific surface area was 23.66 m 2 / g.
  • Example 15 19.85 g of a cellulose acetate DMSO solution (cellulose acetate concentration: 7.8% by mass) was poured into a silicon rectangular parallelepiped container having a width of 55 mm, a length of 105 mm, and a height of 22 mm. The container was placed in a freezer for 4 hours while being kept horizontal with the lid on, and frozen and solidified. After 4 hours, the container is taken out of the freezer, and a sheet-like solidified cellulose acetate DMSO solution formed from the inside of the container is taken out, immersed in 400 mL of a 0.1 mol / L aqueous sodium hydroxide solution, and subjected to solvent exchange with water. The reaction was carried out for 20 hours.
  • a cellulose acetate DMSO solution cellulose acetate concentration: 7.8% by mass
  • the obtained sheet-shaped cellulose monolith molded article was washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith molded body was replaced with ethanol and dried under reduced pressure to obtain a sheet-shaped cellulose monolith molded body (4) of one embodiment of the present invention.
  • the water absorption of the formed cellulose monolith (4) was 9.2 g / g, and the specific surface area was 14.4 m 2 / g.
  • a part of the formed cellulose monolith (4) was cut and immersed in a 10% by mass glycerin aqueous solution. Thereafter, excess glycerin aqueous solution was wiped off with paper, and then dried with a hot air dryer at 90 ° C. to obtain a cellulose monolith molded article (5) of one embodiment of the present invention.
  • the cellulose monolith molding (5) was a flexible sheet even after drying.
  • Example 16 0.9 g of a cellulose acetate DMSO solution (cellulose acetate concentration: 10.2% by mass) was poured into a polyethylene rectangular container having a width of 18 mm, a length of 30 mm, and a height of 13 mm. The container was placed in a freezer for 4 hours while being kept horizontal with the lid on, and frozen and solidified. After 4 hours, the container is taken out of the freezer, a sheet-like DMSO solution of cellulose acetate solidified and formed from the inside of the container is taken out, immersed in 40 mL of a 0.1 mol / L aqueous sodium hydroxide solution, and subjected to solvent exchange with water. The reaction was carried out for 38 hours while deacetylating.
  • a cellulose acetate DMSO solution cellulose acetate concentration: 10.2% by mass
  • FIG. 6 shows an SEM image of the inside of the cellulose monolith molded body (6). A 1% by mass aqueous solution of Congo Red was applied to the obtained cellulose monolith molded product (6). As a result, a red-dyed cellulose monolith molded article (6 ′) was obtained.
  • Example 17 14.66 g of a cellulose acetate DMSO solution (cellulose acetate concentration: 5.4% by mass) was poured into a silicon rectangular parallelepiped container having a width of 55 mm, a length of 105 mm, and a height of 22 mm. The container was placed in a freezer for 16 hours while being kept horizontal with the lid of the container, and was frozen and solidified. After 16 hours, the container is taken out of the freezer, and a sheet-like solidified cellulose acetate DMSO solution formed from the inside of the container is taken out, immersed in 300 mL of a 0.1 mol / L aqueous sodium hydroxide solution, and subjected to solvent exchange with water.
  • a cellulose acetate DMSO solution cellulose acetate concentration: 5.4% by mass
  • the reaction was deacetylated for 22 hours. After 22 hours, the obtained sheet-shaped cellulose monolith molded article was washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith molded body was replaced with ethanol and dried in a hot air dryer at 90 ° C. for 30 minutes to obtain a sheet-shaped cellulose monolith molded body (7) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith molding (7) was 11.7 g / g.
  • the cellulose monolith molded article (7) was immersed in a 10% by mass aqueous glycerin solution, excess excess glycerin aqueous solution was wiped off with paper, and then dried with a hot air dryer at 90 ° C. for 30 minutes to maintain a flexible sheet state after drying. I was
  • Example 18 1.7 g of a cellulose acetate DMSO solution (cellulose acetate concentration: 4.0% by mass) was poured into a polyethylene rectangular parallelepiped container having a width of 18 mm, a length of 30 mm, and a height of 13 mm. The container was placed in a freezer for 2 hours while being kept horizontal with the lid of the container, and was frozen and solidified. After 2 hours, the container is taken out of the freezer, and a sheet-like solidified cellulose acetate DMSO solution molded body taken out of the container is taken out, immersed in 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution, and subjected to solvent exchange with water. The reaction was carried out for 15 hours.
  • a cellulose acetate DMSO solution cellulose acetate concentration: 4.0% by mass
  • the obtained sheet-shaped cellulose monolith molding was washed with water until the filtrate became neutral. After washing with water, the water inside the molded cellulose monolith was replaced with ethanol and dried under reduced pressure to obtain a sheet-like molded cellulose monolith (8) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith molded article (8) was 20.1 g / g, and the specific surface area was 27.99 m 2 / g.
  • Example 19 0.72 g of a cellulose acetate DMSO solution (cellulose acetate concentration: 14.5% by mass) was poured into a polyethylene rectangular parallelepiped container having a width of 18 mm, a length of 30 mm, and a height of 13 mm. The container was placed in a freezer for 2 hours while being kept horizontal with the lid of the container, and was frozen and solidified. After 2 hours, the container is taken out of the freezer, and a sheet-like solidified cellulose acetate DMSO solution molded body taken out of the container is taken out, immersed in 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution, and subjected to solvent exchange with water. The reaction was carried out for 15 hours.
  • a cellulose acetate DMSO solution cellulose acetate concentration: 14.5% by mass
  • the obtained sheet-shaped cellulose monolith molding was washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith molding was replaced with ethanol, and dried under reduced pressure to obtain a sheet-like cellulose monolith molding (9) of one embodiment of the present invention.
  • the water absorption of the formed cellulose monolith (9) was 5.7 g / g, and the specific surface area was 16.71 m 2 / g.
  • Example 20 2.25 g of a DMSO solution of cellulose acetate (cellulose acetate concentration: 5.4% by mass) was placed in a polyethylene container having a capacity of 6 mL (the container size was 18 mm ⁇ 18 mm at the bottom and 30 mm in height). This was put in a freezer for 4 hours together with the container, and was frozen and solidified. After 4 hours, the container is taken out of the freezer, and the solidified and molded DMSO solution of cellulose acetate in a die is taken out of the container, immersed in 30 mL of 0.1 mol / L aqueous sodium hydroxide solution, and subjected to solvent exchange with water. The reaction was deacetylated for 62 hours.
  • the obtained die-shaped cellulose monolith molding was washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith molded body was replaced with ethanol and dried under reduced pressure to obtain a dice-shaped cellulose monolith molded body (10) of one embodiment of the present invention.
  • the water absorption of the formed cellulose monolith (10) was 12.0 g / g, and the specific surface area was 14.98 m 2 / g.
  • Example 21 2.15 g of a DMSO solution of cellulose acetate (cellulose acetate concentration: 5.4% by mass) was placed in a polyethylene container having a capacity of 6 mL (the container size was 18 mm ⁇ 18 mm at the bottom and 30 mm in height). This was put in a freezer for 4 hours together with the container, and was frozen and solidified. After 4 hours, the container was taken out of the freezer, and a die-shaped DMSO solution molded product of cellulose acetate solidified and formed was taken out of the container, immersed in 30 mL of deionized water, solvent-exchanged with water, and reacted for 62 hours. .
  • the obtained die-shaped cellulose monolith molding was washed with water. After washing with water, the water inside the cellulose monolith molded body was replaced with ethanol and dried under reduced pressure to obtain a dice-shaped cellulose monolith molded body (11) of one embodiment of the present invention.
  • the water absorption of the molded cellulose monolith (11) was 7.0 g / g, and the specific surface area was 8.85 m 2 / g.
  • Example 22 2.01 g of a cellulose acetate DMSO solution (cellulose acetate concentration: 5.4% by mass) was placed in a polyethylene container having a capacity of 6 mL (the container size was 18 mm ⁇ 18 mm at the bottom and 30 mm in height). This was put in a freezer for 4 hours together with the container, and was frozen and solidified. After 4 hours, the container was taken out of the freezer, and a die-shaped DMSO solution molded product of cellulose acetate solidified and formed was taken out of the container, immersed in 30 mL of deionized water, solvent-exchanged with water, and reacted for 62 hours. .
  • the obtained dice-like cellulose monolith molding was washed with water and immersed in a 0.1 mol / L aqueous sodium hydroxide solution. After being immersed in an aqueous sodium hydroxide solution for 20 hours, the filtrate was washed with water until the filtrate became neutral. After washing with water, the water in the cellulose monolith molded body was replaced with ethanol and dried under reduced pressure to obtain a dice-shaped cellulose monolith molded body (12) of one embodiment of the present invention.
  • the water absorption of the formed cellulose monolith (12) was 10.0 g / g, and the specific surface area was 15.62 m 2 / g.
  • Example 23 A DMSO solution of cellulose triacetate (cellulose triacetate concentration: 10.8% by mass) was added dropwise to 30 ml of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and the mixture was stirred for 2 hours while being deacetylated while exchanging solvent with water. Continued. Two hours later, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (12) of one embodiment of the present invention. The water absorption of the cellulose monolith particles (12) was 6.7 g / g, and the specific surface area was 39.51 m 2 / g.
  • Example 24 To a DMSO solution of cellulose acetate (cellulose acetate concentration 10.2% by mass), add activated carbon (“Taiko 350SZ” manufactured by Futamura Chemical Co., Ltd.) to a mass of ⁇ of the mass of cellulose acetate in the solution, and uniformly stir the activated carbon. A cellulose acetate solution was prepared. The obtained cellulose acetate solution containing activated carbon was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 18 hours while deacetylation was performed while exchanging the solvent with water. After 18 hours, the obtained activated carbon-containing cellulose monolith particles were washed with water until the filtrate became neutral.
  • activated carbon (“Taiko 350SZ” manufactured by Futamura Chemical Co., Ltd.)
  • cellulose monolith particles (13) After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (13) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith particles (13) was 3.6 g / g, the compression ratio (%) was 45%, the compression stiffness was 0.93, and the specific surface area was 592.2 m 2 / g.
  • Observation of the cross section of the obtained cellulose monolith particles (13) revealed that activated carbon (black particles) was contained inside.
  • the equilibrium concentration of toluidine blue in the solution at different adsorption times was determined from the transmittance and the amount of toluidine blue adsorbed by the cellulose monolith particles (13) was calculated by the following equation.
  • the adsorption test was performed under light shielding.
  • Q (Co-Ct) V / m
  • Q indicates the equilibrium adsorption amount (mg / g)
  • Co and Ct indicate the initial concentration and the equilibrium concentration of toluidine blue in the solution at different time points.
  • V is the volume of the aqueous solution of toluidine blue and m is the weight of the cellulose monolith particles (13).
  • Activated carbon ("Taiko350SZ” manufactured by Futamura Chemical Co., Ltd.) is added to a DMSO solution of cellulose acetate (cellulose acetate concentration: 7.8% by mass) in the same amount as the mass of cellulose acetate in the solution, and the mixture is stirred uniformly and cellulose acetate containing activated carbon is added. A solution was made. The obtained cellulose acetate solution containing activated carbon was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 18 hours while deacetylation was performed while exchanging the solvent with water.
  • the obtained cellulose monolith particles containing activated carbon were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain activated carbon-containing cellulose monolith particles.
  • the activated carbon-containing monolith particles were immersed in a cellulose acetate DMSO solution (cellulose acetate concentration: 10.2% by mass), and the activated carbon-coated monolith particles coated with the obtained cellulose acetate solution were mixed with 30 mL of 0.1 mol / L water. The solution was added dropwise to the aqueous sodium oxide solution with stirring, and stirring was continued for 18 hours while deacetylation was performed while exchanging the solvent with water.
  • Activated carbon-containing monolith particles coated with the obtained cellulose monolith were washed with water until the filtrate became neutral. After washing with water, the water of the activated carbon-containing monolith particles coated with cellulose monolith was replaced with ethanol, and dried under reduced pressure to obtain white cellulose monolith particles (14) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith particles (14) was 4.4 g / g.
  • FIGS. 7 and 8 show the appearance of the cellulose monolith particles (14) and a cross-sectional micrograph after water absorption.
  • the obtained appearance is white, and it is understood that the particles are white particles containing activated carbon inside.
  • 9 and 10 show a cross section of another cellulose monolith particle (14) and a cross section stained with an aqueous solution of Congo Red.
  • the cellulose monolith particle (14) has a new monolith structure outside the previously obtained activated carbon-containing monolith particle. It can be seen that the particles have continuous pores formed in two layers. Therefore, it is possible to form a monolith having a multilayer structure by this method, and it is also possible to produce white cellulose monolith particles containing a coloring material by using a known microencapsulation apparatus.
  • Activated carbon (“Taiko350SZ” manufactured by Futamura Chemical Co., Ltd.) and titanium oxide (AEOXIDE P25 manufactured by Nippon Aerosil Co., Ltd.) were added to a DMSO solution of cellulose acetate (cellulose acetate concentration: 8.5% by mass) the same as the weight of cellulose acetate in the solution. The mass was added and stirred uniformly to prepare a cellulose acetate solution containing activated carbon and titanium oxide. The cellulose acetate solution was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 4 hours while deacetylation was performed while exchanging the solvent with water.
  • FIG. 11 shows a cross-sectional micrograph of the cellulose monolith particles (15) of one embodiment of the present invention.
  • Example 27 To a DMSO solution of cellulose acetate (cellulose acetate concentration 10.2% by mass), add activated carbon (“Taiko 350SZ” manufactured by Futamura Chemical Co., Ltd.) to a mass of ⁇ of the mass of cellulose acetate in the solution, and uniformly stir the activated carbon. A cellulose acetate solution was prepared. This cellulose acetate solution is spread on a filter paper pre-moistened with a 0.1 mol / L aqueous sodium hydroxide solution in a petri dish, and the developed solution is immersed in an additional 0.1 mol / L aqueous sodium hydroxide solution to form a mixture with water. Deacetylation was performed for 18 hours while exchanging the solvent.
  • activated carbon (“Taiko 350SZ” manufactured by Futamura Chemical Co., Ltd.)
  • the obtained activated carbon-containing cellulose monolith molded article was washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith molded product was replaced with ethanol, and dried under reduced pressure to obtain a cellulose monolith molded product (13) containing activated carbon according to one embodiment of the present invention.
  • the molded product (13) had a water absorption of 2.8 g / g, a compression ratio of 45%, and a compression stiffness of 0.68.
  • Activated carbon (“Taiko350SZ” manufactured by Futamura Chemical Co., Ltd.) is added to a DMSO solution of cellulose acetate (cellulose acetate concentration: 7.8% by mass) in the same amount as the mass of cellulose acetate in the solution, and the mixture is stirred uniformly and cellulose acetate containing activated carbon is added. A solution was made. 1.0 g of this cellulose acetate solution was poured into a polyethylene rectangular parallelepiped container having a width of 18 mm, a length of 30 mm, and a height of 13 mm. Activated carbon particles settled at the bottom of the container by allowing the container to stand for 2 hours while keeping the container horizontal with the lid closed.
  • the container was placed in a freezer for 2 hours and frozen and solidified. After 2 hours, the container is taken out of the freezer, and a sheet-like solidified cellulose acetate-containing cellulose acetate DMSO solution formed from the inside of the container is taken out, immersed in 30 mL of a 0.1 mol / L sodium hydroxide aqueous solution, and mixed with water. Deacetylation was performed for 18 hours while exchanging the solvent. After 18 hours, the obtained sheet-shaped cellulose monolith-containing activated carbon molded article was washed with water until the filtrate became neutral.
  • the water inside the cellulose monolith molded body is replaced with ethanol and dried under reduced pressure to obtain a sheet-shaped cellulose monolith molded body having activated carbon particles fixed to the lower part (the activated carbon side is black and the opposite side is white).
  • the activated carbon side is black and the opposite side is white.
  • FIG. 12 shows a stereomicrograph of the appearance and cross section of the cellulose monolith molded article (14) of one embodiment of the present invention.
  • the activated carbon was covered with a white monolith.
  • FIG. 13 shows a stereomicrograph of a cross section of the molded product of cellulose monolith (14 '). The activated carbon was covered with a red monolith.
  • Activated carbon ("Taiko350SZ” manufactured by Futamura Chemical Co., Ltd.) is added to a DMSO solution of cellulose acetate (cellulose acetate concentration: 10.2% by mass), and the same mass as the mass of cellulose acetate in the solution is added. A solution was made. The obtained activated carbon-containing cellulose acetate solution was dropped into 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 4 hours while deacetylation was performed while exchanging the solvent with water. The cellulose monolith particles containing activated carbon were washed with water until the filtrate became neutral.
  • cellulose monolith particles (16) of one embodiment of the present invention After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (16) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith particles (16) was 2.3 g / g, and the specific surface area was 545.69 m 2 / g.
  • 46 mg of the particles were added to 10 g of a 0.0025% by mass aqueous solution of toluidine blue and stirred for 16 hours, the aqueous solution of toluidine blue became transparent.
  • Example 30 To a DMSO solution of cellulose acetate (cellulose acetate concentration 10.2% by mass) was added 1% by mass of a nonionic surfactant (trade name: Pluronic P103) based on the solution to obtain a uniform solution. This solution was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, deacetylated while exchanging the solvent with water, and stirring was continued for 18 hours. After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (17) of one embodiment of the present invention. The water absorption of the cellulose monolith particles (17) was 6.3 g / g.
  • Example 31 A nonionic surfactant (trade name: Pluronic P108) was added to a solution of cellulose acetate in DMSO (cellulose acetate concentration: 10.2% by mass) in an amount of 1% by mass based on the solution to obtain a uniform solution. 1.26 g of this solution was poured into a polyethylene rectangular parallelepiped container having a width of 18 mm, a length of 30 mm, and a height of 18 mm, placed in a freezer for 2 hours while keeping the container horizontal, and frozen and solidified. Frozen sheet (1)).
  • a cellulose acetate DMSO solution (cellulose acetate concentration: 4.0% by mass) was poured into a polyethylene rectangular parallelepiped container having a width of 18 mm, a length of 30 mm, and a height of 18 mm. It was put in a freezer for hours and solidified by freezing (this is referred to as a frozen sheet (3)).
  • the frozen sheets (1) to (3) are taken out of the freezer, overlapped at room temperature in the order of (1), (3), and (2), and covered with a polyethylene film in a state where the three sheets are overlapped. Then, it was put again in a freezer for 1 hour and frozen and solidified. One hour later, the frozen sheet in which the three sheets were overlapped was taken out of the freezer to obtain a molded cellulose acylate product.
  • the obtained cellulose acylate molded product was immersed in 200 mL of a 0.1 mol / L aqueous sodium hydroxide solution, deacetylated while exchanging the solvent with water, and the reaction was performed for 18 hours.
  • the obtained sheet-shaped cellulose monolith molded article was washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith molded body was replaced with ethanol and dried under reduced pressure to obtain a sheet-shaped cellulose monolith molded body (15) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith molding (15) was 11.2 g / g, and the cellulose monolith molding (15) absorbed water and expanded preferentially in the vertical direction.
  • Example 32 1.7 g of a cellulose acetate DMSO solution (cellulose acetate concentration: 4.0% by mass) was poured into a polyethylene rectangular parallelepiped container having a width of 18 mm, a length of 30 mm, and a height of 13 mm. The container was placed in a freezer for 20 hours while being kept horizontal with the lid of the container, and was frozen and solidified. After 20 hours, the container is taken out of the freezer, a sheet-like solidified cellulose acetate DMSO solution molded body is taken out of the container, immersed in 30 mL of a 0.1 mol / L sodium hydroxide aqueous solution, and subjected to solvent exchange with water. The reaction was carried out for 5 hours.
  • a cellulose acetate DMSO solution cellulose acetate concentration: 4.0% by mass
  • the obtained sheet-shaped cellulose monolith molded article was washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith molded body was replaced with ethanol and dried under reduced pressure to obtain a sheet-shaped cellulose monolith molded body (16) of one embodiment of the present invention.
  • the water absorption of the molded product of cellulose monolith (16) was 19.8 g / g.
  • Example 33 A DMSO solution of cellulose acetate (cellulose acetate concentration: 5.4% by mass) was dropped into 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and stirring was continued for 12 hours while deacetylating while exchanging the solvent with water. . After 12 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (18) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith particles (18) is 14.0 g / g, the specific surface area is 35.50 m 2 / g, the water absorption retained in a 0.9% by weight aqueous sodium chloride solution is 6.4 g / g, and the water absorption is deionized water.
  • the retained water absorption was 6.2 g / g.
  • Example 34 An aqueous solution consisting of 150 parts of urea, 20 parts of sodium dihydrogen phosphate dihydrate and 700 parts of deionized water was added to 100 parts of the cellulose monolith particles (18), and the mixture was heated at 145 ° C. for 20 minutes. The heat-treated product is washed with a mixed solvent of methanol / pure water (volume mixing ratio of methanol / pure water: 3: 1), and the washed product is again washed with methanol, and then subjected to suction filtration and drying under reduced pressure to obtain a water swelling solution of the present invention. Cellulose monolith (1) was obtained.
  • the specific surface area of the water-swellable cellulose monolith (1) according to one embodiment of the present invention is 54.02 m 2 / g
  • the retained water absorption in a 0.9% by weight aqueous sodium chloride solution is 12.4 g / g
  • the water absorption is in deionized water.
  • the retained water absorption was 48.1 g / g. From the FT-IR chart, it was confirmed that the water-swellable cellulose monolith (1) had a cellulose carbamate phosphate structure. In addition, it was also confirmed from the SEM image that it had a monolith structure.
  • Example 35 A DMSO solution (cellulose triacetate concentration: 5.4% by mass) of cellulose triacetate (reagent purchased from Fuji Film Wako Pure Chemical Industries, Ltd.) was dropped into 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and water and a solvent were added. Stirring was continued for 16 hours with deacetylation while replacing. After 16 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (19) of one embodiment of the present invention.
  • the water absorption of the cellulose monolith particles (18) is 12.0 g / g, the specific surface area is 29.97 m 2 / g, the water absorption retained in a 0.9% by weight aqueous sodium chloride solution is 5.2 g / g, and the water absorption is deionized water.
  • the retained water absorption was 4.8 g / g.
  • Activated carbon ("Taiko350SZ” manufactured by Futamura Chemical Co., Ltd.) is added to a DMSO solution of cellulose acetate (cellulose acetate concentration: 7.8% by mass) in the same amount as the mass of cellulose acetate in the solution, and the mixture is stirred uniformly and cellulose acetate containing activated carbon is added. A solution was made.
  • the obtained DMSO solution of activated carbon-containing cellulose acetate was poured into the inside of a silicon mold (butterfly) purchased from a cande. The surface was covered with a polyethylene film, and the mold container was placed in a freezer for 20 hours while being kept horizontal, and frozen and solidified.
  • FIG. 14 shows an image of the butterfly-shaped cellulose monolith molding (17).
  • the cellulose monolith molding (17) was placed in a polyethylene bag together with a 190 g Philippine banana, and the bag was sealed. For comparison, 187 g of Philippine banana was placed in a polyethylene bag and the bag was sealed.
  • the Philippine banana containing the cellulose monolith molded article (17) and the Philippine banana not containing were simultaneously put in a refrigerator, refrigerated for one week, taken out of the banana one week later, peeled and peeled, and compared the damage condition of the banana.
  • the banana in which the body (17) was put in the bag was not blackened, but the banana not containing the cellulose monolith molded body (17) was blackened.
  • the activated carbon-containing cellulose monolith molded body (17) had a freshness retaining effect because it adsorbed gas and water.
  • Example 37 An aqueous solution consisting of 152 parts of urea, 50 parts of sodium dihydrogen phosphate dihydrate and 600 parts of deionized water was added to 100 parts of the cellulose monolith particles (19), and the mixture was heated at 145 ° C. for 20 minutes. The heat-treated product is washed with a mixed solvent of methanol / pure water (volume mixing ratio of methanol / pure water: 3: 1). Cellulose monolith (2) was obtained.
  • the water-swellable cellulose monolith (2) of one embodiment of the present invention has a specific surface area of 29.84 m 2 / g, a water absorption retention capacity in a 0.9% by weight aqueous sodium chloride solution of 11.1 g / g, and a water absorption capacity in deionized water.
  • the retained water absorption was 36.5 g / g. From the FT-IR chart, it was confirmed that the water-swellable cellulose monolith (2) had a cellulose carbamate phosphate structure having a carbamoyl group and a phosphate group. In addition, it was also confirmed from the SEM image that it had a monolith structure.
  • Example 38 Synthesis example of cellulose formate (1) 4.86 g of pulverized pulp, 156.9 g of formic acid (88%), 279.3 g of phosphoric acid, and 30 g of water were charged into a flask and stirred at room temperature for 3 days. 450 g of the stirred product was dropped into 1350 g of acetone and stirred for 10 minutes. After filtration under reduced pressure, the residue was washed with acetone three times and dried under reduced pressure to obtain cellulose formate (1). In the FT-IR chart, absorption of the cellulose formate (1) at 1715 cm ⁇ 1 derived from the formyl group was confirmed.
  • Example 39 Synthesis example of cellulose formate (2) 4.86 g of ground pulp, 156.9 g of formic acid (88%), 279.3 g of phosphoric acid, and 30 g of water were charged into a flask, and a homogenizer (manufactured by Hsiang Tai Co., main body model number: HG-200, generator model number: K-12S) was charged. The mixture was stirred at 16,000 rpm at 60 ° C. or lower for 15 minutes, and further stirred at 20,000 rpm for 15 minutes. 450 g of the stirred product was dropped into 1350 g of acetone and stirred for 10 minutes. After filtration under reduced pressure, the residue was washed with acetone three times and dried under reduced pressure to obtain cellulose formate (2).
  • a homogenizer manufactured by Hsiang Tai Co., main body model number: HG-200, generator model number: K-12S
  • Example 40 A DMSO solution in which cellulose formate (1) was dissolved (concentration of cellulose formate: 7.8% by mass) was added dropwise to 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution with stirring, and the mixture was stirred for 0.2 hours. The mixture was allowed to stand for a time, and deacetylated while exchanging the solvent with water. After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (20) of one embodiment of the present invention. The water absorption of the obtained cellulose monolith particles (20) was 3.8 g / g, the compression ratio (%) was 49%, and the compression rigidity was 0.76.
  • Example 41 A DMSO solution (cellulose formate concentration: 5.8% by mass, cellulose acetate concentration: 2.0% by mass) in which cellulose formate (1) and cellulose acetate are dissolved is stirred in 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution. The mixture was added dropwise, stirred for 0.2 hours, allowed to stand for 18 hours, and deacetylated while exchanging the solvent with water. After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (21) of one embodiment of the present invention. The water absorption of the obtained cellulose monolith particles (21) was 13.9 g / g, the compression ratio was 70%, and the compression rigidity was 0.45.
  • Example 42 A DMSO solution (cellulose formate concentration: 3.9% by mass, cellulose acetate concentration: 3.9% by mass) in which cellulose formate (1) and cellulose acetate are dissolved is stirred into 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution. The mixture was added dropwise, deacetylated while exchanging the solvent with water, and stirring was continued for 18 hours. After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (22) of one embodiment of the present invention. The water absorption of the obtained cellulose monolith particles (22) was 9.7 g / g, the compression ratio (%) was 48%, and the compression rigidity was 0.69.
  • Example 43 A DMSO solution (cellulose formate concentration: 2.7% by mass, cellulose acetate concentration: 2.7% by mass) in which cellulose formate (1) and cellulose acetate are dissolved is stirred into 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution. The mixture was added dropwise, deacetylated while exchanging the solvent with water, and stirring was continued for 18 hours. After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (23) of one embodiment of the present invention. The water absorption of the obtained cellulose monolith particles (23) was 18.5 g / g.
  • Example 44 A DMSO solution in which cellulose formate (2) and cellulose acetate are dissolved (concentration of cellulose formate: 2.7% by mass, concentration of cellulose acetate: 2.7% by mass) was stirred under stirring in 30 mL of 0.1 mol / L aqueous sodium hydroxide solution. And the mixture was deacetylated while exchanging the solvent with water, and stirring was continued for 18 hours. After 18 hours, the obtained cellulose monolith particles were washed with water until the filtrate became neutral. After washing with water, the water inside the cellulose monolith particles was replaced with ethanol and dried under reduced pressure to obtain cellulose monolith particles (24) of one embodiment of the present invention. The water absorption of the obtained cellulose monolith particles (24) was 6.8 g / g.
  • Activated carbon-encapsulated cellulose monolith particles were produced using an encapsulator B-390 (manufactured by Buchi). While continuously passing an activated carbon dispersion obtained by dispersing 10.4 g of activated carbon SA1000 (manufactured by Futamura Chemical Co., Ltd.) in 100 mL of cyclohexane through a concentric nozzle (core nozzle (inner diameter: 450 ⁇ m) for inclusions), a DMSO solution of cellulose acetate (cellulose) (Acetate concentration: 5.4% by mass) was passed through a shell nozzle for a film material (inner diameter: 900 ⁇ m) as a shell liquid.
  • an activated carbon dispersion obtained by dispersing 10.4 g of activated carbon SA1000 (manufactured by Futamura Chemical Co., Ltd.) in 100 mL of cyclohexane through a concentric nozzle (core nozzle (inner diameter: 450 ⁇ m) for inclusions)
  • Example 46 An aqueous solution consisting of 200 parts of citric acid and 380 parts of deionized water was added to 100 parts of the cellulose monolith particles (2), and the mixture was heated at 120 ° C. for 60 minutes. The heat-treated product was washed with pure water, and the washed product was washed again with methanol, followed by suction filtration and drying under reduced pressure to obtain a carboxyl group-containing cellulose monolith (1) of one embodiment of the present invention. The carboxyl group-containing cellulose monolith (1) was confirmed to have a carboxyl group from its FT-IR chart. The titration determined that the carboxyl group-containing cellulose monolith (1) had a carboxyl group of 0.45 mmol per gram.
  • the production method of the cellulose monolith of the present invention and the cellulose monolith obtained by the production method include sanitary materials such as disposable diapers and sanitary napkins, cosmetics, freshness preserving agents, soil modifying agents, adsorbents, deodorants, water purifying agents, and metals. It can be applied to various fields such as ion removal, gel filtration chromatography carrier, sustained release drug carrier, desalination of seawater, ion exchange chromatography carrier, affinity chromatography carrier and the like.

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Abstract

La présente invention concerne un procédé de production de monolithe de cellulose et un monolithe de cellulose blanche comprenant des particules colorées, le procédé de production de monolithe de cellulose étant caractérisé par : la production d'un monolithe de cellulose par la mise en contact d'une solution d'acylate de cellulose avec un milieu contenant de l'eau et un agent de déacylation, ce qui permet de déacyler la solution d'acylate de cellulose par échange de solvant avec l'eau, ou la mise en contact d'une solution de formiate de cellulose avec un milieu contenant de l'eau et un agent de déformylation, déformylant ainsi la solution de formiate de cellulose par échange de solvant avec l'eau ; et le traitement thermique du monolithe de cellulose en présence d'urée et d'acide phosphorique (sel).
PCT/JP2019/030107 2018-07-26 2019-07-25 Procédé de production de monolithe de cellulose, et monolithe de cellulose obtenu par ledit procédé de production Ceased WO2020022524A1 (fr)

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