WO2016143439A1 - Corps poreux comprenant une cellulose bactérienne et un polymère, et son procédé de fabrication - Google Patents

Corps poreux comprenant une cellulose bactérienne et un polymère, et son procédé de fabrication Download PDF

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WO2016143439A1
WO2016143439A1 PCT/JP2016/053597 JP2016053597W WO2016143439A1 WO 2016143439 A1 WO2016143439 A1 WO 2016143439A1 JP 2016053597 W JP2016053597 W JP 2016053597W WO 2016143439 A1 WO2016143439 A1 WO 2016143439A1
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polymer
solvent
copolymer
bacterial cellulose
porous body
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宇山浩
土橋歩実
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国立大学法人大阪大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a porous body containing bacterial cellulose and a polymer and a method for producing the same.
  • Porous materials are widely used as a separating agent, an adsorbing agent, and the like.
  • Inorganic porous materials have been extensively researched on silica-based porous materials.
  • silica-based porous bodies a technique for creating porous silica particles is common. This porous silica particle has been put to practical use as an analytical material.
  • a polymer-based porous body a technique for obtaining porous body particles by adding an appropriate diluent during suspension polymerization of a vinyl monomer is known.
  • This polymer-based porous material has been put into practical use as various adsorbents and separation agents by taking advantage of the light weight of polymer materials.
  • a lump of material having a structure in which a continuous skeleton and voids are intertwined with each other is called a monolith.
  • the present inventors have (meth) acrylic acid ester polymer (Patent Document 1), polylactic acid (Patent Document 2), polyvinyl alcohol (Patent Document 3), polycarbonate (Patent Document 4). ), Polyacrylonitrile (Patent Document 5), ethylene vinyl alcohol (Patent Document 6), etc., and a method for producing a polymer porous body (monolith) by heat-induced phase separation or poor solvent-induced phase separation has been reported.
  • bacterial cellulose is a fine cellulose fiber produced by microorganisms.
  • the cellulose fibers form a three-dimensional network structure.
  • the bacterial cellulose hydrogel is a gel in which water is retained in the bacterial cellulose, and the water content is about 99%.
  • An example of the application of bacterial cellulose is Nata de Coco, which has been known for a long time. In recent years, composite materials combining bacterial cellulose and various polymers have been reported.
  • Non-patent Document 1 a method of immersing bacterial cellulose gel in a polyvinyl alcohol aqueous solution to make a composite
  • Non-patent Documents 2 and 3 a method of adding polyvinyl alcohol to a bacterial cellulose dispersion and making a composite
  • Non-patent Documents 2 and 3 A method of adding polyvinyl alcohol to a solution of bacterial cellulose to form a complex
  • Non-patent Document 4 A method of adding polyvinyl alcohol to a solution of bacterial cellulose to form a complex
  • a method of culturing in the presence of polyvinyl alcohol to produce bacterial cellulose and a complex
  • water-soluble polyvinyl alcohol is combined with bacterial cellulose, but there are currently not many types of polymers to be combined with bacterial cellulose.
  • an object of the present invention is to provide a porous body containing bacterial cellulose and a polymer and a method for producing the same.
  • the present invention is a method for producing a porous body comprising bacterial cellulose and a polymer, The method Adding a first solvent to the bacterial cellulose hydrogel to prepare a first mixture; Adding the polymer to the first mixture and heating; dissolving the polymer in a mixture of the first solvent and water to prepare a second mixture; Cooling the second mixture to obtain a precipitated molded body, and immersing the molded body in a second solvent so that the first solvent and water contained in the molded body are Substituting with a solvent to obtain a porous body containing the bacterial cellulose and polymer,
  • the polymer is a polymer capable of forming a porous body by phase separation,
  • the first solvent is a solvent miscible with water.
  • the bacterial cellulose is preferably fibrous.
  • the present invention can provide a method for producing a porous body containing bacterial cellulose and a polymer. Moreover, the porous body containing bacterial cellulose and a polymer can be obtained by the production method of the present invention.
  • FIG. 1 is an SEM photograph of the bacterial cellulose hydrogel obtained in Production Example 1.
  • FIG. 2 a is a SEM photograph of the BC-PAN porous material obtained in Example 1.
  • FIG. 2 b is an SEM photograph of the BC-PAN porous material obtained in Example 1.
  • FIG. 2c shows the photographing directions of FIGS. 2a and 2b of the SEM photograph of the BC-PAN porous material obtained in Example 1.
  • FIG. 3 a is a SEM photograph of BC-PAN activated carbon obtained in Example 2.
  • FIG. 3b is a SEM photograph of the BC-PAN activated carbon obtained in Example 2.
  • FIG. 3 c shows the photographing directions of FIGS. 3 a and 3 b of SEM photographs of the BC-PAN activated carbon obtained in Example 2.
  • FIG. 1 is an SEM photograph of the bacterial cellulose hydrogel obtained in Production Example 1.
  • FIG. 2 a is a SEM photograph of the BC-PAN porous material obtained in Example 1.
  • FIG. 4 is a graph showing the capacity retention ratio of the BC-PAN activated carbon obtained in Example 2 and the PAN activated carbon with respect to the scanning speed using a sulfuric acid aqueous solution (1M).
  • FIG. 5a is a cyclic voltammogram of the BC-PAN porous material obtained in Example 1 and the BC-PAN activated carbon obtained in Example 2.
  • FIG. 5b is a Nyquist plot of the PAN activated carbon for comparison with the BC-PAN charcoal obtained in Example 2.
  • 6a is an SEM photograph of the BC-PMMA porous material obtained in Example 3.
  • FIG. 6b is an SEM photograph of the BC-PMMA porous material obtained in Example 3.
  • FIG. 7 is an SEM photograph of the BC-CA porous material obtained in Example 4.
  • FIG. 5a is a cyclic voltammogram of the BC-PAN porous material obtained in Example 1 and the BC-PAN activated carbon obtained in Example 2.
  • FIG. 5b is a Nyquist plot
  • FIG. 8 is a SEM photograph of the BC-EVOH porous material obtained in Example 5-1.
  • FIG. 9a is an SEM photograph of the BC-EVOH porous material obtained in Example 5-2.
  • FIG. 9b is an SEM photograph of the BC-EVOH porous material obtained in Example 5-2.
  • FIG. 10a is an SEM photograph of the BC-EVOH porous material obtained in Example 5-3.
  • FIG. 10b is an SEM photograph of the BC-EVOH porous material obtained in Example 5-3.
  • FIG. 11 is an SEM photograph of the BC-EVOH porous material obtained in Example 5-4.
  • FIG. 12 is an SEM photograph of the BC-EVOH porous material obtained in Example 5-5.
  • FIG. 13a is a SEM photograph of the BC-EVOH porous material obtained in Example 5-6.
  • FIG. 13b is a SEM photograph of the BC-EVOH porous material obtained in Example 5-6.
  • the hydrogel shrinks or collapses.
  • the present inventors have found that such a phenomenon is not observed for the hydrogel of bacterial cellulose, and that the water in the hydrogel can be replaced with an organic solvent. Based on such knowledge, the present inventors have found that a porous body containing bacterial cellulose and a polymer can be formed by forming a polymer monolith in a bacterial cellulose hydrogel.
  • bacterial cellulose is fine cellulose fibers produced by microorganisms.
  • the microorganism is not limited as long as it is a cellulose-producing bacterium, and examples thereof include bacteria belonging to the genus Acetobacter, Gluconobacter, Agrobacterium, Pseudomonas, Enterobacter, and the like.
  • bacterial cellulose gel the cellulose fibers form a three-dimensional network structure.
  • the bacterial cellulose hydrogel is a gel in which water is retained in the bacterial cellulose, and the water content is about 99%. Nata de coco is a kind of bacterial cellulose hydrogel.
  • the medium for culturing the microorganism is not particularly limited.
  • glucose, mannitol, sucrose, maltose, starch hydrolyzate, molasses, ethanol, acetic acid, citric acid, etc. as a carbon source
  • ammonium sulfate Ammonium salts such as ammonium chloride and ammonium phosphate, nitrates, urea, polypeptone, etc. as inorganic salts, phosphates, calcium salts, iron salts, manganese salts as organic micronutrients, amino acids, vitamins, fatty acids, nucleic acids, etc. Can be used.
  • the polymer is a polymer capable of forming a porous body by phase separation.
  • examples of such polymers include polylactic acid, homopolymers of acrylic esters, copolymers containing acrylic esters, homopolymers of methacrylic esters, copolymers containing methacrylic esters, polyacrylonitrile, and acrylonitrile.
  • Copolymer polyvinyl alcohol, ethylene vinyl alcohol copolymer, poly ( ⁇ -glutamic acid), chitosan, alginic acid, polyethylene oxide, cellulose acetate, and the like
  • polyacrylonitrile, copolymer containing acrylonitrile, polymethyl methacrylate, polyvinyl alcohol, and Ethylene vinyl alcohol copolymers are preferred
  • polyacrylonitrile, copolymers containing acrylonitrile, and ethylene vinyl alcohol copolymers are more preferred. .
  • the polylactic acid is poly L-lactic acid, poly D-lactic acid or poly DL-lactic acid.
  • the optical purity of polylactic acid is preferably 95% or higher, more preferably 96% or higher, and still more preferably 97% or higher.
  • the weight average molecular weight (Mw) of polylactic acid is preferably 30,000 or more, more preferably 50,000 or more, and further preferably 80,000 or more.
  • polylactic acid commercially available polylactic acid may be obtained, or it may be made in-house according to methods known in the literature.
  • Examples of the homopolymers of acrylic acid esters, copolymers containing acrylic acid esters, homopolymers of methacrylic acid esters, and copolymers containing methacrylic acid esters include the following.
  • homopolymers of acrylic esters include lower alkyl alcohols having 1 to 6 carbon atoms which may contain at least one selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group and a halogen atom. And homopolymers of esters of acrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms.
  • Examples of homopolymers of esters of acrylic acid and esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms include, for example, poly Examples thereof include methyl acrylate, polyethyl acrylate, polybutyl acrylate, poly (t-butyl acrylate), polybenzyl benzyl, etc., and homoesters of esters of the above acrylic acid with an epoxy lower alkyl alcohol having 2 to 6 carbon atoms.
  • Examples of the polymer include polyglycidyl acrylate.
  • copolymer containing acrylic esters examples include copolymers of acrylic esters and acrylic acids, copolymers of acrylic esters and methacrylic acids, copolymers of acrylic esters and acrylic esters, and acrylic esters. Examples thereof include copolymers of methacrylic acid esters, copolymers of acrylic acid esters and monomers other than those mentioned above, and the like.
  • homopolymer of the methacrylic acid esters examples include, for example, methacrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom. And homopolymers of esters of methacrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms.
  • Examples of homopolymers of esters of methacrylic acid and esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms include polymethacrylic acid Examples include methyl, polyethyl methacrylate, polybutyl methacrylate, poly-t-butyl methacrylate, polybenzyl methacrylate, poly 2-hydroxyethyl methacrylate, and the like, and methacrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms. Examples of the homopolymer of esters with polyglycidyl methacrylate and the like.
  • Examples of the copolymer containing methacrylic acid esters include, for example, a copolymer of methacrylic acid esters and acrylic acid, a copolymer of methacrylic acid esters and methacrylic acid, a copolymer of methacrylic acid esters and acrylic acid esters, and a methacrylic acid ester. Examples thereof include copolymers of methacrylic acid esters and copolymers of methacrylic acid esters and monomers other than those mentioned above. As the copolymer of the methacrylic acid esters and the other monomers, a copolymer of the methacrylic acid esters and a monomer represented by the following formula (I) is preferable.
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, halogen atom, carbamoyl group, cyano group, lower alkyl group, vinyloxy group, aryl group or halogen atom.
  • a substituted aryl group, or R 1 and R 3 together with the double bond to which R 1 and R 3 are attached form 2,5-dihydrofuran-2,5-dione, and R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a carbamoyl group, a cyano group, a lower alkyl group, a vinyloxy group, an aryl group or an aryl group substituted with a halogen atom.
  • Examples of the copolymer of acrylic acid esters and acrylic acid include lower alkyl having 1 to 6 carbon atoms which may contain at least one selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group and a halogen atom.
  • Examples include esters of alcohol and acrylic acid; and esters of acrylic acid and C2-C6 epoxy lower alkyl alcohol and acrylic acid.
  • a copolymer of acrylic acid and esters of acrylic acid with esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms
  • a copolymer of methyl acrylate and acrylic acid a copolymer of ethyl acrylate and acrylic acid, a copolymer of butyl acrylate and acrylic acid, a copolymer of t-butyl acrylate and acrylic acid, a copolymer of benzyl acrylate and acrylic acid, etc.
  • the copolymer of acrylic acid and esters of acrylic lower alkyl alcohol having 2 to 6 carbon atoms and acrylic acid include, for example, a copolymer of glycidyl acrylate and acrylic acid.
  • Examples of the copolymer of acrylic acid esters and methacrylic acid include, for example, a lower alkyl having 1 to 6 carbon atoms which may contain at least one selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group and a halogen atom. Mention may be made of esters with alcohols and copolymers of methacrylic acid; and copolymers of acrylic acid and epoxy lower alkyl alcohols having 2 to 6 carbon atoms with methacrylic acid.
  • Copolymers of acrylic acid and esters of methacrylic acid with esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms,
  • copolymers of methyl acrylate and methacrylic acid copolymers of ethyl acrylate and methacrylic acid, copolymers of butyl acrylate and methacrylic acid, copolymers of t-butyl acrylate and methacrylic acid, copolymers of benzyl acrylate and methacrylic acid, etc.
  • Examples of the copolymer of acrylic acid and an ester of an acrylic lower alkyl alcohol having 2 to 6 carbon atoms and methacrylic acid include a copolymer of glycidyl acrylate and methacrylic acid.
  • Examples of the copolymer of acrylic acid esters and acrylic acid esters include those having 1 to 6 carbon atoms which may contain at least one selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group and a halogen atom.
  • Another ester of an ester with a lower alkyl alcohol and an acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom Copolymers of acrylic acids and esters of acrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms, acrylic acid and S with C2-6 epoxy lower alkyl alcohol Le such copolymers; and esters of and epoxy lower alkyl alcohols of acrylic acid with 2 to 6 carbon atoms include different esters of epoxy lower alkyl alcohols of 2-6 carbon atoms and acrylic acid.
  • Esters of acrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms, acrylic acid and aryl groups, hydroxy
  • Examples of the copolymer of another ester with a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a group, a carboxyl group and a halogen atom include, for example, methyl acrylate and ethyl acrylate Copolymer, copolymer of methyl acrylate and butyl acrylate, copolymer of methyl acrylate and t-butyl acrylate, copolymer of methyl acrylate and benzyl acrylate, etc., such as acrylic acid and aryl group, hydroxy group, carboxyl group And a group of halogen atoms
  • Examples of the copolymer of acrylic acid esters and methacrylic acid esters may include, for example, acrylic acid and one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group, and a halogen atom.
  • An ester of a lower alkyl alcohol and an ester of methacrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom Copolymer; Esters of acrylic acid and epoxy lower alkyl alcohols having 2 to 6 carbon atoms, and methacrylic acid and one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms 6 copolymers of esters with lower alkyl alcohols; Esters of acrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms, and methacrylic acid and 2 to 6 carbon atoms
  • Esters of acrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms, methacrylic acid and aryl groups, hydroxy
  • Examples of the copolymer of esters with a lower alkyl alcohol having 1 to 6 carbon atoms which may include one or more selected from the group consisting of a group, a carboxyl group and a halogen atom include, for example, a copolymer of methyl acrylate and methyl methacrylate, Examples thereof include a copolymer of methyl acrylate and ethyl methacrylate, a copolymer of methyl acrylate and butyl methacrylate, a copolymer of methyl acrylate and t-butyl methacrylate, and a copolymer of methyl acrylate and benzyl methacrylate.
  • Esters of acrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms, methacrylic acid and 2 to 2 carbon atoms
  • Examples of the ester copolymer of 6 with an epoxy lower alkyl alcohol include a copolymer of methyl acrylate and glycidyl methacrylate.
  • Examples of the copolymer of the acrylate ester and a monomer other than the above include a copolymer of the acrylate ester and a monomer represented by the following formula (I).
  • Examples of the copolymer of the acrylate ester and the monomer represented by the following formula (I) include, for example, one or more selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom.
  • An ester of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom, and is represented by the formula (I)
  • the copolymer of monomers include, for example, a copolymer of methyl acrylate and maleic anhydride, a copolymer of ethyl acrylate and vinyl chloride, a copolymer of butyl acrylate and vinyl ether, a copolymer of t-butyl acrylate and maleic anhydride, benzyl acrylate And vinyl chloride copolymer, methyl acrylate and styrene copolymer, methyl acrylate and acrylonitrile copolymer, methyl acrylate and acrylamide copolymer, and the like.
  • Examples of the copolymer of methacrylic acid esters and acrylic acid include, for example, lower alkyl having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of methacrylic acid and an aryl group, a hydroxy group, a carboxyl group and a halogen atom.
  • Examples include esters of alcohols and copolymers of acrylic acid; and esters of methacrylic acid and epoxy lower alkyl alcohols having 2 to 6 carbon atoms and acrylic acid.
  • a copolymer of acrylic acid with esters of methacrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms
  • a copolymer of methyl methacrylate and acrylic acid a copolymer of ethyl methacrylate and acrylic acid, a copolymer of butyl methacrylate and acrylic acid, a copolymer of t-butyl methacrylate and acrylic acid, a copolymer of benzyl methacrylate and acrylic acid, etc.
  • Examples of the copolymer of methacrylic acid and an ester of lower alkyl alcohol having 2 to 6 carbon atoms and acrylic acid include, for example, a copolymer of glycidyl methacrylate and acrylic acid.
  • Examples of the copolymer of methacrylic acid esters and methacrylic acid include, for example, lower alkyl having 1 to 6 carbon atoms which may contain at least one selected from the group consisting of methacrylic acid and an aryl group, a hydroxy group, a carboxyl group and a halogen atom. Mention may be made of esters with alcohols and copolymers of methacrylic acid; and esters of methacrylic acid with epoxy lower alkyl alcohols having 2 to 6 carbon atoms and copolymers of methacrylic acid.
  • copolymers of methacrylic acid and an ester of a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom
  • copolymers of methyl methacrylate and methacrylic acid copolymers of ethyl methacrylate and methacrylic acid, copolymers of butyl methacrylate and methacrylic acid, copolymers of t-butyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, etc.
  • a copolymers of methacrylic acid and an ester of a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom
  • Examples of the copolymer of methacrylic acid and an ester of an epoxy lower alkyl alcohol having 2 to 6 carbon atoms and methacrylic acid include a copolymer of glycidyl methacrylate and methacrylic acid.
  • Examples of the copolymer of methacrylic acid esters and methacrylic acid esters include, for example, methacrylic acid and 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom
  • Another ester of methacrylic acid and lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl group, hydroxy group, carboxyl group and halogen atom
  • Esters of methacrylic acid and epoxy lower alkyl alcohols having 2 to 6 carbon atoms, and 1 to 1 carbon atoms which may contain one or more selected from the group consisting of methacrylic acid and aryl groups, hydroxy groups, carboxyl groups and halogen atoms
  • Esters of methacrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms, methacrylic acid and aryl groups, hydroxy
  • Examples of another ester copolymer with a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of a group, a carboxyl group and a halogen atom include, for example, methyl methacrylate and ethyl methacrylate Copolymers, copolymers of methyl methacrylate and butyl methacrylate, copolymers of butyl methacrylate and benzyl methacrylate, and the like.
  • Esters of methacrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms; methacrylic acid and 2 to Examples of the copolymer of esters of 6 with an epoxy lower alkyl alcohol include a copolymer of methyl methacrylate and glycidyl methacrylate.
  • Examples of the copolymer of the methacrylic acid esters and the monomer represented by the formula (I) include carbon that may contain at least one selected from the group consisting of methacrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom.
  • Esters of the methacrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms are represented by the formula (I)
  • Examples of the copolymer of monomers include, for example, a copolymer of methyl methacrylate and maleic anhydride, a copolymer of ethyl methacrylate and vinyl chloride, a copolymer of butyl methacrylate and vinyl ether, a copolymer of t-butyl methacrylate and maleic anhydride, and benzyl methacrylate.
  • Examples of the copolymer of the ester of methacrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms and the monomer represented by the formula (I) include a copolymer of glycidyl methacrylate and vinyl ether.
  • the monomer composition ratio is not limited, but examples include a polymer having a low solubility in water.
  • the monomer sequence of the polymer may be random, block or the like.
  • the molecular weight of the polymer is not limited, for example, the number average molecular weight is 1,000 to 100,000,000, preferably 2,000 to 50,000,000, more preferably 3,000 to 20,000,000.
  • the weight average molecular weight is 1,000 to 150,000,000, preferably 2,000 to 80,000,000, and more preferably 3,000 to 40,000,000.
  • the molecular weight of the polyacrylonitrile is not limited, but the average molecular weight is, for example, 10,000 to 5,000,000, preferably 20,000 to 4,000,000, and more preferably 30,000 to 3,000,000.
  • copolymer containing acrylonitrile examples include a copolymer of vinyl acetate and acrylonitrile, a copolymer of methyl acrylate and acrylonitrile, a copolymer of styrene and acrylonitrile, a copolymer of methacrylic acid and acrylonitrile, and a copolymer of butadiene and acrylonitrile.
  • the molecular weight of the polyvinyl alcohol is not limited, but the molecular weight is, for example, 5,000 to 5,000,000, preferably 10,000 to 4,000,000, and more preferably 10,000 to 3,000,000.
  • the degree of polymerization is, for example, 100 to 100,000, preferably 200 to 80,000, more preferably 200 to 60,000.
  • Polyvinyl alcohol has a saponification degree of, for example, 60 mol% or more, preferably 80 mol% or more, more preferably 85 mol% or more.
  • the molecular weight of the ethylene vinyl alcohol copolymer is not limited, but the molecular weight is, for example, 5,000 to 5,000,000, preferably 10,000 to 4,000,000, and more preferably 10,000 to 3,000,000.
  • the degree of polymerization is, for example, 100 to 100,000, preferably 200 to 80,000, more preferably 200 to 60,000.
  • the poly ( ⁇ -glutamic acid) is a linear water-soluble biodegradable polymer that is produced very efficiently by fermentation of microorganisms belonging to the genus Bacillus, and has a carboxyl group contained in the ⁇ -carboxyl group in the side chain. is there.
  • the molecular weight of the poly ( ⁇ -glutamic acid) is not limited, but is, for example, 3,000 to 10,000,000, preferably 5,000 to 8,000,000, and more preferably 10,000 to 5,000,000.
  • the degree of polymerization is, for example, 100 to 100,000, preferably 200 to 80,000, more preferably 200 to 60,000.
  • the chitosan is a natural polysaccharide having an amino group, and is a functional polymer having various uses such as antibacterial properties and metal chelating ability.
  • the porous body containing ethylene vinyl alcohol copolymer and chitosan as main components is a porous body having both the hydroxyl group of ethylene vinyl alcohol copolymer and the amino group of chitosan.
  • the chitosan has a degree of deacetylation of, for example, 60 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more. Chitosan has a degree of polymerization of, for example, 30 to 10,000, preferably 50 to 5,000.
  • the alginic acid is a linear polymer in which two types of blocks, ⁇ -D-mannuronic acid and ⁇ -L-guluronic acid, which is the C-5 epimer, are bonded (1-4).
  • the alginic acid is not limited in molecular weight, but is, for example, 3,000 to 10,000,000, preferably 5,000 to 8,000,000, and more preferably 10,000 to 5,000,000.
  • the molecular weight of the polyethylene oxide is not limited, but is, for example, 3,000 to 10,000,000, preferably 5,000 to 8,000,000, and more preferably 10,000 to 5,000,000.
  • the cellulose acetate is a polymer obtained by esterifying cellulose.
  • the degree of oxidation of cellulose acetate is, for example, 50 to 70.
  • the molecular weight of cellulose acetate is not limited, but the molecular weight is, for example, 3,000 to 10,000,000, preferably 5,000 to 8,000,000, and more preferably 10,000 to 5,000,000.
  • Bacterial cellulose hydrogel has a water content of about 99%.
  • the first solvent is not limited as long as it is miscible with water and is a solvent other than water.
  • a first solvent include methanol, ethanol, isopropanol, glycerin, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2-butanone, nitromethane, Nitroethane, nitrobenzene, benzonitrile, propionitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, methyl ethyl ketone, dimethylacetamide (DMAc), N-methylpyrrolidone, 1,4-dioxane, acetonitrile, 1-propanol is exemplified, and dimethyl sulfoxide, ethanol, methanol, isopropanol, DMF, N-methylpyrroli
  • the first solvent is preferably DMSO or 1,4-dioxane, more preferably DMSO.
  • the polymer is any one of a homopolymer of acrylic esters, a copolymer containing acrylic esters, a homopolymer of methacrylic esters, and a copolymer containing methacrylic esters, Is preferably an aliphatic alcohol containing an aliphatic hydrocarbon having 1 to 8 carbon atoms and having 1 or more hydroxyl groups, and more preferably ethanol or isopropanol.
  • the first solvent is preferably dimethyl sulfoxide, DMF, or DMAc, and more preferably dimethyl sulfoxide, or DMF.
  • the polymer is polyvinyl alcohol, acetone is preferable as the first solvent.
  • the polymer is an ethylene vinyl alcohol copolymer, isopropanol is preferable as the first solvent.
  • the first solvent is preferably dimethyl sulfoxide, DMF, or DMAc, and more preferably dimethyl sulfoxide, or DMF.
  • the first solvent is preferably dimethyl sulfoxide, DMF or DMAc, more preferably dimethyl sulfoxide or DMF.
  • the first solvent is preferably dimethyl sulfoxide, DMF or DMAc, more preferably dimethyl sulfoxide or DMF.
  • the polymer is alginic acid
  • the first solvent is preferably methanol, ethanol and isopropanol, more preferably methanol and ethanol.
  • the first solvent is preferably dimethyl sulfoxide, DMF or DMAc, more preferably dimethyl sulfoxide or DMF.
  • the first solvent is preferably dimethyl sulfoxide, DMF or DMAc, more preferably dimethyl sulfoxide or DMF.
  • the volume ratio of the first solvent and water in the first mixture is preferably 10 to 99.5%, More preferably, it is 20 to 99%. Since the bacterial cellulose hydrogel has a water content of about 99%, the volume of water in the first mixture is substantially the same as the volume of the bacterial cellulose hydrogel.
  • the volume ratio of the first solvent to water (first solvent / water + first solvent) in the first mixture is preferably 75% to 99.5%.
  • the polymer is any one of a homopolymer of acrylic esters, a copolymer containing acrylic esters, a homopolymer of methacrylic esters, and a copolymer containing methacrylic esters, in the first mixture,
  • the volume ratio of the first solvent to water (first solvent / water + first solvent) is preferably 30 to 99%, more preferably 50 to 97%.
  • the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 10 to 95%, 20 to 90% is more preferable.
  • the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 35 to 55%, More preferred is ⁇ 52%.
  • the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is 40 to 90%. Is preferable, and 40 to 80% is more preferable.
  • the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 10 to 95%. 20 to 90% is more preferable.
  • the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is 10 to 95%. Is preferable, and 20 to 90% is more preferable.
  • the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 40 to 90%, preferably 40 to 80% is more preferable.
  • the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 35 to 55%, preferably 50 to 52% is more preferable.
  • the volume ratio of the first solvent and water in the first mixture (first solvent / water + first solvent) is preferably 10 to 95%, ⁇ 90% is more preferred.
  • the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 10 to 95%, ⁇ 90% is more preferred.
  • examples of the second solvent include water, lower alcohol, acetone, methyl ethyl ketone, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone, 1,4-dioxane, and acetonitrile. 1 or more selected from the group consisting of lower alcohol, acetone and acetonitrile, more preferably water, methanol, acetone and acetonitrile.
  • lower alcohol examples include lower alcohols having 1 to 6 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, n-butanol, 2-butanol, i-butanol, t-butanol, n -Pentanol, t-amyl alcohol, n-hexanol.
  • the polymer may be subjected to a physical stimulus when dissolved in the first solvent and water mixture.
  • Examples of the physical stimulation include stirring, shaking, ultrasonic treatment, and the like.
  • the temperature at which the polymer is added to the first mixture and heated is, for example, 15 ° C. to 100 ° C., preferably 20 ° C. to 95 ° C.
  • the second mixture includes the bacterial cellulose, water, the first solvent, and the polymer.
  • the polymer is dissolved in a mixture of water and a first solvent.
  • the heating temperature is preferably 40 ° C. to 100 ° C.
  • the heating temperature is The temperature is preferably 15 ° C. to 65 ° C., and more preferably 20 ° C. to 60 ° C.
  • the heating temperature is preferably 70 ° C. to 95 ° C., more preferably 70 ° C. to 90 ° C.
  • the heating temperature is preferably 30 ° C. to 100 ° C., more preferably 40 ° C. to 100 ° C.
  • the heating temperature is preferably 30 ° C. to 100 ° C., more preferably 40 ° C. to 100 ° C.
  • the heating temperature is preferably 70 ° C. to 95 ° C., more preferably 70 ° C. to 90 ° C.
  • the heating temperature is preferably 70 ° C. to 95 ° C., more preferably 70 ° C. to 90 ° C.
  • the heating temperature is preferably 30 ° C. to 100 ° C., more preferably 40 ° C. to 100 ° C.
  • the heating temperature is preferably 30 ° C. to 100 ° C., more preferably 40 ° C. to 100 ° C.
  • the heating temperature is preferably 70 ° C. to 95 ° C., more preferably 70 ° C. to 90 ° C.
  • the heating temperature is preferably 70 ° C. to 95 ° C., more preferably 70 ° C. to 90 ° C.
  • the concentration of the polymer in the second mixture is, for example, 5 to 300 mg / ml, preferably 10 to 200 mg / ml, more preferably 15 to 150 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 30 to 150 mg / ml, more preferably 30 to 120 mg / ml.
  • the polymer is any one of a homopolymer of acrylic esters, a copolymer containing acrylic esters, a homopolymer of methacrylic esters, and a copolymer containing methacrylic esters, in the second mixture,
  • the concentration of the polymer is preferably 5 to 200 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 10 to 300 mg / ml, more preferably 15 to 200 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 60 to 250 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 60 to 250 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 10 to 300 mg / ml, more preferably 15 to 200 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml.
  • the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml.
  • the temperature for cooling the second mixture is, for example, ⁇ 200 ° C. to 60 ° C., preferably ⁇ 196 ° C. to 45 ° C., more preferably ⁇ 20 ° C. to 40 ° C.
  • the cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours.
  • the temperature for cooling the second mixture is preferably ⁇ 20 ° C. to 30 ° C.
  • the second mixture is The cooling temperature is preferably ⁇ 200 ° C. to 40 ° C., more preferably 0 ° C. to 30 ° C.
  • the temperature for cooling the second mixture is preferably ⁇ 20 ° C. to 60 ° C., more preferably 15 ° C. to 45 ° C.
  • the temperature for cooling the second mixture is preferably ⁇ 196 ° C. to 40 ° C., more preferably ⁇ 196 ° C. to 35 ° C.
  • the temperature for cooling the second mixture is preferably ⁇ 196 ° C. to 40 ° C., more preferably ⁇ 196 ° C. to 35 ° C.
  • the temperature for cooling the second mixture is preferably ⁇ 20 ° C. to 60 ° C., more preferably 15 ° C. to 45 ° C.
  • the temperature for cooling the second mixture is preferably ⁇ 20 ° C. to 60 ° C., more preferably 15 ° C. to 45 ° C.
  • the temperature for cooling the second mixture is preferably ⁇ 196 ° C. to 40 ° C., more preferably ⁇ 196 ° C. to 35 ° C.
  • the temperature for cooling the second mixture is preferably ⁇ 196 ° C. to 40 ° C., more preferably ⁇ 196 ° C. to 35 ° C.
  • the temperature for cooling the second mixture is preferably ⁇ 20 ° C.
  • the temperature for cooling the second mixture is preferably ⁇ 20 ° C. to 60 ° C., more preferably 15 ° C. to 45 ° C.
  • the cooling time is preferably 5 minutes to 3 hours.
  • the cooling time is preferably The time is 1 minute to 24 hours, more preferably 1 minute to 1.5 hours.
  • the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours.
  • the cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours.
  • the cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours.
  • the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours.
  • the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours.
  • the cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours.
  • the cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours.
  • the cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours.
  • the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours.
  • the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours.
  • the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours.
  • the obtained molded body may be dried to obtain a porous body.
  • the drying is performed at, for example, 0 ° C. to 90 ° C., preferably 10 ° C. to 80 ° C.
  • the drying is performed, for example, under reduced pressure to normal pressure, preferably under reduced pressure.
  • the drying may be freeze drying.
  • the drying is preferably performed at 20 ° C. to 80 ° C., more preferably 20 ° C. to 60 ° C.
  • the second mixture is As the cooling temperature, the drying is preferably performed at 10 ° C. to 40 ° C., more preferably 20 ° C. to 30 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 0 ° C. to 80 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 10 ° C. to 80 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 10 ° C. to 80 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 0 ° C. to 80 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 0 ° C. to 80 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 0 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 10 ° C. to 80 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 10 ° C. to 80 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 0 ° C. to 80 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 0 ° C. to 80 ° C.
  • the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 0 ° C. to 80 ° C.
  • the porous body of the present invention includes bacterial cellulose and a polymer as described above, and the polymer is a porous body that is a polymer that can form a porous body by phase separation.
  • the porous body has a structure in which a three-dimensional network structure of the bacterial cellulose (preferably fibrous bacterial cellulose) is entangled with the porous body of the polymer.
  • the porous body of the present invention has, for example, a pore diameter of 0.05 ⁇ m to 30 ⁇ m, a skeleton diameter of, for example, 0.05 ⁇ m to 20 ⁇ m, and preferably a pore diameter of 0.1 ⁇ m to 10 ⁇ m.
  • the diameter is preferably 0.1 ⁇ m to 20 ⁇ m, more preferably the pore diameter is 0.3 ⁇ m to 10 ⁇ m, and the skeleton diameter is more preferably 0.3 ⁇ m to 8 ⁇ m.
  • the pore size of the porous body obtained is preferably 0.1 ⁇ m to 10 ⁇ m, and the skeleton diameter is preferably 0.1 ⁇ m to 10 ⁇ m.
  • the polymer is any one of a homopolymer of acrylic acid esters, a copolymer containing acrylic acid esters, a homopolymer of methacrylic acid esters, and a copolymer containing methacrylic acid esters,
  • the pore diameter is preferably 0.1 ⁇ m to 15 ⁇ m
  • the skeleton diameter is preferably 0.05 ⁇ m to 10 ⁇ m.
  • the pore size of the obtained porous body is preferably 0.1 ⁇ m to 15 ⁇ m, and the skeleton size is preferably 0.05 ⁇ m to 10 ⁇ m.
  • the pore size of the obtained porous body is preferably 0.05 to 30 ⁇ m, and the skeleton size is preferably 0.05 to 10 ⁇ m.
  • the pore size of the obtained porous material is preferably 0.2 ⁇ m to 20 ⁇ m, and the skeleton diameter is preferably 0.3 ⁇ m to 10 ⁇ m.
  • the pore size of the obtained porous body is preferably 0.1 ⁇ m to 15 ⁇ m, and the skeleton size is preferably 0.05 ⁇ m to 10 ⁇ m.
  • the polymer is poly ( ⁇ -glutamic acid)
  • the pore size of the obtained porous body is preferably 0.1 ⁇ m to 15 ⁇ m
  • the skeleton size is preferably 0.05 ⁇ m to 10 ⁇ m.
  • the polymer is chitosan
  • the pore size of the obtained porous body is preferably 0.2 ⁇ m to 20 ⁇ m, and the skeleton size is preferably 0.3 ⁇ m to 10 ⁇ m.
  • the pore size of the obtained porous body is preferably 0.05 ⁇ m to 30 ⁇ m, and the skeleton size is preferably 0.05 ⁇ m to 10 ⁇ m.
  • the pore size of the obtained porous body is preferably 0.1 ⁇ m to 15 ⁇ m, and the skeleton size is preferably 0.05 ⁇ m to 10 ⁇ m.
  • the polymer is cellulose acetate, the pore size of the obtained porous body is preferably 0.1 ⁇ m to 15 ⁇ m, and the skeleton size is preferably 0.05 ⁇ m to 10 ⁇ m.
  • the specific surface area of the porous body of the present invention is, for example, 1 to 1000 m 2 / g, preferably 2 to 500 m 2 / g.
  • specific surface area can be specifically measured by the method as described in an Example. Therefore, such a porous body can be used as, for example, a filter or an adsorbent.
  • the specific surface area of the porous body is preferably 3 to 900 m 2 / g, more preferably 5 to 700 m 2 / g.
  • the specific surface area of the porous body Is preferably 3 to 900 m 2 / g, more preferably 5 to 700 m 2 / g.
  • the specific surface area of the porous body is preferably 3 to 900 m 2 / g, more preferably 5 to 700 m 2 / g.
  • the specific surface area of the porous body is preferably 3 to 900 m 2 / g, more preferably 5 to 700 m 2 / g.
  • the specific surface area of the porous body is preferably 5 to 500 m 2 / g, more preferably 10 to 300 m 2 / g.
  • specific surface area can be specifically measured by the method as described in an Example.
  • the first porous body of the present invention is A multilayer structure of the bacterial cellulose;
  • a porous structure derived from the polymer The polymer is a copolymer including one or more selected from the group consisting of polyacrylonitrile, a copolymer including acrylonitrile, a copolymer including methacrylic acid esters, and an ethylene vinyl alcohol copolymer,
  • the distance between the layers of the multilayer structure is in the range of 0.1 ⁇ m to 20 ⁇ m
  • the thickness of the multilayer structure layer is in the range of 0.2 ⁇ m to 30 ⁇ m.
  • the bacterial cellulose is preferably fibrous.
  • the distance between the layers of the multilayer structure is in the range of 0.1 ⁇ m to 20 ⁇ m, preferably in the range of 0.2 ⁇ m to 15 ⁇ m, more preferably 0.2 ⁇ m. It is in the range of ⁇ 10 ⁇ m.
  • the thickness of the multilayer structure layer is in the range of 0.2 ⁇ m to 30 ⁇ m, preferably in the range of 0.3 ⁇ m to 20 ⁇ m, and more preferably in the range of 0.3 ⁇ m to 10 ⁇ m. Range.
  • the second porous body of the present invention is A multilayer structure of the bacterial cellulose; A layer derived from the polymer,
  • the polymer is an ethylene vinyl alcohol copolymer or a copolymer of cellulose acetate,
  • the distance between the layers of the multilayer structure is in the range of 0.1 ⁇ m to 20 ⁇ m,
  • the thickness of the multilayer structure layer is in the range of 0.2 ⁇ m to 30 ⁇ m.
  • the polymer-derived layer is preferably on the bacterial cellulose.
  • the bacterial cellulose is preferably fibrous.
  • the distance between the layers of the multilayer structure is in the range of 0.1 ⁇ m to 20 ⁇ m, preferably in the range of 0.2 ⁇ m to 15 ⁇ m, more preferably 0.2 ⁇ m. It is in the range of ⁇ 10 ⁇ m.
  • the thickness of the multilayer structure layer is in the range of 0.2 ⁇ m to 30 ⁇ m, preferably in the range of 0.3 ⁇ m to 20 ⁇ m, and more preferably in the range of 0.3 ⁇ m to 10 ⁇ m. Range.
  • the first porous body and the second porous body can be obtained by the method for producing a porous body containing bacterial cellulose and a polymer of the present invention.
  • the porous material of the present invention when the polymer is an ethylene vinyl alcohol copolymer, the porous material obtained by changing the solvent composition of the first solvent and water (phase separation) and the composition of the ethylene vinyl alcohol copolymer.
  • the structure of the mass can be adjusted.
  • the bacterial cellulose has a multilayer structure.
  • a porous body having a structure including a porous layer derived from a polymer on the bacterial cellulose can be obtained.
  • the present invention is activated carbon derived from bacterial cellulose and polymer,
  • the polymer is polyacrylonitrile or a copolymer containing acrylonitrile, A multilayer structure derived from the bacterial cellulose;
  • a porous structure derived from the polymer The distance between the layers of the multilayer structure is in the range of 0.1 ⁇ m to 20 ⁇ m, The thickness of the multilayer structure layer is in the range of 0.2 ⁇ m to 30 ⁇ m, The nitrogen content is in the range of 0.1 to 10% by mass.
  • the porous structure derived from the polymer is porous along the multilayer structure derived from the bacterial cellulose.
  • the distance between the layers of the multilayer structure is in the range of 0.1 ⁇ m to 20 ⁇ m, preferably in the range of 0.2 ⁇ m to 15 ⁇ m, and more preferably in the range of 0.2 ⁇ m to 10 ⁇ m. is there.
  • the thickness of the multilayer structure layer is in the range of 0.2 ⁇ m to 30 ⁇ m, preferably in the range of 0.3 ⁇ m to 20 ⁇ m, and more preferably in the range of 0.3 ⁇ m to 10 ⁇ m.
  • the nitrogen content is in the range of 0.1 to 10% by mass, preferably in the range of 0.3 to 10% by mass, more preferably in the range of 0.3 to 8% by mass. .
  • the present invention also relates to a method for producing activated carbon derived from bacterial cellulose and a polymer, wherein the polymer is polyacrylonitrile or a copolymer containing acrylonitrile, and the method for producing a porous body containing bacterial cellulose and a polymer according to the present invention. A step of firing the obtained porous body is included.
  • Pre-firing may be performed at ⁇ 280 ° C. in air, for example, for 0.5 to 20 hours, preferably 1 to 15 hours.
  • It is preferably 0.1 to 3, for example, 0.1 to 24 hours, preferably 0.2 to 12 hours.
  • the activated carbon is porous and has a high specific surface area, it can be used as an adsorbent such as gas, a deodorizing material, and a methane storage material. Moreover, since the activated carbon has a high carbon content and exhibits conductivity, it can also be used as an electrode material. Examples of the electrode material include electrode materials such as an electric double layer capacitor and a hybrid capacitor.
  • DMSO dimethyl sulfoxide
  • PAN polyacrylonitrile
  • IPA isopropanol
  • SEM scanning electron microscope
  • AC acetylene black
  • PTFE polytetrafluoroethylene
  • SEM Hitachi SU3509 (manufactured by Hitachi High-Technologies Corporation)
  • High-speed / specific surface area / pore distribution analyzer Quantachrome Nova4200e (manufactured by Cantachrome Instruments Japan GK)
  • the pore diameter and the skeleton diameter describe the minimum and maximum values of the pore diameter and the skeleton diameter measured from an image taken using a scanning electron microscope (SEM).
  • the medium was placed in a heat-resistant plastic container and sterilized using an autoclave, and then Acetobacter xylinus (NBRC13693) was planted and cultured at 30 ° C. for 1 week.
  • the gel produced on the surface of the medium was collected. After replacing the medium components in the obtained gel by impregnating with deionized water over 2 days, the gel was sterilized by autoclaving, and further boiled and sterilized with a 2 wt% aqueous sodium hydroxide solution. After sterilization, the sodium hydroxide aqueous solution in the gel was replaced with deionized water over 2 days to obtain a bacterial cellulose hydrogel.
  • An SEM photograph of the obtained bacterial cellulose hydrogel is shown in FIG.
  • Example 1 Production of porous material containing bacterial cellulose and polyacrylonitrile (hereinafter sometimes referred to as “BC-PAN porous material”)
  • BC-PAN porous material porous material containing bacterial cellulose and polyacrylonitrile
  • FIGS. 2a and 2b SEM photographs of the obtained BC-PAN porous material are shown in FIGS. 2a and 2b.
  • FIG. 2c FIG. 2a is a SEM photograph of the BC-PAN porous body observed in the vertical direction and FIG. 2b is observed in the horizontal direction.
  • FIG. 2a it was confirmed that the BC-PAN porous material had a structure in which a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of polyacrylonitrile were intertwined. Further, as shown in FIG.
  • the BC-PAN porous body includes a multilayer structure of bacterial cellulose and a porous structure derived from polyacrylonitrile.
  • the distance between the layers having the multilayer structure was 1 to 5 ⁇ m, and the thickness of the layer having the multilayer structure was 3 to 10 ⁇ m.
  • the ratio (weight ratio) of polyacrylonitrile / bacterial cellulose was 85/15.
  • the BC-PAN body pore diameter was 2 to 5 ⁇ m, and the skeleton diameter was 1 to 2 ⁇ m.
  • Example 2 Production of activated carbon derived from bacterial cellulose and polyacrylonitrile (hereinafter also referred to as “BC-PAN activated carbon”)
  • SEM photographs of the obtained BC-PAN activated carbon are shown in FIGS. 3a and 3b. As shown in FIG. 3c, FIG.
  • BC-PAN activated carbon is a SEM photograph of BC-PAN activated carbon observed in the vertical direction and FIG. 3b is observed in the horizontal direction.
  • BC-PAN activated carbon also has a structure in which a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of polyacrylonitrile are intertwined with each other as in the case of BC-PAN porous bodies. It was. Further, as shown in FIG. 3b, it was confirmed that BC-PAN activated carbon includes a multilayer structure derived from bacterial cellulose and a porous coating derived from polyacrylonitrile on the fiber derived from bacterial cellulose.
  • the distance between the layers having the multilayer structure was 1 to 5 ⁇ m, and the thickness of the layer having the multilayer structure was 3 to 10 ⁇ m.
  • the nitrogen adsorption and desorption isotherm of BC-PAN activated carbon is measured, and the pore diameter distribution is calculated therefrom, whereby BC-PAN activated carbon has micropores having a diameter of 2 nm or less. It was also confirmed that there were many holes.
  • the nitrogen content was 4.0% by mass.
  • BC-PAN charcoal ⁇ Electrochemical measurement of activated carbon derived from bacterial cellulose and polyacrylonitrile (BC-PAN charcoal)>
  • the BC-PAN charcoal obtained in Example 2 was pulverized and classified to 45 ⁇ m or less using a JIS-Z-8801 JIS standard test sieve.
  • the obtained BC-PAN charcoal powder was added to a 1-propanol (Nacalai Tesque, Inc.) solution of 0.8% Nafion (trademark) (De521 CS type, Wako Pure Chemical Industries, Ltd.) so as to be 20 mg / mL.
  • a BC-PAN charcoal dispersion was obtained.
  • This dispersion is applied to a glassy carbon electrode, and the dried one is used as a working electrode, the Pt electrode is used as a counter electrode, the Ag / AgCl electrode is used as a reference electrode, and evaluated by cyclic voltammetry (CV) using a tripolar cell.
  • CV cyclic voltammetry
  • the electrolytic solution three kinds of sulfuric acid aqueous solution (1M), sodium sulfate aqueous solution (1M) and potassium hydroxide aqueous solution (1M) were used for comparison.
  • the potential window was set according to the liquidity of the electrolytic solution, and the scanning speed was changed from 200 mV to 1 mV.
  • FIG. 4 is a graph showing the capacity retention ratio of the BC-PAN activated carbon obtained in Example 2 and the PAN activated carbon with respect to the scanning speed using a sulfuric acid aqueous solution (1M).
  • FIG. 5 is a cyclic voltammogram of BC-PAN activated carbon and PAN activated carbon obtained in Example 2.
  • DMSO dimethyl sulfoxide
  • the precipitate was phase-separated from the mixture by allowing it to stand for 1 hour with a bioshaker set to 20 ° C.
  • the solvent contained in the precipitate was replaced with methanol over 24 hours, and then the precipitate was vacuum-dried with a desiccator to obtain a PAN porous material.
  • the AC sheet electrode was pressed onto a SUS304 current collector mesh (Nirako) measuring 7 mm ⁇ 7 mm at 30 kN to produce a working electrode.
  • a platinum mesh Niraco
  • a silver / silver chloride (Ag / AgCl) electrode intercheme
  • a Lugin tube is used for the reference electrode
  • a 1 mol / L sulfuric acid aqueous solution is used for the electrolyte. Configured. Measurement was performed after the electrode was impregnated with an electrolyte under reduced pressure.
  • the amplitude was measured at 10 mV and the AC frequency was changed from 0.01 to 10,000 Hz.
  • the obtained Nyquist plot (Cole-coll plot) is shown in FIG. 5b.
  • the vertical axis represents imaginary impedance (Z ′′), and the horizontal axis represents real impedance (Z ′).
  • activated carbon BC-PAN charcoal obtained in Example 2 or the PAN activated carbon was used.
  • BC-PAN charcoal had a lower intergranular resistance than PAN activated carbon.
  • Example 3 Production of porous body containing bacterial cellulose and polymethylmethacrylic acid (PMMA) (hereinafter sometimes referred to as “BC-PMMA porous body”)
  • PMMA polymethylmethacrylic acid
  • the gel-like material is taken out from the mixture, placed in another sample bowl and left in a bioshaker at 25 ° C. for 2 hours, and then with a large amount of water for one day with the solvent contained in the gel-like material. Replacement was performed.
  • the obtained gel-like material was freeze-dried to remove water, and a BC-PMMA porous material was obtained.
  • An SEM photograph of the obtained BC-PMMA porous material is shown in FIGS. 6a and 6b.
  • FIGS. 6a and 6b it was confirmed that the BC-PMMA porous body has a structure in which a three-dimensional network structure of nanofibers of bacterial cellulose and a porous structure of polymethylmethacrylic acid are intertwined.
  • the distance between the layers having the multilayer structure was 1 to 5 ⁇ m, and the thickness of the layer having the multilayer structure was 3 to 10 ⁇ m.
  • Example 4 Manufacture of porous material containing bacterial cellulose and cellulose acetate (CA) (hereinafter sometimes referred to as “BC-CA porous material”)
  • BC-CA porous material a mixture of DMSO and water.
  • Water / DMSO 30/70 vol% was impregnated, and the solvent contained in Nata de Coco was replaced with DMSO.
  • cellulose acetate (CA) molecular weight 50,000 was added to the impregnated nata de coco to 100 mg / mL, and this mixture was stirred overnight with a hot stirrer at 85 ° C. to dissolve the cellulose acetate. .
  • the BC-CA body pore diameter was 1.0 ⁇ m to 1.5 ⁇ m, and the skeleton diameter was 0.2 ⁇ m to 0.3 ⁇ m.
  • the ratio (weight ratio) of cellulose acetate / bacterial cellulose was 80/20.
  • EVOH porous body ethylene vinyl alcohol copolymer
  • ethylene vinyl alcohol copolymer (ethylene content 27 mol%) was added to the impregnated bacterial cellulose to a concentration of 100 mg / mL%, and this mixture was stirred with a hot stirrer at 75 ° C. overnight. did.
  • the gel-like material is taken out from the mixture, placed in another sample basket, left in a bioshaker at 4 ° C. for 24 hours, and then with a large amount of acetone over one day with the solvent contained in the gel-like material. Replacement was performed.
  • the obtained gel was freeze-dried to remove water, and a BC-EVOH porous material was obtained.
  • An SEM photograph of the obtained BC-EVOH porous material is shown in FIG. As shown in FIG.
  • the BC-EVOH porous body has a structure including a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed that it had.
  • the obtained BC-EVOH porous material had a pore size of 0.2 ⁇ m to 0.5 ⁇ m and a skeleton size of 0.1 ⁇ m to 0.3 ⁇ m.
  • the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 94/6.
  • Example 5-2 Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”)
  • the ratio of water / isopropanol was 65/35 vol%
  • EVOH A BC-EVOH porous material was obtained in the same manner as in Example 5-1, except that the ethylene content was 27 mol% and the concentration was 150 mg / mL.
  • SEM photographs of the obtained BC-EVOH porous material are shown in FIGS. 9a and 9b.
  • FIG. 9a is a SEM photograph of the BC-EVOH porous body observed in the vertical direction
  • FIG. 9b is a horizontal direction observed. As shown in FIGS.
  • the BC-EVOH porous body has a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed to have a structure including.
  • the obtained BC-EVOH porous material had a pore size of 0.5 ⁇ m to 1.0 ⁇ m and a skeleton size of 0.2 ⁇ m to 0.4 ⁇ m.
  • the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 95/5.
  • Example 5-3 Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”)
  • the ratio of water / isopropanol was 60/40 vol%
  • EVOH A BC-EVOH porous material was obtained in the same manner as in Example 5-1, except that the ethylene content was 27 mol% and the concentration was 150 mg / mL.
  • SEM photographs of the obtained BC-EVOH porous material are shown in FIGS. 10a and 10b.
  • FIG. 10a is an SEM photograph of the BC-EVOH porous body observed in the vertical direction and FIG. 10b is observed in the horizontal direction. As shown in FIGS.
  • the BC-EVOH porous body has a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed to have a structure including.
  • the obtained BC-EVOH porous body had a pore size of 0.5 ⁇ m to 1.0 ⁇ m and a skeleton size of 0.05 ⁇ m to 0.2 ⁇ m.
  • the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 93/7.
  • Example 5-4 Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”) Water / isopropanol ratio is 45/55 vol%, EVOH concentration BC-EVOH in the same manner as in Example 5-1, except that ethylene vinyl alcohol copolymer (EVOH) (ethylene content 44 mol%) (molecular weight 14,000) was used for bacterial cellulose. A porous body was obtained. An SEM photograph of the obtained BC-EVOH porous material is shown in FIG. As shown in FIG.
  • the BC-EVOH porous body has a structure including a multilayer structure of bacterial cellulose nanofibers and a porous coating of ethylene vinyl alcohol copolymer deposited on the bacterial cellulose nanofibers. It was confirmed that it had.
  • the distance between the layers of the multilayer structure was 1 ⁇ m to 5 ⁇ m, and the thickness of the layer of the multilayer structure was 3 ⁇ m to 10 ⁇ m.
  • the obtained BC-EVOH porous material had a pore size of 0.2 ⁇ m to 0.5 ⁇ m and a skeleton size of 0.2 ⁇ m to 0.3 ⁇ m.
  • the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 94/6.
  • Example 5-5 Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”)
  • the ratio of water / isopropanol was 60/40 vol%
  • EVOH A BC-EVOH porous material was obtained in the same manner as in Example 5-4 except that the ethylene content was 44 mol% and the concentration was 150 mg / mL (44 mol%).
  • An SEM photograph of the obtained BC-EVOH porous material is shown in FIG. As shown in FIG.
  • the BC-EVOH porous body has a structure including a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed that it had.
  • the obtained BC-EVOH porous material had a pore size of 0.2 ⁇ m to 1.0 ⁇ m and a skeleton size of 0.1 ⁇ m to 0.3 ⁇ m.
  • the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 95/5.
  • Example 5-6 Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”)
  • the ratio of water / isopropanol was 50/50 vol%
  • EVOH A BC-EVOH porous material was obtained in the same manner as in Example 5-1, except that the ethylene content was 27 mol% and the concentration was 150 mg / mL.
  • SEM photographs of the obtained BC-EVOH porous material are shown in FIGS. 13a and 13b.
  • FIG. 13a is a SEM photograph of the BC-EVOH porous body observed in the vertical direction and FIG. 13b a horizontal direction. As shown in FIGS.
  • the BC-EVOH porous body has a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of an ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed to have a structure including.
  • the obtained BC-EVOH porous material had a pore size of 0.2 ⁇ m to 0.5 ⁇ m and a skeleton size of 0.1 ⁇ m to 0.3 ⁇ m.
  • the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 93/7.
  • the porous material containing bacterial cellulose and polymer obtained by the method of the present invention is expected to be used for filters, adsorbents, electrodes and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention vise à fournir un corps poreux comprenant une cellulose bactérienne et un polymère, et un procédé de fabrication de ce dernier. L'invention concerne un procédé de fabrication d'un corps poreux comprenant une cellulose bactérienne et un polymère, le procédé comportant : une étape de préparation d'un premier mélange par ajout d'un premier solvant à un hydrogel de cellulose bactérienne ; une étape de préparation d'un second mélange par ajout d'un polymère au premier mélange, chauffage, et dissolution du polymère dans une solution mixte du premier solvant et d'eau ; une étape de production d'un corps formé précipité par refroidissement du second mélange ; et une étape d'immersion du corps formé dans un second solvant de façon à remplacer le premier solvant et l'eau compris dans le corps formé par le second solvant et produire un corps poreux comprenant la cellulose bactérienne et le polymère. Le polymère est apte à former un corps poreux au moyen d'une séparation de phases, et le premier solvant est miscible à l'eau.
PCT/JP2016/053597 2015-03-06 2016-02-05 Corps poreux comprenant une cellulose bactérienne et un polymère, et son procédé de fabrication WO2016143439A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107739031A (zh) * 2017-10-18 2018-02-27 中南大学 一种以菌渣废料制备锂离子碳负极材料的方法
CN108244155A (zh) * 2018-01-11 2018-07-06 日照职业技术学院 一种基于微生物法制备的抗菌剂及抗菌包装材料
WO2020149150A1 (fr) * 2019-01-16 2020-07-23 日本電信電話株式会社 Carbone de nanofibres de cellulose et son procédé de fabrication
CN113429616A (zh) * 2021-06-22 2021-09-24 哈尔滨工业大学（深圳） 一种吸湿的双层凝胶聚合物电解质的制备方法及其应用

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003082535A (ja) * 2001-09-12 2003-03-19 Shigenori Kuga セルロース原料由来の微細繊維状炭素材料およびその製造方法
JP2006241450A (ja) * 2005-02-07 2006-09-14 Kyoto Univ 繊維強化複合材料及びその製造方法並びに繊維強化複合材料製造用前駆体
JP2007055865A (ja) * 2005-08-26 2007-03-08 Ube Ind Ltd ネットワーク状炭素材料
JP2008127510A (ja) * 2006-11-22 2008-06-05 Univ Nihon バクテリアセルロースと有機高分子からなる複合材料
JP2010095654A (ja) * 2008-10-17 2010-04-30 Institute Of National Colleges Of Technology Japan 不揮発性バクテリアセルロースゲル及びその製造方法
JP2010180416A (ja) * 2003-07-31 2010-08-19 Kyoto Univ 繊維強化複合材料及びその製造方法並びに配線基板
WO2011093147A1 (fr) * 2010-01-28 2011-08-04 日産化学工業株式会社 Procédé pour la production d'une composition qui comprend de la cellulose et du poly(acide lactique)
JP2012116905A (ja) * 2010-11-30 2012-06-21 Oji Paper Co Ltd 微細繊維状セルロースコンポジット多孔性シートの製造方法
JP2012126912A (ja) * 2004-08-30 2012-07-05 Nihon Univ バクテリアセルロース有機ゲルを利用したリチウムイオン導電性材料
JP2013124301A (ja) * 2011-12-14 2013-06-24 Nissan Chem Ind Ltd 樹脂組成物及びその成形体
JP2013536896A (ja) * 2010-09-07 2013-09-26 イッサム リサーチ ディべロップメント カンパニー オブ ザ ヘブライ ユニバーシティー オブ エルサレム，リミテッド セルロースをベースとする複合材料
JP2013253137A (ja) * 2012-06-05 2013-12-19 Hokuetsu Kishu Paper Co Ltd セルロース多孔質体及びその製造方法
JP2014208721A (ja) * 2013-04-16 2014-11-06 オリンパス株式会社 樹脂多孔質体及びその製造方法

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003082535A (ja) * 2001-09-12 2003-03-19 Shigenori Kuga セルロース原料由来の微細繊維状炭素材料およびその製造方法
JP2010180416A (ja) * 2003-07-31 2010-08-19 Kyoto Univ 繊維強化複合材料及びその製造方法並びに配線基板
JP2012126912A (ja) * 2004-08-30 2012-07-05 Nihon Univ バクテリアセルロース有機ゲルを利用したリチウムイオン導電性材料
JP2006241450A (ja) * 2005-02-07 2006-09-14 Kyoto Univ 繊維強化複合材料及びその製造方法並びに繊維強化複合材料製造用前駆体
JP2007055865A (ja) * 2005-08-26 2007-03-08 Ube Ind Ltd ネットワーク状炭素材料
JP2008127510A (ja) * 2006-11-22 2008-06-05 Univ Nihon バクテリアセルロースと有機高分子からなる複合材料
JP2010095654A (ja) * 2008-10-17 2010-04-30 Institute Of National Colleges Of Technology Japan 不揮発性バクテリアセルロースゲル及びその製造方法
WO2011093147A1 (fr) * 2010-01-28 2011-08-04 日産化学工業株式会社 Procédé pour la production d'une composition qui comprend de la cellulose et du poly(acide lactique)
JP2013536896A (ja) * 2010-09-07 2013-09-26 イッサム リサーチ ディべロップメント カンパニー オブ ザ ヘブライ ユニバーシティー オブ エルサレム，リミテッド セルロースをベースとする複合材料
JP2012116905A (ja) * 2010-11-30 2012-06-21 Oji Paper Co Ltd 微細繊維状セルロースコンポジット多孔性シートの製造方法
JP2013124301A (ja) * 2011-12-14 2013-06-24 Nissan Chem Ind Ltd 樹脂組成物及びその成形体
JP2013253137A (ja) * 2012-06-05 2013-12-19 Hokuetsu Kishu Paper Co Ltd セルロース多孔質体及びその製造方法
JP2014208721A (ja) * 2013-04-16 2014-11-06 オリンパス株式会社 樹脂多孔質体及びその製造方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107739031A (zh) * 2017-10-18 2018-02-27 中南大学 一种以菌渣废料制备锂离子碳负极材料的方法
CN107739031B (zh) * 2017-10-18 2021-07-16 中南大学 一种以菌渣废料制备锂离子碳负极材料的方法
CN108244155A (zh) * 2018-01-11 2018-07-06 日照职业技术学院 一种基于微生物法制备的抗菌剂及抗菌包装材料
CN108244155B (zh) * 2018-01-11 2020-11-10 日照职业技术学院 一种基于微生物法制备的抗菌剂及抗菌包装材料
WO2020149150A1 (fr) * 2019-01-16 2020-07-23 日本電信電話株式会社 Carbone de nanofibres de cellulose et son procédé de fabrication
JP2020111859A (ja) * 2019-01-16 2020-07-27 日本電信電話株式会社 セルロースナノファイバーカーボンとその製造方法
JP7273286B2 (ja) 2019-01-16 2023-05-15 日本電信電話株式会社 セルロースナノファイバーカーボンとその製造方法
CN113429616A (zh) * 2021-06-22 2021-09-24 哈尔滨工业大学（深圳） 一种吸湿的双层凝胶聚合物电解质的制备方法及其应用
CN113429616B (zh) * 2021-06-22 2022-07-12 哈尔滨工业大学（深圳） 一种吸湿的双层凝胶聚合物电解质的制备方法及其应用

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