WO2011043457A1 - 複合多孔材料及びその製造方法 - Google Patents

複合多孔材料及びその製造方法 Download PDF

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WO2011043457A1
WO2011043457A1 PCT/JP2010/067726 JP2010067726W WO2011043457A1 WO 2011043457 A1 WO2011043457 A1 WO 2011043457A1 JP 2010067726 W JP2010067726 W JP 2010067726W WO 2011043457 A1 WO2011043457 A1 WO 2011043457A1
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porous material
polymer
fiber laminate
composite porous
group
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French (fr)
Japanese (ja)
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重則 空閑
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University of Tokyo NUC
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University of Tokyo NUC
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides

Definitions

  • the present invention relates to a composite porous material and a method for producing the same.
  • the present invention relates to a composite porous material having a fiber laminate having a relatively large pore diameter and a porous body filled in the pore and having a relatively small pore diameter, and a method for producing the same.
  • porous materials especially nanoporous materials with typical pore diameters of several hundred nanometers or less, especially sheet-like molded products, are used for filters, catalyst carriers, electrodes, battery and capacitor partition walls (separators), drug-supporting materials, thermal decomposition Applications are expanding as highly functional materials such as carbon precursors.
  • various inorganic and organic substances are used as such a material. This kind of material is sometimes used in a state where the voids are filled with a liquid or a solid in an end use situation, but when shipped as a product, it is desirable that the material is a dry solid that maintains porosity.
  • a method for preparing the nanoporous material it is effective to use a porous body prepared in a liquid, that is, a gel, by maintaining a void by solvent substitution drying (including supercritical drying) to obtain a dry porous body, that is, an airgel.
  • a porous body prepared in a liquid that is, a gel
  • solvent substitution drying including supercritical drying
  • a dry porous body that is, an airgel.
  • silica aerogel obtained by supercritical drying of silica gel obtained by a sol-gel method Non-patent Documents 1 and 2, Patent Documents 1 and 2)
  • cellulose aerogel obtained by solvent-replacement drying of regenerated cellulose gel (non-patent) Documents 3 and 4 and Patent Document 3 can be mentioned.
  • an object of the present invention is to provide a porous material that overcomes the fragility while maintaining a high porosity.
  • the objective of this invention is providing the manufacturing method of such a porous material in addition to the said objective.
  • the porous body may be selected from the group consisting of an organic synthetic polymer and a natural organic polymer.
  • the organic synthetic polymer may be selected from the group consisting of polyimide, polystyrene, polyolefin, halogenated polyolefin, polyester and polyacrylamide, preferably polyimide, polyolefin and halogen. It is preferable to be selected from the group consisting of a modified polyolefin.
  • the natural organic polymer may be selected from the group consisting of cellulose, chitin, agarose and ⁇ -1,3 glucan, particularly cellulose.
  • the fiber laminate is a laminate composed of fibers selected from the group consisting of glass fibers, cellulosic fibers, carbon fibers, and synthetic organic polymer fibers. Is good.
  • the average diameter of the pores of the fiber laminate may be 1 ⁇ m or more, preferably 5 ⁇ m or more and 100 ⁇ m or less.
  • the composite porous material according to any one of the above items ⁇ 1> to ⁇ 6> may be a sheet-like molded body having a thickness of 1 mm or less.
  • a method for producing a composite porous material which is a composite porous material in which pores of a fiber laminate are filled with a porous material selected from the group consisting of silica, organic synthetic polymer, and natural organic polymer, and is a dry material
  • the method comprises A) preparing a fiber laminate; B) Filling the pores of the fiber laminate with a liquid containing a polymer or a precursor thereof; C) a step of preparing a polymer or a precursor thereof into a porous body; and D) a step of drying a fiber laminate filled with the porous body;
  • the above-mentioned method wherein a composite porous material that is a dry body is prepared, and the representative pore diameter of the porous body is 500 nm or less, preferably 200 nm or less.
  • the composite porous material has a nitrogen adsorption BET specific surface area of 20 m 2 / g or more, preferably 40 m 2 /
  • the polymer in step B) or a precursor thereof is i) a natural polymer other than cellulose, silica and / or an organic synthetic polymer, or a precursor thereof; and ii) a mixture of cellulose;
  • step B) the liquid containing the mixture is filled in the pores of the fiber laminate
  • step C) having a step of preparing the porous body, i.e., a natural polymer other than cellulose, silica and / or organic synthetic polymer; and ii) cellulose; Good.
  • C) -2) may include a step of removing cellulose by hydrolysis or thermal decomposition.
  • a step of removing cellulose by hydrolysis or thermal decomposition it is possible to prepare a composite porous material in which a porous body made only of a natural polymer other than cellulose, silica and / or an organic synthetic polymer is filled in the pores of the fiber laminate.
  • the porous body may be selected from the group consisting of organic synthetic polymers and natural organic polymers.
  • the organic synthetic polymer may be selected from the group consisting of polyimide, polystyrene, polyolefin, halogenated polyolefin, polyester and polyacrylamide, preferably polyimide, Preferably selected from the group consisting of polyolefins and halogenated polyolefins.
  • the natural organic polymer may be selected from the group consisting of cellulose, chitin, agarose, and ⁇ -1,3 glucan, particularly cellulose. Good.
  • the fiber laminate is a laminate composed of fibers selected from the group consisting of glass fibers, cellulosic fibers, carbon fibers, and synthetic organic polymer fibers. Is good.
  • the average diameter of the pores of the fiber laminate is 1 ⁇ m or more, preferably 5 ⁇ m or more.
  • the fiber laminate prepared in step A) is preferably in the form of a sheet having a thickness of 1 mm or less.
  • the composite porous material according to any one of the above ⁇ 8> to ⁇ 17> is preferably a sheet-like molded body having a thickness of 1 mm or less.
  • the present invention it is possible to provide a porous material that overcomes fragility while maintaining a high porosity. Moreover, according to this invention, in addition to the said effect, the manufacturing method of such a porous material can be provided.
  • FIG. 2 is a scanning electron microscope (hereinafter abbreviated as “SEM”) image of Example 1.
  • FIG. 2 is an SEM image of Example 1.
  • 2 is a SEM image of Example 2.
  • 4 is a SEM image of Example 3.
  • 2 is an SEM image of glass paper used in Example 1.
  • the present invention provides a composite porous material and a method for producing the same.
  • a composite porous material is obtained by filling the pores of the fiber laminate with a porous body selected from the group consisting of silica, organic synthetic polymer, and natural organic polymer.
  • the fiber laminate has a relatively large average pore diameter, and the average diameter of the pores is 1 ⁇ m or more, preferably 5 ⁇ m or more.
  • the porous body filled in the pores of the fiber laminate has a relatively small representative diameter, and the representative diameter is 500 nm or less, preferably 200 nm or less.
  • the representative diameter is a distance between mesh elements typically observed in a porous network structure observed by surface observation with a scanning electron microscope or ultrathin slice observation with a transmission electron microscope. means.
  • the composite porous material of the present invention has a nitrogen adsorption BET specific surface area of 20 m 2 / g or more, preferably 40 m 2 / g or more.
  • the composite porous material of the present invention having such characteristics can make a porous material that has been brittle conventionally mechanically stable. For this reason, it is possible to provide a material that is easy to handle in transfer, further processing, and the like, for example, a sheet-like material having a thickness of 1 mm or less.
  • the fiber laminate may be a laminate comprising fibers selected from the group consisting of glass fibers, cellulosic fibers, carbon fibers, and synthetic organic polymer fibers.
  • the fiber laminate include paper and paperboard made of natural plant fibers, glass fiber paper, regenerated cellulose sponge, synthetic rubber sponge, porous ceramics, carbon paper, synthetic fiber nonwoven fabric, and regenerated cellulose nonwoven fabric. It is not limited to these.
  • the fiber laminate has a relatively large average pore diameter, and the average pore diameter is 1 ⁇ m or more, preferably 5 ⁇ m or more.
  • the fiber laminate preferably has a thickness of 1 mm or less.
  • the porous body may be one or more selected from the group consisting of silica, organic synthetic polymer and natural organic polymer, preferably organic synthetic polymer and natural organic. It may be one or more selected from the group consisting of polymers.
  • the organic synthetic polymer may be selected from the group consisting of polyimide, polystyrene, polyolefin, halogenated polyolefin, polyester and polyacrylamide, and preferably selected from the group consisting of polyimide, polyolefin and halogenated polyolefin.
  • the natural organic polymer is preferably selected from the group consisting of cellulose, chitin, agarose and ⁇ -1,3 glucan, particularly cellulose.
  • the composite porous material of the present invention can be produced, for example, by the following production method. That is, A) a step of preparing a fiber laminate; B) Filling the pores of the fiber laminate with a liquid containing a polymer or a precursor thereof; C) a step of preparing a polymer or a precursor thereof into a porous body; and D) a step of drying a fiber laminate filled with the porous body;
  • the above-mentioned composite porous material can be prepared. Note that terms used in the manufacturing method, such as “fiber laminate” and “porous body”, which are the same as those described above, have the same contents as described above, and thus description thereof is omitted
  • Step is a step of preparing a fiber laminate.
  • the fiber laminate may be purchased commercially or prepared separately.
  • Step B) is a step of filling the pores of the fiber laminate prepared in step A) with a liquid containing a polymer or a precursor thereof.
  • the precursor refers to a substance that can later become a porous body.
  • the porous body is made of silica
  • examples of the substance that can later become silica include tetramethyl orthosilicate and tetraethyl orthosilicate, but are not limited thereto.
  • examples of the precursor include monomers, dimers, trimers, oligomers, prepolymers, and the like, but are not limited thereto.
  • step B) the filling is performed by immersing the fiber laminate in a liquid containing a polymer or a precursor thereof; a method of applying a liquid containing a polymer or a precursor thereof to the fiber laminate, for example, the liquid is a fiber laminate.
  • the method can be carried out by a method of spraying on the surface, a method of transferring using a roller or the like.
  • the liquid to be used depends on the type of polymer to be used or its precursor, the type of fiber laminate to be used, and the like. Examples of the liquid include a solution or suspension of a polymer or a precursor thereof, and a solution of a polymer or a precursor thereof is preferable.
  • Step C) is a step of preparing a polymer or a precursor thereof into a porous body.
  • a silica precursor for example, tetraethyl orthosilicate (hereinafter sometimes abbreviated as “TEOS”)
  • TEOS tetraethyl orthosilicate
  • sol-gel method a method of preparing a porous silica by a so-called sol-gel method.
  • cellulose when cellulose is used as the polymer, a method in which a cellulose solution is filled in the pores of the fiber laminate is brought into contact with a non-solvent of cellulose, such as methanol, for example, a method of immersing in methanol or the like, Examples thereof include a method for preparing a cellulose porous body.
  • the preparation method of the polymer or its precursor to the porous body in the step C) depends on the polymer to be used, the precursor to be used, the fiber laminate to be used, etc., and is limited to the above-de
  • the step D) is a step of drying the fiber laminate that is obtained after the step C), that is, the fiber laminate filled with the porous body.
  • the porous body filled in the fiber laminate can be made into an airgel.
  • the drying step can be performed by solvent replacement and subsequent drying of the solvent.
  • supercritical carbon dioxide substitution is also included as solvent substitution.
  • drying examples include freeze drying, supercritical drying, and heat drying.
  • the conditions in each method depend on the type of fiber laminate to be used, the type of porous body to be used, the liquid to be used, and the like.
  • the following drying method can be used. That is, glass paper is used as the fiber laminate, and cellulose is used as the polymer that becomes the porous body.
  • a cellulose solution is prepared using an alkali-urea aqueous solution, glass paper is immersed in the cellulose solution, the adhering liquid is removed, and then immersed in methanol to regenerate the cellulose into a gel.
  • the wet cellulose gel is made into an airgel
  • a method of substituting the contained liquid with ethanol, then substituting with a fluorinated solvent, and then freeze-drying can be mentioned.
  • liquid carbon dioxide is used instead of the fluorinated solvent
  • the supercritical drying method can be used.
  • the composite porous material of the present invention can be obtained by using steps A) to D).
  • hole of a fiber laminated body is filled is a natural polymer other than a cellulose, a silica, and / or an organic synthetic polymer
  • it can also prepare using the following methods. That is, a mixture of i) a natural polymer other than cellulose, silica and / or organic synthetic polymer, or a precursor thereof; and ii) cellulose is used as the “polymer or precursor thereof” in step B). . Thereafter, in the same manner as in the above-mentioned step B), the liquid containing the mixture is filled in the pores of the fiber laminate.
  • step C) And C) -1) preparing a porous body from the mixture, i.e., a natural polymer other than cellulose, silica and / or organic synthetic polymer; and ii) cellulose.
  • a step of removing cellulose by hydrolysis or thermal decomposition may be included.
  • a composite porous material is prepared in which only a porous body made of a natural polymer other than cellulose, silica, and / or an organic synthetic polymer is filled in the pores of the fiber laminate.
  • a glass paper (thickness: 50 ⁇ m, fiber diameter: 0.5-2 ⁇ m, density: about 0.14 g / cm 3 , porosity: 90% or more, average pore diameter: 2 to 5 ⁇ m, maximum pore size: 10 to 15 ⁇ m
  • SEM scanning electron microscope
  • the liquid containing the composite gel was replaced with water ⁇ ethanol ⁇ fluorinated solvent (Zeorolla H manufactured by Nippon Zeon Co., Ltd.), the gel was immersed in liquid nitrogen and frozen, and freeze dryer DC ⁇ manufactured by Yamato Scientific Co., Ltd. was used. It lyophilized
  • the airgel had a specific surface area of 43.9 m 2 / g in nitrogen adsorption analysis. Further, as a result of SEM observation, the images shown in FIGS. 1 and 2 were obtained. From FIG. 1 and FIG. 2, the airgel had a typical pore size of 100 to 200 nm. Since the glass paper as the base material had a specific surface area of 26.8m 2 / g by a nitrogen adsorption method, the composition analysis, specific surface area of the supported cellulose airgel was calculated to 143.9m 2 / g It was.
  • Example 2 The same cellulose hydrogel-containing glass paper as in Example 1 was freeze-dried with water using a freeze dryer DC-800 manufactured by Yamato Scientific Co., Ltd. from the state where the liquid contained was water, to obtain a glass paper-supporting cellulose aerogel.
  • the obtained airgel was subjected to nitrogen adsorption analysis and SEM image observation in the same manner as in Example 1. As a result, it was found in the nitrogen adsorption analysis that it has a specific surface area of 31.0 m 2 / g. Further, in SEM image observation, it was found that the pore diameter was a typical value of 200 to 1000 nm (see FIG. 3). Further, from the same calculation as in Example 1, the specific surface area of the supported cellulose airgel was calculated to be 64.9 m 2 / g.
  • Example 2 ⁇ Impregnation and imidization of polyimide precursor solution into glass paper>
  • the same glass paper as in Example 1 was immersed in the polyamic acid solution, and the adhering liquid was removed by filter paper blotting, and then immersed in an acetic anhydride-pyridine mixed solution (1: 1) for chemical imidization.
  • the liquid-containing gel of the composite was dried from supercritical CO 2 (35 ° C., 8000 kPa) by solvent substitution to prepare a glass paper-supported polyimide airgel.
  • the obtained polyimide airgel was subjected to nitrogen adsorption analysis and SEM image observation in the same manner as in Example 1.
  • a filter paper-supporting cellulose was obtained by immersing the filter paper in a cellulose solution and treating the same in the same manner as in Example 1 except that filter paper (quantitative filter paper 5C manufactured by Advantech) was used instead of glass paper in Example 1.
  • An airgel was obtained. When the airgel was observed by SEM, although not shown, the cellulose gel was filled in the gaps between the filter paper fibers and had the same structure as the glass paper-supported cellulose aerogel of FIGS.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
PCT/JP2010/067726 2009-10-09 2010-10-08 複合多孔材料及びその製造方法 Ceased WO2011043457A1 (ja)

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JP5713395B2 (ja) * 2011-03-30 2015-05-07 Jnc株式会社 ヒドロゲルセルロース多孔質膜
JP5689380B2 (ja) * 2011-07-25 2015-03-25 日東電工株式会社 セルロース多孔質体の製造方法
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JP6073210B2 (ja) * 2013-12-02 2017-02-01 北越紀州製紙株式会社 セルロース多孔質体及びその製造方法
JP6428018B2 (ja) * 2014-07-23 2018-11-28 凸版印刷株式会社 多孔質体、多孔質体形成用組成物および多孔質体の製造方法
KR101654795B1 (ko) * 2016-02-05 2016-09-06 김현철 고단열 에어로겔 함침 매트의 제조 방법
JP6212622B2 (ja) * 2016-11-14 2017-10-11 北越紀州製紙株式会社 セルロース多孔質体
CN112175226A (zh) * 2019-07-01 2021-01-05 上海清美绿色食品（集团）有限公司 一种用豆渣制备纤维素海绵的方法
KR20220152086A (ko) * 2021-05-07 2022-11-15 주식회사 엘지화학 리튬 이차전지용 가교구조 함유 분리막의 제조 방법, 이에 따라 제조된 리튬 이차전지용 가교구조 함유 분리막, 및 이를 포함하는 리튬 이차전지

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