WO2011043457A1 - Composite porous material and process for production thereof - Google Patents
Composite porous material and process for production thereof Download PDFInfo
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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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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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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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- 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)
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Abstract
Disclosed are: a porous material which can retain high porosity for a long period and has improved brittleness; and a process for producing the porous material. Specifically disclosed is a composite porous material in which voids in a fibrous laminate are filled with a porous substance selected from the group consisting of silica, a synthetic organic polymer and a natural organic polymer, wherein the composite porous material has a dried form, the porous substance has a representative pore diameter of 500 nm or less, preferably 200 nm or less, and the composite porous material has a nitrogen adsorption BET specific surface area of 20 m2/g or more, preferably 40 m2/g or more.
Description
本発明は、複合多孔材料及びその製造方法に関する。特に、本発明は、相対的に空孔径の大きい繊維積層体と、該空孔に充填される、相対的に空孔径が小さい多孔体とを有する複合多孔材料、及びその製造方法に関する。
The present invention relates to a composite porous material and a method for producing the same. In particular, 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.
近年、多孔材料、特に代表的空孔径が数百ｎｍ以下であるナノ多孔材料、特にシート状成形体は、フィルタ、触媒担体、電極、電池やキャパシタの隔壁（セパレータ）、薬剤担持材料、熱分解炭素前駆体、などの高機能材料として用途が広がっている。
そのような材料として、無機および有機の各種物質が利用される。この種の材料は最終利用場面では空隙に液体または固体を充填した状態で使用されることもあるが、製品として出荷される際には多孔性を維持した乾燥固体であることが望ましい。 In recent years, 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.
As such a material, various inorganic and organic substances are used. 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.
そのような材料として、無機および有機の各種物質が利用される。この種の材料は最終利用場面では空隙に液体または固体を充填した状態で使用されることもあるが、製品として出荷される際には多孔性を維持した乾燥固体であることが望ましい。 In recent years, 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.
As such a material, various inorganic and organic substances are used. 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.
ナノ多孔材料を調製する方法として、液体中で調製した多孔体、即ちゲルを、溶媒置換乾燥（超臨界乾燥を含む）によって空隙を維持して乾燥多孔体、即ちエアロゲルとする方法が有効である。そのような材料の例として、ゾルゲル法で得られるシリカゲルを超臨界乾燥したシリカエアロゲル（非特許文献１及び２、特許文献１及び２）、及び再生セルロースゲルを溶媒置換乾燥したセルロースエアロゲル（非特許文献３及び４、特許文献３）が挙げられる。
As 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. . As examples of such materials, 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), and cellulose aerogel obtained by solvent-replacement drying of regenerated cellulose gel (non-patent) Documents 3 and 4 and Patent Document 3) can be mentioned.
しかしながら、高空隙率のエアロゲルは一般に脆弱であり、特に薄いシート状に成形すると割れや崩壊を生じやすく、取り扱いが困難であった。例えば、エアロゲルのうち無機物からなるもの（例えば特許文献１）は一般に、可撓性に欠け脆弱であり、特に厚さ０．５ｍｍ以下のシート材料として提供することは困難である。他方、有機高分子材料は一般に、可撓性と靭性に富むので、そのエアロゲルをシート材料として提供できるならば利用価値が高い。
そこで、本発明の目的は、高空隙率を維持しつつ、脆弱性を克服した多孔材料を提供することにある。
また、本発明の目的は、上記目的に加えて、そのような多孔材料の製造方法を提供することにある。 However, a high porosity airgel is generally fragile, and particularly when formed into a thin sheet, it tends to crack and collapse, making it difficult to handle. For example, an airgel made of an inorganic material (for example, Patent Document 1) is generally lacking in flexibility and is fragile, and is difficult to provide as a sheet material having a thickness of 0.5 mm or less. On the other hand, since organic polymer materials are generally rich in flexibility and toughness, the utility value is high if the airgel can be provided as a sheet material.
Accordingly, an object of the present invention is to provide a porous material that overcomes the fragility while maintaining a high porosity.
Moreover, the objective of this invention is providing the manufacturing method of such a porous material in addition to the said objective.
そこで、本発明の目的は、高空隙率を維持しつつ、脆弱性を克服した多孔材料を提供することにある。
また、本発明の目的は、上記目的に加えて、そのような多孔材料の製造方法を提供することにある。 However, a high porosity airgel is generally fragile, and particularly when formed into a thin sheet, it tends to crack and collapse, making it difficult to handle. For example, an airgel made of an inorganic material (for example, Patent Document 1) is generally lacking in flexibility and is fragile, and is difficult to provide as a sheet material having a thickness of 0.5 mm or less. On the other hand, since organic polymer materials are generally rich in flexibility and toughness, the utility value is high if the airgel can be provided as a sheet material.
Accordingly, an object of the present invention is to provide a porous material that overcomes the fragility while maintaining a high porosity.
Moreover, the objective of this invention is providing the manufacturing method of such a porous material in addition to the said objective.
本発明者らは、次の発明を見出した。
＜１＞ 繊維積層体の空孔に、シリカ、有機合成高分子及び天然有機高分子からなる群から選ばれる多孔体が充填される複合多孔材料であって、該複合多孔材料は乾燥体であり、多孔体の代表空孔径が５００ｎｍ以下、好ましくは２００ｎｍ以下であり、複合多孔材料の窒素吸着ＢＥＴ比表面積が２０ｍ２／ｇ以上、好ましくは４０ｍ２／ｇ以上である、上記複合多孔材料。 The inventors have found the following invention.
<1> A composite porous material in which pores of a fiber laminate are filled with a porous material selected from the group consisting of silica, an organic synthetic polymer, and a natural organic polymer, and the composite porous material is a dry material The composite porous material, wherein the porous body has a representative pore diameter of 500 nm or less, preferably 200 nm or less, and the composite porous material has a nitrogen adsorption BET specific surface area of 20 m 2 / g or more, preferably 40 m 2 / g or more.
＜１＞ 繊維積層体の空孔に、シリカ、有機合成高分子及び天然有機高分子からなる群から選ばれる多孔体が充填される複合多孔材料であって、該複合多孔材料は乾燥体であり、多孔体の代表空孔径が５００ｎｍ以下、好ましくは２００ｎｍ以下であり、複合多孔材料の窒素吸着ＢＥＴ比表面積が２０ｍ２／ｇ以上、好ましくは４０ｍ２／ｇ以上である、上記複合多孔材料。 The inventors have found the following invention.
<1> A composite porous material in which pores of a fiber laminate are filled with a porous material selected from the group consisting of silica, an organic synthetic polymer, and a natural organic polymer, and the composite porous material is a dry material The composite porous material, wherein the porous body has a representative pore diameter of 500 nm or less, preferably 200 nm or less, and the composite porous material has a nitrogen adsorption BET specific surface area of 20 m 2 / g or more, preferably 40 m 2 / g or more.
＜２＞ 上記＜１＞において、多孔体は、有機合成高分子及び天然有機高分子からなる群から選ばれるのがよい。
＜３＞ 上記＜１＞又は＜２＞において、有機合成高分子は、ポリイミド、ポリスチレン、ポリオレフィン、ハロゲン化ポリオレフィン、ポリエステル及びポリアクリルアミドからなる群から選ばれるのがよく、好ましくはポリイミド、ポリオレフィン及びハロゲン化ポリオレフィンからなる群から選ばれるのがよい。
＜４＞ 上記＜１＞又は＜２＞において、天然有機高分子は、セルロース、キチン、アガロース及びβ-1,3グルカンからなる群から選ばれるのがよく、特にセルロースであるのがよい。 <2> In the above item <1>, the porous body may be selected from the group consisting of an organic synthetic polymer and a natural organic polymer.
<3> In the above <1> or <2>, 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.
<4> In the above item <1> or <2>, the natural organic polymer may be selected from the group consisting of cellulose, chitin, agarose and β-1,3 glucan, particularly cellulose.
＜３＞ 上記＜１＞又は＜２＞において、有機合成高分子は、ポリイミド、ポリスチレン、ポリオレフィン、ハロゲン化ポリオレフィン、ポリエステル及びポリアクリルアミドからなる群から選ばれるのがよく、好ましくはポリイミド、ポリオレフィン及びハロゲン化ポリオレフィンからなる群から選ばれるのがよい。
＜４＞ 上記＜１＞又は＜２＞において、天然有機高分子は、セルロース、キチン、アガロース及びβ-1,3グルカンからなる群から選ばれるのがよく、特にセルロースであるのがよい。 <2> In the above item <1>, the porous body may be selected from the group consisting of an organic synthetic polymer and a natural organic polymer.
<3> In the above <1> or <2>, 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.
<4> In the above item <1> or <2>, the natural organic polymer may be selected from the group consisting of cellulose, chitin, agarose and β-1,3 glucan, particularly cellulose.
＜５＞ 上記＜１＞～＜４＞のいずれかにおいて、繊維積層体は、ガラス繊維、セルロース系繊維、炭素繊維及び合成有機高分子繊維からなる群から選ばれる繊維からなる積層体であるのがよい。
＜６＞ 上記＜１＞～＜５＞のいずれかにおいて、繊維積層体の空孔の平均径は１μｍ以上、好ましくは５μｍ以上、１００μｍ以下であるのがよい。
＜７＞ 上記＜１＞～＜６＞のいずれかの複合多孔材料は、厚さ１ｍｍ以下のシート状成形体であるのがよい。 <5> In any one of the above items <1> to <4>, 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.
<6> In any one of the above items <1> to <5>, the average diameter of the pores of the fiber laminate may be 1 μm or more, preferably 5 μm or more and 100 μm or less.
<7> 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.
＜６＞ 上記＜１＞～＜５＞のいずれかにおいて、繊維積層体の空孔の平均径は１μｍ以上、好ましくは５μｍ以上、１００μｍ以下であるのがよい。
＜７＞ 上記＜１＞～＜６＞のいずれかの複合多孔材料は、厚さ１ｍｍ以下のシート状成形体であるのがよい。 <5> In any one of the above items <1> to <4>, 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.
<6> In any one of the above items <1> to <5>, the average diameter of the pores of the fiber laminate may be 1 μm or more, preferably 5 μm or more and 100 μm or less.
<7> 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.
＜８＞ 繊維積層体の空孔に、シリカ、有機合成高分子及び天然有機高分子からなる群から選ばれる多孔体が充填される複合多孔材料であって乾燥体である複合多孔材料の製造方法であり、該方法が、
Ａ）繊維積層体を準備する工程；
Ｂ）繊維積層体の空孔に高分子又はその前駆体を含む液を充填する工程；
Ｃ）高分子又はその前駆体を多孔体へと調製する工程；及び
Ｄ）多孔体が充填された繊維積層体を乾燥する工程；
を有することにより、乾燥体である複合多孔材料を調製し、多孔体の代表空孔径が５００ｎｍ以下、好ましくは２００ｎｍ以下である、上記方法。
＜９＞ 上記＜８＞において、複合多孔材料の窒素吸着ＢＥＴ比表面積が２０ｍ２／ｇ以上、好ましくは４０ｍ２／ｇ以上であるのがよい。 <8> 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 And 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.
<9> In the above item <8>, the composite porous material has a nitrogen adsorption BET specific surface area of 20 m 2 / g or more, preferably 40 m 2 / g or more.
Ａ）繊維積層体を準備する工程；
Ｂ）繊維積層体の空孔に高分子又はその前駆体を含む液を充填する工程；
Ｃ）高分子又はその前駆体を多孔体へと調製する工程；及び
Ｄ）多孔体が充填された繊維積層体を乾燥する工程；
を有することにより、乾燥体である複合多孔材料を調製し、多孔体の代表空孔径が５００ｎｍ以下、好ましくは２００ｎｍ以下である、上記方法。
＜９＞ 上記＜８＞において、複合多孔材料の窒素吸着ＢＥＴ比表面積が２０ｍ２／ｇ以上、好ましくは４０ｍ２／ｇ以上であるのがよい。 <8> 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 And 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.
<9> In the above item <8>, the composite porous material has a nitrogen adsorption BET specific surface area of 20 m 2 / g or more, preferably 40 m 2 / g or more.
＜１０＞ 上記＜８＞又は＜９＞において、Ｂ）工程の高分子又はその前駆体が、ｉ）セルロース以外の天然高分子、シリカ及び／又は有機合成高分子、もしくはそれらの前駆体；及びｉｉ）セルロース；の混合体であり、
Ｂ）工程において、混合体を含む液を繊維積層体の空孔に充填し、
Ｃ）工程において、
Ｃ）－１） 混合体からその多孔体、即ちｉ）セルロース以外の天然高分子、シリカ及び／又は有機合成高分子；とｉｉ）セルロース；との多孔体、へと調製する工程を有するのがよい。
＜１１＞ 上記＜１０＞において、Ｃ）－１）工程後、Ｃ）－２）セルロースを加水分解又は熱分解によって除去する工程を有してもよい。なお、この場合、セルロース以外の天然高分子、シリカ及び／又は有機合成高分子のみからなる多孔体が繊維積層体の空孔に充填される複合多孔材料を調製することができる。 <10> In the above <8> or <9>, 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;
In step B), the liquid containing the mixture is filled in the pores of the fiber laminate,
C) In step
C) -1) 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.
<11> In the above item <10>, after step C) -1), C) -2) may include a step of removing cellulose by hydrolysis or thermal decomposition. In this case, 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.
Ｂ）工程において、混合体を含む液を繊維積層体の空孔に充填し、
Ｃ）工程において、
Ｃ）－１） 混合体からその多孔体、即ちｉ）セルロース以外の天然高分子、シリカ及び／又は有機合成高分子；とｉｉ）セルロース；との多孔体、へと調製する工程を有するのがよい。
＜１１＞ 上記＜１０＞において、Ｃ）－１）工程後、Ｃ）－２）セルロースを加水分解又は熱分解によって除去する工程を有してもよい。なお、この場合、セルロース以外の天然高分子、シリカ及び／又は有機合成高分子のみからなる多孔体が繊維積層体の空孔に充填される複合多孔材料を調製することができる。 <10> In the above <8> or <9>, 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;
In step B), the liquid containing the mixture is filled in the pores of the fiber laminate,
C) In step
C) -1) 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.
<11> In the above item <10>, after step C) -1), C) -2) may include a step of removing cellulose by hydrolysis or thermal decomposition. In this case, 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.
＜１２＞ 上記＜８＞～＜１１＞のいずれかにおいて、多孔体は、有機合成高分子及び天然有機高分子からなる群から選ばれるのがよい。
＜１３＞ 上記＜８＞～＜１２＞のいずれかにおいて、有機合成高分子は、ポリイミド、ポリスチレン、ポリオレフィン、ハロゲン化ポリオレフィン、ポリエステル及びポリアクリルアミドからなる群から選ばれるのがよく、好ましくはポリイミド、ポリオレフィン及びハロゲン化ポリオレフィンからなる群から選ばれるのがよい。
＜１４＞ 上記＜８＞～＜１３＞のいずれかにおいて、天然有機高分子は、セルロース、キチン、アガロース及びβ-1,3グルカンからなる群から選ばれるのがよく、特にセルロースであるのがよい。 <12> In any one of the above items <8> to <11>, the porous body may be selected from the group consisting of organic synthetic polymers and natural organic polymers.
<13> In any one of the above items <8> to <12>, 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.
<14> In any one of the above items <8> to <13>, the natural organic polymer may be selected from the group consisting of cellulose, chitin, agarose, and β-1,3 glucan, particularly cellulose. Good.
＜１３＞ 上記＜８＞～＜１２＞のいずれかにおいて、有機合成高分子は、ポリイミド、ポリスチレン、ポリオレフィン、ハロゲン化ポリオレフィン、ポリエステル及びポリアクリルアミドからなる群から選ばれるのがよく、好ましくはポリイミド、ポリオレフィン及びハロゲン化ポリオレフィンからなる群から選ばれるのがよい。
＜１４＞ 上記＜８＞～＜１３＞のいずれかにおいて、天然有機高分子は、セルロース、キチン、アガロース及びβ-1,3グルカンからなる群から選ばれるのがよく、特にセルロースであるのがよい。 <12> In any one of the above items <8> to <11>, the porous body may be selected from the group consisting of organic synthetic polymers and natural organic polymers.
<13> In any one of the above items <8> to <12>, 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.
<14> In any one of the above items <8> to <13>, the natural organic polymer may be selected from the group consisting of cellulose, chitin, agarose, and β-1,3 glucan, particularly cellulose. Good.
＜１５＞ 上記＜８＞～＜１４＞のいずれかにおいて、繊維積層体は、ガラス繊維、セルロース系繊維、炭素繊維及び合成有機高分子繊維からなる群から選ばれる繊維からなる積層体であるのがよい。
＜１６＞ 上記＜８＞～＜１５＞のいずれかにおいて、繊維積層体の空孔の平均径は１μｍ以上、好ましくは５μｍ以上であるのがよい。
＜１７＞ 上記＜８＞～＜１６＞のいずれかにおいて、Ａ）工程で準備する繊維積層体が、厚さ１ｍｍ以下のシート状であるのがよい。
＜１８＞ 上記＜８＞～＜１７＞のいずれかの複合多孔材料は、厚さ１ｍｍ以下のシート状成形体であるのがよい。 <15> In any one of the above items <8> to <14>, 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.
<16> In any one of the above items <8> to <15>, the average diameter of the pores of the fiber laminate is 1 μm or more, preferably 5 μm or more.
<17> In any one of the above items <8> to <16>, the fiber laminate prepared in step A) is preferably in the form of a sheet having a thickness of 1 mm or less.
<18> 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.
＜１６＞ 上記＜８＞～＜１５＞のいずれかにおいて、繊維積層体の空孔の平均径は１μｍ以上、好ましくは５μｍ以上であるのがよい。
＜１７＞ 上記＜８＞～＜１６＞のいずれかにおいて、Ａ）工程で準備する繊維積層体が、厚さ１ｍｍ以下のシート状であるのがよい。
＜１８＞ 上記＜８＞～＜１７＞のいずれかの複合多孔材料は、厚さ１ｍｍ以下のシート状成形体であるのがよい。 <15> In any one of the above items <8> to <14>, 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.
<16> In any one of the above items <8> to <15>, the average diameter of the pores of the fiber laminate is 1 μm or more, preferably 5 μm or more.
<17> In any one of the above items <8> to <16>, the fiber laminate prepared in step A) is preferably in the form of a sheet having a thickness of 1 mm or less.
<18> 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.
本発明により、高空隙率を維持しつつ、脆弱性を克服した多孔材料を提供することができる。
また、本発明により、上記効果に加えて、そのような多孔材料の製造方法を提供することができる。 According to 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.
また、本発明により、上記効果に加えて、そのような多孔材料の製造方法を提供することができる。 According to 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.
以下、本発明を詳細に説明する。
本発明は、複合多孔材料及びその製造方法を提供する。以下、順に説明する。
＜複合多孔材料＞
本発明の複合多孔材料は、繊維積層体の空孔に、シリカ、有機合成高分子及び天然有機高分子からなる群から選ばれる多孔体が充填されてなる。
ここで、繊維積層体は、相対的に空孔平均径が大きく、その空孔の平均径は１μｍ以上、好ましくは５μｍ以上であるのがよい。
一方、繊維積層体の空孔に充填される多孔体は、相対的に孔の代表径が小さく、その代表径が５００ｎｍ以下、好ましくは２００ｎｍ以下であるのがよい。
なお、ここで、代表径とは、走査型電子顕微鏡による表面観察、または透過型電子顕微鏡による超薄切片観察で観察される多孔体の網目構造で典型的に観察される網目要素間の間隔を意味する。
また、本発明の複合多孔材料は、その窒素吸着ＢＥＴ比表面積が２０ｍ２／ｇ以上、好ましくは４０ｍ２／ｇ以上であるのがよい。 Hereinafter, the present invention will be described in detail.
The present invention provides a composite porous material and a method for producing the same. Hereinafter, it demonstrates in order.
<Composite porous material>
The composite porous material of the present invention 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.
Here, the fiber laminate has a relatively large average pore diameter, and the average diameter of the pores is 1 μm or more, preferably 5 μm or more.
On the other hand, 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.
Here, 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.
Further, 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.
本発明は、複合多孔材料及びその製造方法を提供する。以下、順に説明する。
＜複合多孔材料＞
本発明の複合多孔材料は、繊維積層体の空孔に、シリカ、有機合成高分子及び天然有機高分子からなる群から選ばれる多孔体が充填されてなる。
ここで、繊維積層体は、相対的に空孔平均径が大きく、その空孔の平均径は１μｍ以上、好ましくは５μｍ以上であるのがよい。
一方、繊維積層体の空孔に充填される多孔体は、相対的に孔の代表径が小さく、その代表径が５００ｎｍ以下、好ましくは２００ｎｍ以下であるのがよい。
なお、ここで、代表径とは、走査型電子顕微鏡による表面観察、または透過型電子顕微鏡による超薄切片観察で観察される多孔体の網目構造で典型的に観察される網目要素間の間隔を意味する。
また、本発明の複合多孔材料は、その窒素吸着ＢＥＴ比表面積が２０ｍ２／ｇ以上、好ましくは４０ｍ２／ｇ以上であるのがよい。 Hereinafter, the present invention will be described in detail.
The present invention provides a composite porous material and a method for producing the same. Hereinafter, it demonstrates in order.
<Composite porous material>
The composite porous material of the present invention 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.
Here, the fiber laminate has a relatively large average pore diameter, and the average diameter of the pores is 1 μm or more, preferably 5 μm or more.
On the other hand, 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.
Here, 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.
Further, 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.
このような特性を有する本発明の複合多孔材料は、従来脆弱であった多孔材料を、機械的に安定したものとすることができる。このため、移送、さらなる加工等において、取り扱いが容易な材料を提供することができ、例えば、厚さ１ｍｍ以下のシート状材料として提供することができる。
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.
＜＜繊維積層体＞＞
本発明の複合多孔材料のうち、繊維積層体は、ガラス繊維、セルロース系繊維、炭素繊維及び合成有機高分子繊維からなる群から選ばれる繊維からなる積層体であるのがよい。
例えば、繊維積層体として、天然植物繊維からなる紙および板紙、ガラス繊維紙、再生セルローススポンジ、合成ゴムスポンジ、多孔セラミックス、カーボンペーパー、合成繊維不織布、及び再生セルロース不織布などを挙げることができるが、これらに限定されない。
繊維積層体は、上述のように、相対的に空孔の平均径が大きく、その空孔の平均径は１μｍ以上、好ましくは５μｍ以上であるのがよい。
本発明の複合多孔材料を上述の厚さのシート状材料とするために、繊維積層体は、その厚さが１ｍｍ以下であるのがよい。 << fiber laminate >>
Of the composite porous material of the present invention, 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.
For example, examples of 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.
As described above, the fiber laminate has a relatively large average pore diameter, and the average pore diameter is 1 μm or more, preferably 5 μm or more.
In order to make the composite porous material of the present invention into a sheet-like material having the above thickness, the fiber laminate preferably has a thickness of 1 mm or less.
本発明の複合多孔材料のうち、繊維積層体は、ガラス繊維、セルロース系繊維、炭素繊維及び合成有機高分子繊維からなる群から選ばれる繊維からなる積層体であるのがよい。
例えば、繊維積層体として、天然植物繊維からなる紙および板紙、ガラス繊維紙、再生セルローススポンジ、合成ゴムスポンジ、多孔セラミックス、カーボンペーパー、合成繊維不織布、及び再生セルロース不織布などを挙げることができるが、これらに限定されない。
繊維積層体は、上述のように、相対的に空孔の平均径が大きく、その空孔の平均径は１μｍ以上、好ましくは５μｍ以上であるのがよい。
本発明の複合多孔材料を上述の厚さのシート状材料とするために、繊維積層体は、その厚さが１ｍｍ以下であるのがよい。 << fiber laminate >>
Of the composite porous material of the present invention, 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.
For example, examples of 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.
As described above, the fiber laminate has a relatively large average pore diameter, and the average pore diameter is 1 μm or more, preferably 5 μm or more.
In order to make the composite porous material of the present invention into a sheet-like material having the above thickness, the fiber laminate preferably has a thickness of 1 mm or less.
＜＜多孔体＞＞
本発明の複合多孔材料のうち、多孔体は、シリカ、有機合成高分子及び天然有機高分子からなる群から選ばれる１種又はそれ以上であるのがよく、好ましくは有機合成高分子及び天然有機高分子からなる群から選ばれる１種又はそれ以上であるのがよい。
有機合成高分子として、ポリイミド、ポリスチレン、ポリオレフィン、ハロゲン化ポリオレフィン、ポリエステル及びポリアクリルアミドからなる群から選ばれるのがよく、好ましくはポリイミド、ポリオレフィン及びハロゲン化ポリオレフィンからなる群から選ばれるのがよい。
また、天然有機高分子として、セルロース、キチン、アガロース及びβ-1,3グルカンからなる群から選ばれるのがよく、特にセルロースであるのがよい。 << porous body >>
Of the composite porous material of the present invention, 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.
Further, the natural organic polymer is preferably selected from the group consisting of cellulose, chitin, agarose and β-1,3 glucan, particularly cellulose.
本発明の複合多孔材料のうち、多孔体は、シリカ、有機合成高分子及び天然有機高分子からなる群から選ばれる１種又はそれ以上であるのがよく、好ましくは有機合成高分子及び天然有機高分子からなる群から選ばれる１種又はそれ以上であるのがよい。
有機合成高分子として、ポリイミド、ポリスチレン、ポリオレフィン、ハロゲン化ポリオレフィン、ポリエステル及びポリアクリルアミドからなる群から選ばれるのがよく、好ましくはポリイミド、ポリオレフィン及びハロゲン化ポリオレフィンからなる群から選ばれるのがよい。
また、天然有機高分子として、セルロース、キチン、アガロース及びβ-1,3グルカンからなる群から選ばれるのがよく、特にセルロースであるのがよい。 << porous body >>
Of the composite porous material of the present invention, 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.
Further, the natural organic polymer is preferably selected from the group consisting of cellulose, chitin, agarose and β-1,3 glucan, particularly cellulose.
本発明の複合多孔材料は、例えば次のような製法により製造することができる。
即ち、Ａ）繊維積層体を準備する工程；
Ｂ）繊維積層体の空孔に高分子又はその前駆体を含む液を充填する工程；
Ｃ）高分子又はその前駆体を多孔体へと調製する工程；及び
Ｄ）多孔体が充填された繊維積層体を乾燥する工程；
を有することにより、上述の複合多孔材料を調製することができる。
なお、製法において用いる語、例えば「繊維積層体」、「多孔体」などの上述と同じ語は、上述と同じ内容を有するため、その説明を省略する。 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;
By having the above, 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.
即ち、Ａ）繊維積層体を準備する工程；
Ｂ）繊維積層体の空孔に高分子又はその前駆体を含む液を充填する工程；
Ｃ）高分子又はその前駆体を多孔体へと調製する工程；及び
Ｄ）多孔体が充填された繊維積層体を乾燥する工程；
を有することにより、上述の複合多孔材料を調製することができる。
なお、製法において用いる語、例えば「繊維積層体」、「多孔体」などの上述と同じ語は、上述と同じ内容を有するため、その説明を省略する。 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;
By having the above, 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.
Ａ）工程は、繊維積層体を準備する工程である。準備には、繊維積層体を市販購入しても、別途調製してもよい。
A) Step is a step of preparing a fiber laminate. For the preparation, the fiber laminate may be purchased commercially or prepared separately.
Ｂ）工程は、上記Ａ）工程で準備した繊維積層体の空孔に、高分子又はその前駆体を含む液を充填する工程である。
ここで、前駆体とは、後に多孔体に成り得る物質をいう。例えば、多孔体がシリカからなる場合、後にシリカに成り得る物質として、テトラメチルオルソシリケート、テトラエチルオルソシリケートなどを挙げることができるがこれに限定されない。
また、多孔体が上述の有機合成高分子の場合、前駆体として、それらのモノマー、ダイマー、トリマー、オリゴマー、プレポリマーなどを挙げることができるがこれに限定されない。 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.
Here, the precursor refers to a substance that can later become a porous body. For example, when 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.
In addition, when the porous body is the above-described organic synthetic polymer, examples of the precursor include monomers, dimers, trimers, oligomers, prepolymers, and the like, but are not limited thereto.
ここで、前駆体とは、後に多孔体に成り得る物質をいう。例えば、多孔体がシリカからなる場合、後にシリカに成り得る物質として、テトラメチルオルソシリケート、テトラエチルオルソシリケートなどを挙げることができるがこれに限定されない。
また、多孔体が上述の有機合成高分子の場合、前駆体として、それらのモノマー、ダイマー、トリマー、オリゴマー、プレポリマーなどを挙げることができるがこれに限定されない。 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.
Here, the precursor refers to a substance that can later become a porous body. For example, when 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.
In addition, when the porous body is the above-described organic synthetic polymer, examples of the precursor include monomers, dimers, trimers, oligomers, prepolymers, and the like, but are not limited thereto.
Ｂ）工程において、充填は、高分子又はその前駆体を含む液に繊維積層体を浸漬する方法；高分子又はその前駆体を含む液を繊維積層体に塗布する方法、例えば液を繊維積層体に噴霧する方法、ローラなどを用いて転写する方法；などにより行うことができる。
ここで、用いる液は、用いる高分子又はその前駆体の種類、用いる繊維積層体の種類などに依存する。液として、高分子又はその前駆体の溶液、懸濁液等を挙げることができ、好ましくは高分子又はその前駆体の溶液であるのがよい。 In 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.
Here, 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.
ここで、用いる液は、用いる高分子又はその前駆体の種類、用いる繊維積層体の種類などに依存する。液として、高分子又はその前駆体の溶液、懸濁液等を挙げることができ、好ましくは高分子又はその前駆体の溶液であるのがよい。 In 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.
Here, 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.
Ｃ）工程は、高分子又はその前駆体を多孔体へと調製する工程である。
例えば、前駆体としてシリカ前駆体、例えば、テトラエチルオルソシリケート（以下、「ＴＥＯＳ」と略記する場合がある）を用いた場合、いわゆるゾルゲル法でシリカ多孔体を調製する方法などを挙げることができる。
また、高分子としてセルロースを用いた場合、繊維積層体の空孔にセルロース溶液が充填されたものを、セルロースの非溶媒、例えばメタノールなどに接触させる方法、例えばメタノールなどに浸漬する方法などにより、セルロース多孔体を調製する手法などを挙げることができる。
なお、Ｃ）工程での、高分子又はその前駆体を多孔体への調製法は、用いる高分子、用いる前駆体、用いる繊維積層体などに依存し、上述の具体的に挙げた手法に限定されない。 Step C) is a step of preparing a polymer or a precursor thereof into a porous body.
For example, when a silica precursor, for example, tetraethyl orthosilicate (hereinafter sometimes abbreviated as “TEOS”) is used as the precursor, a method of preparing a porous silica by a so-called sol-gel method can be exemplified.
Further, 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.
In addition, 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-described specific methods. Not.
例えば、前駆体としてシリカ前駆体、例えば、テトラエチルオルソシリケート（以下、「ＴＥＯＳ」と略記する場合がある）を用いた場合、いわゆるゾルゲル法でシリカ多孔体を調製する方法などを挙げることができる。
また、高分子としてセルロースを用いた場合、繊維積層体の空孔にセルロース溶液が充填されたものを、セルロースの非溶媒、例えばメタノールなどに接触させる方法、例えばメタノールなどに浸漬する方法などにより、セルロース多孔体を調製する手法などを挙げることができる。
なお、Ｃ）工程での、高分子又はその前駆体を多孔体への調製法は、用いる高分子、用いる前駆体、用いる繊維積層体などに依存し、上述の具体的に挙げた手法に限定されない。 Step C) is a step of preparing a polymer or a precursor thereof into a porous body.
For example, when a silica precursor, for example, tetraethyl orthosilicate (hereinafter sometimes abbreviated as “TEOS”) is used as the precursor, a method of preparing a porous silica by a so-called sol-gel method can be exemplified.
Further, 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.
In addition, 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-described specific methods. Not.
Ｄ）工程は、Ｃ）工程後、得られたもの、即ち多孔体が充填された繊維積層体を乾燥する工程である。
この乾燥工程により、繊維積層体に充填された多孔体をエアロゲルとすることができる。
乾燥工程は、溶媒置換及びその後の該溶媒の乾燥により行うことができる。なお、溶媒置換として、超臨界二酸化炭素置換も含まれる。 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.
By this drying step, 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. In addition, supercritical carbon dioxide substitution is also included as solvent substitution.
この乾燥工程により、繊維積層体に充填された多孔体をエアロゲルとすることができる。
乾燥工程は、溶媒置換及びその後の該溶媒の乾燥により行うことができる。なお、溶媒置換として、超臨界二酸化炭素置換も含まれる。 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.
By this drying step, 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. In addition, supercritical carbon dioxide substitution is also included as solvent substitution.
乾燥として、凍結乾燥法、超臨界乾燥法、加熱乾燥法などを挙げることができる。各方法においての条件は、用いる繊維積層体の種類、用いる多孔体の種類、用いる液などに依存するが、例えば、次のような手法を用いた場合、以下の乾燥法を用いることができる。即ち、繊維積層体としてガラスペーパーを、多孔体となる高分子としてセルロースを用いる。アルカリ－尿素水溶液を用いてセルロース溶液とし、該セルロース溶液にガラスペーパーを浸漬し、付着液を除去してからメタノールに浸漬してセルロースをゲル状に再生させる。該湿潤セルロースゲルをエアロゲル化する場合には、含有液をエタノールに置換し、次いでフッ素系溶剤に置換し、次いで凍結乾燥する方法を挙げることができる。なお、上記において、フッ素系溶剤の代りに液体二酸化炭素を用いるならば、超臨界乾燥法で行うことができる。
以上のように、Ａ）～Ｄ）工程を用いることにより、本発明の複合多孔材料を得ることができる。 Examples of the drying 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. For example, when the following method is used, 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. In the case where 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. In the above, if liquid carbon dioxide is used instead of the fluorinated solvent, the supercritical drying method can be used.
As described above, the composite porous material of the present invention can be obtained by using steps A) to D).
以上のように、Ａ）～Ｄ）工程を用いることにより、本発明の複合多孔材料を得ることができる。 Examples of the drying 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. For example, when the following method is used, 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. In the case where 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. In the above, if liquid carbon dioxide is used instead of the fluorinated solvent, the supercritical drying method can be used.
As described above, the composite porous material of the present invention can be obtained by using steps A) to D).
なお、繊維積層体の空孔に充填させる多孔体が、セルロース以外の天然高分子、シリカ及び／又は有機合成高分子である場合、次のような手法を用いて調製することもできる。
即ち、Ｂ）工程の「高分子又はその前駆体」として、ｉ）セルロース以外の天然高分子、シリカ及び／又は有機合成高分子、もしくはそれらの前駆体；及びｉｉ）セルロース；の混合体を用いる。
その後、上述のＢ）工程と同様に、該混合体を含む液を繊維積層体の空孔に充填する。
さらに、Ｃ）工程において、
Ｃ）－１）混合体からその多孔体、即ちｉ）セルロース以外の天然高分子、シリカ及び／又は有機合成高分子；とｉｉ）セルロース；との多孔体、へと調製する工程を有するのがよい。
さらに、Ｃ）－１）工程後、Ｃ）－２）セルロースを加水分解又は熱分解によって除去する工程を有してもよい。この場合、セルロース以外の天然高分子、シリカ及び／又は有機合成高分子からなる多孔体のみが繊維積層体の空孔内に充填される複合多孔材料が調製される。 In addition, when the porous body with which the void | 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.
Furthermore, in 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. Good.
Further, after step C) -1), C) -2) a step of removing cellulose by hydrolysis or thermal decomposition may be included. In this case, 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.
即ち、Ｂ）工程の「高分子又はその前駆体」として、ｉ）セルロース以外の天然高分子、シリカ及び／又は有機合成高分子、もしくはそれらの前駆体；及びｉｉ）セルロース；の混合体を用いる。
その後、上述のＢ）工程と同様に、該混合体を含む液を繊維積層体の空孔に充填する。
さらに、Ｃ）工程において、
Ｃ）－１）混合体からその多孔体、即ちｉ）セルロース以外の天然高分子、シリカ及び／又は有機合成高分子；とｉｉ）セルロース；との多孔体、へと調製する工程を有するのがよい。
さらに、Ｃ）－１）工程後、Ｃ）－２）セルロースを加水分解又は熱分解によって除去する工程を有してもよい。この場合、セルロース以外の天然高分子、シリカ及び／又は有機合成高分子からなる多孔体のみが繊維積層体の空孔内に充填される複合多孔材料が調製される。 In addition, when the porous body with which the void | 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.
Furthermore, in 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. Good.
Further, after step C) -1), C) -2) a step of removing cellulose by hydrolysis or thermal decomposition may be included. In this case, 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.
以下、実施例に基づいて、本発明をさらに詳細に説明するが、本発明は本実施例に限定されるものではない。
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.
＜セルロース溶液の調製＞
水酸化リチウム４．６ｗｔ％と尿素１５ｗｔ％とを含む水溶液１００ｇを－１２℃に冷却し、これにろ紙パルプ（純粋なセルロース。アドバンテック東洋製）２ｇを加えて攪拌するとセルロースは速やかに溶解し透明な溶液を与えた。
該セルロース溶液に、日本板硝子（株）製ガラスペーパー（厚さ：５０μｍ、繊維径：０．５～２μｍ、密度：約０．１４ｇ／ｃｍ３、空隙率：９０％以上、平均孔径：２～５μｍ、最大孔径：１０～１５μｍ。用いたガラスペーパーについて走査型電子顕微鏡（以下、「ＳＥＭ」と略記する）で観察した結果を図５に示す。）を浸漬し、付着液を除去してからメタノールに浸漬し、十分に水洗してセルロースをゲル化させてセルロースヒドロゲル含有ガラスペーパーを得た。 <Preparation of cellulose solution>
When 100 g of an aqueous solution containing 4.6 wt% lithium hydroxide and 15 wt% urea is cooled to −12 ° C., 2 g of filter paper pulp (pure cellulose, manufactured by Advantech Toyo) is added and stirred, the cellulose quickly dissolves and becomes transparent Solution.
To the cellulose solution, a glass paper (thickness: 50 μm, fiber diameter: 0.5-2 μm, density: about 0.14 g / cm 3 , porosity: 90% or more, average pore diameter: 2 to 5 μm, maximum pore size: 10 to 15 μm The results of observation of the used glass paper with a scanning electron microscope (hereinafter abbreviated as “SEM”) are immersed in FIG. The cellulose hydrogel-containing glass paper was obtained by immersing in methanol and thoroughly washing with water to gel the cellulose.
水酸化リチウム４．６ｗｔ％と尿素１５ｗｔ％とを含む水溶液１００ｇを－１２℃に冷却し、これにろ紙パルプ（純粋なセルロース。アドバンテック東洋製）２ｇを加えて攪拌するとセルロースは速やかに溶解し透明な溶液を与えた。
該セルロース溶液に、日本板硝子（株）製ガラスペーパー（厚さ：５０μｍ、繊維径：０．５～２μｍ、密度：約０．１４ｇ／ｃｍ３、空隙率：９０％以上、平均孔径：２～５μｍ、最大孔径：１０～１５μｍ。用いたガラスペーパーについて走査型電子顕微鏡（以下、「ＳＥＭ」と略記する）で観察した結果を図５に示す。）を浸漬し、付着液を除去してからメタノールに浸漬し、十分に水洗してセルロースをゲル化させてセルロースヒドロゲル含有ガラスペーパーを得た。 <Preparation of cellulose solution>
When 100 g of an aqueous solution containing 4.6 wt% lithium hydroxide and 15 wt% urea is cooled to −12 ° C., 2 g of filter paper pulp (pure cellulose, manufactured by Advantech Toyo) is added and stirred, the cellulose quickly dissolves and becomes transparent Solution.
To the cellulose solution, a glass paper (thickness: 50 μm, fiber diameter: 0.5-2 μm, density: about 0.14 g / cm 3 , porosity: 90% or more, average pore diameter: 2 to 5 μm, maximum pore size: 10 to 15 μm The results of observation of the used glass paper with a scanning electron microscope (hereinafter abbreviated as “SEM”) are immersed in FIG. The cellulose hydrogel-containing glass paper was obtained by immersing in methanol and thoroughly washing with water to gel the cellulose.
該複合ゲルの含有液を水→エタノール→フッ素系溶剤（日本ゼオン（株）製ゼオローラＨ）と置換し、該ゲルを液体窒素に浸漬して凍結し、ヤマト科学（株）製フリーズドライヤＤＣ-８００により凍結乾燥して、ガラスペーパー担持セルロースエアロゲルを得た。該エアロゲルは、窒素吸着解析において４３．９ｍ２／ｇの比表面積を有した。
また、ＳＥＭ観察をした結果、図１および図２に示す像を得た。図１及び図２から、該エアロゲルは、代表値１００～２００ｎｍの空隙径を有していた。 基材である該ガラスペーパーは窒素吸着法により２６．８ｍ２／ｇの比表面積を有していたので、組成解析から、担持されたセルロースエアロゲルの比表面積は１４３．９ｍ２／ｇと計算された。 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 | freeze-dried by 800 and the glass paper carrying | support cellulose aerogel was obtained. 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.
また、ＳＥＭ観察をした結果、図１および図２に示す像を得た。図１及び図２から、該エアロゲルは、代表値１００～２００ｎｍの空隙径を有していた。 基材である該ガラスペーパーは窒素吸着法により２６．８ｍ２／ｇの比表面積を有していたので、組成解析から、担持されたセルロースエアロゲルの比表面積は１４３．９ｍ２／ｇと計算された。 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 | freeze-dried by 800 and the glass paper carrying | support cellulose aerogel was obtained. 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.
実施例１と同じセルロースヒドロゲル含有ガラスペーパーを、含有液を水とした状態から、ヤマト科学（株）製フリーズドライヤＤＣ-８００により、水凍結乾燥してガラスペーパー担持セルロースエアロゲルを得た。
得られたエアロゲルを、実施例１と同様に、窒素吸着解析、及びＳＥＭ像観察を行った。その結果、窒素吸着解析において、３１．０ｍ２／ｇの比表面積を有することがわかった。また、ＳＥＭ像観察において、代表値２００～１０００ｎｍの空隙径を有することがわかった（図３参照）。
また、実施例１と同様の計算から、担持されたセルロースエアロゲルの比表面積は６４．９ｍ２／ｇと計算された。 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.
得られたエアロゲルを、実施例１と同様に、窒素吸着解析、及びＳＥＭ像観察を行った。その結果、窒素吸着解析において、３１．０ｍ２／ｇの比表面積を有することがわかった。また、ＳＥＭ像観察において、代表値２００～１０００ｎｍの空隙径を有することがわかった（図３参照）。
また、実施例１と同様の計算から、担持されたセルロースエアロゲルの比表面積は６４．９ｍ２／ｇと計算された。 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.
＜ポリイミド前駆体の合成＞
ポリアミド酸の調製は常法により、以下のように行った。絶乾した4-,4’-ジアミノジフェニルエーテルを脱水N,N’-ジメチルアセトアミド（ＤＭＡｃ）に溶解させておき、当モル量の無水ピロメリット酸の粉末を投入してすばやく攪拌した。この反応系は濃度が１５重量％となるように調製した。 <Synthesis of polyimide precursor>
Preparation of the polyamic acid was carried out as follows by a conventional method. Absolutely dried 4-, 4′-diaminodiphenyl ether was dissolved in dehydrated N, N′-dimethylacetamide (DMAc), and an equimolar amount of pyromellitic anhydride powder was added and rapidly stirred. This reaction system was prepared to have a concentration of 15% by weight.
ポリアミド酸の調製は常法により、以下のように行った。絶乾した4-,4’-ジアミノジフェニルエーテルを脱水N,N’-ジメチルアセトアミド（ＤＭＡｃ）に溶解させておき、当モル量の無水ピロメリット酸の粉末を投入してすばやく攪拌した。この反応系は濃度が１５重量％となるように調製した。 <Synthesis of polyimide precursor>
Preparation of the polyamic acid was carried out as follows by a conventional method. Absolutely dried 4-, 4′-diaminodiphenyl ether was dissolved in dehydrated N, N′-dimethylacetamide (DMAc), and an equimolar amount of pyromellitic anhydride powder was added and rapidly stirred. This reaction system was prepared to have a concentration of 15% by weight.
＜ポリイミド前駆体溶液のガラスペーパーへの含浸とイミド化＞
実施例１と同じガラスペーパーを前記ポリアミド酸溶液に浸漬し、付着液体をろ紙吸取りで除去してから無水酢酸-ピリジン混液（１：１）に浸漬して化学イミド化を行った。
該複合体の含液ゲルを溶媒置換により超臨界ＣＯ２（３５℃、８０００ｋＰａ）から乾燥し、ガラスペーパー担持ポリイミドエアロゲルを調製した。
得られたポリイミドエアロゲルを、実施例１と同様に、窒素吸着解析、及びＳＥＭ像観察を行った。その結果、窒素吸着解析において、６２．２ｍ２／ｇの比表面積を有することがわかった。また、ＳＥＭ像観察において、代表値２００～１０００ｎｍの空隙径を有することがわかった（図４参照）。 <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. As a result, in the nitrogen adsorption analysis, it was found to have a specific surface area of 62.2 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. 4).
実施例１と同じガラスペーパーを前記ポリアミド酸溶液に浸漬し、付着液体をろ紙吸取りで除去してから無水酢酸-ピリジン混液（１：１）に浸漬して化学イミド化を行った。
該複合体の含液ゲルを溶媒置換により超臨界ＣＯ２（３５℃、８０００ｋＰａ）から乾燥し、ガラスペーパー担持ポリイミドエアロゲルを調製した。
得られたポリイミドエアロゲルを、実施例１と同様に、窒素吸着解析、及びＳＥＭ像観察を行った。その結果、窒素吸着解析において、６２．２ｍ２／ｇの比表面積を有することがわかった。また、ＳＥＭ像観察において、代表値２００～１０００ｎｍの空隙径を有することがわかった（図４参照）。 <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. As a result, in the nitrogen adsorption analysis, it was found to have a specific surface area of 62.2 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. 4).
実施例１においてガラスペーパーの代りにろ紙（アドバンテック製定量ろ紙５Ｃ）を用いた以外、実施例１と同様に、該ろ紙をセルロース溶液に浸漬し、その後も同様に処理することにより、ろ紙担持セルロースエアロゲルを得た。該エアロゲルをＳＥＭ観察したところ、図示しないが、セルロースゲルがろ紙繊維間の空隙に充填され、図１及び図２のガラスペーパー担持セルロースエアロゲルと同様の構造を有していた。
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.
Claims (14)
- 繊維積層体の空孔に、シリカ、有機合成高分子及び天然有機高分子からなる群から選ばれる多孔体が充填される複合多孔材料であって、該複合多孔材料は乾燥体であり、前記多孔体の代表空孔径が５００ｎｍ以下であり、前記複合多孔材料の窒素吸着ＢＥＴ比表面積が２０ｍ２／ｇ以上である、上記複合多孔材料。 A composite porous material in which pores of a fiber laminate are filled with a porous body selected from the group consisting of silica, an organic synthetic polymer, and a natural organic polymer, wherein the composite porous material is a dry body, and the porous The above-mentioned composite porous material, wherein the representative pore diameter of the body is 500 nm or less, and the nitrogen adsorption BET specific surface area of the composite porous material is 20 m 2 / g or more.
- 前記多孔体は、有機合成高分子及び天然有機高分子からなる群から選ばれる請求項１記載の複合多孔材料。 The composite porous material according to claim 1, wherein the porous body is selected from the group consisting of organic synthetic polymers and natural organic polymers.
- 前記有機合成高分子は、ポリイミド、ポリスチレン、ポリオレフィン、ハロゲン化ポリオレフィン、ポリエステル及びポリアクリルアミドからなる群から選ばれる請求項１又は２記載の複合多孔材料。 The composite porous material according to claim 1 or 2, wherein the organic synthetic polymer is selected from the group consisting of polyimide, polystyrene, polyolefin, halogenated polyolefin, polyester, and polyacrylamide.
- 前記天然有機高分子は、セルロース、キチン、アガロース及びβ-1,3グルカンからなる群から選ばれる請求項１～３のいずれか１項記載の複合多孔材料。 The composite porous material according to any one of claims 1 to 3, wherein the natural organic polymer is selected from the group consisting of cellulose, chitin, agarose, and β-1,3 glucan.
- 前記繊維積層体は、ガラス繊維、セルロース系繊維、炭素繊維及び合成有機高分子繊維からなる群から選ばれる繊維からなる積層体である請求項１～４のいずれか１項記載の複合多孔材料。 The composite porous material according to any one of claims 1 to 4, wherein 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.
- 前記繊維積層体の空孔の平均径は１μｍ以上である請求項１～５のいずれか１項記載の複合多孔材料。 The composite porous material according to any one of claims 1 to 5, wherein an average diameter of pores of the fiber laminate is 1 µm or more.
- 繊維積層体の空孔に、シリカ、有機合成高分子及び天然有機高分子からなる群から選ばれる多孔体が充填される複合多孔材料であって乾燥体である複合多孔材料の製造方法であり、該方法が、
Ａ）繊維積層体を準備する工程；
Ｂ）繊維積層体の空孔に高分子又はその前駆体を含む液を充填する工程；
Ｃ）高分子又はその前駆体を多孔体へと調製する工程；及び
Ｄ）多孔体が充填された繊維積層体を乾燥する工程；
を有することにより、乾燥体である複合多孔材料を調製し、多孔体の代表空孔径が５００ｎｍ以下である、上記方法。 A method for producing a composite porous material which is a composite porous material in which pores selected from the group consisting of silica, organic synthetic polymer and natural organic polymer are filled in the pores of the fiber laminate and which is a dry body, The method is
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. - 前記Ｂ）工程の高分子又はその前駆体が、ｉ）セルロース以外の天然高分子、シリカ及び／又は有機合成高分子、もしくはそれらの前駆体；及びｉｉ）セルロース；の混合体であり、
前記Ｂ）工程において、混合体を含む液を繊維積層体の空孔に充填し、
前記Ｃ）工程において、
Ｃ）－１） 混合体からその多孔体へと調製する工程を有する請求項７記載の方法。 The polymer of B) or a precursor thereof is a mixture of i) natural polymers other than cellulose, silica and / or organic synthetic polymers, or precursors thereof; and ii) cellulose;
In step B), the liquid containing the mixture is filled in the pores of the fiber laminate,
In step C),
The method according to claim 7, further comprising the step of C) -1) preparing the mixture into a porous body. - 前記Ｃ）－１）工程後、Ｃ）－２）セルロースを加水分解又は熱分解によって除去する工程をさらに有する請求項８記載の方法。 The method according to claim 8, further comprising a step of removing cellulose by hydrolysis or thermal decomposition after the step C) -1).
- 前記多孔体は、有機合成高分子及び天然有機高分子からなる群から選ばれる請求項７～９のいずれか１項記載の方法。 The method according to any one of claims 7 to 9, wherein the porous body is selected from the group consisting of organic synthetic polymers and natural organic polymers.
- 前記有機合成高分子は、ポリイミド、ポリスチレン、ポリオレフィン、ハロゲン化ポリオレフィン、ポリエステル及びポリアクリルアミドからなる群から選ばれる請求項７～１０のいずれか１項記載の方法。 The method according to any one of claims 7 to 10, wherein the organic synthetic polymer is selected from the group consisting of polyimide, polystyrene, polyolefin, halogenated polyolefin, polyester and polyacrylamide.
- 前記天然有機高分子は、セルロース、キチン、アガロース及びβ-1,3グルカンからなる群から選ばれる請求項７～１１のいずれか１項記載の方法。 The method according to any one of claims 7 to 11, wherein the natural organic polymer is selected from the group consisting of cellulose, chitin, agarose, and β-1,3 glucan.
- 前記繊維積層体は、ガラス繊維、セルロース系繊維、炭素繊維及び合成有機高分子繊維からなる群から選ばれる繊維からなる積層体である請求項７～１２のいずれか１項記載の方法。 The method according to any one of claims 7 to 12, wherein 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.
- 前記繊維積層体の空孔の平均径は１μｍ以上である請求項７～１３のいずれか１項記載の方法。 The method according to any one of claims 7 to 13, wherein an average diameter of pores of the fiber laminate is 1 µm or more.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5713395B2 (en) * | 2011-03-30 | 2015-05-07 | Jnc株式会社 | Hydrogel cellulose porous membrane |
| JP5689380B2 (en) * | 2011-07-25 | 2015-03-25 | 日東電工株式会社 | Method for producing cellulose porous body |
| FI125237B (en) | 2011-12-22 | 2015-07-31 | Upm Kymmene Corp | separation Thread |
| JP6073210B2 (en) * | 2013-12-02 | 2017-02-01 | 北越紀州製紙株式会社 | Cellulose porous body and method for producing the same |
| JP6428018B2 (en) * | 2014-07-23 | 2018-11-28 | 凸版印刷株式会社 | Porous body, composition for forming porous body, and method for producing porous body |
| KR101654795B1 (en) | 2016-02-05 | 2016-09-06 | 김현철 | Method for Preparing High-insulation Aerogel - Impregnated Mat |
| JP6212622B2 (en) * | 2016-11-14 | 2017-10-11 | 北越紀州製紙株式会社 | Cellulose porous material |
| CN112175226A (en) * | 2019-07-01 | 2021-01-05 | 上海清美绿色食品（集团）有限公司 | Method for preparing cellulose sponge by using bean dregs |
| KR20220152086A (en) * | 2021-05-07 | 2022-11-15 | 주식회사 엘지화학 | Method for manufacturing a separator containing cross-linked structure for a lithium secondary battery, a separator containing cross-linked structure for a lithium secondary battery manufactured by the method, and a lithium secondary battery comprising the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000154273A (en) * | 1998-09-17 | 2000-06-06 | Matsushita Electric Ind Co Ltd | Porous body and its production |
| JP2003253558A (en) * | 2002-03-01 | 2003-09-10 | Oji Paper Co Ltd | Woven fabric or nonwoven fabric and method for producing the same and laminate using the same |
| JP2007167632A (en) * | 2005-11-22 | 2007-07-05 | Toray Ind Inc | Fiber sheet and its production method, and air filter |
| JP2008231258A (en) * | 2007-03-20 | 2008-10-02 | Univ Of Tokyo | Cellulose aerogel and method for producing the same |
| WO2009122975A1 (en) * | 2008-03-31 | 2009-10-08 | 東レ株式会社 | Deodorant fibrous structure and air filter |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1523512B1 (en) * | 2002-07-22 | 2019-12-25 | Aspen Aerogels Inc. | Polyimide aerogels, carbon aerogels, and metal carbide aerogels and methods of making same |
-
2009
- 2009-10-09 JP JP2009234764A patent/JP4905814B2/en not_active Expired - Fee Related
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2010
- 2010-10-08 WO PCT/JP2010/067726 patent/WO2011043457A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000154273A (en) * | 1998-09-17 | 2000-06-06 | Matsushita Electric Ind Co Ltd | Porous body and its production |
| JP2003253558A (en) * | 2002-03-01 | 2003-09-10 | Oji Paper Co Ltd | Woven fabric or nonwoven fabric and method for producing the same and laminate using the same |
| JP2007167632A (en) * | 2005-11-22 | 2007-07-05 | Toray Ind Inc | Fiber sheet and its production method, and air filter |
| JP2008231258A (en) * | 2007-03-20 | 2008-10-02 | Univ Of Tokyo | Cellulose aerogel and method for producing the same |
| WO2009122975A1 (en) * | 2008-03-31 | 2009-10-08 | 東レ株式会社 | Deodorant fibrous structure and air filter |
Non-Patent Citations (1)
| Title |
|---|
| JIE CAI ET AL.: "Cellulose Aerogel-Nanoporous material from cellulose", CELLULOSE COMMUNICATIONS, vol. 14, no. 4, 30 November 2007 (2007-11-30), pages 146 - 148 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017159438A1 (en) * | 2016-03-18 | 2017-09-21 | パナソニックＩｐマネジメント株式会社 | Thermal insulation sheet and manufacturing method therefor |
| CN108884960A (en) * | 2016-03-18 | 2018-11-23 | 松下知识产权经营株式会社 | Heat Insulation film and its manufacturing method |
| JPWO2017159438A1 (en) * | 2016-03-18 | 2018-11-29 | パナソニックＩｐマネジメント株式会社 | Thermal insulation sheet and manufacturing method thereof |
| US10920367B2 (en) | 2016-03-18 | 2021-02-16 | Panasonic Intellectual Property Management Co., Ltd. | Thermal insulation sheet and manufacturing method therefor |
| CN108884960B (en) * | 2016-03-18 | 2021-09-03 | 松下知识产权经营株式会社 | Heat insulating sheet and method for producing same |
| US11788227B2 (en) | 2016-03-18 | 2023-10-17 | Panasonic Intellectual Property Management Co., Ltd. | Thermal insulation sheet and manufacturing method therefor |
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