JP7093532B1 - Method for preparing a decomposable conductive composite film - Google Patents
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- JP7093532B1 JP7093532B1 JP2021047772A JP2021047772A JP7093532B1 JP 7093532 B1 JP7093532 B1 JP 7093532B1 JP 2021047772 A JP2021047772 A JP 2021047772A JP 2021047772 A JP2021047772 A JP 2021047772A JP 7093532 B1 JP7093532 B1 JP 7093532B1
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 16
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 28
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 24
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 32
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 30
- 241000208125 Nicotiana Species 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 3
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 210000003462 vein Anatomy 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 13
- 238000012360 testing method Methods 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 229920001007 Nylon 4 Polymers 0.000 abstract description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 abstract description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 abstract description 3
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 abstract description 2
- 229920001940 conductive polymer Polymers 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229960002715 nicotine Drugs 0.000 abstract description 2
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 244000061176 Nicotiana tabacum Species 0.000 abstract 1
- 238000010586 diagram Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 235000019504 cigarettes Nutrition 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 210000000416 exudates and transudate Anatomy 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008104 plant cellulose Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000589158 Agrobacterium Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
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Abstract
【解決手段】分解可能の導電複合膜の調製方法であって、バクテリアセルロースをマトリックスとし、高導電性材料を有する金属有機フレームＺＩＦー８と導電高分子ポリピロリドンとを採用して高導電性の複合膜を調製する。【効果】調製した複合膜の導電率はテストにより最高で２１．３３９Ｓ／ｃｍに達し、優れた導電性能を備え、タバコの廃棄物はバクテリアセルロース培養の原料として、大量なフルフラールとニコチンを含み、金属イオンを容易に水素結合させることにより、金属イオンをバクテリアセルロース膜に付着させ、また、ポリピロリドンは高分子材料として本発明の複合膜に優れた機械的性質を与える。【選択図】図１SOLUTION: This is a method for preparing a decomposable conductive composite membrane, in which bacterial cellulose is used as a matrix, and a metal organic frame ZIF-8 having a highly conductive material and a conductive polymer polypyrrolidone are adopted to have high conductivity. Prepare a composite membrane. [Effect] The conductivity of the prepared composite membrane reached a maximum of 21.339 S / cm in the test, and it has excellent conductivity performance. Tobacco waste contains a large amount of furfural and nicotine as a raw material for bacterial cellulose culture. By easily hydrogen-bonding the metal ions, the metal ions are attached to the bacterial cellulose membrane, and polypyrrolidone imparts excellent mechanical properties to the composite membrane of the present invention as a polymer material. [Selection diagram] Fig. 1
Description
本発明は、導電膜材料調製分野に関し、具体的には、分解可能の導電複合膜の調製方法に関する。 The present invention relates to the field of conductive material preparation, and specifically to a method for preparing a decomposable conductive composite film.
セルロースポリマーは繰り返しのグルコース単量体がβ‐１，４グリコシド結合で重合されて形成され、その種類は植物セルロース、動物セルロース及び部分が微生物で合成されたセルロースを含む。自然界でセルロースを生成することができる微生物は、酢酸桿菌属、アグロバクテリウム属、根粒菌属等を含む。ここで、キシリヌムは生産量が最も多い一種の菌種である。植物セルロースと比較して、バクテリアセルロースは微生物により単糖分子を基質として合成され、したがってバクテリアセルロースは高い純度を有する。また、バクテリアセルロースはさらに多くの優れた物理化学的特性、例えば高重合度、高結晶化度、良好な生体適合性、小さい熱膨張係数、高ヤング率及び引張強度及び高含水性を有する。
タバコは特殊な経済作物として、その良質の葉が原料として巻きタバコを製造するために用いられ、その根、茎、枝、頂部及び適用しない葉が廃棄物として廃棄され、巻きタバコ製造加工過程において約２０％～２５％のタバコ廃棄物を生成し、大量の場所を占用するだけでなく、長期に堆積してカビが発生して環境問題を引き起こす。煙管の処理に対して、一部はバイオカーボンを生成し、燃料として使用し、その燃焼エネルギーは基本的に等量の石炭燃焼のレベルに達するが、燃焼残留物は環境に対して深刻な汚染をもたらす。
Cellulose polymers are formed by polymerizing repeated glucose monomers with β-1,4 glycosidic bonds, including plant cellulose, animal cellulose and partially microbially synthesized cellulose. Microorganisms capable of producing cellulose in nature include the genus Bacillus acetate, the genus Agrobacterium, the genus Rhizobia, and the like. Here, xylinum is a kind of fungal species with the highest production. Compared to plant cellulose, bacterial cellulose is synthesized by microorganisms using monosaccharide molecules as a substrate, and therefore bacterial cellulose has a high purity. Bacterial cellulose also has many more excellent physicochemical properties such as high degree of polymerization, high crystallinity, good biocompatibility, low coefficient of thermal expansion, high Young's modulus and tensile strength and high water content.
Cigarette is a special economic crop, its good quality leaves are used as raw material to produce cigarettes, its roots, stems, branches, tops and non-applicable leaves are discarded as waste, in the process of producing cigarettes. It produces about 20% to 25% of cigarette waste, occupies a large amount of space, and accumulates for a long period of time, causing mold and causing environmental problems. For the treatment of smoke tubes, some produce biocarbon and use it as fuel, the combustion energy basically reaches the level of equal amount of coal combustion, but the combustion residue is a serious pollution to the environment. Bring.
本発明は、従来技術における上記問題を解決するために、分解可能の導電複合膜の調製方法を提供することを目的とする。 An object of the present invention is to provide a method for preparing a decomposable conductive composite film in order to solve the above problems in the prior art.
分解可能の導電複合膜の調製方法であって、ステップ１～ステップ４を含み、
前記ステップ１は、タバコ廃棄物を粉砕し、８０～１００メッシュの篩に通した後に容器に入れ、そして水を加えて十分に撹拌して６～１０ｈ浸し、この時、前記タバコ廃棄物と前記水の質量比を１：８～１２とし、濾過して浸出液と濾滓を収集し、
前記ステップ２は、前記浸出液に質量分率が６０～８５％の酢酸溶液または質量分率が８０～９０％のリン酸溶液を加え、そして９５～１１０℃下で３０～６０ｍｉｎ撹拌し、アルカリ性過酸化水素を滴加してＰＨ値を６．２～７．０に調節して該温度下で引き続き４５～６０ｍｉｎ撹拌し、前記濾滓をエタノール溶液でソックスレー抽出してソックスレー抽出液を得て、そしてＰＨ値調節後に撹拌した前記浸出液と前記ソックスレー抽出液とを混合して高温殺菌した後に培地に加え、そしてバクテリアセルロース生成菌を加えて３５～３７℃下で５～８日間培養し、バクテリアセルロース膜を得、
前記ステップ３は、前記バクテリアセルロース膜を蒸留水で洗浄してビーカーの底部に平らに広げ、メタノール水溶液をガラス棒で適量加えた後、コバルト塩を加え、振動台で８～１５ｈ揺らした後に２‐メチルイミダゾールを適量加え、３～６ｈ揺らし、
前記ステップ４は、前記ステップ３を経た膜をもう一つのビーカーに平らに広げ、Ｎ，Ｎ‐ジメチルホルムアミドと脱イオン水とをガラス棒で適量加え、この時、前記Ｎ，Ｎ‐ジメチルホルムアミドと前記脱イオン水の体積比を１：１とし、そしてピロールを適量加えて該ビーカーを０～５℃の環境に置いて酸化剤溶液を適量滴加して前記ピロールを７～１０ｈ重合反応させた後、乾燥して複合膜を得る。
A method for preparing a decomposable conductive composite film, which comprises steps 1 to 4.
In step 1, the tobacco waste is crushed, passed through an 80-100 mesh sieve and then placed in a container, and water is added and sufficiently stirred to soak for 6 to 10 hours, at which time the tobacco waste and the above. Set the mass ratio of water to 1: 8-12 and filter to collect leachate and slag.
In step 2, an acetic acid solution having a mass component of 60 to 85% or a phosphoric acid solution having a mass component of 80 to 90% is added to the leachate, and the mixture is stirred at 95 to 110 ° C. for 30 to 60 min to make it alkaline. Hydrogen oxide was added dropwise to adjust the pH value to 6.2 to 7.0, and the mixture was continuously stirred at the temperature for 45 to 60 min. Then, the leachate and the soxley extract, which were stirred after adjusting the pH value, were mixed and sterilized at high temperature, then added to the medium, and bacterial cellulose-producing bacteria were added and cultured at 35 to 37 ° C. for 5 to 8 days. Get the film
In step 3, the bacterial cellulose film is washed with distilled water, spread flat on the bottom of the beaker, an appropriate amount of methanol aqueous solution is added with a glass rod, cobalt salt is added, and the mixture is shaken on a shaking table for 8 to 15 hours, and then 2 -Add an appropriate amount of methylimidazole and shake for 3 to 6 hours.
In step 4, the film that has passed through step 3 is spread flat on another beaker, and an appropriate amount of N, N-dimethylformamide and deionized water are added with a glass rod, and at this time, the N, N-dimethylformamide and the said N, N-dimethylformamide are added. The volume ratio of the deionized water was 1: 1 and an appropriate amount of pyrrole was added, the beaker was placed in an environment of 0 to 5 ° C., and an appropriate amount of an oxidizing agent solution was added to polymerize the pyrrole for 7 to 10 hours. After that, it is dried to obtain a composite film.
前記ステップ３において、前記バクテリアセルロース膜におけるバクテリアセルロースは、三次元網目構造を有するため、金属コバルトイオンが水素結合作用により前記バクテリアセルロース膜の内表面に付着し、そして前記２‐メチルイミダゾールを加えることにより、前記２‐メチルイミダゾールが前記金属コバルトイオンと室温下で前記メタノール水溶液において金属有機フレームＺＩＦ‐８を形成し、形成した金属有機フレーム材料のほとんどが膜の表面に付着する。 In step 3, since the bacterial cellulose in the bacterial cellulose membrane has a three-dimensional network structure, metal cobalt ions adhere to the inner surface of the bacterial cellulose membrane by hydrogen bonding action, and the 2-methylimidazole is added. 2-Methylimidazole forms a metal organic frame ZIF-8 in the methanol aqueous solution at room temperature with the metal cobalt ion, and most of the formed metal organic frame material adheres to the surface of the membrane.
優先的には、前記タバコ廃棄物は、タバコの栽培、生産および加工過程に生じる廃棄物であり、タバコの茎と、タバコと、タバコの花と、タバコの葉と、タバコの種と、葉脈と、タバコの粉末と、を含む。 Priority is given that the tobacco waste is waste generated during the cultivation, production and processing of tobacco, such as tobacco stems, tobacco, tobacco flowers, tobacco leaves, tobacco seeds and veins. And, including tobacco powder.
優先的には、前記酸溶液は、質量分率が６０～８５％の酢酸溶液または質量分率が８０～９０％のリン酸溶液である。 Preferentially, the acid solution is an acetic acid solution having a mass fraction of 60 to 85% or a phosphoric acid solution having a mass fraction of 80 to 90%.
優先的には、前記亜鉛塩は、二硝酸コバルト六水和物と、酢酸コバルト四水和物と、硫酸コバルト・７水和物と、のいずれか一つである。 Priority is given to the zinc salt being any one of cobalt dinitrate hexahydrate, cobalt acetate tetrahydrate, and cobalt sulfate heptahydrate.
優先的には、前記酸化剤溶液は、塩化第二鉄の塩酸溶液である。 Priority is given that the oxidant solution is a hydrochloric acid solution of ferric chloride.
優先的には、前記塩酸溶液は、質量分率が３０～３６％である。 Priority is given that the hydrochloric acid solution has a mass fraction of 30-36%.
優先的には、前記ピロールと前記酸化剤溶液との質量体積比は、（０．４～０．８５）ｇ：（０．０９６～０．２５５）ｍＬである。 Priority, the mass-volume ratio of the pyrrole to the oxidant solution is (0.4 to 0.85) g: (0.096 to 0.255) mL.
本発明は、バクテリアセルロースをマトリックスとし、高導電性材料を有する金属有機フレームＺＩＦ‐８と導電高分子ポリピロリドンとを採用して高導電性の複合膜を調製し、その導電率はテストにより最高で２１．３３９ Ｓ／ｃｍに達し、優れた導電性能を備え、タバコの廃棄物はバクテリアセルロース培養の原料として、大量なフルフラールとニコチンを含み、金属イオンを容易に水素結合させることにより、金属イオンをバクテリアセルロース膜に付着させ、また、ポリピロリドンは高分子材料として本発明の複合膜に優れた機械的性質を与える。 In the present invention, a highly conductive composite membrane is prepared by using a metal organic frame ZIF-8 having a highly conductive material and a conductive polymer polypyrrolidone using bacterial cellulose as a matrix, and the conductivity thereof is the highest by a test. It reaches 21.339 S / cm and has excellent conductivity. Tobacco waste contains a large amount of furfural and nicotine as a raw material for bacterial cellulose culture, and metal ions are easily hydrogen-bonded to form metal ions. And polypyrrolidone, as a polymer material, imparts excellent mechanical properties to the composite membrane of the present invention.
実施例１
分解可能の導電複合膜の調製方法であって、ステップ１～ステップ４を含み、
前記ステップ１は、タバコ廃棄物を粉砕し、８０メッシュの篩に通した後に容器に入れ、そして水を加えて十分に撹拌して６ｈ浸し、この時、前記タバコ廃棄物と前記水の質量比を１：８とし、濾過して浸出液と濾滓を収集し、
前記ステップ２は、前記浸出液に質量分率が６０％の酢酸溶液を加え、そして９５℃下で３０ｍｉｎ撹拌し、アルカリ性過酸化水素を滴加してＰＨ値を６．２に調節して該温度下で引き続き４５ｍｉｎ撹拌し、前記濾滓をエタノール溶液でソックスレー抽出してソックスレー抽出液を得て、そしてＰＨ値調節後に撹拌した前記浸出液と前記ソックスレー抽出液とを混合して高温殺菌した後に培地に加え、そしてバクテリアセルロース生成菌を加えて３５℃下で５日間培養し、バクテリアセルロース膜を得、
前記ステップ３は、前記バクテリアセルロース膜を蒸留水で洗浄してビーカーの底部に平らに広げ、メタノール溶液をガラス棒で適量加えた後、二硝酸コバルト六水和物を適量加え、振動台で８ｈ揺らした後に２‐メチルイミダゾールを適量加え、３ｈ揺らし、
前記ステップ４は、前記ステップ３を経た膜をもう一つのビーカーに平らに広げ、Ｎ，Ｎ‐ジメチルホルムアミドと脱イオン水とをガラス棒で適量加え、この時、前記Ｎ，Ｎ‐ジメチルホルムアミドと前記脱イオン水の体積比を１：１とし、そしてピロールを適量加えて該ビーカーを０℃の環境に置いて塩化第二鉄の質量濃度が３０％の塩酸溶液を適量滴加し、この時、前記ピロールと塩化第二鉄の塩酸溶液との質量体積比を０．４ｇ：０．０９６ｍＬとする。次に、前記ピロールを７ｈ重合反応させた後、乾燥して複合膜を得る。
Example 1
A method for preparing a decomposable conductive composite film, which comprises steps 1 to 4.
In step 1, the tobacco waste is crushed, passed through an 80 mesh sieve and then placed in a container, and water is added and sufficiently stirred to soak for 6 hours, at which time the mass ratio of the tobacco waste to the water. 1: 8 and filter to collect leachate and slag.
In step 2, an acetic acid solution having a mass fraction of 60% is added to the leachate, and the mixture is stirred at 95 ° C. for 30 minutes, and alkaline hydrogen peroxide is added dropwise to adjust the pH value to 6.2 at the temperature. Continue to stir for 45 minutes underneath , socksley extract the filter with an ethanol solution to obtain a socksley extract, and after adjusting the pH value, the stirred exudate and the socksley extract are mixed and sterilized at high temperature, and then the medium. Then, the bacterial cellulose-producing bacterium was added and cultured at 35 ° C. for 5 days to obtain a bacterial cellulose film.
In step 3, the bacterial cellulose film is washed with distilled water, spread flat on the bottom of the beaker, an appropriate amount of methanol solution is added with a glass rod, an appropriate amount of cobalt dinitrate hexahydrate is added, and the shaking table is used for 8 hours. After shaking, add an appropriate amount of 2-methylimidazole and shake for 3 hours.
In step 4, the film that has undergone step 3 is spread flat on another beaker, and an appropriate amount of N, N-dimethylformamide and deionized water are added with a glass rod, and at this time, the N, N-dimethylformamide and the said N, N-dimethylformamide are added. The volume ratio of the deionized water was 1: 1, and an appropriate amount of pyrrole was added, the beaker was placed in an environment of 0 ° C., and an appropriate amount of a hydrochloric acid solution having a ferric chloride mass concentration of 30% was added dropwise at this time. , The mass-volume ratio of the pyrrole to the hydrochloric acid solution of ferric chloride is 0.4 g: 0.096 mL. Next, the pyrrole is polymerized for 7 hours and then dried to obtain a composite film.
実施例２
分解可能の導電複合膜の調製方法であって、ステップ１～ステップ４を含み、
前記ステップ１は、タバコ廃棄物を粉砕し、１００メッシュの篩に通した後に容器に入れ、そして水を加えて十分に撹拌して１０ｈ浸し、この時、前記タバコ廃棄物と前記水の質量比を１：１２とし、濾過して浸出液と濾滓を収集し、
前記ステップ２は、前記浸出液に質量分率が９０％のリン酸溶液を加え、そして１１０℃下で６０ｍｉｎ撹拌し、アルカリ性過酸化水素を滴加してＰＨ値を７．０に調節して該温度下で引き続き６０ｍｉｎ撹拌し、前記濾滓をエタノール溶液でソックスレー抽出してソックスレー抽出液を得て、そしてＰＨ値調節後に撹拌した前記浸出液と前記ソックスレー抽出液とを混合して高温殺菌した後に培地に加え、そしてバクテリアセルロース生成菌を加えて３７℃下で８日間培養し、バクテリアセルロース膜を得、
前記ステップ３は、前記バクテリアセルロース膜を蒸留水で洗浄してビーカーの底部に平らに広げ、メタノール水溶液をガラス棒で適量加えた後、酢酸コバルト四水和物を適量加え、振動台で１５ｈ揺らした後に２‐メチルイミダゾールを適量加え、６ｈ揺らし、
前記ステップ４は、前記ステップ３を経た膜をもう一つのビーカーに平らに広げ、Ｎ，Ｎ‐ジメチルホルムアミドと脱イオン水とをガラス棒で適量加え、この時、前記Ｎ，Ｎ‐ジメチルホルムアミドと前記脱イオン水の体積比を１：１とし、そしてピロールを適量加えて該ビーカーを５℃の環境に置いて塩化第二鉄の質量濃度が３６％の塩酸溶液を適量滴加し、この時、前記ピロールと塩化第二鉄の塩酸溶液の質量体積比を０．８５ｇ： ０．２５５ｍＬとする。次に、前記ピロールを１０ｈ重合反応させた後、乾燥して複合膜を得る。
Example 2
A method for preparing a decomposable conductive composite film, which comprises steps 1 to 4.
In step 1, the tobacco waste is crushed, passed through a 100 mesh sieve, placed in a container, and water is added, and the mixture is sufficiently stirred and soaked for 10 hours. At this time, the mass ratio of the tobacco waste to the water. 1:12, filter to collect leachate and slag,
In step 2, a phosphate solution having a mass fraction of 90% is added to the leachate, and the mixture is stirred at 110 ° C. for 60 minutes, and alkaline hydrogen peroxide is added dropwise to adjust the pH value to 7.0. After continuing to stir for 60 minutes at a temperature , the filter slag was extracted with an ethanol solution to obtain a socksley extract, and the leachate and the socksley extract that were stirred after adjusting the pH value were mixed and sterilized at high temperature. Add to the medium and add the bacterial cellulose-producing bacterium and incubate at 37 ° C. for 8 days to obtain a bacterial cellulose film.
In step 3, the bacterial cellulose film is washed with distilled water, spread flat on the bottom of the beaker, an appropriate amount of an aqueous methanol solution is added with a glass rod, an appropriate amount of cobalt acetate tetrahydrate is added, and the shaking table is used for 15 hours. After shaking, add an appropriate amount of 2-methylimidazole, shake for 6 hours, and shake.
In step 4, the film that has passed through step 3 is spread flat on another beaker, and an appropriate amount of N, N-dimethylformamide and deionized water are added with a glass rod, and at this time, the N, N-dimethylformamide and the said N, N-dimethylformamide are added. The volume ratio of the deionized water was 1: 1, and an appropriate amount of pyrrole was added, the beaker was placed in an environment of 5 ° C., and an appropriate amount of a hydrochloric acid solution having a ferric chloride mass concentration of 36% was added in an appropriate amount . , The mass-volume ratio of the hydrochloric acid solution of pyrrole and ferric chloride is 0.85 g: 0.255 mL. Next, the pyrrole is polymerized for 10 hours and then dried to obtain a composite film.
実施例３
分解可能の導電複合膜の調製方法であって、ステップ１～ステップ４を含み、
前記ステップ１は、タバコ廃棄物を粉砕し、９０メッシュの篩に通した後に容器に入れ、そして水を加えて十分に撹拌して８ｈ浸し、この時、前記タバコ廃棄物と前記水の質量比を１：１０とし、濾過して浸出液と濾滓を収集し、
前記ステップ２は、前記浸出液に質量分率が８５％の酢酸溶液を加え、そして１０５℃下で５０ｍｉｎ撹拌し、アルカリ性過酸化水素を滴加してＰＨ値を６．６に調節して該温度下で引き続き５０ｍｉｎ撹拌し、前記濾滓をエタノール溶液でソックスレー抽出してソックスレー抽出液を得て、そしてＰＨ値調節後に撹拌した前記浸出液と前記ソックスレー抽出液とを混合して高温殺菌した後に培地に加え、そしてバクテリアセルロース生成菌を加えて３６℃下で７日間培養し、バクテリアセルロース膜を得、
前記ステップ３は、前記バクテリアセルロース膜を蒸留水で洗浄してビーカーの底部に平らに広げ、メタノール水溶液をガラス棒で適量加えた後、硫酸コバルト・７水和物を適量加え、振動台で１２ｈ揺らした後に２‐メチルイミダゾールを適量加え、５ｈ揺らし、
前記ステップ４は、前記ステップ３を経た膜をもう一つのビーカーに平らに広げ、Ｎ，Ｎ‐ジメチルホルムアミドと脱イオン水とをガラス棒で適量加え、この時、前記Ｎ，Ｎ‐ジメチルホルムアミドと前記脱イオン水の体積比を１：１とし、そしてピロールを適量加えて該ビーカーを２℃の環境に置いて塩化第二鉄の質量濃度が３４％の塩酸溶液を滴加し、この時、前記ピロールと塩化第二鉄の塩酸溶液の質量体積比を０．６５ｇ： ０．１７２ｍＬとする。次に、前記ピロールを８ｈ重合反応させた後、乾燥して複合膜を得る。
Example 3
A method for preparing a decomposable conductive composite film, which comprises steps 1 to 4.
In step 1, the tobacco waste is crushed, passed through a 90 mesh sieve and then placed in a container, and water is added and sufficiently stirred to soak for 8 hours, at which time the mass ratio of the tobacco waste to the water. 1:10, filter to collect leachate and slag,
In step 2, an acetic acid solution having a mass fraction of 85% is added to the leachate, and the mixture is stirred at 105 ° C. for 50 minutes, and alkaline hydrogen peroxide is added dropwise to adjust the pH value to 6.6 at the temperature. Continue to stir for 50 minutes underneath , socksley extract the filter with an ethanol solution to obtain a socksley extract, and after adjusting the PH value, the stirred exudate and the socksley extract are mixed and sterilized at high temperature, and then the medium. Then, the bacterial cellulose-producing bacterium was added and cultured at 36 ° C. for 7 days to obtain a bacterial cellulose film.
In step 3, the bacterial cellulose film is washed with distilled water, spread flat on the bottom of the beaker, an appropriate amount of an aqueous methanol solution is added with a glass rod, an appropriate amount of cobalt sulfate heptahydrate is added, and the shaking table is used. After shaking for 12 hours, add an appropriate amount of 2-methylimidazole, and shake for 5 hours.
In step 4, the film that has passed through step 3 is spread flat on another beaker, and an appropriate amount of N, N-dimethylformamide and deionized water are added with a glass rod, and at this time, the N, N-dimethylformamide and the said N, N-dimethylformamide are added. The volume ratio of the deionized water was 1: 1 and an appropriate amount of pyrrole was added, the beaker was placed in an environment of 2 ° C., and a hydrochloric acid solution having a mass concentration of ferric chloride of 34% was added dropwise at this time. The mass-volume ratio of the hydrochloric acid solution of pyrrole and ferric chloride is 0.65 g: 0.172 mL. Next, the pyrrole is polymerized for 8 hours and then dried to obtain a composite film.
試験例
性能テスト１（導電率テスト）：実施例１～３に調製の導電複合膜に対し、Ｍ‐６手持ち式四プローブ試験装置を使用して４×２ｃｍの矩形膜サンプルをテストし、プローブの間隔を２ｍｍとし、サンプルの厚さを測定範囲０～２５ ｍｍの外側マイクロメーターで測定して薄片に加圧成形する。前記薄片の抵抗率測定は、それぞれ使用マニュアルの付録を参照して厚さ補正係数（Ｇ）と形状位置補正係数（Ｄ）を得て、サンプルの抵抗率をテストし、換算してサンプルの導電率を得て、サンプルの抵抗率ρ（Ω・ｃｍ）を得た後に、公式σ＝１／ρで導電率σ（Ｓ／ｃｍ）を得る。テスト結果を表１に示す。
性能テスト２（耐引裂強度）：実施例１～３に調製の導電複合膜をＰＮ‐ＴＴ１０００コンピューター紙引裂強さ測定器でテストし、ＧＢ／Ｔ ４５０の標準で試料を取り、試料を大きさを６０±０．５ｍｍ×５０±２ｍｍとし、それぞれサンプルの縦横向きに沿って切り取り、テスト結果を表１に示す。
性能テスト３（引張強さ）：実施例１～３に調製の導電複合膜をＰＮ‐ＴＴ３００コンピューター紙引裂強さ測定器でテストし、ＧＢ／Ｔ ４５０の標準で試料を取り、試験に規定の方向に沿って、少なくともそれぞれ１０枚の試料を切り取り、試料の幅を１５．０ｍｍ±０．１ｍｍとし、試料の両辺がなめらかであり且つ互いに平行し、テスト結果を表１に示す。
Test Example Performance Test 1 (Conductivity Test): A 4 × 2 cm rectangular membrane sample was tested on the conductive composite membrane prepared in Examples 1 to 3 using an M-6 handheld four-probe test device, and a probe was used. The thickness of the sample is measured with an outer micrometer having a measurement range of 0 to 25 mm, and pressure-molded into thin pieces. For the resistivity measurement of the strip, refer to the appendix of the usage manual to obtain the thickness correction coefficient (G) and the shape position correction coefficient (D), test the resistivity of the sample, and convert the conductivity of the sample. After obtaining the rate and obtaining the resistivity ρ (Ω · cm) of the sample, the conductivity σ (S / cm) is obtained by the formula σ = 1 / ρ. The test results are shown in Table 1.
Performance test 2 (tear resistance): The conductive composite film prepared in Examples 1 to 3 was tested with a PN-TT1000 computer paper tear strength measuring instrument, a sample was taken according to the standard of GB / T 450, and the sample was sized. Is 60 ± 0.5 mm × 50 ± 2 mm, and each sample is cut out along the vertical and horizontal directions, and the test results are shown in Table 1.
Performance test 3 (tensile strength): The conductive composite film prepared in Examples 1 to 3 was tested with a PN-TT300 computer paper tear strength measuring instrument, a sample was taken according to the GB / T 450 standard, and specified in the test. At least 10 samples are cut out along the direction, the width of the sample is 15.0 mm ± 0.1 mm, both sides of the sample are smooth and parallel to each other, and the test results are shown in Table 1.
表１からわかるように、本発明の実施例１～３に調製の導電膜は、いずれも２０．７９６ Ｓ／ｃｍを超えた導電率を有するとともに、耐引裂強度がいずれも２９３．５６ ｍＮを超え、引張強さがいずれも３．９７ ｋＮ／ｍを超え、本発明の導電膜は優れた機械的性質を有する。 As can be seen from Table 1, the conductive films prepared in Examples 1 to 3 of the present invention all have a conductivity exceeding 20.796 S / cm and a tear resistance of 293.56 mN. The tensile strength exceeds 3.97 kN / m, and the conductive film of the present invention has excellent mechanical properties.
Claims (6)
前記ステップ１は、タバコ廃棄物を粉砕し、８０～１００メッシュの篩に通した後に容器に入れ、そして水を加えて十分に撹拌して６～１０ｈ浸し、この時、前記タバコ廃棄物と前記水の質量比を１：８～１２とし、濾過して浸出液と濾滓を収集し、
前記ステップ２は、前記浸出液に質量分率が６０～８５％の酢酸溶液または質量分率が８０～９０％のリン酸溶液を加え、そして９５～１１０℃下で３０～６０ｍｉｎ撹拌し、アルカリ性過酸化水素を滴加してＰＨ値を６．２～７．０に調節して該温度下で引き続き４５～６０ｍｉｎ撹拌し、前記濾滓をエタノール溶液でソックスレー抽出してソックスレー抽出液を得て、そしてＰＨ値調節後に撹拌した前記浸出液と前記ソックスレー抽出液とを混合して高温殺菌した後に培地に加え、そしてバクテリアセルロース生成菌を加えて３５～３７℃下で５～８日間培養し、バクテリアセルロース膜を得、
前記ステップ３は、前記バクテリアセルロース膜を蒸留水で洗浄してビーカーの底部に平らに広げ、メタノール水溶液をガラス棒で適量加えた後、コバルト塩を適量加え、振動台で８～１５ｈ揺らした後に２‐メチルイミダゾールを適量加え、３～６ｈ揺らし、
前記ステップ４は、前記ステップ３を経た膜をもう一つのビーカーに平らに広げ、Ｎ，Ｎ‐ジメチルホルムアミドと脱イオン水とをガラス棒で適量加え、この時、前記Ｎ，Ｎ‐ジメチルホルムアミドと前記脱イオン水の体積比を１：１とし、そしてピロールを適量加えて該ビーカーを０～５℃の環境に置いて酸化剤溶液を適量滴加して前記ピロールを７～１０ｈ重合反応させた後、乾燥して複合膜を得る、
ことを特徴とする分解可能の導電複合膜の調製方法。 A method for preparing a decomposable conductive composite film, which comprises steps 1 to 4.
In step 1, the tobacco waste is crushed, passed through an 80-100 mesh sieve and then placed in a container, and water is added and sufficiently stirred to soak for 6 to 10 hours, at which time the tobacco waste and the above. Set the mass ratio of water to 1: 8-12 and filter to collect leachate and slag.
In step 2, an acetic acid solution having a mass component of 60 to 85% or a phosphoric acid solution having a mass component of 80 to 90% is added to the leachate, and the mixture is stirred at 95 to 110 ° C. for 30 to 60 min to make it alkaline. Hydrogen oxide was added dropwise to adjust the pH value to 6.2 to 7.0, and the mixture was continuously stirred at the temperature for 45 to 60 min. Then, the leachate and the soxley extract, which were stirred after adjusting the pH value, were mixed and sterilized at high temperature, then added to the medium, and bacterial cellulose-producing bacteria were added and cultured at 35 to 37 ° C. for 5 to 8 days. Get the film
In step 3, the bacterial cellulose film is washed with distilled water, spread flat on the bottom of the beaker, an appropriate amount of methanol aqueous solution is added with a glass rod, an appropriate amount of cobalt salt is added, and the mixture is shaken on a shaking table for 8 to 15 hours. Add an appropriate amount of 2-methylimidazole and shake for 3 to 6 hours.
In step 4, the film that has passed through step 3 is spread flat on another beaker, and an appropriate amount of N, N-dimethylformamide and deionized water are added with a glass rod, and at this time, the N, N-dimethylformamide and the said N, N-dimethylformamide are added. The volume ratio of the deionized water was 1: 1 and an appropriate amount of pyrrole was added, the beaker was placed in an environment of 0 to 5 ° C., and an appropriate amount of an oxidizing agent solution was added to polymerize the pyrrole for 7 to 10 hours. After that, it dries to obtain a composite film,
A method for preparing a decomposable conductive composite film.
ことを特徴とする請求項１に記載の分解可能の導電複合膜の調製方法。 The tobacco waste is waste generated during the cultivation, production and processing of tobacco, and is tobacco stem, tobacco, tobacco flower, tobacco leaf, tobacco seed, leaf vein, and tobacco powder. And, including,
The method for preparing a decomposable conductive composite film according to claim 1.
ことを特徴とする請求項１に記載の分解可能の導電複合膜の調製方法。 The cobalt salt is one of cobalt dinitrate hexahydrate, cobalt acetate tetrahydrate, and cobalt sulfate heptahydrate.
The method for preparing a decomposable conductive composite film according to claim 1.
ことを特徴とする請求項１に記載の分解可能の導電複合膜の調製方法。 The oxidizing agent solution is a hydrochloric acid solution of ferric chloride.
The method for preparing a decomposable conductive composite film according to claim 1.
ことを特徴とする請求項５に記載の分解可能の導電複合膜の調製方法。 The hydrochloric acid solution has a mass fraction of 30 to 36%.
The method for preparing a decomposable conductive composite film according to claim 5.
ことを特徴とする請求項１に記載の分解可能の導電複合膜の調製方法。 The mass-volume ratio of the pyrrole to the oxidizing agent solution is (0.4 to 0.85) g: (0.096 to 0.255) mL.
The method for preparing a decomposable conductive composite film according to claim 1.
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