WO2013172316A1 - 改質グラフェンライク炭素材料の製造方法、改質グラフェンライク炭素材料、及び改質グラフェンライク炭素材料を含む樹脂複合材料 - Google Patents
改質グラフェンライク炭素材料の製造方法、改質グラフェンライク炭素材料、及び改質グラフェンライク炭素材料を含む樹脂複合材料 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/54—Ortho- or ortho- and peri-condensed systems containing more than five condensed rings
Definitions
- the present invention relates to a method for producing a modified graphene-like carbon material into which a hydroxyl group is introduced, a modified graphene-like carbon material, and a resin composite material containing the modified graphene-like carbon material.
- Graphite is a laminate in which exfoliated graphite is laminated.
- a graphene-like carbon material such as exfoliated graphite or graphene having a smaller number of layers than graphite can be obtained. Since graphene-like carbon materials are excellent in conductivity and thermal conductivity, they are expected to be applied to conductive materials and thermal conductive materials.
- Patent Document 1 discloses a modified carbon material in which a fragment obtained by radical decomposition of an azo radical polymerization initiator containing a carboxyl group is added to a carbon material having a graphene sheet structure.
- the main object of the present invention is to provide a modified graphene-like carbon material having a hydroxyl group introduced therein.
- the graphene-like carbon material and hydrogen peroxide are reacted to introduce a hydroxyl group into the graphene-like carbon material.
- a hydroxyl group is introduced into the graphene-like carbon material in the presence of an iron catalyst.
- the modified graphene-like carbon material of the present invention can be obtained by the above production method.
- the modified graphene-like carbon material of the present invention has a hydroxyl group amount of 0.3 mmol / g to 10.0 mmol / g as measured by a quantitative method using 2,2′-diphenyl-1-picrylhydrazyl. is there.
- the amount of carboxyl groups as measured by a quantitative method using NaHCO 3 is 1.0 mmol / g or less.
- the resin composite material of the present invention is obtained by dispersing the modified graphene-like carbon material of the present invention in a resin.
- a modified graphene-like carbon material into which a hydroxyl group has been introduced can be provided.
- modified graphene-like carbon material manufacturing method the modified graphene-like carbon material, and the resin composite material including the modified graphene-like carbon material according to the present invention will be described in detail.
- a hydroxyl group is introduced into the graphene-like carbon material by reacting the graphene-like carbon material with hydrogen peroxide.
- the modified graphene-like carbon material of the present invention is obtained by introducing a hydroxyl group into a graphene-like carbon material that is a raw material.
- Graphene-like carbon material refers to graphene or exfoliated graphite.
- exfoliated graphite is a laminate of graphene sheets composed of one layer of graphene.
- Exfoliated graphite is a laminate of graphene sheets that is thinner than the original graphite.
- the number of graphene sheets laminated in exfoliated graphite is 2 or more, and usually 200 or less.
- the exfoliated graphite is commercially available and can be produced by a conventionally known method. Exfoliated graphite can be obtained, for example, by exfoliating graphite.
- Exfoliated graphite is, for example, a chemical treatment method in which ions such as nitrate ions are inserted between graphite layers, a heat treatment method, a physical treatment method such as applying ultrasonic waves to graphite, and electrolysis using graphite as a working electrode. It can be obtained by a method such as an electrochemical method.
- Graphene-like carbon material has a shape with a large aspect ratio. Therefore, if the modified graphene-like carbon material is uniformly dispersed in the resin composite material described later, the reinforcing effect against the external force applied in the direction intersecting the laminated surface of the graphene-like carbon material can be effectively enhanced. Note that if the aspect ratio of the modified graphene-like carbon material is too small, the reinforcing effect against external force applied in the direction intersecting the laminated surface may not be sufficient. If the aspect ratio of the modified graphene-like carbon material is too large, the effect may be saturated and a further reinforcing effect may not be expected. Therefore, the aspect ratio of the graphene-like carbon material is preferably 50 or more, and more preferably 100 or more.
- the aspect ratio of the graphene-like carbon material is preferably 5000 or less.
- the aspect ratio of the graphene-like carbon material refers to the ratio of the maximum dimension in the stacking surface direction of the graphene-like carbon material to the thickness of the graphene-like carbon material.
- the average particle size of the graphene-like carbon material is preferably about 1 ⁇ m to 5 ⁇ m, and more preferably about 3 ⁇ m to 5 ⁇ m.
- the reaction between the graphene-like carbon material and hydrogen peroxide can be performed, for example, by mixing the graphene-like carbon material and hydrogen peroxide water.
- the concentration of hydrogen peroxide in the hydrogen peroxide water can be about 10 mass% to 27 mass%.
- the reaction temperature can be about 0 ° C. to 50 ° C.
- the reaction time can be about 0.5 to 48 hours.
- the reaction between the graphene-like carbon material and hydrogen peroxide may be performed in the air or in the presence of an inert gas such as argon or nitrogen.
- the reaction between the graphene-like carbon material and hydrogen peroxide is preferably performed in the presence of an iron catalyst.
- an iron catalyst examples include a method using a Fenton reagent (Fenton reagent).
- the Fenton reagent is an aqueous solution of hydrogen peroxide and an iron catalyst (divalent iron ion).
- the reaction between the graphene-like carbon material and hydrogen peroxide is more preferably performed by using a Fenton reagent. Thereby, the introduction of a hydroxyl group into the graphene-like carbon material can be performed more efficiently.
- a modified graphene-like carbon material in which a hydroxyl group is introduced into a graphene-like carbon material is obtained by reacting the graphene-like carbon material with hydrogen peroxide.
- modified graphene-like carbon material The modified graphene-like carbon material according to the present invention can be produced, for example, by the above-described method for producing a modified graphene-like carbon material according to the present invention.
- the modified graphene-like carbon material according to the present invention is obtained by introducing a hydroxyl group into a graphene-like carbon material.
- the modified graphene-like carbon material has a hydroxyl group amount of 0.3 mmol / g to 10.0 mmol / g as measured by a quantitative method using 2,2′-diphenyl-1-picrylhydrazyl.
- the modified graphene-like carbon material preferably has a carboxyl group amount of 1.0 mmol / g or less as measured by a quantitative method using NaHCO 3 .
- the aspect ratio of the modified graphene-like carbon material is the same as the aspect ratio of the graphene-like carbon material.
- the average particle size of the modified graphene-like carbon material is the same as the average particle size of the graphene-like carbon material.
- the number of stacked graphene sheets of the modified graphene-like carbon material is the same as the number of stacked graphene sheets of exfoliated graphite.
- the resin composite material of the present invention is obtained by dispersing the modified graphene-like carbon material of the present invention in a resin.
- the resin composite material preferably contains about 0.01 to 40 parts by mass, more preferably about 0.1 to 20 parts by mass of the modified graphene-like carbon material with respect to 100 parts by mass of the resin. . Thereby, the mechanical strength of the resin composite material can be effectively increased.
- Resins include thermoplastic resins and thermosetting resins.
- a thermoplastic resin is preferable.
- thermoplastic resin is not particularly limited, and a known thermoplastic resin can be used.
- specific examples of the thermoplastic resin include polyolefin, polystyrene, polyacrylate, polyacrylonitrile, polyester, polyamide, polyurethane, polyethersulfone, polyetherketone, polyimide, polydimethylsiloxane, and at least two kinds of these copolymers. Is mentioned.
- the thermoplastic resin contained in the resin composite material may be one type or two or more types.
- thermoplastic resin polyolefin is preferable.
- Polyolefin is inexpensive and easy to mold under heating. For this reason, by using polyolefin as the thermoplastic resin, the manufacturing cost of the resin composite material can be reduced, and the resin composite material can be easily molded.
- polystyrene resin examples include polyethylene, polypropylene, ethylene homopolymer, ethylene- ⁇ -olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-acetic acid.
- Polyethylene resins such as vinyl copolymers, propylene homopolymers, propylene- ⁇ -olefin copolymers, polypropylene resins such as propylene-ethylene random copolymers, propylene-ethylene block copolymers, butene homopolymers, Examples thereof include homopolymers or copolymers of conjugated dienes such as butadiene and isoprene.
- a polypropylene resin is particularly preferable.
- the amount of hydroxyl group measured by a quantitative method using 2,2′-diphenyl-1-picrylhydrazyl is 0.3 mmol / g to A modified graphene-like carbon material of 10.0 mmol / g can be easily produced. Since such a modified graphene-like carbon material has many hydroxyl groups introduced therein, it has a high affinity with a polar solvent and can be uniformly dispersed in the polar solvent. In addition, a hydroxyl group in the modified graphene-like carbon material can be used to form a urethane bond with a compound having an isocyanate group.
- the graphite sheet having a density of 0.7 obtained as described above was cut into a size of 5 cm ⁇ 5 cm to obtain a graphite sheet as an electrode material.
- two slits were formed by cutting with a cutter knife so that the length of the slit was 1 cm.
- An electrode made of Pt was inserted into the graphite sheet on which the two slits were formed.
- the graphite sheet thus prepared was immersed in a 60 wt% aqueous nitric acid solution as a working electrode (anode) together with a reference electrode (cathode) made of Pt and a reference electrode made of Ag / AgCl.
- the graphite sheet portion from the lower end of the 5 cm ⁇ 5 cm graphite sheet to a position 4 cm high was immersed in the nitric acid aqueous solution, and the upper portion of the graphite sheet was not immersed in the nitric acid aqueous solution.
- a DC voltage was applied to perform electrochemical treatment. In this way, the portion of the original graphite sheet used as the working electrode that was immersed in the aqueous nitric acid solution was used as expanded graphite.
- the obtained expanded graphite was dried at a low temperature, cut into 1 cm squares, one of which was placed in a carbon crucible and subjected to electromagnetic induction heat treatment.
- the induction heating device MU1700D manufactured by SK Medical Co., Ltd. was used, and the current was 14 A so that the maximum temperature reached 550 ° C. in an argon gas atmosphere.
- the expanded graphite was exfoliated by electromagnetic induction heating, and the specific surface area of the obtained exfoliated graphite powder was measured using nitrogen gas with Shimadzu Corporation's specific surface area measuring device ASAP-2000. Showed a specific surface area of 640 m 2 / g.
- Example 1 In the atmosphere, 0.5 g of exfoliated graphite obtained as described above, 2.8 ml of concentrated sulfuric acid, and 150 ml of pure water were added to a four-necked flask equipped with a nitrogen introduction tube, a thermometer, and two dropping funnels. The inside of the flask was replaced with nitrogen gas. Hydrogen peroxide water (27%) was added to one dropping funnel, and 27.8 g FeSO 4 / 7H 2 O, 5.6 ml concentrated sulfuric acid, and 57 ml pure water were added to the other dropping funnel.
- the amount of hydroxyl group as measured by a quantitative method using 2,2′-diphenyl-1-picrylhydrazyl was 0.39 mmol / g. Further, when the amount of the carboxyl group was measured by a quantification method of the carboxyl group using NaHCO 3 , the carboxyl group was negligibly small.
- the amount of hydroxyl group introduced was 0.28 mmol / g as measured by a quantitative method using 2,2′-diphenyl-1-picrylhydrazyl of the modified graphene-like carbon material into which a hydroxyl group was introduced.
- the amount of carboxyl groups was measured by a quantification method of carboxyl groups using NaHCO 3 , the amount of carboxyl groups was 1.52 mmol / g.
Abstract
Description
本発明に係るグラフェンライク炭素材料の製造方法では、グラフェンライク炭素材料と過酸化水素とを反応させて、グラフェンライク炭素材料に水酸基を導入する。本発明の改質グラフェンライク炭素材料は、原料であるグラフェンライク炭素材料に水酸基が導入されたものである。
本発明に係る改質グラフェンライク炭素材料は、例えば、上記の本発明に係る改質グラフェンライク炭素材料の製造方法によって製造することができる。
本発明の樹脂複合材料は、本発明の改質グラフェンライク炭素材料が樹脂中に分散されてなる。
原料の黒鉛シートとして東洋炭素社製、品番:PF100-UHPを用意した。この黒鉛シートと同じ製法で、圧延処理時の圧延倍率を下げて密度0.7、厚み1mmの低密度黒鉛シートを用意した。
大気中において、窒素導入管、温度計と2つの滴下ロートを取り付けた四つ口フラスコに、上記のようにして得た薄片化黒鉛0.5g、濃硫酸2.8ml、純水150mlを加え、フラスコ内を窒素ガスで置換した。一方の滴下ロートに過酸化水素水(27%)を、他方の滴下ロートに、FeSO4/7H2O27.8g、濃硫酸5.6ml、純水57mlを加えた。氷水浴で四つ口フラスコを冷却しながら、二つの滴下ロートから過酸化水素水とFeSO4溶液とを滴下すると、反応液の温度が急激に上昇したため、反応液の温度が20℃を超えないように滴下速度を調整しながら約30分にわたって滴下した。その後、反応液を20℃に保ちながら、48時間反応させた。反応後、反応液を水酸化ナトリウムで中和し、濾過により水酸基が導入された改質グラフェンライク炭素材料を得た。水酸基が導入された改質グラフェンライク炭素材料について、2,2’-ジフェニル-1-ピクリルヒドラジルを用いた定量法で測定したときの水酸基の量は、0.39mmol/gであった。また、NaHCO3を用いたカルボキシル基の定量法によりカルボキシル基の量を測定したところ、カルボキシル基は無視できるほど少なかった。
還流冷却器を取り付けた100mlナス型フラスコにスターラーバー、上記のようにして得た薄片化黒鉛0.2g、混酸(HNO3/H2SO4=1/3(v/v))50mlを加え、マグネチックスターラーでかき混ぜながら40℃で10時間反応させた。反応後、反応生成物を大量の純水に注いで、濾過し、濾液が中性になるまで洗浄して、水酸基が導入された改質グラフェンライク炭素材料を得た。水酸基が導入された改質グラフェンライク炭素材料の2,2’-ジフェニル-1-ピクリルヒドラジルを用いた定量法で測定したときの水酸基の導入量は、0.28mmol/gであった。NaHCO3を用いたカルボキシル基の定量法によりカルボキシル基の量を測定したところ、カルボキシル基の量は、1.52mmol/gであった。
Claims (6)
- グラフェンライク炭素材料と過酸化水素とを反応させて、前記グラフェンライク炭素材料に水酸基を導入する、改質グラフェンライク炭素材料の製造方法。
- 前記グラフェンライク炭素材料への水酸基の導入を鉄触媒の存在下に行う、請求項1に記載の改質グラフェンライク炭素材料の製造方法。
- 請求項1または2に記載の製造方法によって得られる、改質グラフェンライク炭素材料。
- 2,2’-ジフェニル-1-ピクリルヒドラジルを用いた定量法で測定したときの水酸基の量が、0.3mmol/g~10.0mmol/gである、改質グラフェンライク炭素材料。
- NaHCO3を用いた定量法で測定したときのカルボキシル基の量が、1.0mmol/g以下である、請求項4に記載の改質グラフェンライク炭素材料。
- 請求項4または5に記載の改質グラフェンライク炭素材料が樹脂中に分散されてなる、樹脂複合材料。
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EP13790270.6A EP2851341B1 (en) | 2012-05-14 | 2013-05-14 | Modified-graphene-like carbon material, and resin composite material containing modified-graphene-like carbon material |
CN201380011296.0A CN104136369A (zh) | 2012-05-14 | 2013-05-14 | 改性石墨烯类碳材料的制造方法、改性石墨烯类碳材料以及含有改性石墨烯类碳材料的树脂复合材料 |
JP2013526653A JP5364866B1 (ja) | 2012-05-14 | 2013-05-14 | 改質グラフェンライク炭素材料の製造方法、改質グラフェンライク炭素材料、及び改質グラフェンライク炭素材料を含む樹脂複合材料 |
KR1020147015229A KR101922755B1 (ko) | 2012-05-14 | 2013-05-14 | 개질 그래핀 라이크 탄소 재료의 제조 방법, 개질 그래핀 라이크 탄소 재료, 및 개질 그래핀 라이크 탄소 재료를 포함하는 수지 복합 재료 |
US14/386,955 US9688594B2 (en) | 2012-05-14 | 2013-05-14 | Method for producing modified-graphene-like carbon material, modified-graphene-like carbon material, and resin composite material containing modified-graphene-like carbon material |
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JP6958814B2 (ja) | 2016-07-22 | 2021-11-02 | 積水化学工業株式会社 | 調光材料、調光フィルム及び調光積層体 |
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CN114040889A (zh) * | 2019-06-17 | 2022-02-11 | 堪萨斯州立大学研究基金会 | 石墨烯/氧化石墨烯核/壳颗粒及其制备和使用方法 |
CN110760159A (zh) * | 2019-11-01 | 2020-02-07 | 嘉兴烯成新材料有限公司 | 一种“苍耳型”碳材料增强环氧树脂力学性能的制备方法 |
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EP2851341A4 (en) | 2016-04-06 |
JP5364866B1 (ja) | 2013-12-11 |
CN104136369A (zh) | 2014-11-05 |
KR101922755B1 (ko) | 2018-11-27 |
EP2851341B1 (en) | 2018-07-04 |
JPWO2013172316A1 (ja) | 2016-01-12 |
EP2851341A1 (en) | 2015-03-25 |
KR20150020159A (ko) | 2015-02-25 |
US20150080513A1 (en) | 2015-03-19 |
US9688594B2 (en) | 2017-06-27 |
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