WO2012128114A1 - 酸化薄片化黒鉛誘導体、その樹脂複合材料及びその樹脂複合材料の製造方法 - Google Patents
酸化薄片化黒鉛誘導体、その樹脂複合材料及びその樹脂複合材料の製造方法 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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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
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- 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
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/46—Graphite
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
Definitions
- the present invention relates to an oxidized exfoliated graphite derivative excellent in dispersibility in a thermoplastic resin, a resin composite material in which the oxidized exfoliated graphite derivative is uniformly dispersed in a thermoplastic resin, and a method for producing the resin composite material About.
- carbon materials having a graphene sheet structure have attracted attention because of their high elastic modulus and high conductivity.
- a product made of the synthetic resin can be reinforced or imparted with conductivity.
- graphene sheets, carbon nanotubes, thinned graphite, and the like are nano-sized and have a large specific surface area. Therefore, when the carbon material is combined with a resin, it is considered that the above effect can be expressed more.
- Patent Document 1 discloses a method for obtaining uniform dispersion using a common solvent for a carbon material and a resin. According to this method, as long as a common solvent exists between the resin and the carbon material, it is possible to obtain a resin composite material in a uniformly dispersed state.
- the above carbon material has a problem that its dispersibility in a solvent is extremely poor because of its large cohesive force due to ⁇ stacking force. Moreover, in the manufacturing method described in Patent Document 1, a large amount of solvent is required to disperse the carbon material in the resin. For this reason, there are problems such as high cost of the solvent and difficulty in removing the solvent.
- oxide exfoliated graphite obtained by oxidizing the exfoliated graphite because it contains sp 3 structure, [pi stacking strength is weak.
- Oxidized exfoliated graphite has a large steric hindrance because it has functional groups such as hydroxyl groups, carboxyl groups, and epoxy groups on the surface. Therefore, oxide exfoliated graphite is known to generally have better dispersibility than exfoliated graphite.
- An object of the present invention is to provide an oxidized exfoliated graphite derivative excellent in dispersibility in a thermoplastic resin, a resin composite material of the oxidized exfoliated graphite derivative and a thermoplastic resin, and a method for producing the resin composite material.
- the oxidized exfoliated graphite derivative of the present invention has an exfoliated graphite having a C / O ratio of 8 or less obtained by elemental analysis, a compound having the structure of the following formula (1), and a structure of the formula (2): It is obtained by reacting at least one compound selected from the group consisting of a compound, a compound having the structure of formula (3), and a compound having the structure of formula (4).
- R 1 ⁇ R 4 in the formula (1) is a silyl group, a siloxy group, an alkoxy group, a vinyl group, a chlorine atom, an aryl group, an alkyl group, an ether group, an ester group, an amine group, an amide group, a hydrogen atom, a thiol And a functional group independently selected from the group consisting of an epoxy group and at least one of R 1 to R 4 is a siloxy group or an alkoxy group.
- R 5 and R 6 in the formula (2) is an alkyl group, an aryl group, a vinyl group, an ether group, an alkoxy group, a functional group independently selected from the group consisting of a chlorine atom and a hydroxyl group, R 5 or At least one of R 6 is a functional group of any one of a chlorine atom, an alkoxy group, and a hydroxyl group.
- R 7 in the formula (3) is any functional group of an alkyl group, an aryl group, an ether group, and a vinyl group.
- R 8 ⁇ R 10 in the formula (4) is an alkyl group or hydrogen, at least one of R 8 ⁇ R 10 is an alkyl group having 8 or more carbon atoms.
- the resin composite material of the present invention contains the oxidized exfoliated graphite derivative and a thermoplastic resin.
- the thermoplastic resin is a polyolefin.
- the polyolefin is polypropylene.
- the oxidized exfoliated graphite derivative is dispersed in the thermoplastic resin by kneading the oxidized exfoliated graphite derivative and a thermoplastic resin.
- the highly polar group on the oxidized exfoliated graphite surface has a compound having the structure of formula (1), a compound having the structure of formula (2), and a compound having the structure of formula (3)
- the surface polarity of the exfoliated graphite derivative is reduced by being modified with at least one compound selected from the group consisting of compounds having the structure of formula (4).
- due to the bulkiness of the functional group modified by the compound steric hindrance due to the functional group of the oxidized exfoliated graphite derivative is increased. Therefore, the cohesive force of the oxidized exfoliated graphite derivative is reduced.
- the oxidized exfoliated graphite of the present invention has a C / O ratio of 8 or less obtained by elemental analysis of the oxidized exfoliated graphite, the cohesive force of the oxidized exfoliated graphite becomes smaller.
- thermoplastic resin in which the exfoliated graphite oxide is uniformly dispersed in a thermoplastic resin and the mechanical strength is increased.
- an oxidized exfoliated graphite derivative that is excellent in dispersibility in a low-polarity thermoplastic resin such as a polyolefin resin and can effectively increase the mechanical strength of the thermoplastic resin. it can.
- the oxidized exfoliated graphite derivative is uniformly dispersed in the thermoplastic resin. Therefore, according to the present invention, it is possible to provide a resin composite material having increased mechanical strength due to the reinforcing effect of the oxidized exfoliated graphite derivative.
- the oxidized exfoliated graphite derivative of the present invention includes oxidized exfoliated graphite having a C / O ratio of 8 or less obtained by elemental analysis, a compound having the structure of formula (1), a compound having the structure of formula (2), It is obtained by reacting at least one compound selected from the group consisting of a compound having the structure of formula (3) and a compound having the structure of formula (4).
- the C / O ratio obtained by elemental analysis refers to the ratio of the number of moles of carbon atoms and oxygen atoms obtained by elemental analysis.
- oxidized exfoliated graphite is obtained by exfoliating exfoliated graphite obtained by exfoliating the original graphite, or obtained by exfoliating graphite oxide, and is oxidized less than the original graphite or oxidized graphite.
- Oxidized exfoliated graphite contains an sp 3 structure and therefore has a lower ⁇ stacking force than exfoliated graphite.
- Oxidized exfoliated graphite has a large steric hindrance because it has functional groups such as hydroxyl groups, carboxyl groups, and epoxy groups on the surface. Due to the above effect, the cohesive force of the exfoliated graphite is reduced. Therefore, the exfoliated graphite is generally more dispersible than exfoliated graphite.
- a functional group such as a hydroxyl group, a carboxyl group, or an epoxy group on the oxidized exfoliated graphite surface is a compound having a structure of formula (1), a compound having a structure of formula (2), a compound having a structure of formula (3), And by modifying with at least one compound selected from the group consisting of compounds having the structure of formula (4), the surface polarity of the oxidized exfoliated graphite derivative is lowered. Therefore, the cohesive force of the oxidized exfoliated graphite derivative is reduced in a nonpolar thermoplastic resin such as polyolefin.
- the steric hindrance due to the functional group of the oxidized exfoliated graphite derivative becomes greater due to the bulk of the functional group modified with the compound. For this reason, the cohesive force of the oxidized exfoliated graphite derivative becomes smaller.
- the oxidized exfoliated graphite derivative has high dispersibility in nonpolar thermoplastic resins such as polyolefin.
- the oxidized exfoliated graphite has a shape with a relatively large aspect ratio.
- the aspect ratio refers to the ratio of the maximum dimension of the oxide exfoliated graphite in the stacking surface direction to the thickness of the oxide exfoliated graphite. If the aspect ratio is too low, the reinforcing effect against an external force applied in the direction intersecting the laminated surface may not be sufficient. On the other hand, even if the aspect ratio is too high, the effect may be saturated and a further reinforcing effect may not be expected. Therefore, the preferable lower limit of the aspect ratio is 50, and the preferable upper limit is 5000.
- the C / O ratio obtained by elemental analysis of the oxidized exfoliated graphite is 8 or less. Thereby, the cohesive force of the oxidized exfoliated graphite becomes smaller. Therefore, the dispersibility of the oxidized exfoliated graphite is effectively enhanced.
- the compounding ratio of the compound having the structure of formulas (1) to (4) with respect to the oxidized exfoliated graphite is not particularly limited, but for example, it is preferably in the range of 1 mmol to 6000 mmol with respect to 1 g of oxidized exfoliated graphite.
- R 1 to R 4 in the formula (1) are silyl group, siloxy group, alkoxy group, vinyl group, chlorine atom, aryl group, alkyl group, ether group, ester group, amine group, amide group, hydrogen atom, thiol A functional group independently selected from the group consisting of groups and epoxy groups.
- R 1 ⁇ R 4 are independently selected from the group consisting of alkyl groups, alkoxy groups and siloxy groups. At least one of R 1 to R 4 is a siloxy group or an alkoxy group.
- the hydrocarbon group may have a branch or a cyclic structure.
- R 5 and R 6 in the formula (2) are independently selected from the group consisting of an alkyl group, an aryl group, a vinyl group, an ether group, an alkoxy group, a chlorine atom and a hydroxyl group.
- R 5 and R 6 are functional groups independently selected from the group consisting of alkyl groups, chlorine atoms, alkoxy groups and hydroxyl groups.
- at least one of R 5 and R 6 is any one of a chlorine atom, an alkoxy group, and a hydroxyl group.
- R 5 or R 6 contains a hydrocarbon group
- the number of carbon atoms of the hydrocarbon group is not particularly limited, but is preferably 5 or more. By setting the carbon number to 5 or more, the dispersibility of the oxidized exfoliated graphite derivative can be effectively enhanced. More preferably, the hydrocarbon group has 10 or more carbon atoms.
- the hydrocarbon group may have a branching or a cyclic structure.
- R 7 in the formula (3) is any functional group of an alkyl group, an aryl group, an ether group, and a vinyl group.
- the number of carbon atoms in R 7 is not particularly limited, but is preferably 5 or more. By setting the carbon number to 5 or more, the dispersibility of the oxidized exfoliated graphite derivative can be effectively enhanced. More preferably, R 7 has 10 or more carbon atoms. R 7 may have a branching or a cyclic structure.
- R 8 ⁇ R 10 in the formula (4) is an alkyl group or hydrogen, at least one of R 8 ⁇ R 10 is 8 or more alkyl groups having a carbon number.
- the compound having the structure of the formula (4) may be any of primary amine, secondary amine or tertiary amine.
- primary amines include n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, and n-pentadecylamine.
- the compound having the structure of formula (4) is a secondary amine or a tertiary amine, as long as the carbon number of at least one alkyl group included in the compound having the structure of formula (4) is 8 or more
- the number of carbon atoms of the other alkyl group provided in the compound having the structure of the formula (4) may be less than 8.
- the resin composite material of the present invention contains the oxidized exfoliated graphite derivative and the thermoplastic resin.
- the oxidized exfoliated graphite derivative has high dispersibility in a nonpolar solvent such as a thermoplastic resin. Therefore, in the resin composite material of the present invention, the oxidized exfoliated graphite derivative is uniformly dispersed in the thermoplastic resin. Accordingly, it is possible to effectively enhance the reinforcing effect against the external force applied in the direction intersecting the laminated surface of the exfoliated graphite.
- the blending ratio of the oxidized exfoliated graphite derivative is not particularly limited, but is preferably in the range of 0.5 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If it is less than 0.5 part by weight, the reinforcing effect by the oxidized exfoliated graphite derivative may be insufficient. If the amount exceeds 40 parts by weight, the resin composite material can have high rigidity, but it may be brittle and easily cracked.
- thermoplastic resin is not particularly limited.
- Polypropylene resins such as copolymers, ethylene-vinyl acetate copolymers, propylene homopolymers, propylene- ⁇ -olefin copolymers, propylene-ethylene random copolymers, propylene-ethylene block copolymers, etc.
- thermoplastic resin is polypropylene. Since the thermoplastic resin can be easily molded under heating, the resin composite material of the present invention containing the thermoplastic resin can be formed into various molded articles by using various molding methods under heating.
- the oxidized exfoliated graphite derivative and the thermoplastic resin are kneaded to disperse the oxidized exfoliated graphite derivative in the thermoplastic resin.
- exfoliated graphite oxide a compound having the structure of the above formula (1), a compound having the structure of the formula (2), a compound having the structure of the formula (3), and the formula (4)
- surface treatment agent At least one compound selected from the group consisting of compounds having a structure
- the oxidized exfoliated graphite and the surface treatment agent are dispersed in a solvent.
- the said solvent is not specifically limited, In order to disperse
- the solvent include water, alcohol, tetrahydrofuran, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, acetone, chlorobenzene, dichlorobenzene, dichlorobenzene, chloroform and the like. Can be used.
- water, alcohol, tetrahydrofuran, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide or the like can be used as the solvent.
- the solvent may be acidic according to the properties of the surface treatment agent, and may be neutral or basic.
- the dispersion method of the oxidized exfoliated graphite and the surface treatment agent is not particularly limited, and can be dispersed, for example, by applying ultrasonic waves to the solvent.
- the oxidized exfoliated graphite and the surface treatment agent may be dispersed simultaneously or separately.
- the oxidized exfoliated graphite and the surface treatment agent are mixed in the solvent in which the oxidized exfoliated graphite and the surface treatment agent are dispersed.
- the mixing conditions are not particularly limited, and are appropriately selected depending on the surface treatment agent and solvent used.
- the reaction temperature can be preferably ⁇ 20 to 200 ° C. If the reaction temperature is too high, the surface treatment agent, solvent, and exfoliated graphite may be deteriorated. If the reaction temperature is too low, the reaction between the exfoliated graphite oxide and the surface treatment agent may not proceed well.
- the reaction temperature can be more preferably 0 to 150 ° C.
- the mixing time is preferably 3 minutes to 96 hours. If the mixing time is too long, the surface treatment agent, solvent, and exfoliated graphite may be deteriorated. If the mixing time is too short, the reaction between the exfoliated graphite oxide and the surface treatment agent may not proceed well. More preferably, the mixing time can be 30 minutes to 72 hours.
- the oxidized exfoliated graphite derivative of the present invention can be obtained by removing the solvent and the unreacted surface treatment agent.
- the method for removing the solvent and the unreacted surface treatment agent is not particularly limited, and can be performed by, for example, filtration, ultrasonic cleaning, evaporation or the like.
- the method for producing the resin composite material of the present invention is not particularly limited, and the resin composite material of the present invention can be obtained by mixing the oxidized exfoliated graphite derivative of the present invention and a thermoplastic resin by a known method. .
- the resin composite material of the present invention can be obtained by melt-kneading the oxidized exfoliated graphite derivative of the present invention and a thermoplastic resin.
- Carbon material Graphite manufactured by SEC Carbon Corporation, trade name “SNO-5”, average particle size 5 ⁇ m, specific surface area 15 m 2 / g Carbon nanotube (CNT): manufactured by Tokyo Chemical Industry Co., Ltd., trade name “C2151”.
- Treatment agent Siloxy oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KR-500”
- treatment agent Siloxy oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KR-500”
- KR-500 trade name
- the exfoliated graphite used in the examples and comparative examples was produced by the following methods 1 to 4.
- oxidized exfoliated graphite was treated by the following treatment methods A to D to obtain oxidized exfoliated graphite derivatives.
- A As an example of a compound having the structure of the above formula (1), an oxidized exfoliated graphite derivative was obtained using the following three compounds.
- A-1 Treatment with methyltriethoxysilane Oxidized exfoliated graphite was dispersed in a water / ethanol (50/50) mixed solution using ultrasonic waves, and a mixture having an oxidized exfoliated graphite concentration of 1 mg / ml was obtained. Obtained. Next, acetic acid was added to the mixture to adjust the pH of the mixture to 5. Subsequently, methyltriethoxysilane was added so that the mass% of methyltriethoxysilane in the mixture was 0.5 mass%.
- A-2 Treatment with phenyltriethoxysilane An oxidized exfoliated graphite derivative was obtained in the same manner as A-1, except that phenyltriethoxysilane was used instead of methyltriethoxysilane.
- A-3 Treatment with siloxy oligomer An oxidized exfoliated graphite derivative was obtained in the same manner as A-1, except that a siloxy oligomer was used instead of methyltriethoxysilane.
- B As an example of a compound having the structure of the above formula (2), an oxidized exfoliated graphite derivative was obtained using the following three compounds.
- B-1 Treatment with decanoic acid chloride 5.0 g of oxidized exfoliated graphite, 50 g of decanoic acid chloride, and 21 g of pyridine were dispersed in 5 L of DMF using ultrasonic waves. The resulting mixture was then stirred at 130 ° C. for 72 hours under a nitrogen atmosphere. Next, this mixture was put into 5 L of toluene, and the liquid was removed by filtration to obtain a product.
- B-2 Treatment with decanoic acid 5000 g of decanoic acid was subjected to ultrasonic treatment in a warm bath to disperse 5.0 g of oxidized exfoliated graphite. Next, the mixture was stirred at 120 ° C. for 2 hours under reduced pressure (0.1 mmHg) while removing water from the mixture. Next, the obtained mixture was subjected to ultrasonic cleaning and filtration twice in 5 L of acetone to remove the liquid and unreacted substances to obtain an oxidized exfoliated graphite derivative.
- C As an example of a compound having the structure of the above formula (3), an oxidized exfoliated graphite derivative was obtained using the following three compounds.
- C-1 Treatment with octadecyl isocyanate 5.0 g of oxidized exfoliated graphite, 50 g of octadecyl isocyanate, and 1 g of triethylamine were dispersed in 5 L of DMF using ultrasonic waves. The resulting mixture was then stirred at 130 ° C. for 72 hours under a nitrogen atmosphere. Next, the obtained mixture was put into 5 L of toluene, and the liquid was removed by filtration.
- C-2 Treatment with phenyl isocyanate An oxidized exfoliated graphite derivative was obtained in the same manner as C-1, except that phenyl isocyanate was used instead of octadecyl isocyanate.
- C-3 Treatment with 4-ethoxyphenyl isocyanate An oxidized exfoliated graphite derivative was obtained in the same manner as C-1, except that 4-ethoxyphenyl isocyanate was used instead of octadecyl isocyanate.
- D As an example of a compound having the structure of the above formula (4), an oxidized exfoliated graphite derivative was obtained using the following three compounds.
- D-1 Treatment with n-octylamine Oxidized exfoliated graphite was mixed in DMF to obtain a 1 mg / ml oxidized exfoliated graphite / DMF mixture. Next, 10 mmol of n-octylamine per 1 g of exfoliated graphite was added to the resulting mixture. Subsequently, the exfoliated graphite oxide and n-octylamine were dispersed in the mixture using ultrasonic waves. The dispersed mixture was then stirred at 120 ° C. for 3 days.
- D-2 Treatment with n-dodecylamine Oxidized exfoliated graphite derivative was obtained in the same manner as D-1, except that n-dodecylamine was used instead of n-octylamine.
- D-3 Treatment with didodecylamine An oxidized exfoliated graphite derivative was obtained in the same manner as D-1, except that didodecylamine was used instead of n-octylamine.
- D-4 Treatment with n-butylamine An oxidized exfoliated graphite derivative was obtained in the same manner as D-1, except that n-butylamine was used instead of n-octylamine.
- the tensile elastic modulus at 23 ° C. of the obtained resin composite material sheet was measured according to JIS K6767.
- Tables 1 to 4 show the tensile elastic moduli of composite materials of exfoliated graphite derivatives and resins obtained by the processing methods A to D, respectively.
- the tensile modulus of the composite sheet obtained using exfoliated graphite oxide and a matrix resin not subjected to the treatments A to D was measured in the same manner. The results are shown in Table 5.
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Abstract
Description
本発明の酸化薄片化黒鉛誘導体は、元素分析により得られるC/O比が8以下である酸化薄片化黒鉛と、式(1)の構造を有する化合物、式(2)の構造を有する化合物、式(3)の構造を有する化合物、及び式(4)の構造を有する化合物からなる群から選択される少なくとも1つの化合物とを反応させることにより得られる。なお、本発明において、元素分析により得られるC/O比とは、元素分析により得られる炭素原子と酸素原子とのモル数の比をいう。
本発明の樹脂複合材料は、上記酸化薄片化黒鉛誘導体と上記熱可塑性樹脂とを含んでいる。上述したように、酸化薄片化黒鉛誘導体は、熱可塑性樹脂等の非極性溶媒中において高い分散性を有する。そのため、本発明の樹脂複合材料では、熱可塑性樹脂中に酸化薄片化黒鉛誘導体が均一に分散されている。従って、酸化薄片化黒鉛の積層面に交差する方向に加わる外力に対する補強効果を効果的に高めることができる。
次に、本発明の酸化薄片化黒鉛誘導体の製造方法について説明する。
黒鉛:SECカーボン社製、商品名「SNO-5」、平均粒径5μm、比表面積15m2/g
カーボンナノチューブ(CNT):東京化成社製、商品名「C2151」。
ポリプロピレン(PP):プライムポリマー社製、商品名「J-721GR」
ポリエチレン(PE):プライムポリマー社製、商品名「7800M」
ポリカーボネート:出光興産社製、商品名「R2200」
ポリエステル:三菱エンジニアリングプラスチックス、商品名「5010R3-2」
ポリアミド:クラレ社製、商品名「N1000A」
ポリスチレン:DIC社製、商品名「CR-3500」
ポリメチルメタクリレート:三菱レーヨン社製、商品名「VH001」。
シロキシオリゴマー:信越化学社製、商品名「KR-500」
その他の処理剤としては、東京化成製の試薬を使用した。
実施例及び比較例において使用する酸化薄片化黒鉛は、以下の1~4の方法により製造した。
1.元素分析で得られるC/O比=2の酸化薄片化黒鉛は、ハマーズの方法で製造した(J.Chem.Soc.W.S.Hummers et.al.1958,80,1339を参照)。
2.元素分析で得られるC/O比=8の酸化薄片化黒鉛は、上記C/O比=2である酸化薄片化黒鉛を空気中において200℃で2時間加熱することで製造した。
3.元素分析で得られるC/O比=10の酸化薄片化黒鉛は、上記C/O比=2である酸化薄片化黒鉛を空気中において200℃で5時間加熱することで製造した。
4.元素分析で得られるC/O比=12の酸化薄片化黒鉛は、上記C/O比=2である酸化薄片化黒鉛を空気中において200℃で8時間加熱することで製造した。
実施例及び比較例においては、酸化薄片化黒鉛を下記A~Dの処理方法により処理し、酸化薄片化黒鉛誘導体を得た。
A-1:メチルトリエトキシシランによる処理
酸化薄片化黒鉛を、水/エタノール(50/50)混合液中に、超音波を用いて分散させ、酸化薄片化黒鉛の濃度が1mg/mlの混合物を得た。次に、この混合物に酢酸を加えて、混合物のpHを5に調整した。続いて、この混合物中におけるメチルトリエトキシシランの質量%が0.5質量%になるように、メチルトリエトキシシランを加えた。次に、得られた混合物を1時間超音波処理して、室温でエタノールを蒸発させた。次に、得られた混合物を120℃で2時間加熱した。次に、得られた混合物をアセトン中で超音波処理して、濾過により液体を除去して、酸化薄片化黒鉛誘導体を得た。
A-2:フェニルトリエトキシシランによる処理
メチルトリエトキシシランの代わりにフェニルトリエトキシシランを用いたこと以外は、A-1と同様にして、酸化薄片化黒鉛誘導体を得た。
A-3:シロキシオリゴマーによる処理
メチルトリエトキシシランの代わりにシロキシオリゴマーを用いたこと以外は、A-1と同様にして、酸化薄片化黒鉛誘導体を得た。
B-1:デカン酸クロリドによる処理
酸化薄片化黒鉛5.0gと、デカン酸クロリド50gと、ピリジン21gとを、超音波を用いて5LのDMF中に分散させた。次に、得られた混合物を、窒素雰囲気下において、130℃で72時間攪拌した。次に、この混合物をトルエン5Lに投入し、濾過により液体を除去して生成物を得た。その後、得られた生成物をアセトン中で超音波洗浄して、濾過により液体及び未反応物を除去して、酸化薄片化黒鉛誘導体を得た。
B-2:デカン酸による処理
デカン酸5000gに温浴中での超音波処理を行い、酸化薄片化黒鉛5.0gを分散させた。次に、減圧下(0.1mmHg)において、この混合物から水分を除去しながら2時間120℃で攪拌した。次に、得られた混合物をアセトン5L中で超音波洗浄、濾過を2回行い、液体及び未反応物を除去して、酸化薄片化黒鉛誘導体を得た。
B-3:デカン酸メチルによる処理
デカン酸メチル5000gに超音波処理を行い、酸化薄片化黒鉛5.0gを分散させた。次に、この混合物を150℃で2時間攪拌し、生成するメタノールを除去した。次に、得られた混合物から液体成分を濾過にて除去した。次に、得られた固形物に対して、アセトン5L中で超音波洗浄及び濾過を行い、未反応物を除去して、酸化薄片化黒鉛誘導体を得た。
C-1:オクタデシルイソシアネートによる処理
酸化薄片化黒鉛5.0gと、オクタデシルイソシアネート50gと、トリエチルアミン1gとを、超音波を用いて5LのDMF中に分散させた。次に、得られた混合物を、窒素雰囲気下において、130℃で72時間攪拌した。次に、得られた混合物を、トルエン5Lに投入し、濾過により液体を除去した。その後、得られた生成物をトルエン中で超音波洗浄して、濾過により液体及び未反応物を除去して、酸化薄片化黒鉛誘導体を得た。
C-2:フェニルイソシアネートによる処理
オクタデシルイソシアネートの代わりにフェニルイソシアネートを用いたこと以外は、C-1と同様にして、酸化薄片化黒鉛誘導体を得た。
C-3:4-エトキシフェニルイソシアネートによる処理
オクタデシルイソシアネートの代わりに4-エトキシフェニルイソシアネートを用いたこと以外は、C-1と同様にして、酸化薄片化黒鉛誘導体を得た。
D-1:n-オクチルアミンによる処理
酸化薄片化黒鉛をDMF中に混合し、1mg/mlの酸化薄片化黒鉛/DMF混合物を得た。次に、得られた混合物に、薄片化黒鉛1gあたり10mmolのn-オクチルアミンを加えた。続いて、超音波を用いて、酸化薄片化黒鉛及びn-オクチルアミンを混合物中に分散させた。次に、分散された混合物を、120℃で3日間撹拌した。次に、得られた混合物を約5倍重量相当のトルエン中に注ぎ、15分撹拌した。その後、撹拌された混合物を濾過して、撹拌された混合物から液体及び未反応物を除去して、酸化薄片化黒鉛誘導体を得た。
D-2:n-ドデシルアミンによる処理
n-オクチルアミンの代わりにn-ドデシルアミンを用いたこと以外は、D-1と同様にして、酸化薄片化黒鉛誘導体を得た。
D-3:ジドデシルアミンによる処理
n-オクチルアミンの代わりにジドデシルアミンを用いたこと以外は、D-1と同様にして、酸化薄片化黒鉛誘導体を得た。
D-4:n-ブチルアミンによる処理
n-オクチルアミンの代わりにn-ブチルアミンを用いたこと以外は、D-1と同様にして、酸化薄片化黒鉛誘導体を得た。
表1~5示される組み合わせになるようにして、上記のマトリクス樹脂100質量部と、上記A~Dの処理方法で得た酸化薄片化黒鉛誘導体の5質量部とを、プラストミルに供給して混練し、プレス成形することによって、厚み1mmのマトリクス樹脂/酸化薄片化黒鉛樹脂複合材料シートを得た。
得られた樹脂複合材料シートの23℃における引張弾性率をJIS K6767により測定した。A~Dの処理方法で得られた薄片化黒鉛誘導体と樹脂との複合材料の引張弾性率をそれぞれ表1~4に示す。また、A~Dの処理を行わなかった薄片化酸化黒鉛とマトリクス樹脂とを用いて得られた複合材料シートについても、同様にして引張弾性率を測定下。この結果を表5に示す。
Claims (5)
- 元素分析により得られるC/O比が8以下である酸化薄片化黒鉛と、下記の式(1)の構造を有する化合物、式(2)の構造を有する化合物、式(3)の構造を有する化合物、及び式(4)の構造を有する化合物からなる群から選択される少なくとも1つの化合物とを反応させることにより得られる酸化薄片化黒鉛誘導体。
- 請求項1に記載の酸化薄片化黒鉛誘導体と、熱可塑性樹脂とを含む樹脂複合材料。
- 前記熱可塑性樹脂がポリオレフィンである、請求項2に記載の樹脂複合材料。
- 前記ポリオレフィンがポリプロピレンである、請求項3に記載の樹脂複合材料。
- 請求項1に記載の酸化薄片化黒鉛誘導体と、熱可塑性樹脂とを混練することにより、前記酸化薄片化黒鉛誘導体を前記熱可塑性樹脂中に分散させる、樹脂複合材料の製造方法。
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JP2015023036A (ja) * | 2013-07-16 | 2015-02-02 | 東レ株式会社 | 電磁波吸収体およびその製造方法 |
JP2016124762A (ja) * | 2015-01-06 | 2016-07-11 | 国立大学法人広島大学 | グラフェン/シリカ複合体の製造方法およびその方法により製造されたグラフェン/シリカ複合体 |
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