WO2014032378A1 - Methods for preparing functionalized graphene and the composite electroconductive glue thereof - Google Patents

Methods for preparing functionalized graphene and the composite electroconductive glue thereof Download PDF

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WO2014032378A1
WO2014032378A1 PCT/CN2012/086895 CN2012086895W WO2014032378A1 WO 2014032378 A1 WO2014032378 A1 WO 2014032378A1 CN 2012086895 W CN2012086895 W CN 2012086895W WO 2014032378 A1 WO2014032378 A1 WO 2014032378A1
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graphene
acid
preparing
epoxy resin
parts
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PCT/CN2012/086895
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刘岚
刘孔华
罗远芳
贾德民
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华南理工大学
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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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention relates to a method for preparing graphene by functionalized graphite, in particular to a method for preparing functionalized graphene and a composite material thereof.
  • the ideal graphene structure is sp2
  • Graphene not only has excellent electrical properties (electron mobility at room temperature up to 2 ⁇ 105cm2 / (V • s)), outstanding thermal conductivity (5000 W/(m•K)), an extraordinary specific surface area (2630 m2/g), and a Young's modulus (1100 GPa) and a breaking strength (125 GPa) comparable to those of carbon nanotubes.
  • Graphene also has a room temperature quantum Hall effect (Hall Effect) and special properties such as room temperature ferromagnetism.
  • the preparation of graphene mainly includes physical methods and chemical methods. Physical methods are usually based on cheap graphite or expanded graphite. Single or multiple layers of graphene are prepared by micromechanical stripping, liquid or gas phase direct stripping. The other is a graphite oxide-reduction method commonly used in the preparation of graphene, which is obtained by oxidation of a strong acid to obtain an oxide group containing an epoxy group such as an epoxy group and a carbonyl group, and then exfoliating to obtain graphene oxide by external force. Further reduction produces a reduced yield of high yield stone.
  • graphene Due to its excellent mechanical and electrical properties, graphene has enhanced function as a polymer matrix.
  • the object of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a method for preparing functionalized graphene and a composite material thereof, and the specific technical solutions are as follows.
  • a method for preparing functionalized graphene which uses natural graphite as a raw material to obtain modified graphite by Friedel-Crafts reaction, and the obtained modified graphite is extracted and purified, and then uniformly dispersed in the organic by ultrasonic. A stable graphene suspension is formed in the solvent.
  • the Friedel-Crafts reaction is a mixture of graphite, an acid anhydride compound or an acid halide or a halogenated alkane, and a catalyst, under mechanical stirring, at 50 ⁇ .
  • the reaction was heated at 150 ° C for 5 to 72 hours.
  • the acid anhydride compound or acid halide or halogenated alkane is p-aminobenzoic acid, m-aminobenzoic acid, 3,5-diaminobenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-amino-4-chlorobenzoic acid, 2-amino-5-methylbenzoic acid, benzoyl chloride, terephthaloyl chloride, o-chlorobenzoyl chloride, p-chlorobenzoyl chloride, o-chlorophenol, p-chlorophenol And one of o-chloroaniline and 4-chloroaniline;
  • the catalyst is one of ferric chloride, aluminum chloride, zinc chloride, phosphoric acid, polyphosphoric acid, hydrofluoric acid, sulfuric acid, boric acid, and hydrochloric acid.
  • the organic solvent is one of ethanol, acetone, acetonitrile, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, and N-methylpyrrolidone.
  • the mass ratio of the graphite to the halogenated alkane or the acid halide or the acid anhydride is 5:1 to 1:5; and the solubility of the graphene suspension is 0.01 mg/ml to 5 mg/ml.
  • a method for preparing a graphene polymer composite material according to the present invention wherein an epoxy resin is added to the graphene suspension to be stirred and dissolved, ultrasonically mixed uniformly, and the organic solvent is distilled off under reduced pressure to obtain a graphene/epoxy resin composite. Then, an epoxy resin curing agent, an accelerator, and a micron silver sheet are sequentially added and heat-cured at 150 ° C for 3 hours to obtain the graphene polymer composite material, that is, a graphene/epoxy conductive composite material.
  • the amount of the raw materials used is as follows:
  • the graphene has a mass of 0.5 to 10% by weight of the epoxy resin.
  • the accelerator is 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ) -CN), or a mixture of one or more of methylimidazole.
  • the amount of the raw material by weight is preferably as follows:
  • the invention adopts natural graphite as a starting material, firstly obtains an alkylated or acylated modified graphite at the edge of the graphite by a Friedel-Crafts reaction, and the functionalized graphite is easily dispersed uniformly by physical means such as ultrasound.
  • a stable graphene suspension is formed in the organic solvent.
  • the epoxy resin is added to the graphene suspension to dissolve, ultrasonically mixed to form the initial nanocomposite, and finally the epoxy resin curing agent, the accelerator and the micron silver flake are added to prepare the conductive graphene filled epoxy resin with high conductivity. Nanocomposites.
  • the invention firstly prepares an edge-functionalized graphene, and then uses it as a nano-filler to be added into an epoxy resin to prepare a conductive nano-composite. Compared with the prior art, the invention has the following advantages:
  • the present invention does not use a redox reaction to prepare graphene, but through a Friedel-Craft reaction, only an organic functional group is embedded at the edge of the graphite, and the graphite layer is mutually interacted by a simple physical means by affinity between the functional group and the organic solvent. Sliding away, the graphene is obtained, and the main structure of the graphene itself is not damaged, so the performance is maintained.
  • the obtained edge functionalized graphene has a strong interaction between the functional groups at the edges and the polymer matrix, which can promote the dispersion of graphene in the polymer matrix, reduce the degree of agglomeration, and enhance the interfacial properties of the composite.
  • the parts by weight of the raw materials are as follows:
  • the epoxy resin, the curing agent, 2E4MZ-CN and the silver flakes were stirred and mixed uniformly, and cured at 150 ° C for 3 h to obtain an epoxy conductive paste.
  • the resistance is tested using a low resistance test system and its volume resistivity is calculated. Volume resistivity is 5.2x10-4 Ohm•cm.
  • the resistance is tested using a low resistance test system and its volume resistivity is calculated.
  • the volume resistivity is 3.9x10-4 Ohm•cm.
  • the modified graphite is ultrasonically dispersed in an acetonitrile solvent at an initial solubility of 1 mg/ml, and an epoxy resin is added, ultrasonically mixed uniformly, and acetonitrile is distilled off under reduced pressure, and a curing agent, a promoter, a silver plate are sequentially added, and the mixture is uniformly stirred. Curing at 150 ° C / 3 h to obtain an epoxy conductive paste.
  • the resistance is tested using a low resistance test system and its volume resistivity is calculated.
  • the volume resistivity is 1.4x10-4 Ohm•cm.
  • the modified graphite is ultrasonically dispersed in an ethanol solvent at a initial solubility of 5 mg/ml, epoxy resin is added, ultrasonically mixed uniformly, ethanol is distilled off under reduced pressure, and a curing agent, a promoter, a silver plate are sequentially added, and the mixture is uniformly stirred. Curing at 150 ° C / 3 h to obtain an epoxy conductive paste.
  • the resistance is tested using a low resistance test system and its volume resistivity is calculated.
  • the volume resistivity is 2.4 x 10 -4 Ohm•cm.
  • the modified graphite is ultrasonically dispersed in an ethanol solvent at an initial solubility of 0.01 mg/ml, epoxy resin is added, ultrasonically mixed uniformly, ethanol is distilled off under reduced pressure, and a curing agent, a promoter, a silver plate are sequentially added, and the mixture is uniformly stirred. Curing at 150 ° C / 3 h to obtain an epoxy conductive paste.
  • the resistance is tested using a low resistance test system and its volume resistivity is calculated.
  • the volume resistivity is 2.2x10-4 Ohm•cm.
  • the modified graphite was ultrasonically dispersed in a dichloromethane solvent at a initial solubility of 2 mg/ml, epoxy resin was added, ultrasonically mixed uniformly, dichloromethane was distilled off under reduced pressure, and a curing agent, a promoter, and a silver flake were sequentially added. Stir well and cure at 150 ° C / 3 h to obtain epoxy conductive adhesive.
  • the resistance is tested using a low resistance test system and its volume resistivity is calculated.
  • the volume resistivity is 8.9 x 10-5 Ohm•cm.
  • the epoxy conductive adhesive of the modified graphene added has a significantly improved electrical conductivity compared with the epoxy conductive adhesive without graphene, which indicates the structure of the graphene itself prepared by the method.
  • the preservation is relatively intact, has not been damaged to a large extent, and the functionalized graphene has an interaction between the organic group at the edge and the resin matrix, and the graphene is uniformly dispersed in the composite material, thereby maximally exerting its own excellentness.
  • the physical properties of the composite material are significantly improved.

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Abstract

Provided are methods for preparing a functionalized graphene and the composite electroconductive glue thereof. The method for preparing a functionalized graphene comprising: using natural graphite as a raw material to obtain modified graphite by Friedel-Crafts reaction, after extracting and purifying, then uniformly dispersing the modified graphite into an organic solvent by ultrasonic, so as to form a stable graphene suspension. The method for preparing the composite electroconductive glue comprises: adding epoxy resin to the above-mentioned graphene suspension to dissolve under stirring, and mixing uniformly by ultrasonic, carrying out reduced pressure distillation to remove the organic solvent, successively adding an epoxy resin curing agent, an accelerator and micron silver slices, after heat curing, the graphene polymer composite is obtained, i.e. a graphene/epoxy resin electroconductive glue. The edge functionalized graphene prepared by the method has a strong interaction between the functional groups at the edge and the polymer matrix, promotes the dispersion of graphene in the polymer matrix, reduces the degree of agglomeration, and enhances the interface properties of the composite material.

Description

一种功能化石墨烯及其复合材料的制备方法 Method for preparing functionalized graphene and composite material thereof
技术领域Technical field
本发明涉及一种功能化石墨制备石墨烯的方法，具体涉及一种功能化石墨烯及其复合材料的制备方法。  The invention relates to a method for preparing graphene by functionalized graphite, in particular to a method for preparing functionalized graphene and a composite material thereof.
背景技术Background technique
2004 年, 英国曼彻斯特大学的Geim研究小组首次制备出稳定的石墨烯，掀起了石墨烯的研究热潮。理想的石墨烯结构结构为sp2 杂化碳原子形成的类六元环苯单元并无限扩展的二维晶体材料，是目前世界上最薄的单原子层厚度的材料。石墨烯不仅有优异的电学性能(室温下电子迁移率可达2×105cm2/(V•s))，突出的导热性能(5000 W/(m•K)), 超常的比表面积(2630 m2/g)，也有可与碳纳米管媲美的杨氏模量(1100 GPa)和断裂强度(125 GPa), 另外, 石墨烯还具有室温量子霍尔效应(Hall effect)及室温铁磁性等特殊性质。石墨烯的制备主要有物理方法和化学方法。物理方法通常是以廉价的石墨或膨胀石墨为原料, 通过微机械剥离法、液相或气相直接剥离法来制备单层或多层石墨烯。另外一种则是制备石墨烯常用的氧化石墨-还原法，它是石墨先经强酸氧化得到含有环氧及羰基等含氧基团的氧化石墨，再通过外力剥离得到氧化石墨烯, 进一步还原制备得到高产量石的还原墨烯。但是这种方法由于经过了强酸氧化过程，对原有石墨杂化结构破坏程度非常大，即使经过化学还原或高温热处理还原也无法达到程度较大的程度，这直接较大程度的影响了所得石墨烯本身应具有的一系列特殊性能。year 2004, The Geim research team at the University of Manchester in the United Kingdom first produced stable graphene, which set off a research boom in graphene. The ideal graphene structure is sp2 A two-dimensional crystalline material of a six-membered cyclic benzene unit formed by hybrid carbon atoms and infinitely expanding is the world's thinnest single-atom layer thickness material. Graphene not only has excellent electrical properties (electron mobility at room temperature up to 2 × 105cm2 / (V • s)), outstanding thermal conductivity (5000 W/(m•K)), an extraordinary specific surface area (2630 m2/g), and a Young's modulus (1100 GPa) and a breaking strength (125 GPa) comparable to those of carbon nanotubes. Graphene also has a room temperature quantum Hall effect (Hall Effect) and special properties such as room temperature ferromagnetism. The preparation of graphene mainly includes physical methods and chemical methods. Physical methods are usually based on cheap graphite or expanded graphite. Single or multiple layers of graphene are prepared by micromechanical stripping, liquid or gas phase direct stripping. The other is a graphite oxide-reduction method commonly used in the preparation of graphene, which is obtained by oxidation of a strong acid to obtain an oxide group containing an epoxy group such as an epoxy group and a carbonyl group, and then exfoliating to obtain graphene oxide by external force. Further reduction produces a reduced yield of high yield stone. However, this method has a great degree of damage to the original graphite hybrid structure due to the strong acid oxidation process, and even if it is reduced by chemical reduction or high-temperature heat treatment, it can not reach a large extent, which directly affects the obtained graphite to a large extent. The alkene itself should have a range of special properties.
由于石墨烯具有优异的力学性能和电学性能，在作为聚合物基体的功能增强Due to its excellent mechanical and electrical properties, graphene has enhanced function as a polymer matrix.
方面被认为具有广泛的研究前景。在聚合物纳米复合材料的制备过程中，要使复合材料的性能达到最大化的体现，不仅与纳米填料本身优异的性能有关，更重要的是纳米填料在聚合物基体中的分散程度及界面化学性质等方面。因此，通过共价和非共价的方法来修饰纳米填料的表面，使其在聚合物基体中达到均匀的分散一直是人们努力的目标。Aspects are considered to have broad research prospects. In the preparation process of polymer nanocomposites, the performance of the composite material should be maximized, which is not only related to the excellent performance of the nanofiller itself, but more importantly, the dispersion degree and interface chemistry of the nanofiller in the polymer matrix. Nature and other aspects. Therefore, it has been an effort to modify the surface of nanofillers by covalent and non-covalent methods to achieve uniform dispersion in the polymer matrix.
发明内容Summary of the invention
本发明的目的在于克服现有技术存在的上述不足，提供一种功能化石墨烯及其复合材料的制备方法，具体技术方案如下。The object of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a method for preparing functionalized graphene and a composite material thereof, and the specific technical solutions are as follows.
一种功能化石墨烯的制备方法，该方法以天然石墨为原料，通过傅克（Friedel-Crafts）反应，得到改性石墨，将所得改性石墨经过抽提纯化，再通过超声均匀分散在有机溶剂中形成稳定的石墨烯悬浮液。A method for preparing functionalized graphene, which uses natural graphite as a raw material to obtain modified graphite by Friedel-Crafts reaction, and the obtained modified graphite is extracted and purified, and then uniformly dispersed in the organic by ultrasonic. A stable graphene suspension is formed in the solvent.
上述的功能化石墨烯的制备方法中，所述傅克（Friedel-Crafts）反应即将石墨，酸酐化合物或酰卤或卤代烷中一种化合物，和催化剂混合，在机械力搅拌作用下，在50~150℃加热反应5~72h。In the above method for preparing functionalized graphene, the Friedel-Crafts reaction is a mixture of graphite, an acid anhydride compound or an acid halide or a halogenated alkane, and a catalyst, under mechanical stirring, at 50~. The reaction was heated at 150 ° C for 5 to 72 hours.
上述的功能化石墨烯的制备方法中，所述酸酐化合物或酰卤或卤代烷为对氨基苯甲酸，间氨基苯甲酸，3,5-二氨基苯甲酸，4-氨基-3-羟基苯甲酸，2-氨基-4-氯苯甲酸，2-氨基-5-甲基苯甲酸，苯甲酰氯，对苯二甲酰氯，邻氯苯甲酰氯，对氯苯甲酰氯，邻氯苯酚，对氯苯酚，邻氯苯胺，4-氯苯胺中的一种；所述催化剂为氯化铁，氯化铝，氯化锌，磷酸，多聚磷酸，氢氟酸，硫酸，硼酸，盐酸中的一种。In the above method for preparing functionalized graphene, the acid anhydride compound or acid halide or halogenated alkane is p-aminobenzoic acid, m-aminobenzoic acid, 3,5-diaminobenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-amino-4-chlorobenzoic acid, 2-amino-5-methylbenzoic acid, benzoyl chloride, terephthaloyl chloride, o-chlorobenzoyl chloride, p-chlorobenzoyl chloride, o-chlorophenol, p-chlorophenol And one of o-chloroaniline and 4-chloroaniline; the catalyst is one of ferric chloride, aluminum chloride, zinc chloride, phosphoric acid, polyphosphoric acid, hydrofluoric acid, sulfuric acid, boric acid, and hydrochloric acid.
上述的功能化石墨烯的制备方法中，所述有机溶剂为乙醇，丙酮，乙腈，二氯甲烷，四氢呋喃，N,N-二甲基甲酰胺，N-甲基吡咯烷酮中的一种。In the above method for producing functionalized graphene, the organic solvent is one of ethanol, acetone, acetonitrile, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, and N-methylpyrrolidone.
上述的功能化石墨烯的制备方法中，所述石墨与卤代烷或酰卤或酸酐质量比例为5:1~1:5；所述石墨烯悬浮液溶度为0.01mg/ml~5mg/ml。In the above method for preparing functionalized graphene, the mass ratio of the graphite to the halogenated alkane or the acid halide or the acid anhydride is 5:1 to 1:5; and the solubility of the graphene suspension is 0.01 mg/ml to 5 mg/ml.
本发明的石墨烯聚合物复合材料的制备方法，其将环氧树脂加入所述石墨烯悬浮液中搅拌溶解，超声混合均匀，减压蒸馏除去所述有机溶剂得到石墨烯/环氧树脂复合物，依次加入环氧树脂固化剂，促进剂，微米银片，在150℃加热固化3h后，得到所述的石墨烯聚合物复合材料，即石墨烯/环氧树脂导电复合材料。A method for preparing a graphene polymer composite material according to the present invention, wherein an epoxy resin is added to the graphene suspension to be stirred and dissolved, ultrasonically mixed uniformly, and the organic solvent is distilled off under reduced pressure to obtain a graphene/epoxy resin composite. Then, an epoxy resin curing agent, an accelerator, and a micron silver sheet are sequentially added and heat-cured at 150 ° C for 3 hours to obtain the graphene polymer composite material, that is, a graphene/epoxy conductive composite material.
上述的石墨烯聚合物复合材料的制备方法中，所述原料重量份数用量如下：In the above preparation method of the graphene polymer composite material, the amount of the raw materials used is as follows:
环氧树脂 100份Epoxy resin 100 parts
固化剂 50～90份Curing agent 50 to 90 parts
促进剂 1～5 份Promoter 1~5 parts
石墨烯 0.5～10 份Graphene 0.5 to 10 parts
银片 500～1000份Silver tablets 500 to 1000 copies
上述的石墨烯聚合物复合材料的制备方法中，所述石墨烯质量为环氧树脂的0.5~10wt%。In the above method for preparing a graphene polymer composite, the graphene has a mass of 0.5 to 10% by weight of the epoxy resin.
上述的石墨烯聚合物复合材料的制备方法中，所述促进剂为2-乙基-4-甲基咪唑（2E4MZ）、1-氰乙基-2-乙基-4-甲基咪唑（2E4MZ-CN）、或甲基咪唑中的一种或多种的混合物。In the above method for preparing a graphene polymer composite, the accelerator is 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ) -CN), or a mixture of one or more of methylimidazole.
上述的石墨烯聚合物复合材料的制备方法中，所述原料重量份数用量优选如下：In the above method for preparing a graphene polymer composite material, the amount of the raw material by weight is preferably as follows:
环氧树脂 100份Epoxy resin 100 parts
固化剂 70～90份Curing agent 70 to 90 parts
促进剂 1～3 份Promoter 1~3 parts
石墨烯 0～5 份Graphene 0 to 5 parts
银片 700～800份。Silver tablets 700 to 800 copies.
本发明以天然石墨为初始原料，首先通过傅克（Friedel-Crafts）反应，得到了在石墨边缘处烷基化或酰基化改性石墨，该功能化石墨很容易通过超声等物理手段均匀分散在有机溶剂中形成稳定的石墨烯悬浮液。将环氧树脂加入到石墨烯悬浮液中溶解，超声混合均匀形成初始纳米复合物，最后加入环氧树脂固化剂，促进剂及微米银片，制备得到高导电性能的填充石墨烯环氧树脂导电纳米复合材料。The invention adopts natural graphite as a starting material, firstly obtains an alkylated or acylated modified graphite at the edge of the graphite by a Friedel-Crafts reaction, and the functionalized graphite is easily dispersed uniformly by physical means such as ultrasound. A stable graphene suspension is formed in the organic solvent. The epoxy resin is added to the graphene suspension to dissolve, ultrasonically mixed to form the initial nanocomposite, and finally the epoxy resin curing agent, the accelerator and the micron silver flake are added to prepare the conductive graphene filled epoxy resin with high conductivity. Nanocomposites.
本发明首先制备了一种边缘功能化的石墨烯，然后将其作为纳米填料，加入到环氧树脂中制备导电纳米复合材料。本发明与现有技术相比具有如下优点：The invention firstly prepares an edge-functionalized graphene, and then uses it as a nano-filler to be added into an epoxy resin to prepare a conductive nano-composite. Compared with the prior art, the invention has the following advantages:
（1）本发明不采用氧化还原反应制备石墨烯，而是通过傅克反应，只在石墨边缘处嵌入有机官能团，通过官能团和有机溶剂之间的亲和性，简单物理手段使石墨层间相互滑离，得到石墨烯，石墨烯本身的主体结构未受到破坏，因此性能得以维持。(1) The present invention does not use a redox reaction to prepare graphene, but through a Friedel-Craft reaction, only an organic functional group is embedded at the edge of the graphite, and the graphite layer is mutually interacted by a simple physical means by affinity between the functional group and the organic solvent. Sliding away, the graphene is obtained, and the main structure of the graphene itself is not damaged, so the performance is maintained.
（2）所得的边缘功能化石墨烯在边缘处的官能团与聚合物基体之间有着强的相互作用，可以促进石墨烯在聚合物基体中的分散，减少团聚程度，增强复合材料的界面性能。(2) The obtained edge functionalized graphene has a strong interaction between the functional groups at the edges and the polymer matrix, which can promote the dispersion of graphene in the polymer matrix, reduce the degree of agglomeration, and enhance the interfacial properties of the composite.
具体实施方式detailed description
以下结合实例对本发明的具体实施作进一步说明，但本发明的实施和保护范围不限于此。 The specific embodiments of the present invention are further illustrated by the following examples, but the scope of the present invention is not limited thereto.
对比例1：Comparative example 1:
不添加石墨烯,直接制备导电胶:Directly prepare conductive paste without adding graphene:
原料的重量份数如下：The parts by weight of the raw materials are as follows:
环氧树脂 100份Epoxy resin 100 parts
甲基六氢苯酐固化剂 85份 Methyl hexahydrophthalic anhydride curing agent 85 parts
2E4MZ-CN： 1.85份2E4MZ-CN: 1.85 parts
银片： 800 份Silver: 800 copies
将环氧树脂、固化剂、2E4MZ-CN及银片，搅拌混合均匀，在150℃固化3h后得到环氧导电胶。采用低阻测试系统测试其的电阻，并计算其体积电阻率。体积电阻率为5.2x10-4 Ohm•cm。The epoxy resin, the curing agent, 2E4MZ-CN and the silver flakes were stirred and mixed uniformly, and cured at 150 ° C for 3 h to obtain an epoxy conductive paste. The resistance is tested using a low resistance test system and its volume resistivity is calculated. Volume resistivity is 5.2x10-4 Ohm•cm.
实施例1：Example 1:
（1）功能化石墨的制备：将石墨（0.1g），对氨基苯甲酸(0.5g)，无水氯化铝三者混合盛入三口烧瓶中，在机械搅拌作用下,加热90℃反应5h,抽提后得到纯化改性石墨。(1) Preparation of functionalized graphite: Mixing graphite (0.1g), p-aminobenzoic acid (0.5g) and anhydrous aluminum chloride into a three-necked flask, and heating at 90 ° C for 5 h under mechanical stirring. After extraction, purified modified graphite is obtained.
（2）将改性石墨以0.5mg/ml初始溶度超声分散在丙酮溶剂中，加入环氧树脂，超声混合均匀，减压蒸馏除去丙酮，依次加入固化剂，促进剂，银片，搅拌均匀，150℃/3h固化得到环氧导电胶。(2) Ultrasonic dispersion of modified graphite in acetone solvent with initial solubility of 0.5mg/ml, adding epoxy resin, mixing by ultrasonication, distilling off acetone under vacuum, adding curing agent, accelerator, silver plate, and stirring evenly. Curing at 150 ° C / 3 h to obtain an epoxy conductive paste.
上述配置导电胶重量份数：The above configuration of conductive adhesive parts:
环氧树脂 100份Epoxy resin 100 parts
甲基六氢苯酐固化剂 85份Methyl hexahydrophthalic anhydride curing agent 85 parts
2E4MZ-CN 1.85份2E4MZ-CN 1.85
银片 800份Silver tablets 800 copies
石墨烯 0.5份Graphene 0.5 parts
采用低阻测试系统测试其的电阻，并计算其体积电阻率。体积电阻率为3.9x10-4 Ohm•cm。The resistance is tested using a low resistance test system and its volume resistivity is calculated. The volume resistivity is 3.9x10-4 Ohm•cm.
实施例2：Example 2:
（1）功能化石墨的制备：将石墨（0.2g），3,5-二氨基苯甲酸(0.2g)，多聚磷酸/五氧化二磷三者混合盛入三口烧瓶中，在机械搅拌作用下,加热150℃反应72h,抽提后得到纯化改性石墨。(1) Preparation of functionalized graphite: graphite (0.2g), 3,5-diaminobenzoic acid (0.2g), polyphosphoric acid/phosphorus pentoxide were mixed into a three-necked flask for mechanical agitation The reaction was heated at 150 ° C for 72 h, and the purified modified graphite was obtained after extraction.
（2）将改性石墨以1mg/ml初始溶度超声分散在乙腈溶剂中，加入环氧树脂，超声混合均匀，减压蒸馏除去乙腈，依次加入固化剂，促进剂，银片，搅拌均匀，150℃/3h固化得到环氧导电胶。(2) The modified graphite is ultrasonically dispersed in an acetonitrile solvent at an initial solubility of 1 mg/ml, and an epoxy resin is added, ultrasonically mixed uniformly, and acetonitrile is distilled off under reduced pressure, and a curing agent, a promoter, a silver plate are sequentially added, and the mixture is uniformly stirred. Curing at 150 ° C / 3 h to obtain an epoxy conductive paste.
上述配置导电胶重量份数：The above configuration of conductive adhesive parts:
环氧树脂 100份Epoxy resin 100 parts
甲基六氢苯酐固化剂 80份Methyl hexahydrophthalic anhydride curing agent 80 parts
2E4MZ 1份2E4MZ 1 serving
银片 1000份Silver tablets 1000 copies
石墨烯 5份Graphene 5 parts
采用低阻测试系统测试其的电阻，并计算其体积电阻率。体积电阻率为1.4x10-4 Ohm•cm。The resistance is tested using a low resistance test system and its volume resistivity is calculated. The volume resistivity is 1.4x10-4 Ohm•cm.
实施例3：Example 3:
（1）功能化石墨的制备：将石墨（0.4g），对氨基苯甲酸(0.2g)，多聚磷酸/五氧化二磷三者混合盛入三口烧瓶中，在机械搅拌作用下,加热130℃反应48h,抽提后得到纯化改性石墨。(1) Preparation of functionalized graphite: graphite (0.4g), p-aminobenzoic acid (0.2g), polyphosphoric acid/phosphorus pentoxide were mixed into a three-necked flask and heated 130 under mechanical stirring. The reaction was carried out for 48 h at ° C, and the purified modified graphite was obtained after extraction.
（2）将改性石墨以5mg/ml初始溶度超声分散在乙醇溶剂中，加入环氧树脂，超声混合均匀，减压蒸馏除去乙醇，依次加入固化剂，促进剂，银片，搅拌均匀，150℃/3h固化得到环氧导电胶。(2) The modified graphite is ultrasonically dispersed in an ethanol solvent at a initial solubility of 5 mg/ml, epoxy resin is added, ultrasonically mixed uniformly, ethanol is distilled off under reduced pressure, and a curing agent, a promoter, a silver plate are sequentially added, and the mixture is uniformly stirred. Curing at 150 ° C / 3 h to obtain an epoxy conductive paste.
上述配置导电胶重量份数：The above configuration of conductive adhesive parts:
环氧树脂 100份Epoxy resin 100 parts
甲基六氢苯酐固化剂 85份Methyl hexahydrophthalic anhydride curing agent 85 parts
2E4MZ-CN 1.85份2E4MZ-CN 1.85
银片 500份Silver tablets 500 copies
石墨烯 1份Graphene 1 part
采用低阻测试系统测试其的电阻，并计算其体积电阻率。体积电阻率为2.4x10-4 Ohm•cm。The resistance is tested using a low resistance test system and its volume resistivity is calculated. The volume resistivity is 2.4 x 10 -4 Ohm•cm.
实施例4：Example 4:
（1）功能化石墨的制备：将石墨（0.5g），苯甲酰氯(0.1g)，无水氯化铝三者混合盛入三口烧瓶中，在机械搅拌作用下,加热100℃反应48h,抽提后得到纯化改性石墨。(1) Preparation of functionalized graphite: Mixing graphite (0.5g), benzoyl chloride (0.1g) and anhydrous aluminum chloride into a three-necked flask, and heating at 100 ° C for 48 hours under mechanical stirring. Purified modified graphite was obtained after extraction.
（2）将改性石墨以0.01mg/ml初始溶度超声分散在乙醇溶剂中，加入环氧树脂，超声混合均匀，减压蒸馏除去乙醇，依次加入固化剂，促进剂，银片，搅拌均匀，150℃/3h固化得到环氧导电胶。(2) The modified graphite is ultrasonically dispersed in an ethanol solvent at an initial solubility of 0.01 mg/ml, epoxy resin is added, ultrasonically mixed uniformly, ethanol is distilled off under reduced pressure, and a curing agent, a promoter, a silver plate are sequentially added, and the mixture is uniformly stirred. Curing at 150 ° C / 3 h to obtain an epoxy conductive paste.
上述配置导电胶重量份数：The above configuration of conductive adhesive parts:
环氧树脂 100份Epoxy resin 100 parts
甲基六氢苯酐固化剂 85份Methyl hexahydrophthalic anhydride curing agent 85 parts
甲基咪唑 3份Methylimidazole 3 parts
银片 700份Silver tablets 700
石墨烯 3份Graphene 3 parts
采用低阻测试系统测试其的电阻，并计算其体积电阻率。体积电阻率为2.2x10-4 Ohm•cm。The resistance is tested using a low resistance test system and its volume resistivity is calculated. The volume resistivity is 2.2x10-4 Ohm•cm.
实施例5：Example 5:
（1）功能化石墨的制备：将石墨（0.2g），邻氯苯胺(0.4g)，氯化铁三者混合盛入三口烧瓶中，在机械搅拌作用下,加热50℃反应72h,抽提后得到纯化改性石墨。(1) Preparation of functionalized graphite: graphite (0.2g), o-chloroaniline (0.4g), and ferric chloride were mixed into a three-necked flask, and heated at 50 ° C for 72 h under mechanical stirring. The purified modified graphite is obtained.
（2）将改性石墨以2mg/ml初始溶度超声分散在二氯甲烷溶剂中，加入环氧树脂，超声混合均匀，减压蒸馏除去二氯甲烷，依次加入固化剂，促进剂，银片，搅拌均匀，150℃/3h固化得到环氧导电胶。(2) The modified graphite was ultrasonically dispersed in a dichloromethane solvent at a initial solubility of 2 mg/ml, epoxy resin was added, ultrasonically mixed uniformly, dichloromethane was distilled off under reduced pressure, and a curing agent, a promoter, and a silver flake were sequentially added. Stir well and cure at 150 ° C / 3 h to obtain epoxy conductive adhesive.
上述配置导电胶重量份数：The above configuration of conductive adhesive parts:
环氧树脂 100份Epoxy resin 100 parts
甲基六氢苯酐固化剂 85份Methyl hexahydrophthalic anhydride curing agent 85 parts
甲基咪唑 1份Methylimidazole 1 part
银片 500份Silver tablets 500 copies
石墨烯 10份Graphene 10 parts
采用低阻测试系统测试其的电阻，并计算其体积电阻率。体积电阻率为8.9x10-5 Ohm•cm。The resistance is tested using a low resistance test system and its volume resistivity is calculated. The volume resistivity is 8.9 x 10-5 Ohm•cm.
通过比较对比例可以发现，加入了制备的改性石墨烯的环氧导电胶比未加入石墨烯的环氧导电胶，导电性能均得到了明显的提高，这说明该方法制备的石墨烯本身结构保存较完整，未受到较大程度破坏，而且功能化石墨烯在边缘处的有机基团与树脂基体之间存在相互作用，石墨烯在复合材料中分散均匀，从而最大化地发挥出其本身优异的物理性能，使得复合材料导电性明显提高。By comparing the comparative examples, it can be found that the epoxy conductive adhesive of the modified graphene added has a significantly improved electrical conductivity compared with the epoxy conductive adhesive without graphene, which indicates the structure of the graphene itself prepared by the method. The preservation is relatively intact, has not been damaged to a large extent, and the functionalized graphene has an interaction between the organic group at the edge and the resin matrix, and the graphene is uniformly dispersed in the composite material, thereby maximally exerting its own excellentness. The physical properties of the composite material are significantly improved.

Claims (10)

  1. 一种功能化石墨烯的制备方法，其特征在于以天然石墨为原料，通过傅克反应，得到改性石墨，将所得改性石墨经过抽提纯化，再通过超声均匀分散在有机溶剂中形成稳定的石墨烯悬浮液。 A method for preparing functionalized graphene, characterized in that natural graphite is used as a raw material, and modified graphite is obtained by a Friedel-Craft reaction, and the obtained modified graphite is extracted and purified, and then uniformly dispersed in an organic solvent by ultrasonic to form a stable Graphene suspension.
  2. 根据权利要求1所述的功能化石墨烯的制备方法，其特征在于所述傅克（Friedel-Crafts）反应即将石墨，酸酐化合物或酰卤或卤代烷中一种化合物，和催化剂混合，在机械力搅拌作用下， 在50~150℃加热反应5~72h。The method for preparing functionalized graphene according to claim 1, wherein the Friedel-Crafts reaction is a combination of graphite, an acid anhydride compound or an acid halide or a halogenated alkane, and a catalyst, in mechanical force. Under stirring, Heat the reaction at 50~150 °C for 5~72h.
  3. 根据权利要求2所述的功能化石墨烯的制备方法，其特征在于所述酸酐化合物或酰卤或卤代烷为对氨基苯甲酸，间氨基苯甲酸，3,5-二氨基苯甲酸，4-氨基-3-羟基苯甲酸，2-氨基-4-氯苯甲酸，2-氨基-5-甲基苯甲酸，苯甲酰氯，对苯二甲酰氯，邻氯苯甲酰氯，对氯苯甲酰氯，邻氯苯酚，对氯苯酚，邻氯苯胺，4-氯苯胺中的一种；所述催化剂为氯化铁，氯化铝，氯化锌，磷酸，多聚磷酸，氢氟酸，硫酸，硼酸，盐酸中的一种。 The method for preparing functionalized graphene according to claim 2, wherein the acid anhydride compound or acid halide or halogenated alkane is p-aminobenzoic acid, m-aminobenzoic acid, 3,5-diaminobenzoic acid, 4-amino group. 3-hydroxybenzoic acid, 2-amino-4-chlorobenzoic acid, 2-amino-5-methylbenzoic acid, benzoyl chloride, terephthaloyl chloride, o-chlorobenzoyl chloride, p-chlorobenzoyl chloride, One of o-chlorophenol, p-chlorophenol, o-chloroaniline, 4-chloroaniline; the catalyst is ferric chloride, aluminum chloride, zinc chloride, phosphoric acid, polyphosphoric acid, hydrofluoric acid, sulfuric acid, boric acid One of hydrochloric acid.
  4. 根据权利要求1所述的功能化石墨烯的制备方法，其特征在于所述有机溶剂为乙醇，丙酮，乙腈，二氯甲烷，四氢呋喃，N,N-二甲基甲酰胺，N-甲基吡咯烷酮中的一种。The method for preparing functionalized graphene according to claim 1, wherein the organic solvent is ethanol, acetone, acetonitrile, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, and N-methylpyrrolidone. One of them.
  5. 根据权利要求2所述的功能化石墨烯的制备方法，其特征在于所述石墨与卤代烷或酰卤或酸酐质量比例为5:1~1:5；所述石墨烯悬浮液溶度为0.01mg/ml~5mg/ml。The method for preparing functionalized graphene according to claim 2, wherein the mass ratio of the graphite to the halogenated alkane or the acid halide or the acid anhydride is 5:1 to 1:5; and the solubility of the graphene suspension is 0.01 mg. /ml~5mg/ml.
  6. 石墨烯聚合物复合材料的制备方法，其特征在于将环氧树脂加入权利要求1所述石墨烯悬浮液中搅拌溶解，超声混合均匀，减压蒸馏除去所述有机溶剂得到石墨烯/环氧树脂复合物，依次加入环氧树脂固化剂，促进剂，微米银片，150℃加热固化3h后，得到所述的石墨烯聚合物复合材料，即石墨烯/环氧树脂导电复合材料。 A method for preparing a graphene polymer composite material, characterized in that an epoxy resin is added to a graphene suspension according to claim 1 to be stirred and dissolved, ultrasonically mixed uniformly, and the organic solvent is distilled off under reduced pressure to obtain a graphene/epoxy resin. The composite, which is sequentially added with an epoxy resin curing agent, a promoter, and a micron silver sheet, is cured by heating at 150 ° C for 3 hours to obtain the graphene polymer composite material, that is, a graphene/epoxy conductive composite material.
  7. 根据权利要求6所述的石墨烯聚合物复合材料的制备方法，其特征在于所述原料重量份数用量如下：The method for preparing a graphene polymer composite according to claim 6, wherein the raw materials are used in the following amounts by weight:
    环氧树脂 100份Epoxy resin 100 parts
    固化剂 50～90份Curing agent 50 to 90 parts
    促进剂 1～5 份Promoter 1~5 parts
    石墨烯 0.5～10 份Graphene 0.5 to 10 parts
    银片 500～1000份 。 Silver tablets 500 to 1000 copies.
  8. 根据权利要求6所述的石墨烯聚合物复合材料的制备方法，其特征在于所述石墨烯质量为环氧树脂的0.5~10wt%。The method for preparing a graphene polymer composite according to claim 6, wherein the graphene has a mass of 0.5 to 10% by weight of the epoxy resin.
  9. 根据权利要求6所述的石墨烯聚合物复合材料的制备方法，其特征在于所述促进剂为2-乙基-4-甲基咪唑（2E4MZ）、1-氰乙基-2-乙基-4-甲基咪唑（2E4MZ-CN）、或甲基咪唑中的一种或多种的混合物。 The method for preparing a graphene polymer composite according to claim 6, wherein the promoter is 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl- A mixture of one or more of 4-methylimidazole (2E4MZ-CN), or methylimidazole.
  10. 根据权利要求8所述的石墨烯聚合物复合材料的制备方法，其特征在于所述原料重量份数用量如下：The method for preparing a graphene polymer composite according to claim 8, wherein the raw materials are used in the following amounts by weight:
    环氧树脂 100份Epoxy resin 100 parts
    固化剂 70～90份Curing agent 70 to 90 parts
    促进剂 1～3 份Promoter 1~3 parts
    石墨烯 0～5 份Graphene 0 to 5 parts
    银片 700～800份。Silver tablets 700 to 800 copies.
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