CN102862976A - Method for preparing functionalized graphene and composite material of functionalized graphene - Google Patents
Method for preparing functionalized graphene and composite material of functionalized graphene Download PDFInfo
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Abstract
The invention discloses a method for preparing functionalized graphene and a composite material of the functionalized graphene. The method for preparing the functionalized graphene comprises the following steps of: performing Friedel-Crafts reaction on natural graphite which is taken as a raw material to obtain modified graphite, extracting, purifying, and uniformly dispersing in an organic solvent with ultrasonic to form stable graphene suspension liquid. The method for preparing the composite material comprises the following steps of: adding epoxy resin into the graphene suspension liquid, stirring for dissolving, uniformly mixing with ultrasonic, distilling under reduced pressure to remove the organic solvent to obtain a graphene/epoxy resin composite; and adding an epoxy resin curing agent, an accelerant and micrometer silver sheets sequentially, and heating for curing to obtain the composite material of a graphene polymer, namely a graphene/epoxy resin conducting composite material. The edge functionalized graphene has a high interaction between functional groups at the edge and a polymer matrix, so that the dispersion of the graphene in the polymer matrix can be promoted, the agglomeration degree can be reduced, and the interface performance of the composite material can be enhanced.
Description
Technical field
The present invention relates to a kind of method of functionalization preparing graphite alkene, be specifically related to a kind of functionalization graphene and composite manufacture method thereof.
Background technology
2004, the Geim research group of Univ Manchester UK prepared stable Graphene first, has started the research boom of Graphene.Desirable graphene-structured structure is the class six-ring benzene unit of sp2 hydridization carbon atom formation and the two dimensional crystal material of infinite expanding, is the present in the world material of the thinnest monoatomic layer thickness.Graphene not only has excellent electric property, and (electronic mobility can reach 2 * 10 under the room temperature
5Cm
2/ (Vs)), outstanding heat conductivility (5000 W/ (mK)), extraordinary specific surface area (2630 m
2/ g), Young's modulus (1100 GPa) and the breaking tenacity (125 GPa) that can match in excellence or beauty with carbon nanotube are arranged also, in addition, Graphene also has the special propertys such as room temperature quantum hall effect (Hall effect) and room-temperature ferromagnetic.The preparation of Graphene mainly contains physical method and chemical process.Physical method normally take the graphite of cheapness or expanded graphite as raw material, prepares the single or multiple lift Graphene by the direct stripping method of micromechanics stripping method, liquid phase or gas phase.Another then is preparation Graphene graphite oxide-reduction method commonly used, it is graphite obtains containing first the oxy radicals such as epoxy and carbonyl through the strong acid oxidation graphite oxide, peel off by external force and obtain graphene oxide, further reduction prepares the reduction China ink alkene of high yield stone.But this method is owing to having passed through the strong acid oxidising process, very large to original graphite hybrid structure destructiveness, even also can't reach more degree through chemical reduction or high-temperature heat treatment reduction, this has directly affected a series of properties that gained Graphene itself should have largely.
Because Graphene has excellent mechanical property and electric property, in the increased functionality as polymeric matrix
The aspect is considered to have widely Research Prospects.In the preparation process of polymer nanocomposites, make the performance of matrix material reach maximized embodiment, not only relevant with the excellent performance of Nano filling itself, the more important thing is degree of scatter and the aspect such as interfacial chemistry character of Nano filling in polymeric matrix.Therefore, come the surface of decorated nanometer filler by covalency and non-covalent method, make it reach uniform dispersion in polymeric matrix is the target that people make great efforts always.
Summary of the invention
The object of the invention is to overcome the prior art above shortcomings, a kind of functionalization graphene and composite manufacture method thereof are provided, concrete technical scheme is as follows.
A kind of preparation method of functionalization graphene, the method by Fu Ke (Friedel-Crafts) reaction, obtains modified graphite take natural graphite as raw material, the gained modified graphite through extracting and purifying, is dispersed in the stable graphene suspension of formation in the organic solvent by ultrasonic again.
Among the preparation method of above-mentioned functionalization graphene, described Fu Ke (Friedel-Crafts) reaction is about to graphite, a kind of compound in anhydride compound or carboxylic acid halides or the haloalkane, and catalyst mix, under the mechanical force stirring action, at 50 ~ 150 ℃ of reacting by heating 5 ~ 72h.
Among the preparation method of above-mentioned functionalization graphene, described anhydride compound or carboxylic acid halides or haloalkane are para-amino benzoic acid, gavaculine, 3,5-diaminobenzoic acid, 4-amino-3-hydroxy formic acid, 2-amino-4-chloro-benzoic acid, 2-amino-5-tolyl acid, Benzoyl chloride, p-phthaloyl chloride, o-chlorobenzoyl chloride, parachlorobenzoyl chloride, ortho chloro phenol, para-chlorophenol, Ortho-Chloro aniline, a kind of in the 4-chloroaniline; Described catalyzer is iron(ic) chloride, aluminum chloride, zinc chloride, phosphoric acid, polyphosphoric acid, hydrofluoric acid, sulfuric acid, boric acid, a kind of in the hydrochloric acid.
Among the preparation method of above-mentioned functionalization graphene, described organic solvent is ethanol, acetone, acetonitrile, methylene dichloride, tetrahydrofuran (THF), DMF, a kind of in the N-Methyl pyrrolidone.
Among the preparation method of above-mentioned functionalization graphene, described graphite and haloalkane or carboxylic acid halides or acid anhydrides mass ratio are 5:1 ~ 1:5; Described graphene suspension solubility is 0.01mg/ml ~ 5mg/ml.
The preparation method of Graphene polymer composites of the present invention, it adds stirring and dissolving in the described graphene suspension with Resins, epoxy, ultrasonic mixing, underpressure distillation is removed described organic solvent and is obtained Graphene/epoxy resin composite, adds successively epoxy curing agent, promotor, the micron silver strip, behind 150 ℃ of 3h that are heating and curing, obtain described Graphene polymer composites, i.e. Graphene/Resins, epoxy conducing composite material.
Among the preparation method of above-mentioned Graphene polymer composites, described raw material weight umber consumption is as follows:
100 parts of Resins, epoxy
50～90 parts in solidifying agent
1～5 part of promotor
0.5～10 part of Graphene
500～1000 parts of silver strips
Among the preparation method of above-mentioned Graphene polymer composites, described Graphene quality is 0.5 ~ 10wt% of Resins, epoxy.
Among the preparation method of above-mentioned Graphene polymer composites, described promotor is one or more the mixture in 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) or the Methylimidazole.
Among the preparation method of above-mentioned Graphene polymer composites, described raw material weight umber consumption is preferably as follows:
100 parts of Resins, epoxy
70～90 parts in solidifying agent
1～3 part of promotor
0.5～5 part of Graphene
700～800 parts of silver strips.
The present invention is take natural graphite as initial feed; at first by Fu Ke (Friedel-Crafts) reaction; obtained at the alkylation of graphite edge or acylations modified graphite, this functionalization graphite is easy to be dispersed in the stable graphene suspension of formation in the organic solvent by the ultrasonic physical means that waits.Resins, epoxy joined in the graphene suspension dissolve, ultrasonic mixing forms initial nano-complex, add at last epoxy curing agent, promotor and micron silver strip prepare the filling Graphene Resins, epoxy conductive nano composite material of high conduction performance.
The present invention has at first prepared a kind of Graphene of limbic function, then with it as Nano filling, join and prepare conductive nano composite material in the Resins, epoxy.The present invention compared with prior art has following advantage:
(1) the present invention does not adopt redox reaction to prepare Graphene, but pass through Friedel-Crafts reaction, only embed organo-functional group in graphite edge, by the affinity between functional group and the organic solvent, the simple physical means slip away graphite layers mutually, obtain Graphene, the agent structure of Graphene itself is not damaged, so performance is maintained.
(2) the limbic function functionalized graphene of gained has strong interaction between the functional group of edge and polymeric matrix, can promote the dispersion of Graphene in polymeric matrix, reduces the reunion degree, the interface performance of reinforced composite.
Embodiment
Below in conjunction with example implementation of the present invention is described further, but enforcement of the present invention and protection domain are not limited to this.
Comparative Examples 1:
Do not add Graphene, directly prepare conductive resin:
The parts by weight of raw material are as follows:
100 parts of Resins, epoxy
85 parts in methyl hexahydrophthalic anhydride solidifying agent
2E4MZ-CN:1.85 part
Silver strip: 800 parts
With Resins, epoxy, solidifying agent, 2E4MZ-CN and silver strip, mix, behind 150 ℃ of curing 3h, obtain epoxy conducting.Adopt its resistance of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 5.2x10
-4Ohmcm.
Embodiment 1:
(1) preparation of functionalization graphite: with graphite (0.1g), para-amino benzoic acid (0.5g), the Aluminum chloride anhydrous three mixes Sheng and enters in the there-necked flask, under mechanical agitation, heats 90 ℃ of reaction 5h, obtains the purifying modified graphite after the extracting.
(2) with modified graphite with the initial solubility ultra-sonic dispersion of 0.5mg/ml in acetone solvent, add Resins, epoxy, ultrasonic mixing, acetone is removed in underpressure distillation, adds successively solidifying agent, promotor, silver strip stirs, and 150 ℃/3h curing obtains epoxy conducting.
Above-mentioned configuration conductive resin parts by weight:
100 parts of Resins, epoxy
85 parts in methyl hexahydrophthalic anhydride solidifying agent
1.85 parts of 2E4MZ-CN
800 parts of silver strips
0.5 part of Graphene
Adopt its resistance of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 3.9x10
-4Ohmcm.
Embodiment 2:
(1) preparation of functionalization graphite: with graphite (0.2g), 3,5-diaminobenzoic acid (0.2g), polyphosphoric acid/Vanadium Pentoxide in FLAKES three mixes Sheng and enters in the there-necked flask, under mechanical agitation, heat 150 ℃ of reaction 72h, obtain the purifying modified graphite after the extracting.
(2) with modified graphite with the initial solubility ultra-sonic dispersion of 1mg/ml in acetonitrile solvent, add Resins, epoxy, ultrasonic mixing, acetonitrile is removed in underpressure distillation, adds successively solidifying agent, promotor, silver strip stirs, 150 ℃/3h solidifies and obtains epoxy conducting.
Above-mentioned configuration conductive resin parts by weight:
100 parts of Resins, epoxy
80 parts in methyl hexahydrophthalic anhydride solidifying agent
1 part of 2E4MZ
1000 parts of silver strips
5 parts of Graphenes
Adopt its resistance of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 1.4x10
-4Ohmcm.
Embodiment 3:
(1) preparation of functionalization graphite: with graphite (0.4g), para-amino benzoic acid (0.2g), polyphosphoric acid/Vanadium Pentoxide in FLAKES three mixes Sheng and enters in the there-necked flask, under mechanical agitation, heat 130 ℃ of reaction 48h, obtain the purifying modified graphite after the extracting.
(2) with modified graphite with the initial solubility ultra-sonic dispersion of 5mg/ml in alcohol solvent, add Resins, epoxy, ultrasonic mixing, ethanol is removed in underpressure distillation, adds successively solidifying agent, promotor, silver strip stirs, 150 ℃/3h solidifies and obtains epoxy conducting.
Above-mentioned configuration conductive resin parts by weight:
100 parts of Resins, epoxy
85 parts in methyl hexahydrophthalic anhydride solidifying agent
1.85 parts of 2E4MZ-CN
500 parts of silver strips
1 part of Graphene
Adopt its resistance of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 2.4x10
-4Ohmcm.
Embodiment 4:
(1) preparation of functionalization graphite: with graphite (0.5g), Benzoyl chloride (0.1g), the Aluminum chloride anhydrous three mixes Sheng and enters in the there-necked flask, under mechanical agitation, heats 100 ℃ of reaction 48h, obtains the purifying modified graphite after the extracting.
(2) with modified graphite with the initial solubility ultra-sonic dispersion of 0.01mg/ml in alcohol solvent, add Resins, epoxy, ultrasonic mixing, ethanol is removed in underpressure distillation, adds successively solidifying agent, promotor, silver strip stirs, and 150 ℃/3h curing obtains epoxy conducting.
Above-mentioned configuration conductive resin parts by weight:
100 parts of Resins, epoxy
85 parts in methyl hexahydrophthalic anhydride solidifying agent
3 parts of Methylimidazoles
700 parts of silver strips
3 parts of Graphenes
Adopt its resistance of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 2.2x10
-4Ohmcm.
Embodiment 5:
(1) preparation of functionalization graphite: with graphite (0.2g), Ortho-Chloro aniline (0.4g), the iron(ic) chloride three mixes Sheng and enters in the there-necked flask, under mechanical agitation, heats 50 ℃ of reaction 72h, obtains the purifying modified graphite after the extracting.
(2) with modified graphite with the initial solubility ultra-sonic dispersion of 2mg/ml in dichloromethane solvent, add Resins, epoxy, ultrasonic mixing, methylene dichloride is removed in underpressure distillation, adds successively solidifying agent, promotor, silver strip stirs, and 150 ℃/3h curing obtains epoxy conducting.
Above-mentioned configuration conductive resin parts by weight:
100 parts of Resins, epoxy
85 parts in methyl hexahydrophthalic anhydride solidifying agent
1 part of Methylimidazole
500 parts of silver strips
10 parts of Graphenes
Adopt its resistance of low-resistance test system and test, and calculate its volume specific resistance.Volume specific resistance is 8.9x10
-5Ohmcm.
Can find by comparing Comparative Examples, added the epoxy conducting of the modified graphene for preparing than the epoxy conducting that does not add Graphene, conductivity all is significantly improved, this body structure of Graphene of this explanation the method preparation is preserved more complete, destroyed largely, and functionalization graphene exists between the organic group of edge and resin matrix and interacts, Graphene is uniformly dispersed in matrix material, thereby given play to substantially the physicals of itself excellence, so that conductivity of composite material obviously improves.
Claims (10)
1. the preparation method of a functionalization graphene, it is characterized in that take natural graphite as raw material, react by Fu Ke (Friedel-Crafts), obtain modified graphite, the gained modified graphite through extracting and purifying, is dispersed in the stable graphene suspension of formation in the organic solvent by ultrasonic again.
2. the preparation method of functionalization graphene according to claim 1, it is characterized in that described Fu Ke (Friedel-Crafts) reaction is about to graphite, a kind of compound in anhydride compound or carboxylic acid halides or the haloalkane, and catalyst mix, under the mechanical force stirring action, at 50 ~ 150 ℃ of reacting by heating 5 ~ 72h.
3. the preparation method of functionalization graphene according to claim 2 is characterized in that described anhydride compound or carboxylic acid halides or haloalkane are para-amino benzoic acid, gavaculine, 3,5-diaminobenzoic acid, 4-amino-3-hydroxy formic acid, 2-amino-4-chloro-benzoic acid, 2-amino-5-tolyl acid, Benzoyl chloride, p-phthaloyl chloride, o-chlorobenzoyl chloride, parachlorobenzoyl chloride, ortho chloro phenol, para-chlorophenol, Ortho-Chloro aniline, a kind of in the 4-chloroaniline; Described catalyzer is iron(ic) chloride, aluminum chloride, zinc chloride, phosphoric acid, polyphosphoric acid, hydrofluoric acid, sulfuric acid, boric acid, a kind of in the hydrochloric acid.
4. the preparation method of functionalization graphene according to claim 1 is characterized in that described organic solvent is ethanol, acetone, acetonitrile, methylene dichloride, tetrahydrofuran (THF), DMF, a kind of in the N-Methyl pyrrolidone.
5. the preparation method of functionalization graphene according to claim 2 is characterized in that described graphite and haloalkane or carboxylic acid halides or acid anhydrides mass ratio are 5:1 ~ 1:5; Described graphene suspension solubility is 0.01mg/ml ~ 5mg/ml.
6. the preparation method of Graphene polymer composites, it is characterized in that Resins, epoxy is added stirring and dissolving in the described graphene suspension of claim 1, ultrasonic mixing, underpressure distillation is removed described organic solvent and is obtained Graphene/epoxy resin composite, adds successively epoxy curing agent, promotor, the micron silver strip, behind 150 ℃ of 3h that are heating and curing, obtain described Graphene polymer composites, i.e. Graphene/Resins, epoxy conducing composite material.
7. the preparation method of Graphene polymer composites according to claim 6 is characterized in that described raw material weight umber consumption is as follows:
100 parts of Resins, epoxy
50～90 parts in solidifying agent
1～5 part of promotor
0.5～10 part of Graphene
500～1000 parts of silver strips.
8. the preparation method of Graphene polymer composites according to claim 6 is characterized in that described Graphene quality is 0.5 ~ 10wt% of Resins, epoxy.
9. the preparation method of Graphene polymer composites according to claim 6 is characterized in that described promotor is one or more the mixture in 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) or the Methylimidazole.
10. the preparation method of Graphene polymer composites according to claim 8 is characterized in that described raw material weight umber consumption is as follows:
100 parts of Resins, epoxy
70～90 parts in solidifying agent
1～3 part of promotor
0.5～5 part of Graphene
700～800 parts of silver strips.
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| CN2012103047049A CN102862976A (en) | 2012-08-25 | 2012-08-25 | Method for preparing functionalized graphene and composite material of functionalized graphene |
| PCT/CN2012/086895 WO2014032378A1 (en) | 2012-08-25 | 2012-12-19 | Methods for preparing functionalized graphene and the composite electroconductive glue thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009143405A2 (en) * | 2008-05-22 | 2009-11-26 | The University Of North Carolina At Chapel Hill | Synthesis of graphene sheets and nanoparticle composites comprising same |
| CN102153835A (en) * | 2011-03-15 | 2011-08-17 | 北京航空航天大学 | Modified graphene/epoxy resin composite material and preparation method thereof |
| CN102153976A (en) * | 2011-03-01 | 2011-08-17 | 华南理工大学 | Preparation method of graphene/nano silver epoxy conductive adhesive |
| CN102320595A (en) * | 2011-06-16 | 2012-01-18 | 华南理工大学 | Dispersible ethanolamine functionalized graphene and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010685B (en) * | 2010-12-03 | 2013-01-09 | 烟台德邦科技有限公司 | Epoxy resin conductive adhesive and preparation method thereof |
-
2012
- 2012-08-25 CN CN2012103047049A patent/CN102862976A/en active Pending
- 2012-12-19 WO PCT/CN2012/086895 patent/WO2014032378A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009143405A2 (en) * | 2008-05-22 | 2009-11-26 | The University Of North Carolina At Chapel Hill | Synthesis of graphene sheets and nanoparticle composites comprising same |
| CN102153976A (en) * | 2011-03-01 | 2011-08-17 | 华南理工大学 | Preparation method of graphene/nano silver epoxy conductive adhesive |
| CN102153835A (en) * | 2011-03-15 | 2011-08-17 | 北京航空航天大学 | Modified graphene/epoxy resin composite material and preparation method thereof |
| CN102320595A (en) * | 2011-06-16 | 2012-01-18 | 华南理工大学 | Dispersible ethanolamine functionalized graphene and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| IN-YUP JEON等: "Formation of Large-Area Nitrogen-Doped Graphene Film Prepared from Simple Solution Casting of Edge-Selectively Functionalized Graphite and Its Electrocatalytic Activity", 《CHEMISTRY OF MATERIALS》 * |
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