CN102690426B - Method for preparing graphene/polymer composite material based on infrared irradiation - Google Patents
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Abstract
The invention discloses a method for preparing a graphene/polymer composite material based on infrared irradiation. The method comprises the following steps: 1) mixing a graphite oxide solution with a polymer solution or polymer emulsion to obtain a mixed solution, casting or spinning, and drying until the weight percentage of the total solvent is less than or equal to 50 percent so as to obtain a composite product; and 2) removing the solvent from the composite product under the irradiation of an infrared heating lamp, and performing reduction reaction of graphite oxide to obtain the graphene/polymer composite material. By the preparation method, the graphene/polymer composite material is prepared under the irradiation of the infrared heating lamp, the process is simple and convenient, the production cost is low, the method is suitable for large-scale industrial production, different polymers can be selected for preparing different graphene/polymer composite materials so as to meet the production and use requirements, and the graphene/polymer composite material has a wide application prospect in the fields such as conductive polymer composite materials, films and fibers.
Description
Technical field
The present invention relates to the preparation field of Graphene/polymer composites, be specifically related to a kind of preparation method of the Graphene/polymer composites based on infrared irridiation.
Background technology
Graphene is a kind of monolayer carbon material that is made of carbon atom.The A.K.Geim of University of Manchester in 2004 and co-worker thereof report that for the first time the method for graphite being peeled off with plastic adhesive tape obtains Graphene (K.S.Novoselov, A.K.Geim, S.V.Morozov, D.Jiang, Y.Zhang, S.V.Dubonos, I.V.Grigorieva, A.A.Firsov, Electric Field Effect in Atomically Thin Carbon Films, Science, 306,22,2004,666-669).Subsequently, Graphene begins to be subject to whole world investigator's favor.
Graphene has larger specific surface area (2360m
2G
-1), higher electronic mobility (200000cm
2V
-1S
-1), higher Young's modulus (1.0TPa), higher thermal conductivity (5000Wm
-1K
-1) and light transmission (97.7%), the aspects such as being on the scene effect transistor, sensor, transparent conductive film, graphene battery, electron detection device, heat transfer equipment and polymer matrix composite (the Yanwu Zhu that has broad application prospects, Shanthi Murali, Weiwei Cai, Xuesong Li, Ji Won Suk, Jeffrey R.Potts, Rodney S.Ruoff, Graphene and Graphene Oxide:Synthesis, Properties, and Applications, Adv.Mater.2010).
Mainly contain at present six kinds of methods and prepare Graphene:
One, epitaxy Graphene, namely make Graphene be grown in the metallic surface of orientation by chemical gaseous phase depositing process, can accomplish the Graphene thin layer of endless, non-constant width on this theoretical method, but need high temperature and Graphene is being needed to use corrosive chemical from the process that metallic substrate surface is peeled off;
Two, micromechanics stripping means, this method are applicable to study electrical property and other performances of Graphene, but the resulting graphene sheet layer size of the method and thickness also are difficult to control at present, and are not suitable for preparing in a large number Graphene;
Three, the chemical reduction method of graphite oxide namely reduces graphite oxide with chemical process and obtains Graphene (also being reduction-oxidation graphite) in solution.The reductive agent that adopts at present mainly contains hydrazine hydrate, sodium borohydride, glucose, xitix, sodium hydroxide and potassium hydroxide etc.These methods prepare that reduction-oxidation graphite speed is slow, and energy consumption is higher, and some chemical reagent that uses has higher toxicity;
Four, the high temperature pyrolysis reduction method of graphite oxide is about to graphite oxide and heats under protection of inert gas and make graphite oxide deviate from oxy radical to be reduced into Graphene.The temperature of reduction reaction is generally 500 ℃ to 1200 ℃.The method can prepare Graphene in enormous quantities, but have that energy consumption is high, the heating and cooling cycle is long, the shortcomings such as matrix (as plastics, textiles) that are not suitable for non-refractory;
Five, (publication number is the Chinese patent application of CN 101559941A to Electron Beam Irradiation for Zhao Bing etc., the method for preparing graphite alkenyl nanometer materials by electron beam irradiation method; Chen Wufeng, Yan Lifeng, Prakriti R.Bangal, Preparation of graphene by the rapid and mild thermal reduction of graphene oxide induced by microwaves, Carbon, 48,2010,1146-1152).The method need to be used expensive rumbatron, and the cost of its preparation is higher, is unfavorable for industrialization promotion and production;
Six, xenon lamp irradiation reduction method (Laura J.Cote, Rodolfo Cruz-Silva, Jiaxing Huang, Flash Reduction and Patterning of Graphite Oxide and Its Polymer Composite, J.Am.Chem.Soc.2009.131.11207-11032).The method reduction rate is very fast, but only is fit to the reduction of graphite oxide film, and its operating process simultaneously is step, is difficult to carry out the reduction processing of serialization, is difficult to satisfy the reduction demand of big area or a large amount of graphite oxides.
Aspect the preparation of Graphene/polymer composites, how with Graphene and polymkeric substance evenly compound be the key that obtains high-performance Graphene/polymer composites.Normally adopt first at present graphite oxide is reduced, more compound with polymkeric substance, but because the standby Graphene self of reduction-oxidation graphite legal system is easy to reunite, therefore be difficult to obtain finely dispersed Graphene/polymer composites.
Summary of the invention
The invention provides a kind of preparation method of the Graphene/polymer composites based on infrared irridiation, its preparation Simple fast, can be continuously produced.
A kind of preparation method of the Graphene/polymer composites based on infrared irridiation comprises the following steps:
1) graphite oxide solution is mixed with polymers soln or polymer emulsion, obtain mixed solution, cast or spinning are dried to the weight percentage of total solvent less than or equal to 50%, obtain combination product;
Described mixed solution comprises total soluble matters and total solvent, total soluble matters is graphite oxide and polymkeric substance, total solvent is solvent in graphite oxide solution and the solvent sum in polymers soln, in drying process, in mixed solution, the weight of total solvent can reduce thereupon, the weight percentage that is total solvent can reduce accordingly, the weight percentage of total solvent=dried total solvent weight/(dried total solvent weight+dried total soluble matters weight);
2) solvent in the combination product in step 1) is removed and carried out the reduction reaction of graphite oxide under infrared heating lamp irradiation, obtain Graphene/polymer composites.
The preparation of graphite oxide is referring to disclosed preparation method (Laura J.Cote in " xenon lamp reduction, patterning and the polymer composite thereof of graphite oxide ", Franklin Kim, and Jiaxing Huang, Flash Reduction and Patterning of Graphite Oxide and Its Polymer Composite, J.Am.Chem.Soc.2009,131,10431049).Preparation process can brief overview be with graphite disperse in the vitriol oil, SODIUMNITRATE and potassium permanganate, intercalation, heated oxide then, then through overpickling, washing filtering, separation, take out throw out stand-by, throw out is graphite oxide.
In step 1), as preferably, the weight ratio of described graphite oxide and polymkeric substance is 0.001 ~ 40: 1, and the weight ratio of raw material is limited in suitable scope, is conducive to reduction-oxidation graphite and polymkeric substance compound preferably.
For graphite oxide solution and polymers soln or polymer emulsion have better mixed effect, and be conducive to follow-up processing, in described graphite oxide solution, the weight percentage of graphite oxide is 0.1% ~ 2%, and in described polymers soln or polymer emulsion, the weight percentage of polymkeric substance is 0.5% ~ 20%.Further preferred, in described graphite oxide solution, the weight percentage of graphite oxide is 0.1% ~ 0.5%, and in described polymers soln or polymer emulsion, the weight percentage of polymkeric substance is 1% ~ 10%.
Solvent in described graphite oxide solution is water, N,N-DIMETHYLACETAMIDE or dimethyl formamide, primary solvent in described polymers soln or polymer emulsion is water, N,N-DIMETHYLACETAMIDE or dimethyl formamide, be conducive to graphite oxide and polymkeric substance are evenly dispersed in solvent on the one hand, on the other hand, these solvents are easily removed in preparation process.
Described polymers soln or polymer emulsion are dimethylacetamide solution, ptfe emulsion, perfluoroethylene-propylene emulsion, organic silicon emulsion, polyaryletherketone emulsion, polyetherimide emulsion or the polyethersulfone emulsion of polyvinyl alcohol water solution, polyamic acid.These polymkeric substance all can be compound preferably with reduction-oxidation graphite, obtains the Graphene/polymer composites of excellent property.
As preferably, the weight percentage that is dried to total solvent is 5% ~ 50%, is conducive to carry out the reduction reaction of graphite oxide under infrared heating lamp irradiation.Step 2) in, as preferably, the power of described infrared heating lamp is 5W to 10kW, and the time of described infrared heating lamp irradiation is 10 seconds to 60 minutes, during infrared heating lamp irradiation, the distance of described infrared heating lamp and combination product is 1 millimeter to 1000 millimeters; Under this condition, infrared heating lamp can reduce graphite oxide preferably, and makes reduction-oxidation graphite (being Graphene) and polymkeric substance compound more equably, makes the Graphene/polymer composites that obtains embody performance preferably.
Compared with prior art, have the following advantages:
Infrared irridiation heating has that thermal conversion efficiency is high, heat-up rate fast, be easy to the advantages such as serialization, mass-producing, has been widely used in heating, the purpose such as dry in industrial and agricultural production and daily life.In preparation method of the present invention, utilize under infrared heating lamp irradiation to prepare Graphene/polymer composites, technique is very easy, production cost is very low, is conducive to large-scale industrialization production, has broad application prospects.In preparation method of the present invention, polymkeric substance can be selected different kinds, can prepare different Graphene/polymer composites, can satisfy different production and service requirements, be conducive to utilization and extention, have broad application prospects in fields such as conductive polymer composite and film, fibers.
Compare with the electron beam irradiation method of reducing, preparation method of the present invention does not need expensive equipment, and the production cost of Graphene/polymer composites is lower; Compare with chemical reduction method, preparation method of the present invention does not need to add any catalyzer or chemical reducing agent, and a step can obtain reduction-oxidation graphite, prepares very easy; Compare with the Pintsch process reduction method, preparation method's reduction temperature of the present invention is low, the heating and cooling cycle is short, be easy to mass-producing, is suitable for the preparation of the lower polymer composites of thermotolerance.
Description of drawings
Fig. 1 is the electron scanning micrograph of the reduction-oxidation graphite in preparation example 1;
Fig. 2 is the X-ray diffractogram of graphite oxide in preparation example 1 (curve 1) and reduction-oxidation graphite (curve 2);
Fig. 3 is electron-microscope scanning (SEM) photo of the reduction-oxidation graphite/polyvinyl alcohol compound film of embodiment 1 preparation;
Fig. 4 is the square resistance of reduction-oxidation graphite/polyvinyl alcohol compound film of each different thickness in embodiment 2 and the relation curve of transmittance;
Fig. 5 is electron-microscope scanning (SEM) photo of the reduction-oxidation graphite/tetrafluoroethylene laminated film of embodiment 3 preparation.
Embodiment
Be below the embodiment that the present invention provides, invention is further introduced, need to prove, the invention is not restricted to following examples.Umber in embodiment is weight part.Volume specific resistance in the present embodiment and square resistance all use four probe method (RTS-2 type four point probe tester, Guangzhou four point probe Science and Technology Ltd.) to measure.
Preparation example 1
With 3g graphite, 3g SODIUMNITRATE, the 60mL vitriol oil (98%) and 6g potassium permanganate under 35 ℃ the reaction 2 hours after, add the 100mL deionized water, then adding the hydrogen peroxide weight percentage is 3% aqueous hydrogen peroxide solution 200mL, and pickling and washing obtain the graphite oxide jelly after standing 12 hours.The graphite oxide jelly is placed in 25 ℃ of lower vacuum-dryings of room temperature or lyophilize, obtains oxidation graphite solid.Adjust the distance oxidation graphite solid 10 millimeters places to its irradiation 1 minute with the power infrared heating lamp that is 275W, reduction reaction namely occurs, obtain the reduction-oxidation graphite solid.The electron scanning micrograph of reduction-oxidation graphite solid as shown in Figure 1, as seen, the reduction-oxidation graphite-structure that obtains with this understanding is loose, porous, illustrates that reduction process is more violent, discharges a large amount of gases.The X-ray diffractogram of oxidation graphite solid is as shown in curve in Fig. 21, and the X-ray diffractogram of reduction-oxidation graphite solid is as shown in curve in Fig. 22.As shown in Figure 2, after the reduction of graphite oxide infrared radiation, diffraction peak disappears, and illustrates that reduction process is relatively more violent, discharges gas and graphite flake layer is peeled off.
The graphite oxide aqueous solution in embodiment 1 ~ 16 all obtains after in embodiment 1, the preparation oxidation graphite solid is dissolved in deionized water.
1) be 200 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide be that 10 parts of 10% polyvinyl alcohol water solutions mix with the weight percentage of polyvinyl alcohol, wherein the number-average molecular weight of polyvinyl alcohol is 1799, obtain mixed solution after stirring, be cast in sample cell, drying is 12 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 35%, obtains graphite oxide/polyvinyl alcohol compound film (combination product), and this laminated film is nonconducting;
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/polyvinyl alcohol compound film 100 millimeters places to its irradiation 30 minutes, obtain the reduction-oxidation graphite/polyvinyl alcohol compound film (being Graphene/polymer composites) of the conduction of 1.5 parts, volume specific resistance is 1.1 * 10
3Ω cm, the electron-microscope scanning picture of the reduction-oxidation graphite/polyvinyl alcohol compound film of preparation as shown in Figure 3.As shown in Figure 3, the thickness of film is approximately 800 nanometers, and section structure is dense does not have obvious pore.
1) be 100 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide be that 1 part of 10% the aqueous solution mixes with the weight percentage of polyvinyl alcohol, wherein the number-average molecular weight of polyvinyl alcohol is 5000, obtain mixed solution after stirring, the weight percentage that mixed solution is diluted with water to respectively graphite oxide in mixed solution is 0.01%, 0.02%, 0.05%, 0.1%, 0.2% and 0.4%, getting respectively 10 portions of mixed solutions after dilution is cast on the silica glass surface, drying is 12 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 25%, obtain graphite oxide/polyvinyl alcohol compound film (combination product), this laminated film is nonconducting,
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/polyvinyl alcohol compound film 100 millimeters places to its irradiation 30 minutes, obtain having certain transparency, reduction-oxidation graphite/the polyvinyl alcohol compound film (being Graphene/polymer composites) of each different thickness of conduction, then survey respectively square resistance (ohm/sq) and the transmittance of the reduction-oxidation graphite/polyvinyl alcohol compound film of each different thickness, its test result as shown in Figure 4, in Fig. 4 from left to right point successively the weight percentage of corresponding graphite oxide be 0.01%, 0.02%, 0.05%, 0.1%, 0.2% and 0.4%.The electroconductibility of reduction-oxidation graphite/polyvinyl alcohol compound film significantly increases along with the increase of thickness, and this is because graphite oxide under the irradiation of infrared light, reduction has occured, and changes into the good Graphene of electroconductibility.
Embodiment 3
1) be 200 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide be that 2.5 parts of 1% ptfe emulsions (adding the deionized water dilution by Daikin D210 ptfe emulsion obtains) mix with weight percentage, obtain mixed solution after stirring, be cast in sample cell, drying is 2 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 43%, obtain graphite oxide/tetrafluoroethylene laminated film (combination product), this laminated film is nonconducting;
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/100 millimeters of tetrafluoroethylene laminated films place to its irradiation 10 minutes, obtain the reduction-oxidation graphite of the conduction of 0.5 part/tetrafluoroethylene laminated film (being Graphene/polymer composites), volume specific resistance is 106 Ω cm, the electron-microscope scanning picture of the reduction-oxidation graphite/tetrafluoroethylene laminated film of preparation as shown in Figure 5, this product is that thickness is the densification of 6 microns left and right, imperforate film.
Embodiment 4
1) be 100 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide be that 2.5 parts of 1% ptfe emulsions (adding the deionized water dilution by Daikin D210 ptfe emulsion obtains) mix with the weight percentage of tetrafluoroethylene, obtain mixed solution after stirring, be cast in sample cell, drying is 2 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 40%, obtain graphite oxide/tetrafluoroethylene laminated film (combination product), this laminated film is nonconducting;
2) with power be the infrared heating lamp of 5W in the distance step 1) graphite oxide/1 millimeter of tetrafluoroethylene laminated film place to its irradiation 60 minutes, obtain the reduction-oxidation graphite/tetrafluoroethylene laminated film (being Graphene/polymer composites) of 0.2 part, volume specific resistance is 3.4 * 10
8Ω cm.
Embodiment 5
1) be 2000 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide be that 5 parts of 10% perfluoroethylene-propylene emulsions (adding the deionized water dilution by hugeization F46 emulsion) are mixed with the weight percentage of perfluoroethylene-propylene, obtain mixed solution after stirring, be cast in sample cell, drying is 2 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 45%, obtain graphite oxide/perfluoroethylene-propylene laminated film (combination product), this laminated film is nonconducting;
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/100 millimeters of perfluoroethylene-propylene laminated films place to its irradiation 10 minutes, obtain the reduction-oxidation graphite/perfluoroethylene-propylene laminated film (being Graphene/polymer composites) of 5 parts, volume specific resistance is 1.1 Ω cm.
Embodiment 6
1) be 1000 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide be that 5 parts of 10% perfluoroethylene-propylene emulsions are mixed (adding the deionized water dilution by hugeization F46 emulsion) with the weight percentage of perfluoroethylene-propylene, obtain mixed solution after stirring, be cast in sample cell, drying is 2 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 40%, obtain graphite oxide/perfluoroethylene-propylene laminated film (combination product), this laminated film is nonconducting;
2) with power be the infrared heating lamp of 10kW in the distance step 1) graphite oxide/50 millimeters of perfluoroethylene-propylene laminated films place to its irradiation 10 seconds, obtain the reduction-oxidation graphite/perfluoroethylene-propylene laminated film (being Graphene/polymer composites) of 3 parts, volume specific resistance is 250 Ω cm.
Embodiment 7
1) be 20 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide be 10% organic silicon emulsion (Wacker with organosilyl weight percentage, E101CN) 1000 parts of mixing, obtain mixed solution after stirring, be cast in sample cell, drying is 2 hours in the baking oven of 70 ℃, be dried to that in mixed solution, the weight of solvent equals 37% of mixed solution gross weight, obtain graphite oxide/Organosilicone Thin Film (combination product), this laminated film is nonconducting;
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/Organosilicone Thin Film 100 millimeters places to its irradiation 10 minutes, obtain the reduction-oxidation graphite/Organosilicone Thin Film (being Graphene/polymer composites) of 98.7 parts, volume specific resistance is 1.1 * 10
11Ω cm.
Embodiment 8
1) be 20 parts of 0.5% the graphite oxide aqueous solution with the weight percentage of graphite oxide be 10% organic silicon emulsion (Wacker with organosilyl weight percentage, E101CN) 500 parts of mixing, obtain mixed solution after stirring, be cast in sample cell, drying is 2 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 33%, obtains graphite oxide/Organosilicone Thin Film (combination product), and this laminated film is nonconducting;
2) with power be the infrared heating lamp of 10kW in the distance step 1) graphite oxide/Organosilicone Thin Film 1000 millimeters places to its irradiation 60 minutes, obtain the reduction-oxidation graphite/Organosilicone Thin Film (being Graphene/polymer composites) of 49 parts, volume specific resistance is 1.1 * 10
11Ω cm.
Embodiment 9
1) be that 20 parts of weight percentages with polyethersulfone (German BASF E2010) of the graphite oxide aqueous solution of 0.5% are that 18 parts of 10% polyethersulfone emulsions are mixed with the weight percentage of graphite oxide, obtain mixed solution after stirring, be cast in sample cell, drying is 2 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 30%, obtain graphite oxide/polyethersulfone laminated film (combination product), this laminated film is nonconducting;
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/100 millimeters of polyethersulfone laminated films place to its irradiation 10 minutes, obtain the reduction-oxidation graphite/polyethersulfone laminated film (being Graphene/polymer composites) of 1.8 parts, volume specific resistance is 1.1 * 10
5Ω cm.
1) with the weight percentage of graphite oxide be 20 parts of 0.5% the graphite oxide aqueous solution and polyaryletherketone (012P, Changchun Jida special plastic engineering Co., Ltd) weight percentage is 15 parts of mixing of polyaryletherketone emulsion of 10%, obtain mixed solution after stirring, be cast in sample cell, drying is 2 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 29%, obtain graphite oxide/polyaryletherketone laminated film (combination product), this laminated film is nonconducting;
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/100 millimeters of polyaryletherketone laminated films place to its irradiation 10 minutes, obtain the reduction-oxidation graphite/polyaryletherketone laminated film (being Graphene/polymer composites) of 1.4 parts, volume specific resistance is 1.1 * 10
10Ω cm.
Embodiment 11
1) be that 20 parts of weight percentages with polyetherimide (GE ULTEM 1000) of the graphite oxide aqueous solution of 0.5% are that 10 parts of 10% polyetherimide emulsions are mixed with the weight percentage of graphite oxide, obtain mixed solution after stirring, be cast in sample cell, drying is 2 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 28%, obtain graphite oxide/polyetherimide laminated film (combination product), this laminated film is nonconducting;
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/100 millimeters of polyetherimide laminated films place to its irradiation 10 minutes, obtain the reduction-oxidation graphite/polyetherimide laminated film (being Graphene/polymer composites) of 0.9 part, volume specific resistance is 2.7 * 10
3Ω cm.
Embodiment 12
1) be that 20 parts of weight percentages with polyamic acid of dimethylacetamide solution of 0.2% graphite oxide are the dimethylacetamide solution (ZKPI-305IA of 1% polyamic acid with the weight percentage of graphite oxide, Beijing Bomi Sci. ﹠ Tech. Co., Ltd.) 20 parts of mixing, obtain mixed solution after stirring, be cast in sample cell, drying is 48 hours in the baking oven of 120 ℃, the weight percentage that is dried to total solvent equals 5%, obtain graphite oxide/polyamic acid laminated film (combination product), this laminated film is nonconducting;
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/100 millimeters of polyamic acid laminated films place to its irradiation 10 minutes, obtain the reduction-oxidation graphite/polyamic acid laminated film (being Graphene/polymer composites) of 0.14 part, volume specific resistance is 6.4 * 10
5Ω cm.
Embodiment 13
1) be that 100 parts of weight percentages with polyamic acid of dimethyl formamide solution of 0.5% graphite oxide are the dimethylacetamide solution (ZKPI-305IA of 10% polyamic acid with the weight percentage of graphite oxide, Beijing Bomi Sci. ﹠ Tech. Co., Ltd.) 100 parts of mixing, obtain mixed solution after stirring, spinning, drying is 2 hours in the baking oven of 160 ℃, the weight percentage that is dried to total solvent equals 5%, obtain graphite oxide/polyamic acid conjugated fibre (combination product), this conjugated fibre is nonconducting;
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/100 millimeters of polyamic acid conjugated fibres place to its irradiation 30 minutes, obtain the reduction-oxidation graphite/polyamic acid conjugated fibre (being Graphene/polymer composites) of 7.6 parts, volume specific resistance is 2.6 * 10
3Ω cm.
Embodiment 14
1) with the weight percentage of graphite oxide be 100 parts of 0.1% the graphite oxide aqueous solution and polyaryletherketone (012P, Changchun Jida special plastic engineering Co., Ltd) weight percentage is 100 parts of mixing of polyaryletherketone emulsion of 10%, obtain mixed solution after stirring, again while stirring 70 ℃ of heating, volatilization along with water, the graphite oxide of formation colloidal/polyaryletherketone mixture, mixture is watered in sample cell, drying is 24 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 20%, obtain graphite oxide/polyaryletherketone matrix material (combination product), this matrix material is nonconducting,
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/100 millimeters, polyaryletherketone matrix material place to its irradiation 10 minutes, obtain the reduction-oxidation graphite/polyaryletherketone matrix material (being Graphene/polymer composites) of 1.4 parts, volume specific resistance is 5.3 * 10
4Ω cm.
Embodiment 15
1) be that 100 parts of weight percentages with polyetherimide (GE ULTEM 1000) of the graphite oxide aqueous solution of 0.1% are that 10 parts of 1% polyetherimide emulsions are mixed with the weight percentage of graphite oxide, obtain mixed solution after stirring, again while stirring 70 ℃ of heating, volatilization along with water, the graphite oxide of formation colloidal/polyetherimide amine mixt, mixture is watered in sample cell, drying is 24 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 17%, obtain graphite oxide/polyetherimide composite material (combination product), this matrix material is nonconducting,
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/polyetherimide composite material 100 millimeters places to its irradiation 10 minutes, obtain the reduction-oxidation graphite/polyetherimide composite material (being Graphene/polymer composites) of 0.15 part, volume specific resistance is 3.8 * 10
2Ω cm.
Embodiment 16
1) be 100 parts of 0.1% the graphite oxide aqueous solution with the weight percentage of graphite oxide be that 100 parts of 10% polyethersulfone (BASF Ultrason E3010) emulsions are mixed with the weight percentage of polyethersulfone, obtain mixed solution after stirring, again while stirring 70 ℃ of heating, volatilization along with water, the graphite oxide of formation colloidal/polyethersulfone mixture, mixture is watered in sample cell, drying is 24 hours in the baking oven of 70 ℃, the weight percentage that is dried to total solvent equals 25%, obtain graphite oxide/Polyethersulfone Composites (combination product), this matrix material is nonconducting,
2) with power be the infrared heating lamp of 275W in the distance step 1) graphite oxide/Polyethersulfone Composites 100 millimeters places to its irradiation 10 minutes, obtain the reduction-oxidation graphite/Polyethersulfone Composites (being Graphene/polymer composites) of 9.8 parts, volume specific resistance is 2.9 * 10
2Ω cm.
Claims (7)
1. preparation method based on the Graphene/polymer composites of infrared irridiation comprises the following steps:
1) graphite oxide solution is mixed with polymers soln or polymer emulsion, obtain mixed solution, cast or spinning are dried to the weight percentage of total solvent less than or equal to 50%, obtain combination product;
2) solvent in the combination product in step 1) is removed and carried out the reduction reaction of graphite oxide under infrared heating lamp irradiation, obtain Graphene/polymer composites;
The power of described infrared heating lamp is 5W to 10kW, and the time of described infrared heating lamp irradiation is 10 seconds to 60 minutes, and the distance of described infrared heating lamp and combination product is 1 millimeter to 1000 millimeters.
2. preparation method according to claim 1, is characterized in that, the weight ratio of described graphite oxide and polymkeric substance is 0.001～40:1.
3. preparation method according to claim 1, is characterized in that, in described graphite oxide solution, the weight percentage of graphite oxide is 0.1%～2%, and in described polymers soln or polymer emulsion, the weight percentage of polymkeric substance is 0.5%～20%.
4. preparation method according to claim 3, is characterized in that, in described graphite oxide solution, the weight percentage of graphite oxide is 0.1%～0.5%, and in described polymers soln or polymer emulsion, the weight percentage of polymkeric substance is 1%～10%.
5. preparation method according to claim 1, is characterized in that, the solvent in described graphite oxide solution is water, N,N-DIMETHYLACETAMIDE or dimethyl formamide.
6. preparation method according to claim 1, it is characterized in that, described polymers soln or polymer emulsion are dimethylacetamide solution, ptfe emulsion, perfluoroethylene-propylene emulsion, organic silicon emulsion, polyaryletherketone emulsion, polyetherimide emulsion or the polyethersulfone emulsion of polyvinyl alcohol water solution, polyamic acid.
7. preparation method according to claim 1, is characterized in that, the weight percentage that is dried to total solvent is 5%～50%.
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| CN103541043A (en) * | 2013-08-01 | 2014-01-29 | 华为技术有限公司 | Preparation method of electric graphene composite fiber |
| CN104211977B (en) * | 2014-09-10 | 2017-01-25 | 浙江碳谷上希材料科技有限公司 | Preparation method of graphene-based composite membrane |
| CN104650574B (en) * | 2015-02-10 | 2017-02-22 | 郴州功田电子陶瓷技术有限公司 | Polyphenyl ether copper-clad laminate composition |
| CN106317728A (en) * | 2015-07-03 | 2017-01-11 | 上海伟星新型建材有限公司 | High-efficiency and high-strength composite material with far infrared radiation heating and preparation method thereof |
| CN104947227B (en) * | 2015-07-13 | 2017-06-13 | 黑龙江大学 | Polyvinylpyrrolidone/Graphene composite nano-fiber material and preparation method thereof |
| CN104988592B (en) * | 2015-07-17 | 2017-05-17 | 黑龙江大学 | Polyvinyl alcohol/graphene composite nano fiber material and preparation method thereof |
| CN105688515B (en) * | 2016-03-23 | 2018-05-04 | 钟校 | A kind of preparation method of perfluoroethylene-propylene strainer |
| CN107082417A (en) * | 2017-06-06 | 2017-08-22 | 烟台市烯能新材料股份有限公司 | A kind of preparation method of low granularity graphene |
| CN107164817B (en) * | 2017-06-06 | 2019-03-26 | 烟台市烯能新材料有限责任公司 | A kind of preparation method of graphene-graphene oxide composite nylon fiber |
| CN107722595B (en) * | 2017-10-23 | 2019-12-17 | 沈阳航空航天大学 | Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material |
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| CN101559941B (en) * | 2009-05-26 | 2012-02-22 | 上海大学 | Method for preparing graphite alkenyl nanometer materials by electron beam irradiation method |
| CN101844761B (en) * | 2010-05-28 | 2012-08-15 | 上海师范大学 | Method of adopting laser radiation for preparing reduction-oxidation graphene |
| CN101864098B (en) * | 2010-06-03 | 2012-01-04 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN101941694A (en) * | 2010-09-07 | 2011-01-12 | 湘潭大学 | Preparation method of high-dispersivity graphene |
| CN102180462B (en) * | 2011-02-17 | 2013-01-02 | 无锡第六元素高科技发展有限公司 | Method for preparing modified graphene material in controlled atmosphere environment by microwave irradiation |
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