CN102766304A - Three-dimensional graphene network-contained high conductivity polymer composite material and preparation method thereof - Google Patents
Three-dimensional graphene network-contained high conductivity polymer composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional graphene network-contained high conductivity polymer composite material and a preparation method thereof. The preparation method includes: enabling graphene oxide and cationic polymer emulsion particles to form a condensate in a solvent by means of static self-assembly and leaching for film formation; and using reductant to restore the graphene oxide in the condensate film, washing, drying and mould pressing to obtain the three-dimensional graphene network-contained high conductivity polymer composite material. The preparation method is simple, easy to operate and high in controllability and can be used for large-scale production. In addition, the three-dimensional graphene network structure enables graphene to be uniformly dispersed in polymer matrix and enables graphene sheets to be mutually connected closely, so that contact resistance among the graphene sheets is greatly reduced. Consequently, the obtained polymer composite material with low amount of the graphene added is quite high in conductivity and has important application value in fields of electromagnetic shielding, highly conductive glue, sensors, brakes and the like.
Description
Technical field
The invention belongs to Graphene/polymer composites preparation field, relate in particular to a kind of high conductivity polymer composites that contains three-dimensional Graphene network and preparation method thereof.
Background technology
Graphene is a kind of blacking of closely being piled up the bi-dimensional cellular shape crystalline network that forms by the monolayer carbon atom.Although Graphene has only a carbon atom thickness, be the thinnest a kind of in the known materials,, it has the charming character of many uniquenesses, like high Young's modulus (1100 GPa), thermal conductivity (5000 W/mk) and carrier mobility (2 * 10
5Cm
2V
-1s
-1).These superior characteristic and two-dirnentional structure make Graphene be with a wide range of applications.One of them very important application is the polymer composites that utilizes the high conduction of these character preparations of Graphene.
Yet, have strong π-π effect and hydrophobic force effect between the Graphene lamella, very easily reunite, in solvent commonly used, do not dissolve yet very difficult the dispersion.In addition, Graphene not fusion under hot conditions, processing difficulties, these shortcomings are had a greatly reduced quality the high-performance of Graphene, even can't bring into play.Thereby the Graphene that solvent method or scorification obtain/polymer composites specific conductivity is lower, has limited its application in a lot of fields.The functionalization of Graphene can be the dispersiveness of raising Graphene in polymeric matrix a valid approach is provided.
In recent years, more existing relevant reports about the surface-functionalized modification of Graphene are connected the Graphene surface as containing the phenyl ring organic molecule through covalent linkage; Improve its dispersiveness in the PS matrix; The polymer composites conductivity value that contains 2.5 these functionalization graphenes of vol% reaches 1 S/m (S. Stankovich, et al. nature, 2006; 442,04969.); Perhaps adopt the ion liquid functionalization Graphene, the specific conductivity that contains the polymer composites of 4.19 vol% ion liquid functionalization Graphenes reaches 13.84 S/m.
Yet functionalization graphene/polymer composites conductivity value is still far below theoretical value.Its reason is, even functionalization graphene is evenly dispersed in the polymeric matrix, still has high contact resistance between the graphene film, and in addition, the functionalization group has also reduced the resistance of Graphene self.
In polymeric matrix, make up three-dimensional mutual close-connected Graphene network Graphene is evenly distributed in the polymeric matrix, and greatly reduced the contact resistance between the graphene film.In addition, three-dimensional Graphene network need not organics functionization carry out in the Graphene surface, reduces the resistance of Graphene self.Yet how in polymeric matrix, to make up three-dimensional Graphene network simply and effectively is a challenge job.
Summary of the invention
To the above-mentioned deficiency of prior art, first purpose of the present invention provides a kind of high conductivity polymer composites that contains three-dimensional Graphene network, and it can obtain high conductivity under low Graphene percentage composition.
Second purpose of the present invention provides a kind of preparation method who contains the high conductivity polymer composites of three-dimensional Graphene network.
Technical scheme of the present invention is following:
A kind of high conductivity polymer composites that contains three-dimensional Graphene network comprises three-dimensional interconnective Graphene network in the matrix of said polymer composites, in this Graphene network, Graphene is evenly distributed, and its percentage composition is in the 5%-20% scope.
A kind of preparation method of the above-mentioned high conductivity polymer composites that contains three-dimensional Graphene network, this method comprises following synthesis step:
(1) graphene oxide and cationic polymers emulsion particle are formed condensation prod through the mode of static self-assembly in solvent, afterwards through the suction filtration film forming;
(2) adopt reductive agent to reduce the graphene oxide in the above-mentioned condensation prod film, temperature of reaction is 50-90
oC then through washing, oven dry, mold pressing, obtains containing the high conductivity polymer composites of three-dimensional Graphene network.
Preferably, the Graphene content in the said high conductivity polymer composites that contains three-dimensional Graphene network can be regulated through the mass ratio of controlled oxidation Graphene and cationic polymers emulsion particle.
Preferably, the solvent in the said synthesis step (1) is a water.
Preferably; In the said synthesis step (1); Mode through the static self-assembly forms condensation prod and under solutions of weak acidity, carries out, and comprising: at first with graphene oxide with the cationic polymers emulsion particle is dispersed in the solvent respectively and transfer pH value to 2-5 respectively, mix forming condensation prod and stir then.
Preferably, the concentration of said graphene oxide is 0.2-2 mg/ml, and the concentration of said cationic polymers emulsion particle is 1-5 mg/ml.
Preferably; In the said synthesis step (1), the cationic polymers emulsion particle is selected from one or more of cation polystyrene emulsion particle, cationic ethylene vinyl acetate emulsion particle, cation polyurethane emulsion particle or positively charged ion polymethylmethacrylate emulsion particle.
Preferably, in the condensation prod of said synthesis step (1), graphene oxide is coated on the surface of emulsion particle equably and interconnects the formation network.
Preferably, the reduction process in the said synthesis step (2) is carried out in reductant solution;
Said reductive agent is selected from Hydrazine Hydrate 80, hydroiodic acid HI, sodium borohydride, xitix or vat powder.
Preferably, the oven dry in the said synthesis step (2) is vacuum-drying.
Compared with prior art, beneficial effect of the present invention is following:
First; The present invention is a raw material with graphene oxide and polyalcohol emulsion particle, adopts static self-assembly approach to obtain to contain the polymer composites of three-dimensional Graphene network, and this matrix material has high specific conductivity; Compare with traditional solvent blending method, specific conductivity exceeds an one magnitude at least.
The second, preparation process of the present invention environmental protection, the solvent of use is the aqueous solution, need not a large amount of organic solvents.
The 3rd, preparation method of the present invention is simple to operation, and controllability is strong, but production is amplified in mass-producing.
Certainly, arbitrary product of embodiment of the present invention might not reach above-described all advantages simultaneously.
Description of drawings
Fig. 1 is the PS and Graphene condensation prod sem (SEM) picture of the embodiment of the invention 1, and Graphene content is 10 %;
Fig. 2 is the ethylene vinyl acetate and the Graphene condensation prod SEM picture of the embodiment of the invention 2, and Graphene content is 5%;
Fig. 3 is the Graphene/poly styrene composite material and the Graphene/poly styrene composite material that adopts the preparation of organic solvent blending method and the specific conductivity comparison diagram of carbon nano-tube/poly benzene composite material of the embodiment of the invention 1 and embodiment 3 preparations;
The SEM picture of the three-dimensional Graphene network that Fig. 4 keeps after for the polymeric matrix high temperature pyrolysis in the PS/graphene composite material of the embodiment of the invention 1 preparation.
Embodiment
The high conductivity polymer composites that contains three-dimensional Graphene network of the present invention is to be raw material with graphene oxide and polyalcohol emulsion particle; Obtain through the self-assembly approach; In the polymeric matrix of this matrix material; Graphene is evenly distributed and interconnects, and its percentage composition is in the 5%-20% scope, and the content of Graphene can be regulated through the mass ratio of controlled oxidation Graphene and cationic polymers emulsion particle.
The preparation method who contains the high conductivity polymer composites of three-dimensional Graphene network of the present invention mainly comprises following two steps:
(1) graphene oxide and cationic polymers emulsion particle form condensation prod through the mode of static self-assembly in solvent, and through the suction filtration film forming, preferably, this process can be carried out under solutions of weak acidity, but is not limited to solutions of weak acidity;
(2) adopt reductive agent to reduce the graphene oxide in the above-mentioned condensation prod film, temperature of reaction is 50-90
oC through washing, oven dry, mold pressing, obtains containing the high conductivity polymer composites of three-dimensional Graphene network.
Below in conjunction with specific embodiment, further set forth the present invention.Should be appreciated that these embodiment only are used to explain the present invention, and are not used in qualification protection scope of the present invention.Improvement that the technician makes according to the present invention in practical application and adjustment still belong to protection scope of the present invention.
The preparation method of the high conductivity polymer composites that contains three-dimensional Graphene network in the present embodiment is following:
(1) 0.1 g graphene oxide and 0.95 g cation polystyrene emulsion particle are dispersed in respectively in the 200 ml aqueous solution; And pH value of aqueous solution is adjusted to 4-5 respectively, then, under stirring and adjusting; Above-mentioned two kinds of solution are slowly joined in the empty receptacle simultaneously; Graphene oxide with form condensation prod immediately after emulsion particle contacts, stir 10 min after, with the condensation prod suction filtration film forming that obtains;
(2) obtain graphene oxide-latex granulosa to be immersed in 200 ml concentration be redox graphene in 50% the hydroiodic acid HI solution above-mentioned, 90
oAfter C reacts 4 h, with deionized water repeated washing Graphene-latex granulosa, then 60
oC vacuum-drying and 120
oThe C mold pressing, acquisition contains the high conductivity polymer composites of three-dimensional Graphene network.This matrix material is characterized as follows:
Pattern characterizes: Fig. 1 is the polystyrene latex grain of present embodiment and the SEM picture of Graphene condensation prod, and is visible among Fig. 1, and Graphene is coated on the surface of emulsion particle equably and is interconnected to form three-dimensional Graphene network; The polymeric matrix of the high conductivity polymer composites that contains three-dimensional Graphene network that present embodiment is obtained carries out high temperature pyrolysis; And the three-dimensional Graphene network that keeps is carried out SEM characterize; Referring to Fig. 4, visible among Fig. 4, Graphene has formed three-dimensional net structure.
Specific conductivity characterizes: the high conductivity polymer composites that contains three-dimensional Graphene network that present embodiment is obtained carries out conductivity measurement; As shown in Figure 3; And it is compared with the carbon nano-tube/poly benzene composite material with Graphene/poly styrene composite material of organic solvent blending method preparation; Can find out among Fig. 3; The specific conductivity of the matrix material that present embodiment obtains exceeds an one magnitude at least, and high specific conductivity mainly gives the credit to this matrix material and contains three-dimensional close-connected Graphene network, and is as shown in Figure 4.
In the present embodiment, the percentage composition that contains Graphene in the high conductivity polymer composites of three-dimensional Graphene network is 5% (volume(tric)fraction percentage composition 2.4%).
Embodiment 2
The preparation method of the high conductivity polymer composites that contains three-dimensional Graphene network in the present embodiment is following:
(1) 0.1 g graphene oxide and 0.95 g cationic ethylene vinyl acetate emulsion particle are dispersed in respectively in the 200 ml aqueous solution; And pH value of aqueous solution is adjusted to 2-4 respectively, then, under stirring and adjusting; Above-mentioned two kinds of solution are slowly joined in the empty receptacle simultaneously; Graphene oxide with form condensation prod immediately after emulsion particle contacts, stir 10 min after, with the condensation prod suction filtration film forming that obtains;
(2) obtain graphene oxide-latex granulosa to be immersed in 200 ml concentration be redox graphene in 50% the hydroiodic acid HI solution above-mentioned, 90
oAfter C reacts 4 h, with deionized water repeated washing Graphene-latex granulosa, then 50
oC vacuum-drying and 75
oThe C mold pressing, acquisition contains the high conductivity polymer composites of three-dimensional Graphene network.Fig. 2 is the plastic of poly vinyl acetate emulsion particle and the Graphene condensation prod SEM picture of present embodiment, and is visible among Fig. 2, and Graphene is coated on the surface of emulsion particle equably and is interconnected to form three-dimensional Graphene network.
In the present embodiment, the percentage composition that contains Graphene in the high conductivity polymer composites of three-dimensional Graphene network is 5%.
Embodiment 3
The preparation method of the high conductivity polymer composites that contains three-dimensional Graphene network in the present embodiment is following:
(1) 0.2 g graphene oxide and 0.9 g polystyrene latex grain are dispersed in respectively in the 200 ml aqueous solution; And pH value of aqueous solution is adjusted to 2-4 respectively, then, under stirring and adjusting; Above-mentioned two kinds of solution are slowly joined in the empty receptacle simultaneously; Graphene oxide with form condensation prod immediately after emulsion particle contacts, stir 10 min after, with the condensation prod suction filtration film forming that obtains;
(2) obtain graphene oxide-latex granulosa to be immersed in 200 ml concentration be redox graphene in 10% the hydrazine hydrate solution above-mentioned, 80
oAfter C reacts 4 h, with deionized water repeated washing Graphene-latex granulosa, then 50
oC vacuum-drying and 120
oThe C mold pressing, acquisition contains the high conductivity polymer composites of three-dimensional Graphene network.
The high conductivity polymer composites that contains three-dimensional Graphene network that present embodiment is obtained carries out conductivity measurement; As shown in Figure 3; And it is compared with the carbon nano-tube/poly benzene composite material with Graphene/poly styrene composite material of organic solvent blending method preparation; Can find out among Fig. 3 that the specific conductivity of the matrix material that present embodiment obtains exceeds an one magnitude at least, high specific conductivity mainly gives the credit to this matrix material and contains three-dimensional close-connected Graphene network.
In the present embodiment, the percentage composition that contains Graphene in the high conductivity polymer composites of three-dimensional Graphene network is 10% (volume(tric)fraction percentage composition 4.8%).
The preparation method of the high conductivity polymer composites that contains three-dimensional Graphene network in the present embodiment is following:
(1) 0.2 g graphene oxide and 0.6 g polyurethane latex grain are dispersed in respectively in the 200 ml aqueous solution; And pH value of aqueous solution is adjusted to 2-3 respectively, then, under stirring and adjusting; Above-mentioned two kinds of solution are slowly joined in the empty receptacle simultaneously; Graphene oxide with form condensation prod immediately after emulsion particle contacts, stir 10 min after, with the condensation prod suction filtration film forming that obtains;
(2) obtain graphene oxide-latex granulosa to be immersed in 200 ml concentration be redox graphene in 30% the ascorbic acid solution above-mentioned, 80
oAfter C reacts 4 h, with deionized water repeated washing Graphene-latex granulosa, then 50
oC vacuum-drying and 100
oThe C mold pressing, acquisition contains the high conductivity polymer composites of three-dimensional Graphene network.
In the present embodiment, the percentage composition that contains Graphene in the high conductivity polymer composites of three-dimensional Graphene network is 15%.
Embodiment 5
The preparation method of the high conductivity polymer composites that contains three-dimensional Graphene network in the present embodiment is following:
(1) 0.3 g graphene oxide and 0.6 g polymethyl acrylic acid emulsion particle are dispersed in respectively in the 200 ml aqueous solution; And pH value of aqueous solution is adjusted to 2-4 respectively, then, under stirring and adjusting; Above-mentioned two kinds of solution are slowly joined in the empty receptacle simultaneously; Graphene oxide with form condensation prod immediately after emulsion particle contacts, stir 10 min after, will obtain condensation prod suction filtration film forming;
(2) obtain graphene oxide-latex granulosa to be immersed in 200 ml concentration be redox graphene in 20% the safety powder solution above-mentioned, 80
oAfter C reacts 10 h, with deionized water repeated washing Graphene-latex granulosa, then 50
oC vacuum-drying and 120
oThe C mold pressing, acquisition contains the high conductivity polymer composites of three-dimensional Graphene network.
In the present embodiment, the percentage composition that contains Graphene in the high conductivity polymer composites of three-dimensional Graphene network is 20%.
Embodiment 6
The preparation method of the high conductivity polymer composites that contains three-dimensional Graphene network in the present embodiment is following:
(1) 0.04 g graphene oxide and 0.2 g polymethyl acrylic acid emulsion particle are dispersed in respectively in the 200 ml aqueous solution; And pH value of aqueous solution is adjusted to 2-4 respectively, then, under stirring and adjusting; Above-mentioned two kinds of solution are slowly joined in the empty receptacle simultaneously; Graphene oxide with form condensation prod immediately after emulsion particle contacts, stir 10 min after, will obtain condensation prod suction filtration film forming;
(2) obtain graphene oxide-latex granulosa to be immersed in 200 ml concentration be redox graphene in 10% the sodium borohydride solution above-mentioned, 80
oAfter C reacts 10 h, with deionized water repeated washing Graphene-latex granulosa, then 50
oC vacuum-drying and 120
oThe C mold pressing, acquisition contains the high conductivity polymer composites of three-dimensional Graphene network.
In the present embodiment, the percentage composition that contains Graphene in the high conductivity polymer composites of three-dimensional Graphene network is 9%.
Embodiment 7
The preparation method of the high conductivity polymer composites that contains three-dimensional Graphene network in the present embodiment is following:
(1) 0.4 g graphene oxide and 1.0 g polymethyl acrylic acid emulsion particles are dispersed in respectively in the 200 ml aqueous solution; And pH value of aqueous solution is adjusted to 2-4 respectively, then, under stirring and adjusting; Above-mentioned two kinds of solution are slowly joined in the empty receptacle simultaneously; Graphene oxide with form condensation prod immediately after emulsion particle contacts, stir 10 min after, will obtain condensation prod suction filtration film forming;
(2) obtain graphene oxide-latex granulosa to be immersed in 200 ml concentration be redox graphene in 10% the sodium borohydride solution above-mentioned, 80
oAfter C reacts 10 h, with deionized water repeated washing Graphene-latex granulosa, then 50
oC vacuum-drying and 120
oThe C mold pressing, acquisition contains the high conductivity polymer composites of three-dimensional Graphene network.
In the present embodiment, the percentage composition that contains Graphene in the high conductivity polymer composites of three-dimensional Graphene network is 17%.
More than the disclosed preferred embodiment of the present invention just be used for help setting forth the present invention.Preferred embodiment does not have all details of detailed descriptionthe, does not limit this invention yet and is merely described embodiment.Obviously, according to the content of this specification sheets, can do a lot of modifications and variation.These embodiment are chosen and specifically described to this specification sheets, is in order to explain principle of the present invention and practical application better, thereby the present invention can understood and utilize to person skilled well under making.The present invention only receives the restriction of claims and four corner and equivalent.
Claims (10)
1. high conductivity polymer composites that contains three-dimensional Graphene network; It is characterized in that, comprise three-dimensional interconnective Graphene network in the matrix of said polymer composites, in this Graphene network; Graphene is evenly distributed, and its percentage composition is in the 5%-20% scope.
2. preparation method who contains the high conductivity polymer composites of three-dimensional Graphene network as claimed in claim 1 is characterized in that this method comprises following synthesis step:
(1) graphene oxide and cationic polymers emulsion particle are formed condensation prod through the mode of static self-assembly in solvent, afterwards through the suction filtration film forming;
(2) adopt reductive agent to reduce the graphene oxide in the above-mentioned condensation prod film, temperature of reaction is 50-90
OC,, obtain containing the high conductivity polymer composites of three-dimensional Graphene network then through washing, oven dry, mold pressing.
3. preparation method as claimed in claim 2 is characterized in that, the Graphene content in the said high conductivity polymer composites that contains three-dimensional Graphene network can be regulated through the mass ratio of controlled oxidation Graphene and cationic polymers emulsion particle.
4. preparation method as claimed in claim 2 is characterized in that, the solvent in the said synthesis step (1) is a water.
5. preparation method as claimed in claim 2; It is characterized in that; In the said synthesis step (1); Mode through the static self-assembly forms condensation prod and under solutions of weak acidity, carries out, and comprising: at first with graphene oxide with the cationic polymers emulsion particle is dispersed in the solvent respectively and transfer pH value to 2-5 respectively, mix forming condensation prod and stir then.
6. preparation method as claimed in claim 5 is characterized in that, the concentration of said graphene oxide is 0.2-2 mg/ml, and the concentration of said cationic polymers emulsion particle is 1-5 mg/ml.
7. preparation method as claimed in claim 2; It is characterized in that; In the said synthesis step (1), the cationic polymers emulsion particle is selected from one or more of cation polystyrene emulsion particle, cationic ethylene vinyl acetate emulsion particle, cation polyurethane emulsion particle or positively charged ion polymethylmethacrylate emulsion particle.
8. preparation method as claimed in claim 2 is characterized in that, in the condensation prod of said synthesis step (1), graphene oxide is coated on the surface of emulsion particle equably and interconnects the formation network.
9. preparation method as claimed in claim 2 is characterized in that, the reduction process in the said synthesis step (2) is carried out in reductant solution;
Said reductive agent is selected from Hydrazine Hydrate 80, hydroiodic acid HI, sodium borohydride, xitix or vat powder.
10. preparation method as claimed in claim 2 is characterized in that, the oven dry in the said synthesis step (2) is vacuum-drying.
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| CN110343347A (en) * | 2019-07-19 | 2019-10-18 | 广州特种承压设备检测研究院 | Kynoar SiO2Modified graphene composite material and preparation method |
| CN110343347B (en) * | 2019-07-19 | 2021-09-14 | 广州特种承压设备检测研究院 | Polyvinylidene fluoride SiO2Modified graphene composite material and preparation method thereof |
| CN113604133A (en) * | 2021-08-30 | 2021-11-05 | 航天科工武汉磁电有限责任公司 | Light carbon-based electromagnetic shielding coating and preparation method thereof |
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