CN103554702A - Graphene polymer composite material with network graphene, and preparation method thereof - Google Patents
Graphene polymer composite material with network graphene, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene polymer composite material with network graphene. An ordered network structure with a three-dimensional long-range height is formed by the graphene in polymer matrix. A corresponding preparation method comprises the following steps: firstly, coating the surface of a polymer microsphere by the graphene, so as to obtain polymer/graphene composite particles; then pressing or pouring and molding the obtained polymer/graphene composite particles, so as to obtain the graphene polymer composite material with the network graphene.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to Graphene polymer composite and technology of preparing thereof.
Technical background
Graphene is led because self having excellent thermal conductance, electricity, mechanical property and the huge features such as specific surface area have received increasing concern, in battery, sensing, super capacitor, energy storage, the technical field such as nano combined, gathers around and has wide practical use.Although now can use the method for low consumption to prepare in a large number Graphene, how more efficiently using mineral carbon alkene is still a science difficult problem.Wherein, preparing Graphene polymer composite is a kind of feasible technological approaches, and still, its gordian technique is, how effectively by graphene uniform be dispersed in matrix material, thereby give full play to the performance of Graphene and compound brought structural advantage.Up to now, preparing the most general method of Graphene polymer composite is that the dispersion liquid of Graphene is mixed with high molecular solution or colloid, or direct pouring moulding under liquid state, or drying obtains carrying out after solid mixture hot-forming again.But in the process of solvent evaporates or removal medium, Graphene is obviously easy to reassemble or original homogeneously dispersed state is destroyed.For fear of this situation, conventionally need to use some any special measures such as rapid precipitation and lyophilize, for example, Stankovich etc. first by polystyrene and Graphene at N, blend in N-dimethylformamide, is then dropwise added drop-wise to dispersion liquid in a large amount of methyl alcohol, after polystyrene rapid precipitation, obtain Graphene polymer composite (reference 1:Nature, 2006,442,282).The people such as Brinson use similar rapid subsidence method to make Graphene in polymethacrylate, keep disperseing uniformly (reference 2:Nature Nanotechnology, 2008,3,327).The people such as Loose carry out blend by previously prepared Graphene aqueous dispersions and polystyrene emulsion, then by this mixture liquid nitrogen quick freezing, carry out again lyophilize, finally obtain polystyrene/graphene composite powder (reference 3:Journal of Materials Chemistry, 2010,20,3035).Wang Zhaoqun etc. once carried out simple blend by graphene oxide and polystyrene microsphere, under blend state, graphene oxide is reduced, Graphene is closely wrapped in to Surfaces of Polystyrene Microparticles, obtain polystyrene/graphene composite particle (reference 4: Chinese invention patent micro-, nanoscale, the preparation method of polystyrene/graphene composite particle, application number: 201110189423.9).This composite particles with miniature scale can be used to further prepare the Graphene polymer composite of big scale.
In brief, prior art has following features: the first, for graphene uniform is dispersed in polymer, adopt above-mentioned liquid-phase mixing method generally need to use a large amount of organic solvents, both raised the cost, be more unfavorable for environmental protection; The second, for the homogeneously dispersed state that obtain early stage is kept, often need to use rapid precipitation and lyophilize etc. fixing and freeze the means of original structure rapidly, can bring undoubtedly the weakness such as the complicated and energy consumption raising of process; Three, prior art can not make Graphene in macromolecule matrix, reach complete and farthest dispersed, can not be more effectively and control in an orderly manner the structure of Graphene polymer composite.In other words, these conventional methods cannot be prepared the three-dimensional structure of strict high-sequential.
Summary of the invention
The object of the invention is to the method that proposes the network-like Graphene polymer composite of a kind of Graphene and prepare this matrix material.
The Graphene polymer composite of three-dimensional high-sequential proposed by the invention, its internal structure can be described as, and in macromolecule matrix, Graphene is the network-like of three-dimensional long-range high-sequential.
The matrix material with said structure proposed by the invention, its preparation method is: first with graphene coated polymer microsphere, make polymer/graphene composite particle, then gained polymer/graphene composite particle is repressed or casting, obtains the network-like Graphene polymer composite of a kind of Graphene.
Graphene polymer composite of the present invention, wherein polymer is polystyrene, polymethacrylate, polyacrylate(s), cinnamic acrylic ester analog copolymer, vinylformic acid-Polymers, polyacrylamide, polyethylene, polysiloxane, poly-alkylsiloxane, phenyl silicone, resol, resorcinol formaldehyde resin.The mass ratio of polymer and Graphene is 500:1-50.
Matrix material proposed by the invention and preparation method thereof has following outstanding feature: (1) Graphene is dispersed in macromolecule matrix, forms regular, even, complete three-dimensional network; (2) in technology of preparing, adopted the assembling of " by matrix to whole " to build theory, its process is simple, controllability strong, low-loss, less energy-consumption; (3) not with an organic solvent, environmental protection.
The preparation method of Graphene polymer composite proposed by the invention is as follows:
1. the preparation of polymer/graphene composite particle
The aqueous dispersions of polymer microsphere is mixed with the aqueous dispersions of graphene oxide, after stirring, graphene oxide is carried out to chemical reduction, by centrifugation, remove water medium, more after drying, obtain the polymer/graphene composite particle of Graphene parcel polymer microsphere.
Above-mentioned polymer microsphere used can obtain by various chemistry or physical method, also can adopt commercially available commodity; The graphene oxide adopting can obtain by conventional preparation method, also can adopt commercially available commodity.
2. the preparation of Graphene polymer composite
Adopt above-mentioned gained polymer/graphene composite particle to prepare the Graphene polymer composite of three-dimensional high-sequential, forming method can adopt any one in following three kinds of approach:
A. cold press process: at room temperature select certain pressure that polymer/graphene composite particle is pressed, resulting materials carries out aftertreatment at a certain temperature, finally obtains Graphene polymer composite.
In this process, pressure used is not less than 10MPa, and be 2～120 minutes clamping time; Temperature used can be selected according to the second-order transition temperature of macromolecular material used (Tg), and its scope is (Tg+10)～(Tg+30) ℃, and the time is 1～5 hour.
B. pressure sintering: select at a certain temperature certain pressure that polymer/graphene composite particle is pressed.
In this process, pressure used is not less than 1MPa, and temperature range used may be selected to be (Tg+10)～(Tg+30) ℃, and be 2～120 minutes clamping time.
C. casting: polymer/graphene composite particle is carried out to centrifuge washing, water is configured to dispersion liquid and drops in mould, first dry at 60～90 ℃, after being evaporated, most of moisture content improves temperature to certain limit, or apply certain pressure simultaneously, carry out later stage moulding, finally obtain graphene-based polymer composite.
During later stage moulding, the temperature range that adopts is (Tg+20)～(Tg+50) ℃, as exerted pressure simultaneously, is not less than 1MPa, and the treatment time is 1～5 hour.
Accompanying drawing explanation
Accompanying drawing 1
Polymer microsphere/graphene composite particle and three-dimensional high-sequential Graphene polymer composite transverse section stereoscan photograph in kind is to adopt HIT to produce S-4800 type scanning electronic microscope to record:
(A) be polymer microsphere/graphene composite particle, magnification: 10,000 times, in figure, visible Graphene is wrapped in the surface of polymer microsphere;
(B) transverse section of three-dimensional high-sequential Graphene polymer composite any direction, magnification: 5000 times;
(C) transverse section of three-dimensional high-sequential Graphene polymer composite any direction, magnification: 9000 times;
(D) transverse section of three-dimensional high-sequential Graphene polymer composite any direction, magnification: 2.2 ten thousand times.
(B)～(D) in, the orderly regular network structure being formed by Graphene section as seen, obviously, by the control of moulding process and the selection of mould, can realize this Graphene network large-scale high-sequential on three dimension scale.
Accompanying drawing 2
Structure and the preparation process schematic diagram thereof of three-dimensional high-sequential Graphene polymer composite, first with Graphene, wrap up polymer microsphere, make polymer microsphere/graphene composite particle, as construction unit, adopt corresponding moulding process, make the three-dimensional high-sequential Graphene polymer composite with big scale, wherein the Graphene of polymer microsphere surface overlaps each other, interconnects, and forms one and complete is embedded in the Graphene network in macromolecule matrix.
Specific embodiments
Embodiment 1
The polystyrene microsphere that adopts conventional dispersion copolymerization method to make, its number average bead diameter is 2.2 microns, is dispersed in water and obtains the polystyrene emulsion that solid content is 10wt%.
In four-necked bottle, by 5g Graphite Powder 99,2.5gNaNO
3, the 115mL vitriol oil mixes, and mechanical stirring in 0 ℃ of ice-water bath, slowly adds 15g potassium permanganate under vigorous stirring, strictly control temperature lower than 20 ℃, stirs 2 hours.Move to 35 ℃ of stirred in water bath reactions 1 hour.After reaction finishes, slowly add 100mL deionized water under stirring, temperature remains on 50 ℃ of left and right, continue to stir 30 minutes, drip 3% superoxol, with 10% hydrochloric acid centrifuge washing, with deionized water, be washed till neutrality again, be dispersed in deionized water through the ultrasonic graphene oxide dispersion liquid that obtains.
In mechanical stirring and ultrasonic in the situation that, to adding 10mL particle diameter in 100mL deionized water, be polystyrene microsphere dispersion liquid (solid content is 10wt%) and the 2mL graphene oxide dispersion liquid (solid content is 1mg/mL) of 2.2 microns successively, this mixed system is moved in 100 ℃ of oil baths, under magnetic agitation, the 45wt%HI solution that adds 1mL, continues reaction 24 hours.After reaction finishes, centrifugal removal medium, by 60 ℃ of dried overnight after ethanol and deionized water wash product, obtains polystyrene/graphene composite particle.The mass ratio of polystyrene and Graphene is 500:1.
Under 30MPa, gained polystyrene/graphene composite particle is put into the compacting of mould normal temperature, pressurize 2 minutes is then heated 1 hour at 120 ℃, finally obtains Graphene poly styrene composite material.
Embodiment 2
Adopt polystyrene particle and graphene oxide solution in embodiment 1.
In mechanical stirring and ultrasonic in the situation that, to adding 10mL particle diameter in 100mL deionized water, be polystyrene microsphere dispersion liquid (solid content is 10wt%) and the 100mL graphene oxide dispersion liquid (solid content is 1mg/mL) of 2.2 microns successively, this mixed system is moved in 100 ℃ of oil baths, under magnetic agitation, the 45wt%HI solution that adds 10mL, continues reaction 24 hours.After reaction finishes, centrifugal removal medium, by 60 ℃ of dried overnight after ethanol and deionized water wash product, obtains polystyrene/graphene composite particle.The mass ratio of polystyrene and Graphene is 10:1.
Under 30MPa, gained polystyrene/graphene composite particle is put into the compacting of mould normal temperature, pressurize 2 minutes is then heated 3 hours at 135 ℃, finally obtains Graphene poly styrene composite material.
Embodiment 3
Adopt polystyrene particle and graphene oxide solution in embodiment 1.
In mechanical stirring and ultrasonic in the situation that, to adding 10mL particle diameter in 100mL deionized water, be polystyrene microsphere dispersion liquid (solid content is 10wt%) and the 2mL graphene oxide dispersion liquid (solid content is 1mg/mL) of 2.2 microns successively, this mixed system is moved in 100 ℃ of oil baths, under magnetic agitation, the 45wt%HI solution that adds 1mL, continues reaction 24 hours.After reaction finishes, centrifugal removal medium, by 60 ℃ of dried overnight after ethanol and deionized water wash product, obtains polystyrene/graphene composite particle.The mass ratio of polystyrene and Graphene is 500:1.
Under 5MPa, gained polystyrene/graphene composite particle is put into mould and at 130 ℃, suppress 20 minutes, finally obtain Graphene poly styrene composite material.
Embodiment 4
Adopting dispersion copolymerization method to prepare particle diameter is the polystyrene microsphere of 3.5 microns, is dispersed in water and obtains the polystyrene emulsion that solid content is 10wt%.
Adopt the graphene oxide solution in embodiment 1.
In mechanical stirring and ultrasonic in the situation that, to adding 10mL particle diameter in 100mL deionized water, be polystyrene microsphere dispersion liquid (solid content is 10wt%) and the 2mL graphene oxide dispersion liquid (solid content is 1mg/mL) of 2.2 microns successively, this mixed system is moved in 100 ℃ of oil baths, under magnetic agitation, the 45wt%HI solution that adds 1mL, continues reaction 24 hours.After reaction finishes, centrifugal removal medium, by 60 ℃ of dried overnight after ethanol and deionized water wash product, obtains polystyrene/graphene composite particle.The mass ratio of polystyrene and Graphene is 100:1.
Under 30MPa, gained polystyrene/graphene composite particle is put into the compacting of mould normal temperature, pressurize 3 minutes is then heated 3 hours at 135 ℃, finally obtains Graphene poly styrene composite material.
Embodiment 5
Adopt dispersion polymerization to carry out the copolymerization of polystyrene-ethyl propenoate, making particle diameter is poly-(styrene-propene acetoacetic ester) microballoon of 3 microns, and obtains the dispersion liquid that solid content is 10wt%.
Adopt the graphene oxide solution in embodiment 1.
In mechanical stirring and ultrasonic in the situation that, in 100mL deionized water, add poly-(styrene-propene acetoacetic ester) particle dispersion (solid content is 10wt%) of 10mL and 10mL graphene oxide dispersion liquid (solid content is 1mg/mL) successively, this mixed system is moved in 100 ℃ of oil baths, under magnetic agitation, the 45wt%HI solution that adds 2mL, continues reaction 24 hours.After reaction finishes, centrifugal removal medium, by 60 ℃ of dried overnight after ethanol and deionized water wash product, obtains poly-(styrene-propene acetoacetic ester)/graphene composite particle.The mass ratio of poly-(styrene-propene acetoacetic ester) and Graphene is 100:1.
Under 30MPa, poly-(styrene-propene the acetoacetic ester)/graphene composite particle of gained is put into the compacting of mould normal temperature, pressurize 2 minutes is then heated 2 hours at 110 ℃, finally obtains poly-(styrene-propene acetoacetic ester) matrix material of Graphene.
Embodiment 6
Adopt dispersion polymerization to carry out the copolymerization of polystyrene-ethyl propenoate, making particle diameter is poly-(styrene-propene acetoacetic ester) microballoon of 5 microns, and obtains the dispersion liquid that solid content is 10wt%.
Adopt the graphene oxide solution in embodiment 1.
In mechanical stirring and ultrasonic in the situation that, in 100mL deionized water, add poly-(styrene-propene acetoacetic ester) particle dispersion (solid content is 10wt%) of 10mL and 10mL graphene oxide dispersion liquid (solid content is 1mg/mL) successively, this mixed system is moved in 100 ℃ of oil baths, under magnetic agitation, the 45wt%HI solution that adds 2mL, continues reaction 24 hours.After reaction finishes, centrifugal removal medium, by 60 ℃ of dried overnight after ethanol and deionized water wash product, obtains poly-(styrene-propene acetoacetic ester)/graphene composite particle.The mass ratio of poly-(styrene-propene acetoacetic ester) and Graphene is 100:1.
Gained composite particles is dispersed in appropriate amount of deionized water, directly pours mould into, at 90 ℃, be heated to after most of water evaporates, be warmed up to 110 ℃ of heating 4 hours, obtain poly-(styrene-propene acetoacetic ester) matrix material of final Graphene.
Embodiment 7
Adopting particle diameter is the commercial polyethylene microballoon of 70 microns and the graphene oxide solution in embodiment 1.
In mechanical stirring and ultrasonic in the situation that, in 100mL deionized water, add 1g polyethylene microballoon and 10mL graphene oxide dispersion liquid (solid content is 1mg/mL) successively, this mixed system is moved in 100 ℃ of oil baths, under magnetic agitation, the 45wt%HI solution that adds 2mL, continues reaction 24 hours.After reaction finishes, centrifugal removal medium, by 60 ℃ of dried overnight after ethanol and deionized water wash product, obtains polyethylene/graphene composite particles.The mass ratio of polyethylene and Graphene is 100:1.
Under 30MPa, gained polystyrene/graphene composite particle is put into the compacting of mould normal temperature, pressurize 10 minutes is then heated 3 hours at 150 ℃, finally obtains Graphene composite polyethylene material.
Embodiment 8
Adopting particle diameter is 50 microns commercially available or the resitol microballoon making by physical method and the graphene oxide solution in embodiment 1.
In mechanical stirring and ultrasonic in the situation that, in 100mL deionized water, add 1g resitol microballoon and 10mL graphene oxide dispersion liquid (solid content is 1mg/mL) successively, this mixed system is moved in 100 ℃ of oil baths, under magnetic agitation, the 45wt%HI solution that adds 2mL, continues reaction 24 hours.After reaction finishes, centrifugal removal medium, by 60 ℃ of dried overnight after ethanol and deionized water wash product, obtains resol/graphene composite particle.The mass ratio of resol and Graphene is 100:1.
Under 30MPa, gained resol/graphene composite particle is put into mould and at 150 ℃, suppress 2 hours, finally obtain graphene-based phenolic resin composite.
Claims (5)
1. the network-like Graphene polymer composite of Graphene, is characterized in that: in macromolecule matrix, graphene uniform disperses to be the network-like of three-dimensional long-range high-sequential, and the mass ratio of polymer and Graphene is 500:1-50.
2. according to Graphene polymer composite claimed in claim 1, it is characterized in that described polymer is polystyrene, polymethacrylate, polyacrylate(s), cinnamic acrylic ester analog copolymer, vinylformic acid-Polymers, polyacrylamide, polyethylene, polysiloxane, poly-alkylsiloxane, phenyl silicone, resol, asks dihydroxy-benzene formaldehyde resin.
3. the preparation method of the network-like Graphene polymer composite of a Graphene, it is characterized in that first preparing Graphene and be wrapped in the polymer/graphene composite particle on polymer microsphere, then by the method for compacting or casting, make Graphene polymer composite.
4. according to the preparation method of Graphene polymer composite claimed in claim 3, it is characterized in that described shaping method to suppress: select at a certain temperature certain pressure that polymer/graphene composite particle is pressed, pressure used is not less than 1MPa, temperature range used may be selected to be (Tg+10)～(Tg+30) ℃, and be 2～120 minutes clamping time.
5. according to the preparation method of Graphene polymer composite claimed in claim 3, it is characterized in that described cast shaping process: polymer/graphene composite particle is carried out to centrifuge washing, water is configured to dispersion liquid and drops in mould, first dry at 60～90 ℃, after being evaporated, most of moisture content improves temperature to certain limit, or apply certain pressure simultaneously, and carry out later stage moulding, finally obtain graphene-based polymer composite; During later stage moulding, the temperature range that adopts is (Tg+20)～(Tg+50) ℃, as exerted pressure simultaneously, is not less than 1MPa, and the treatment time is 1～5 hour.
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| CN109796682A (en) * | 2018-12-18 | 2019-05-24 | 武汉金牛经济发展有限公司 | Heat-resisting PPR pipe of toughening and preparation method thereof |
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| CN113999445A (en) * | 2021-10-20 | 2022-02-01 | 国网电力科学研究院有限公司 | Graphene/polyethylene composite material and preparation method thereof |
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