CN102827315B - Graphene oxide/polystyrene nano composite and preparation method thereof - Google Patents
Graphene oxide/polystyrene nano composite and preparation method thereof Download PDFInfo
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- CN102827315B CN102827315B CN201210313556.7A CN201210313556A CN102827315B CN 102827315 B CN102827315 B CN 102827315B CN 201210313556 A CN201210313556 A CN 201210313556A CN 102827315 B CN102827315 B CN 102827315B
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Abstract
The invention discloses a graphene oxide/polystyrene nano composite and a preparation method thereof. The preparation method includes preparing a graphene oxide nanosheet; using graphene oxide as a solid surfactant to obtain stable Pickering emulsion under actions of coordination and stabilization of salt; and polymerizing the in-situ emulsion to obtain the graphene oxide/polystyrene nano composite. The specific steps of the preparation method include oxidizing natural flake graphite by oxidants to obtain graphite oxide, carrying out ultrasonic exfoliation and centrifugal separation to obtain graphene oxide, adding the graphene oxide into salt solution and stirring the mixed solution to form a uniform dispersed system containing the graphene oxide and salt; and adding styrene into the dispersed system, carrying out ultrasonic treatment to obtain the stable Pickering emulsion, adding initiators into the Pickering emulsion, stirring and polymerizing to obtain the graphene oxide/polystyrene nano composite. The preparation method is good in repeatability, has the advantages of mild reaction conditions, low energy consumption and easiness in operation and brings convenience for industrialized implementation.
Description
One, technical field
The present invention relates to a kind of polymer composite and preparation method thereof, it is specifically dispersion medium with water, with stannic oxide/graphene nano sheet for solid surfactant, under the synergistic stability effect of salt, simply, stable Pickering emulsion has effectively been prepared, after in-situ emulsion polymerization, obtain graphene oxide/polystyrene nano composite material.
Two, background technology
Due to the special property of Graphene in mechanics, quantum and electricity, the preparation of recent Graphene/polymer composites is subject to people and more and more pays close attention to.
Graphite oxide is considered to the strategic starting point of extensive synthesizing graphite alkene, after Brodie in 1859 prepares, just obtains and studies widely.Graphene oxide (GO) is the monoatomic layer material (thickness is about 1nm) after graphite oxide is peeled off further, it is the precursor of the Graphene with accurate two-dirnentional structure, compare with carbon nanotube with the soccerballene of costliness, it is cheap, raw material is easy to get, and is expected to the high quality filler becoming polymer nanocomposites.Structurally, graphene oxide is made up of the basal plane (on basal plane containing many oh groups and cycloalkyl groups) of hydrophobic unoxidized aromatic region and the edge of hydrophilic carboxylic group, present hydrophobic to hydrophilic property distribution (Lerf from central authorities to edge, A., et al.Structure of graphiteoxide revisited.J.Phys.Chem.B, 1998,102:4477-4482).Stannic oxide/graphene nano sheet is because having ionizable edge :-COOH group, make it in water, have superior dispersiveness, therefore GO is also considered as hydroaropic substance by people for a long time, but recent result of study shows, in fact GO has amphipathic, the energy between interface can be reduced, play the effect of interfacial agent.As: Huang method (the Jiaxing Huang of simple shaking, et al.Graphene oxidesheets at interfaces.J.Am.Chem.Soc., 2010, 132:8180-8186) and Sharif etc. use high-power ultrasonic method (Sharif, F., et al.Self assembly of graphene oxide at the liquid – liquid interface:A new route to thefabrication of graphene based composites.Soft Matter, 2011, Pickering emulsion and corresponding graphene oxide/polymer composites 7:3432-3440) are prepared, but operationally also have a certain distance with aspects such as energy consumptions far from actual industrial production.
At present, the compound of graphene oxide and polymkeric substance mainly adopts the method for mechanically mixing: generally first synthesize macromolecular material under certain conditions, and then added in graphene oxide lamella, carry out mechanically mixing.The shortcoming of the method is that the unable bonding interface of graphene oxide sheet and polymkeric substance is in poor shape, and dispersed uneven.This makes the performance of the single-material in graphene oxide/polymer composites, especially the characteristic of graphene oxide, is difficult to better play in the composite, and the over-all properties of matrix material is not high; The method complex operation step, preparation condition are harsher in addition, thus limit its further industrial application.
Three, summary of the invention
The present invention aims to provide a kind of graphene oxide/polystyrene nano composite material and preparation method thereof, technical problem to be solved improves emulsifying capacity when graphene oxide uses as solid surfactant, promote its absorption on oil/water interface, obtain stable Pickering emulsion, and for polyreaction.
The present invention is by the complex role of salt, reduce the surface potential of chip solid tensio-active agent (stannic oxide/graphene nano sheet), thus the absorption of accelerating oxidation graphene nanometer sheet on oil/water interface, obtain stable Pickering emulsion, and for polyreaction.
Technical solution problem of the present invention adopts following technical scheme:
Graphene oxide/polystyrene nano composite material of the present invention, it is characterized in that: described matrix material is is dispersion medium with water, be solid surfactant with graphene oxide, take vinylbenzene as polymerization single polymerization monomer, by graphene oxide/polystyrene nano composite material that the method for in-situ emulsion polymerization obtains under the synergistic stability effect of salt;
Wherein graphene oxide and cinnamic mass ratio are 0.03-0.5:1.0-10;
Described salt is selected from sodium-chlor, Repone K or ammonium chloride.
The preparation method of graphene oxide/polystyrene nano composite material of the present invention, comprises the preparation of graphene oxide, the preparation of Pickering emulsion, polymerization and each unit process of aftertreatment:
The preparation of described graphene oxide be by 230mL concentration be 98% sulphuric acid soln and 5g SODIUMNITRATE mixing, be cooled under ice-water bath lower than 5 DEG C, 10g crystalline flake graphite is added under stirring, 30g potassium permanganate is added after mixing, control temperature of reaction is 10-15 DEG C, react after 2 hours and be warming up to 35 DEG C of continuation stirring reactions 2 hours, the mode added water continuously is adopted to add deionized water 460mL, control reacting liquid temperature at 98 DEG C, continue to stir 30min, then 1.4L deionized water termination reaction is added, add the hydrogen peroxide of 25mL mass concentration 30% again, filtered while hot, and wash to filtrate without SO with hydrochloric acid soln
4 2-, then with deionized water wash to neutral.The filter cake of gained is re-dispersed in water, form uniform solution, after ultrasonic stripping, with whizzer high speed centrifugation (10000r/min) 5min, be separated the graphite oxide of the unoxidized graphite of removing and multilayer, obtain stannic oxide/graphene nano sheet (Hummers WS.and Offeman RE.Preparation of graphitic oxide.J.Am.Chem.Soc., 1958,80:1339.).
The preparation of described Pickering emulsion joins in the salts solution of 89-98 mass parts concentration 0.05-1.0M by the graphene oxide of 0.03-0.5 mass parts, add the styrene monomer of 1.0-10 mass parts after stirring, ultrasonic disperse forms stable Pickering emulsion; Described salt is selected from sodium-chlor, Repone K or ammonium chloride;
Described polymerization is added by initiator in described Pickering emulsion, the mass ratio of described initiator and styrene monomer is 0.5-1:100, in 65-85 DEG C of stirring reaction 2-6 hour, be cooled to room temperature after reaction terminates, filtration, washing also vacuum-drying obtain graphene oxide/polystyrene nano composite material.
Described initiator is water soluble starter.
Described initiator is selected from Potassium Persulphate, Sodium Persulfate or ammonium persulphate.
The present invention take water as dispersion medium, with stannic oxide/graphene nano sheet for solid surfactant, under the synergistic stability effect of salt, simply, effectively prepare stable Pickering emulsion, after in-situ emulsion polymerization, obtain graphene oxide/polystyrene nano composite material.The inventive method reproducible, have reaction conditions gentleness, energy consumption is low, and the feature of easy handling, is convenient to industrializing implementation.
Four, accompanying drawing explanation
Fig. 1 is the atomic force microscope figure of graphene oxide.As can be seen from Figure 1, the thickness of stannic oxide/graphene nano sheet is about about 1nm, this graphene oxide for individual layer obtained, and its lateral dimension is not of uniform size, presents polymolecularity.
Fig. 2 is the stable Pickering emulsion photo of graphene oxide and salt.As can be seen from Figure 2, Pickering emulsion dispersion is even, does not occur demixing phenomenon.
Fig. 3 is the stable Pickering emulsion photo (concentration of NaCl is respectively from left to right: 0,0.01,0.05,0.1,0.5,1.0mol/L) of salt (NaCl) the synergistic oxidation Graphene of placement different concns after 3 days.As can be seen from Figure 3, under comparatively low salt concn, exist obvious profit from phenomenon; Along with the raising of salt concn, stability of emulsion improves gradually, and effect is best when concentration reaches 0.1M; But when salt concn continues to improve, bottom has aqueous phase to separate out.
Fig. 4 is the transmission electron microscope photo of graphene oxide/polystyrene nano composite material.As can be seen from Figure 4, in matrix material, polystyrene length is on graphene oxide sheet, and the mean diameter of polystyrene is 30-100nm, defines graphene oxide/pipe/polyhenylethylene nano mixture.
Five, embodiment
Embodiment 1:
1, the preparation of graphene oxide
In the beaker of drying, add the vitriol oil and the 5g SODIUMNITRATE of 230mL mass concentration 98%, cool under ice-water bath, when the temperature of system is lower than 5 DEG C, stirs and add 10g crystalline flake graphite, mix and slowly add 30g potassium permanganate (KMnO afterwards
4), control temperature of reaction is 10-15 DEG C, react the water bath with thermostatic control after 2 hours, beaker being placed in 35 DEG C, continue stirring reaction 2 hours, adopt the mode added water continuously to add deionized water 460mL, control reacting liquid temperature at 98 DEG C, continue to stir 30min, add 1.4L deionized water termination reaction, then add the hydrogen peroxide of 25mL mass concentration 30%, filtered while hot, and with dilute hydrochloric acid (l:10 volume ratio), product is washed to filtrate without SO
4 2-(BaC1
2solution detects without precipitation), then with deionized water wash to neutral.The filter cake of gained is re-dispersed in water, forms uniform solution, after ultrasonic stripping, with whizzer high speed centrifugation (10000r/min) 5min, be separated the graphite oxide of the unoxidized graphite of removing and multilayer, obtain graphene oxide as shown in Figure 1.
2, the preparation of Pickering emulsion
Graphene oxide prepared by 60mg step 1 is joined 40mL(42.3g) concentration is in the NaCl solution of 1.0M, after stirring, form the dispersed system of graphene oxide and salt, 2.0g styrene monomer is added in the dispersion system of gained, ultrasonic disperse 10-60min forms stable Pickering emulsion, as shown in Figures 2 and 3, concentration of styrene 0.48mol/L.
3, be polymerized
By 10mg initiator K
2s
2o
8add in Pickering emulsion, in 65-85 DEG C of stirring reaction 2-6 hour, be cooled to room temperature after reaction terminates, filtration, washing also vacuum-drying obtain graphene oxide/poly styrene composite material.
The transmission electron microscope photo of matrix material prepared by the present embodiment is shown in Fig. 4.As can be seen from Figure 4, in matrix material, polystyrene sphere length is on graphene oxide sheet, and the mean diameter of polystyrene is 30-100nm, defines graphene oxide/pipe/polyhenylethylene nano mixture.
Embodiment 2:
1, the preparation method of graphene oxide is with embodiment 1.
2, the preparation of Pickering emulsion
Graphene oxide prepared by 60mg step 1 is joined in the NaCl solution of 40mL concentration 0.5M, after stirring, form the dispersed system of graphene oxide and salt, 2.0g styrene monomer is added in the dispersion system of gained, ultrasonic disperse 10-60min forms stable Pickering emulsion, concentration of styrene 0.48mol/L.
3, be polymerized
By 10mg initiator K
2s
2o
8add in Pickering emulsion, in 65-85 DEG C of stirring reaction 2-6 hour, be cooled to room temperature after reaction terminates, filtration, washing also vacuum-drying obtain graphene oxide/poly styrene composite material.
Embodiment 3:
1, the preparation method of graphene oxide is with embodiment 1.
2, the preparation of Pickering emulsion
Graphene oxide prepared by 100mg step 1 being joined 40mL concentration is in the NaCl solution of 0.2M, after stirring, form the dispersed system of graphene oxide and salt, 2.0g styrene monomer is added in the dispersion system of gained, ultrasonic disperse 10-60min forms stable Pickering emulsion, concentration of styrene 0.48mol/L.
3, be polymerized
By 10mg initiator K
2s
2o
8add in Pickering emulsion, in 65-85 DEG C of stirring reaction 2-6 hour, be cooled to room temperature after reaction terminates, filtration, washing also vacuum-drying obtain graphene oxide/poly styrene composite material.
Embodiment 4:
1, the preparation method of graphene oxide is with embodiment 1.
2, the preparation of Pickering emulsion
Graphene oxide prepared by 72mg step 1 is joined the NH of 30mL concentration 0.1M
4in Cl solution, after stirring, form the dispersed system of graphene oxide and salt, add in the dispersion system of gained by 1.8g styrene monomer, ultrasonic disperse 10-60min forms stable Pickering emulsion, concentration of styrene 0.58mol/L.
3, be polymerized
By 9mg initiator K
2s
2o
8add in Pickering emulsion, in 65-85 DEG C of stirring reaction 2-6 hour, be cooled to room temperature after reaction terminates, filtration, washing also vacuum-drying obtain graphene oxide/poly styrene composite material.
Embodiment 5:
1, the preparation method of graphene oxide is with embodiment 1.
2, the preparation of Pickering emulsion
Graphene oxide prepared by 60mg step 1 is joined in the KCl solution of 35mL concentration 0.2M, after stirring, form the dispersed system of graphene oxide and salt, 1.2g styrene monomer is added in the dispersion system of gained, ultrasonic disperse 10-60min forms stable Pickering emulsion, concentration of styrene 0.32mol/L.
3, be polymerized
By 5mg initiator Na
2s
2o
8add in Pickering emulsion, in 65-85 DEG C of stirring reaction 2-6 hour, be cooled to room temperature after reaction terminates, filtration, washing also vacuum-drying obtain graphene oxide/poly styrene composite material.
Embodiment 6:
1, the preparation method of graphene oxide is with embodiment 1.
2, the preparation of Pickering emulsion
Graphene oxide prepared by 80mg step 1 is joined in the NaCl solution of 50mL concentration 0.3M, after stirring, form the dispersed system of graphene oxide and salt, 2g styrene monomer is added in the dispersion system of gained, ultrasonic disperse 10-60min forms stable Pickering emulsion, concentration of styrene 0.38mol/L.
3, be polymerized
By 8mg initiator (NH
4)
2s
2o
8add in Pickering emulsion, in 65-85 DEG C of stirring reaction 2-6 hour, be cooled to room temperature after reaction terminates, filtration, washing also vacuum-drying obtain graphene oxide/poly styrene composite material.
Claims (1)
1. a graphite oxide alkene ∕ polystyrene nano composite material, it is characterized in that preparing according to the following steps:
1) preparation of graphene oxide
The vitriol oil and the 5g SODIUMNITRATE of 230mL mass concentration 98% is added in the beaker of drying, cool under ice-water bath, when the temperature of system is lower than 5 DEG C, stirring adds 10g crystalline flake graphite, mix and slowly add 30g potassium permanganate afterwards, control temperature of reaction is 10-15 DEG C, react the water bath with thermostatic control after 2 hours, beaker being placed in 35 DEG C, continue stirring reaction 2 hours, the mode added water continuously is adopted to add deionized water 460mL, control reacting liquid temperature at 98 DEG C, continue to stir 30min, add 1.4L deionized water termination reaction, add the hydrogen peroxide of 25mL mass concentration 30% again, filtered while hot, and with dilute hydrochloric acid, product is washed to filtrate without SO
4 2-, then with deionized water wash to neutral, the filter cake of gained is re-dispersed in water, forms uniform solution, after ultrasonic stripping, with whizzer with the centrifugal 5min of 10000r/min, be separated the graphite oxide of the unoxidized graphite of removing and multilayer, obtain graphene oxide,
2) preparation of Pickering emulsion
It is in the NaCl solution of 1.0M that graphene oxide prepared by 60 mg step 1) is joined 40mL concentration, after stirring, form the dispersed system of graphene oxide and salt, 2.0g styrene monomer is added in the dispersion system of gained, ultrasonic disperse 10-60 min forms stable Pickering emulsion, concentration of styrene 0.48mol/L;
3) be polymerized
By 10mg initiator K
2s
2o
8add in Pickering emulsion, in 65-85 DEG C of stirring reaction 2-6 hour, be cooled to room temperature after reaction terminates, filtration, washing also vacuum-drying obtain graphite oxide Xi ∕ poly styrene composite material.
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