CN101864005A - Method for preparing polymer/graphene composite material - Google Patents
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Abstract
The invention discloses a method for preparing a polymer/graphene composite material, which comprises: firstly, uniformly dispersing graphite powder in a polymer liquid medium, and grinding and stripping the graphite by using grinding balls to obtain polymer/graphene suspension; and secondly, obtaining the polymer/graphene composite material by adopting a method of adding a precipitator into the polymer/graphene suspension to precipitate the polymer and graphene from the solution, or a method of directly initiating the polymerization of a polymer monomer or a method of curing a prepolymer of the polymer. The method is a new in-situ graphene preparation and compounding method. Once generated, the graphene is enveloped and isolated by polymer molecules or the prepolymer monomer, so the self-agglomeration of the graphene is prevented effectively. In addition, the mechanical grinding in the polymer liquid medium ensures the full mixing of the filler and the polymer, so that the graphene can disperse in a polymer substrate more effectively. And the mechanical ball grinding process makes scale expansion and the realization of industrial production easier.
Description
Technical field
The present invention relates to a kind of method for preparing the polymer-based carbon graphene composite material, belong to technical field of nano material.
Background technology
Current research shows that when the thickness of graphite crystal is less than 10 carbon atomic layers (thickness is generally less than 5 nanometers) graphite material will show and the distinct a series of excellent properties of common three-dimensional graphite.This graphite flake with atom level thickness is referred to as Graphene (Graphene).Studies show that the specific surface area of Graphene can be up to 2600m2/g; Young's modulus is about 1100GPa; Breaking tenacity is 125GPa; Keep good physical strength and the thermal conductivity of graphite crystal, be respectively 1060GPa and 5000W/mK.In addition, Graphene also shows excellent electron transport ability, and its electronic mobility is up to 15000cm2/VS under the room temperature.The a series of performances of this of Graphene make it show huge magnetism as the performance function filler in the polymer composites field.
The Graphene that the key point of preparation high-performance polymer/graphene composite material is how effectively to obtain q.s is used for polymkeric substance is filled and its homogeneous is dispersed in polymeric matrix.(micromechanics is peeled off method yet in existing numerous graphene preparation method, graphite oxidation is peeled off method, chemical vapour deposition and epitaxial growth method, ultrasonic wave is peeled off method, electrolytic oxidation etc.) in, only there is this approach of graphite oxide can provide abundant Graphene to be used for the preparation of polymer composites.Therefore, existing polymer/graphene composite material makes by graphite oxide.But, graphite oxide is different from the original crystalline structure of graphite linings fully because, peeling off the structure of the resulting graphene oxide sheet in back by the high strength oxidation.Though graphene oxide structure in follow-up reduction process can be more prone to graphite itself, but still be difficult to return to fully the original crystalline structure of graphite linings, cause structural defective, not only influence its specific conductivity, also can bring very serious reunion certainly in the recombination process, Graphene can not be disperseed in polymkeric substance most effectively, and the reinforced effects of Graphene and intrinsic advantage are difficult to give full play to.
Before this, though there have been some reports to relate to nano-graphite microplate (or Graphene microplate) matrix material (Jiang BZ et al.J Mater Sci 2,008 43,5092-5101 (2008); Du XF et al.Chem Mater 20 (6), 2066-2091 (2008); Chen et al.Adv Funct Mater17 (6): 898-904 (2007)), but, since its sheet thickness all at dozens of to hundreds of carbon atomic layers, and its preparation method all adopts traditional blend compounding technology, Nano filling is difficult to obtain effective homogeneous and disperses in polymeric matrix.
Summary of the invention
The invention provides a kind of preparation method of simple and direct effective polymer/graphene composite material, it can realize that when obtaining the Graphene of q.s the homogeneous of Graphene in polymeric matrix disperses, thereby can prepare the polymer/graphene composite material of conduction diafiltration value low (the filler loading level is few).
Technical scheme of the present invention is such: a kind of method for preparing polymer/graphene composite material, realize as follows:
One, the liquid medium of abrading-ball, Graphite Powder 99 and polymkeric substance is placed ball-grinding machine, carry out the mechanical mill of certain hour, Graphite Powder 99 is ground stripping, and the mixing suspension that the graphite dispersion liquid after then the liquid medium of polymkeric substance being shelled together with mill is formed takes out from ball-grinding machine;
Two, with the mixing suspension of step 1 gained by cohesion, separate out or directly the method for initiated polymerization obtain polymer/graphene composite material.
Above-mentioned polymer liquid body medium is a polymers soln, and in the above-mentioned steps two, the adding precipitation agent makes polymer composites condense to separate out from solvent and obtains polymer/graphene composite material in the mixing suspension of step 1 gained.
Above-mentioned polymer liquid body medium is one or more the mixture in liquid polymer monomer, polymer monomer solution, liquid polymer performed polymer or the polymkeric substance prepolymer solution, in the above-mentioned steps two, the mixing suspension of step 1 gained is carried out polymerization obtain polymer/graphene composite material.
Above-mentioned polymer liquid body medium is one or more the mixture in polymers soln and liquid polymer monomer, polymer monomer solution, liquid polymer performed polymer, the polymkeric substance prepolymer solution, in the above-mentioned steps two, mixture to the polymer monomer in the mixing suspension of step 1 gained, polymkeric substance performed polymer or polymer monomer and polymkeric substance performed polymer carries out polymerization earlier, in mixed system, add precipitation agent then, make polymer composites from solvent, condense to separate out and obtain polymer/graphene composite material.
In the above-mentioned steps one, earlier Graphite Powder 99 is dispersed in the polymer liquid body medium, forms graphite suspension, carry out mechanical mill in the ball-grinding machine of again this graphite suspension and abrading-ball being packed into, milling time is more than 4 hours.
The used raw material of above-mentioned Graphite Powder 99 is one or more the mixture in crystalline flake graphite, expansible black lead, expanded graphite, high orientation graphite and the thermo-cracking graphite.
Polymkeric substance in the above-mentioned polymers soln comprises all oil solubles and water-soluble polymer.
Above-mentioned abrading-ball is one or more the combination in zirconium oxide balls, steel ball, agate abrading-ball, aluminum oxide abrading-ball or the silicon nitride abrading-ball.
Above-mentioned mechanical mill is planetary ball mill, bedroom ball mill, basket shredder or stirring ball mill.
After adopting such scheme, the inventive method combines the compound and solution combined advantage of original position, selects for use the mechanical milling tech that is widely used in actual production that graphite is peeled off and to carry out original position compound, compared with prior art, it is advantageous that:
1) directly with Graphite Powder 99 as raw material, under the effect of mechanical shear stress, generate Graphene, do not relate to any chemical processes such as intercalation, oxidation, reduction that graphite is carried out, guaranteed that original Chemical bond is not damaged in the graphite linings.
2) in the polymer liquid body medium graphite is peeled off, Graphene has effectively overcome Graphene from the generation of reuniting in case generation is aggregated the thing molecule immediately or the polymer monomer parcel is isolated.
3) it is compound to adopt solution method to carry out, and by the efficient stirring shearing action that mechanical mill produces, filler and polymkeric substance can thorough mixing, make Graphene obtain more effectively dispersion in polymeric matrix.
4) adopt mechanical milling tech, simple, easier accomplishing scale production.
5) polymer/graphene composite material of producing by this method, the thickness of its Graphene can reach the 1-5 nanometer.
Description of drawings
Fig. 1 is the preparation principle synoptic diagram of polymer/graphene composite material among the present invention;
Fig. 2 is the transmission electron microscope picture of polymer/graphene composite material among the present invention;
Fig. 3 for by the compound polymer/graphene composite material that obtains of the inventive method original position with by the direct diafiltration comparison diagram of the compound matrix material that obtains of nano-graphite microplate.
Embodiment
A kind of method for preparing polymer/graphene composite material of the present invention, its preparation principle is as shown in Figure 1; Dispersion state by Graphene in the prepared polymer/graphene composite material of the inventive method as shown in Figure 2; By the compound polymer/graphene composite material that obtains of the inventive method original position with by the nano-graphite microplate directly the compound matrix material that obtains conduction diafiltration contrast situation as shown in Figure 3.
Embodiment 1:
A kind of method for preparing polymer/graphene composite material, be achieved by the following scheme: accurately take by weighing expanded graphite micro mist 0.1g, by mechanical stirring it is dispersed in the 320mL styrene monomer, form expanded graphite micro mist suspension, after this expanded graphite micro mist suspension is divided into 4 parts, per 1 part is in the tetrafluoroethylene ball grinder of 100mL with the zirconium oxide balls volume of packing into respectively, in per 1 part, the weight ratio of zirconium oxide balls and expanded graphite micro mist is about 10000: 1, the tetrafluoroethylene ball grinder symmetry of four zirconium oxide balls that are equipped with and expanded graphite suspension is put into planetary mills with 300 rev/mins rotating speed ball milling 30 hours, obtain Graphene/styrene suspension liquid, Graphene/styrene suspension liquid that ball milling obtains is poured in the beaker, and the Diisopropyl azodicarboxylate that adds with respect to styrene monomer 1.0-1.5wt% massfraction carries out initiated polymerization as initiator, obtains polystyrene/graphene composite material.
Embodiment 2:
A kind of method for preparing polymer/graphene composite material, be achieved by the following scheme: accurately take by weighing crystalline flake graphite micro mist 20.0g, by mechanical stirring it is dispersed in the 1000mL methyl methacrylate, form crystalline flake graphite micro mist suspension, is in the basket shredder grinding pot of 1500mL with this crystalline flake graphite micro mist suspension with the aluminum oxide abrading-ball volume of packing into, with 320 rev/mins rotating speed ball millings 50 hours, obtain Graphene/methyl methacrylate suspension.Graphene/methyl methacrylate suspension that ball milling obtains is poured in the beaker, and add with respect to the dibenzoyl peroxide of the methyl methacrylate monomer 0.1-2.5wt% massfraction initiated polymerization as initiator, obtain polymethylmethacrylate/graphene composite material.
Embodiment 3:
A kind of method for preparing polymer/graphene composite material, be achieved by the following scheme: accurately take by weighing high orientation Graphite Powder 99 30.0g and it is dispersed in the N that 3000mL contains the 100g polystyrene by mechanical stirring, in the dinethylformamide solution, form high orientation Graphite Powder 99 suspension, is in the horizontal ball mill tank body of 5000mL with this high orientation Graphite Powder 99 suspension with the agate abrading-ball volume of packing into, weight ratio between agate abrading-ball and the high orientation Graphite Powder 99 is about 4500: 1, with 350 rev/mins rotating speed ball millings 60 hours, obtain the styrene solution suspension of Graphene, the styrene solution suspension of the Graphene that ball milling is obtained is poured in the beaker, and add the water of q.s or alcohol and as precipitation agent polystyrene/graphene complex is precipitated from solvent and separate out, polystyrene/graphene complex is leached the back thorough washing, obtain polystyrene/graphene composite material after the drying.
Embodiment 4:
A kind of method for preparing polymer/graphene composite material, be achieved by the following scheme: accurately take by weighing expansible black lead powder 0.2g, by mechanical stirring it is dispersed in the Resins, epoxy of 320mL after with acetone diluted, form expansible black lead powder suspension, after this expansible black lead powder suspension is divided into 4 parts, per 1 part is in the tetrafluoroethylene ball grinder of 100mL with the steel ball volume of packing into respectively, in per 1 part, weight ratio between steel ball and the expansible black lead powder is about 13000: 1, four tetrafluoroethylene ball grinder symmetries that steel ball and expansible black lead powder suspension is housed are put into planetary mills with 320 rev/mins rotating speed ball milling 40 hours, obtain Resins, epoxy/graphene suspension, Resins, epoxy/graphene suspension that ball milling obtains is poured in the beaker, after adding heat extraction acetone, adding as solidifying agent, obtains Resins, epoxy/graphene composite material with respect to the quadrol of Resins, epoxy 8wt% massfraction after the curing in Resins, epoxy/graphene suspension.
Embodiment 5:
A kind of method for preparing polymer/graphene composite material, be achieved by the following scheme: accurately take by weighing thermo-cracking Graphite Powder 99 10.0g, by mechanical stirring it is dispersed in the 500mL unsaturated polyester, form thermo-cracking Graphite Powder 99 suspension, is in the stirring ball mill ball grinder of 800mL with this thermo-cracking Graphite Powder 99 suspension with the silicon nitride abrading-ball volume of packing into, weight ratio between silicon nitride abrading-ball and the expansible black lead powder is about 13000: 1, with 300 rev/mins rotating speed ball millings 60 hours, obtain unsaturated polyester/graphene suspension, unsaturated polyester/graphene suspension that ball milling obtains is poured in the beaker, and add with respect to the solidifying agent methylethyl ketone peroxide of unsaturated polyester 4wt% massfraction and the hot cobalt of promotor cycloalkanes of 2wt% massfraction, obtain unsaturated polyester/graphene composite material after the curing.Embodiment 6
A kind of method for preparing polymer/graphene composite material, be achieved by the following scheme: accurately take by weighing expansible black lead micro mist 0.3g, by mechanical stirring it is dispersed in 320mL and contains the 5.0g polyacrylonitrile, the N of 20g acrylonitrile monemer and 1.5g methacrylate monomer, in the dinethylformamide solution, form expansible black lead micro mist suspension, after this expansible black lead micro mist suspension is divided into 4 parts, per 1 part is in the tetrafluoroethylene ball grinder of 100mL with the agate abrading-ball volume of packing into respectively, in per 1 part, weight ratio between agate abrading-ball and the expansible black lead micro mist is about 4500: 1, four tetrafluoroethylene ball grinder symmetries that agate abrading-ball and expansible black lead micro mist suspension is housed are put into planetary mills with 300 rev/mins rotating speed ball milling 50 hours, obtain the polyacrylonitrile/acrylonitrile/methyl acrylate solution suspension of Graphene, polyacrylonitrile/acrylonitrile/methyl acrylate solution the suspension of the Graphene that ball milling is obtained is poured in the beaker, the Diisopropyl azodicarboxylate that adds with respect to vinyl cyanide and methacrylate monomer total mass 0.020.1wt% massfraction carries out initiated polymerization as initiator earlier, the alcohol that adds q.s then precipitates polyacrylonitrile/graphene complex as precipitation agent from solvent separates out, polyacrylonitrile/graphene complex is leached the back thorough washing, obtain polyacrylonitrile/graphene composite material after the drying.
Claims (9)
1. method for preparing polymer/graphene composite material is characterized in that: realize as follows:
One, the liquid medium of abrading-ball, Graphite Powder 99 and polymkeric substance is placed ball-grinding machine, carry out the mechanical mill of certain hour, Graphite Powder 99 is ground stripping, and the mixing suspension that the graphite dispersion liquid after then the liquid medium of polymkeric substance being shelled together with mill is formed takes out from ball-grinding machine;
Two, with the mixing suspension of step 1 gained by cohesion, separate out or directly the method for initiated polymerization obtain polymer/graphene composite material.
2. a kind of method for preparing polymer/graphene composite material according to claim 1, it is characterized in that: above-mentioned polymer liquid body medium is a polymers soln, in the above-mentioned steps two, the adding precipitation agent makes polymer composites condense to separate out from solvent and obtains polymer/graphene composite material in the mixing suspension of step 1 gained.
3. a kind of method for preparing polymer/graphene composite material according to claim 1, it is characterized in that: above-mentioned polymer liquid body medium is one or more the mixture in liquid polymer monomer, polymer monomer solution, liquid polymer performed polymer or the polymkeric substance prepolymer solution, in the above-mentioned steps two, the mixing suspension of step 1 gained is carried out polymerization obtain polymer/graphene composite material.
4. a kind of method for preparing polymer/graphene composite material according to claim 1, it is characterized in that: above-mentioned polymer liquid body medium is polymers soln and liquid polymer monomer, polymer monomer solution, the liquid polymer performed polymer, the mixture of one or more in the polymkeric substance prepolymer solution, in the above-mentioned steps two, earlier to the polymer monomer in the mixing suspension of step 1 gained, the polymkeric substance performed polymer, or the mixture of polymer monomer and polymkeric substance performed polymer carries out polymerization, in mixed system, add precipitation agent then, make polymer composites from solvent, condense to separate out and obtain polymer/graphene composite material.
5. according to each described a kind of method for preparing polymer/graphene composite material of claim 1-4, it is characterized in that: in the above-mentioned steps one, earlier Graphite Powder 99 is dispersed in the polymer liquid body medium, form graphite suspension, this graphite suspension and abrading-ball are packed into again and carry out mechanical mill in the ball-grinding machine, milling time is more than 4 hours.
6. according to each described a kind of method for preparing polymer/graphene composite material of claim 1-4, it is characterized in that: the used raw material of above-mentioned Graphite Powder 99 is one or more the mixture in crystalline flake graphite, expansible black lead, expanded graphite, high orientation graphite and the thermo-cracking graphite.
7. a kind of method for preparing polymer/graphene composite material according to claim 2, it is characterized in that: the polymkeric substance in the above-mentioned polymers soln comprises all oil solubles and water-soluble polymer.
8. according to each described a kind of method for preparing polymer/graphene composite material of claim 1-4, it is characterized in that: above-mentioned abrading-ball is one or more the combination in zirconium oxide balls, steel ball, agate abrading-ball, aluminum oxide abrading-ball or the silicon nitride abrading-ball.
9. according to each described a kind of method for preparing polymer/graphene composite material of claim 1-4, it is characterized in that: above-mentioned mechanical mill is planetary ball mill, bedroom ball mill, basket shredder or stirring ball mill.
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Address after: Fengze District of Quanzhou city of Fujian Province east of Huaqiao University, 362000 Patentee after: Huaqiao University Patentee after: XIAMEN KNANO GRAPHENE TECHNOLOGY CORPORATION LIMITED Address before: Fengze District of Quanzhou city of Fujian Province east of Huaqiao University, 362000 Patentee before: Huaqiao University Patentee before: Xiamen Knano Graphene Technology Corporation Limited |