CN101831130A - Method for grafting polyvinylpyrrolidone onto surface of graphene - Google Patents
Method for grafting polyvinylpyrrolidone onto surface of graphene Download PDFInfo
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- CN101831130A CN101831130A CN 201010142588 CN201010142588A CN101831130A CN 101831130 A CN101831130 A CN 101831130A CN 201010142588 CN201010142588 CN 201010142588 CN 201010142588 A CN201010142588 A CN 201010142588A CN 101831130 A CN101831130 A CN 101831130A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- 229920000036 polyvinylpyrrolidone Polymers 0.000 title claims abstract description 43
- 239000001267 polyvinylpyrrolidone Substances 0.000 title claims abstract description 43
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 33
- 239000010439 graphite Substances 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 229940001516 sodium nitrate Drugs 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 10
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- 238000005303 weighing Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000007306 functionalization reaction Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
The invention discloses a method for grafting polyvinylpyrrolidone onto the surface of graphene in the technical field of nanometer materials, which comprises the following steps: preparing tawny water solution of graphene oxide; and sequentially adding the polyvinylpyrrolidone and a reducer into the water solution of graphene oxide, fully stirring and dissolving the polyvinylpyrrolidone and the reducer, heating the mixed solution with oil bath for reaction, and after the reaction, obtaining the graphene of which the surface is grafted with the polyvinylpyrrolidone. The method comprises the simple steps and has the advantages of quickly realizing the preparation of graphene-based composite materials, obtaining the graphene-based composite materials mono-dispersed in the water solution by utilizing the high water-solubility of the polyvinylpyrrolidone, simultaneously realizing technology of spreading the graphene-based composite materials into films on substrates and laying the foundation for the application of the graphene-based composite materials in the fields of biomedicine and sensors and to research on the basic physical properties of the graphene.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of nano material, specifically is a kind of method that realizes Graphene surface grafting polyvinylpyrrolidone.
Background technology
Graphene, a kind of novel individual layer two-dimensional nano material has unique electricity, calorifics, mechanics, is the ideal base material of preparation polymer composite.As Stankovich etc. at " Nature " (nature) (2006,442, delivered the article that is entitled as " Graphene-based composite materials " (based on the matrix material of Graphene) 282-285), the author utilizes the oxy radical effect of isocyanate and graphite oxide, obtain at organic solvent (N, dinethylformamide) graphite oxide of the chemically modified of stable dispersion in, with polyethylene blend after chemical reduction, obtain homodisperse single-layer graphene mixture in polymeric matrix at last, and had good electrical conductivity.Yu etc. are at " The journal of physical chemical C " (physical chemistry periodical C) (2007,111, delivered the article that is entitled as " Graphite nanoplatelet-epoxy compositethermal interface materials " (Nano graphite layer-epoxy resin composite heat interfacial material) 7565-7569), intercalation by graphite has been proposed in the literary composition, thermal spalling, disperse to prepare the method for Graphene, and point out that Resins, epoxy-graphene complex has good heat conductivity, can be used as the heat interfacial material of Electronic Packaging.Ramanathan etc. are in " Nature nanotechnology " (natural nanotechnology) (2008,3,327-331) deliver the article that is entitled as " Functionalized graphene sheets for polymernanocomposites " (based on the high molecular nanometer mixture of functionalization graphene), point out in the literary composition that the graphene oxide of complete oxidation can obtain having the functionalization graphene of high-specific surface area after Rapid Thermal expands.When adding 0.05% functionalization graphene in polymethylmethacrylate, its second-order transition temperature raises 30 ℃; When its addition was 1%, the Young's modulus of polymethylmethacrylate increased by 80%, and limit tensile strength has then improved 20%.Salavagione etc. are at " Macromolecules " (macromole) (2009,42, deliver the article that is entitled as " Polymeric modification of graphene throughesterification of graphite oxide and poly (vinyl aclcohol) " (esterification by graphite oxide and polyvinyl alcohol obtains polymer-modified Graphene) 6331-6334), reported that the carboxyl that utilizes graphite oxide and polyvinyl alcohol carry out esterification and obtained solubility Graphene by the polyvinyl alcohol covalent modification.Bourlinos etc. are at " Solid StateCommunications " (solid wall bulletin) (2009,149, delivered the article that is entitled as " Aqueous-phaseexfoliation of graphite in the presence of polyvinylpyrrolidone for the productionof water-soluble graphemes " (in polyvinylpyrrolidone aqueous solution peel off prepare water-soluble Graphene by the liquid phase of graphite) 2172-2176), reported in the aqueous solution of non-toxic polyethylene pyrrolidone, by supersound process crystalline graphite powder, utilize the sterically hindered of nonionic hydrophilic high mol and vacancy stabilization, obtain water miscible single-layer graphene.Yet, utilize graphite can make high quality Graphene dispersion liquid, but the single-layer graphene productive rate that obtains is lower as starting raw material.Therefore, it is starting raw material that present technique is selected graphite oxide for use, polyvinylpyrrolidone with good biocompatibility is as the chemical graft material, prepare high yield, monodispersed polyvinylpyrrolidone-graphene composite material, be expected to have a wide range of applications in chemistry, biology, medicine and other fields.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of method that realizes Graphene surface grafting polyvinylpyrrolidone is provided, by single stage method prepared in reaction monodispersed surface grafting polyvinylpyrrolidone graphene composite material in water.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
The first step in deionized water, is made filemot graphite oxide aqueous solution with the graphite oxide ultra-sonic dispersion;
Described graphite oxide is meant: by natural graphite is carried out being scattered in the aqueous hydrogen peroxide solution behind the low-temp reaction with SODIUMNITRATE, the vitriol oil and potassium permanganate successively, at last after filtration, pickling and drying treatment obtain.
Described low-temp reaction is meant: make temperature of reaction be lower than 10 ℃ by cryostat;
Described pickling is meant: adopting volume percent is the filter cake washing that under 45 ℃ of environment filtration obtained of 3% aqueous hydrochloric acid 3 times;
Described drying treatment is meant: adopt vacuum drying oven to be arranged at 40 ℃ of environment under drying 24 hours;
Described supersound process is meant: utilizing operating frequency is 40～100kHz; Ultrasonic power 100～200W; Ultrasonic time is the ultrasonication of 30～120min.
Graphite oxide concentration in the described graphite oxide aqueous solution is: 0.1mg/ml～1mg/ml.
Second step added in the graphite oxide aqueous solution polyvinylpyrrolidone and reductive agent and abundant stirring and dissolving successively, adopted the oil bath reacting by heating again, obtained the Graphene of surface grafting polyvinylpyrrolidone after reaction finishes.
Described abundant stirring is meant: utilize magnetic agitation, rotating speed is 200～1000rpm/min, churning time 5min～20min.
Described polyvinylpyrrolidone consumption is: 10 times～1/10 times of graphene oxide quality.
Described reductive agent is meant: xitix or hydrazine hydrate, consumption are 4 times～1 times of the rare quality of graphite oxide.
Described oil bath reacting by heating is meant: adopt magnetic agitation under 60 ℃～95 ℃ environment, rotating speed is 200～1000rpm/min, reaction times 2h～6h.
Compare with existing preparation method, the invention has the advantages that provide a kind of simply, the multiple preparation methods of Graphene fast, utilize the polyvinylpyrrolidone good water-solubility, obtained monodispersed graphene composite material in the aqueous solution, realized simultaneously opening up film forming technology, for its development in Application Areas is laid a good foundation on the substrate upper berth.
Description of drawings
Fig. 1 is a step synoptic diagram of the present invention.
Fig. 2 is Graphene-polyvinylpyrrolidone mixture synoptic diagram;
Wherein: a is Graphene-polyvinylpyrrolidone mixture atomic force microscope picture; B is Graphene-polyvinylpyrrolidone mixture altitude distribution figure.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
As shown in Figure 1, the described preparation method of present embodiment may further comprise the steps:
1, at room temperature, take by weighing the homemade graphite oxide in 0.1g laboratory, measure 200mlH
2O adds in the 250ml there-necked flask, is 40kHz in operating frequency, and the supersound process 30min of ultrasonic power 200w comes off graphite oxide, and obtaining concentration is the graphene oxide dispersion liquid of 0.5mg/ml.
2, take by weighing after the 1g polyvinylpyrrolidone adds in the graphene oxide dispersion liquid, fully stir 10min, make it dissolving.
3, take by weighing the 0.4g xitix and add in the above-mentioned system, fully stir 5min, make it dissolving.
4, place oil bath to be heated to 70 ℃ mixed system, fully react 6h after, obtain black even solution.
Embodiment 2
1, at room temperature, take by weighing the homemade graphite oxide in 0.2g laboratory, measure 200mlH
2O adds in the 250ml there-necked flask, is 40kHz in operating frequency, and the supersound process 30min of ultrasonic power 200w comes off graphite oxide, and obtaining concentration is the graphene oxide dispersion liquid of 1mg/ml.
2, take by weighing after the 1g polyvinylpyrrolidone adds in the graphene oxide dispersion liquid, fully stir 10min and make it dissolving.
3, measure the 1ml hydrazine hydrate and add in the above-mentioned system, fully stir 5min and make it dissolving.
4, place oil bath to be heated to 80 ℃ mixed system, fully react 4h after, obtain black even solution.
Embodiment 3
1, at room temperature, take by weighing the homemade graphite oxide in 0.02g laboratory, measure 200mlH
2O adds in the 250ml there-necked flask, is 40kHz in operating frequency, and the supersound process 1h of ultrasonic power 200w comes off graphite oxide, and obtaining concentration is the graphene oxide dispersion liquid of 0.1mg/ml.
2, take by weighing after the 0.04g polyvinylpyrrolidone adds in the graphene oxide dispersion liquid, fully stir 5min and make it dissolving.
3, take by weighing the 0.02g xitix and add in the above-mentioned system, fully stir 5min and make it dissolving.
4, place oil bath to be heated to 90 ℃ mixed system, fully react 2h after, obtain black even solution.
In the Graphene preparation process of surface grafting polyvinylpyrrolidone,, determined the consumption of best polyvinylpyrrolidone by adjusting 10～1/10 times of polyvinylpyrrolidone consumptions to graphite oxide; In addition, by adjusting 6～2 hours reaction times, determined optimum reacting time.Simultaneously, in experimentation, adopt different reductive agents, and experimental result is analyzed, when determining that reductive agent is xitix, the reaction of graphene oxide and polyvinylpyrrolidone is more abundant, obtains the Graphene that the surface is coated with polyvinylpyrrolidone.Utilize shown in atomic power electron microscope Fig. 2, the surface topography and the structure of the Graphene of surperficial grafted polyethylene pyrrolidone characterized.Shown in atomic force microscope picture Fig. 2 a of graphene complex, show that graphene complex realized single dispersion, it is polyvinylpyrrolidone that while single-layer graphene laminar surface is coated with a large amount of polymer beads equably, shown in the thickness chart 2b, is about 1.5～1.8nm.
The successful preparation of single dispersion, water-soluble graphene composite material, not only opened up new path for the batch preparations of Graphene, based on the functionalization of polyvinylpyrrolidone good biocompatibility and avtive spot thereof, make it be applied to biological medicine, sensor field and Graphene basis physics and created condition simultaneously.
Claims (10)
1. a method that realizes Graphene surface grafting polyvinylpyrrolidone is characterized in that, may further comprise the steps:
The first step in deionized water, is made filemot graphite oxide aqueous solution with the graphite oxide ultra-sonic dispersion;
Second step added in the graphite oxide aqueous solution polyvinylpyrrolidone and reductive agent and abundant stirring and dissolving successively, adopted the oil bath reacting by heating again, obtained the Graphene of surface grafting polyvinylpyrrolidone after reaction finishes.
2. the method for realization Graphene surface grafting polyvinylpyrrolidone according to claim 1, it is characterized in that, described graphite oxide is meant: by natural graphite is carried out being scattered in the aqueous hydrogen peroxide solution behind the low-temp reaction with SODIUMNITRATE, the vitriol oil and potassium permanganate successively, at last after filtration, pickling and drying treatment obtain.
3. the method for realization Graphene surface grafting polyvinylpyrrolidone according to claim 2 is characterized in that described low-temp reaction is meant: make temperature of reaction be lower than 10 ℃ by cryostat.
4. the method for realization Graphene surface grafting polyvinylpyrrolidone according to claim 2, it is characterized in that, described pickling and drying treatment are meant: adopting volume percent is the filter cake washing that under 45 ℃ of environment filtration obtained of 3% aqueous hydrochloric acid 3 times, adopts vacuum drying oven to be arranged at 40 ℃ of environment under drying 24 hours again.
5. the method for realization Graphene surface grafting polyvinylpyrrolidone according to claim 1 is characterized in that described supersound process is meant: operating frequency is 40～100kHz; Ultrasonic power 100～200W; Ultrasonic time is 30～120min.
6. the method for realization Graphene surface grafting polyvinylpyrrolidone according to claim 1 is characterized in that the graphite oxide concentration in the described graphite oxide aqueous solution is: 0.1mg/ml～1mg/ml.
7. the method for realization Graphene surface grafting polyvinylpyrrolidone according to claim 1 is characterized in that, described abundant stirring is meant: utilize magnetic agitation, rotating speed is 200～1000rpm/min, churning time 5min～20min.
8. the method for realization Graphene surface grafting polyvinylpyrrolidone according to claim 1 is characterized in that, described polyvinylpyrrolidone consumption is: 1/10 times～10 times of graphene oxide quality.
9. the method for realization Graphene surface grafting polyvinylpyrrolidone according to claim 1 is characterized in that described reductive agent is meant: xitix or hydrazine hydrate, consumption are 4 times～1 times of the rare quality of graphite oxide.
10. the method for realization Graphene surface grafting polyvinylpyrrolidone according to claim 1, it is characterized in that, described oil bath reacting by heating is meant: adopt magnetic agitation under 60 ℃～95 ℃ environment, rotating speed is 200～1000rpm/min, reaction times 2h～6h.
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