CN103724898A - Polymer based nanocomposite and preparing method thereof - Google Patents
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- CN103724898A CN103724898A CN201310664292.4A CN201310664292A CN103724898A CN 103724898 A CN103724898 A CN 103724898A CN 201310664292 A CN201310664292 A CN 201310664292A CN 103724898 A CN103724898 A CN 103724898A
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Abstract
The invention discloses a polymer based nanocomposite and a preparing method thereof. According to the invention, an organic covalent modification technology is adopted, polyhydroxy cyclodextrin molecules are anchored on a graphene oxide nanosheet through a coupling agent, excellent dispersion in various solvents is realized through utilizing the hydroxyl on the cyclodextrin to simulate the characteristic that the graphene oxide is enriched with oxygen species, the capacity of cyclodextrin on the graphene oxide is controlled through adjusting the reaction temperature, further the solvent dispersing performance and thermal stability of functionalized hybrid materials can be effectively regulated and controlled; besides, the solvent blending technology is adopted, the cyclodextrin functionalized grapheme based nano hybrid materials are used as fillers to prepare different-polymer based nanocomposite; through the adoption of the method, the intermolecular and intramolecular interfacial interaction are further enhanced so as to improve the thermal stability of the functionalized nano materials and polymer based nanocomposite adopting the nano materials as fillers, besides, the synthetic steps are simple and efficient, the aftertreatment is simple and concise, and large-scale preparation is facilitated.
Description
Technical field
The present invention relates to a kind of polymer nanocomposites and preparation method thereof, polymer nanocomposites that particularly a kind of cyclodextrin functionalized graphene base nano-hybrid material is filler and preparation method thereof, belongs to field of material preparation.
Background technology
Polymer based nanocomposites is a kind of advanced composite material by various nano units and organic polymer material composite molding in every way.Due to the combination of sciences of the premium propertiess such as surface-interface effect, small-size effect and the quantum size effect of nanoparticle and density polymer is little, easy processing, can present the new kink characteristics that is better than conventional polymer.The Application and Development of matrix material has become the study hotspot of new millennium Materials science.
Graphene (Graphene) is a kind of novel material of the individual layer sheet structure consisting of carbon atom.Be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness, and its discoverer Geim etc. has obtained the Nobel Prize in physics of 2010.Come from its outstanding physical and chemical performance, now become a kind of very popular new nano material in charcoal family.The preparation of Graphene and polymer matrix composite thereof is the important breakthrough in nano science field, development tool to present nanometer science and technology is of great significance, and especially in hydrogen storage material, support of the catalyst, electron device, electrode materials, fire retardant material, prepare composite, is with a wide range of applications.
The performance of polymer nanocomposites depends on surface finishing status and their dispersion staties in polymer materials of nano material to a great extent.But Graphene surface is unreactiveness, do not contain any chemical functional group, interlayer has again stronger interaction, and it is very easily reunited, and is difficult to be scattered in any solvent, has limited the application in polymer nanocomposites.
Oxidation-reduction method is still a kind of important method of macroscopic preparation of graphene.Wherein, graphene oxide (Graphene oxide, GO) is as important presoma, and a large amount of oxy radicals (according to Lerf-Klinowski model) such as carboxyl, hydroxyl, epoxy group(ing) are contained on layer surface, are typical accurate two-dimensional layer materials.The preparation technology of graphite oxide is relatively ripe, and more traditional chemical process mainly contains Brodie method, Staudenmaier method, Hummers method.Features such as wherein, Hummer method is simple because having reaction, and the reaction times is short, and security is higher, the less pollution to environment and become one of method of generally using at present.Existing bibliographical information, GO directly prepares polymer nanocomposites as Nano filling and improves material property.But GO can only be scattered in water and high polar organic solvent, greatly limited its application in low polar polymer matrix material.And GO is heat-labile, the very easily degraded of being heated, and weightless temperature interval is narrow, has further limited its application in the thermally-stabilised field of compound material of flame retardant type.Therefore, researchist often utilize its surface containing oxygen functional group as anchor point, utilize organic synthesis modification technique, GO is carried out to chemistry functional.When realization and many polymeric matrixs have better consistency, improve its thermal stability, and then strengthen the thermal property of polymer/graphene nano composite material.Researchist has adopted isocyanic ester method, esterification, amidation, silanization, nucleophilic substitution and phase transfer of technology etc. to build different types of functionalization graphene hybrid nano-material.Practical function functionalized graphene has a series of problem in science such as polymolecularity and high thermal stability concurrently, also becomes one of work that at present most important and tool is challenged.（1.Sasha?Stankovich,Richard?D.Piner,SonBinh?T.Nguyen,et?al.Carbon.2006,44:3342-3347.2.Xu?Y?X,Hong?W?J,Bai?H,et?al.Carbon,2009,47(15):3538-3543.）
But in aforesaid method, it is different from the strategy that the present invention adopts that material is prepared adopted method.The filler of the structure polymer nanocomposites of usually, reporting in document mostly is GO; Even while carrying out functional modification based on GO surface oxy radical, adopt hypertoxicity material more, such as tolylene diisocyanate (TDI) etc., this material is met water capacity and is easily decomposed, and pollutes highly, is difficult to large-scale industrialization and produces.Especially, method in document, all to pay close attention to how to introduce organic molecule and enter GO surface and improve performance, the molecule of introducing mostly is non-oxy radical, consider that increasing oxy radical improves solvent dispersion performance and thermal stability by improving intermolecular and intramolecular interface interaction simultaneously very less, and then reach and put forward high performance object.
Summary of the invention
The present invention is directed to that complex operation, coupling reagent toxicity that prior art exists are huge, the preparation deficiencies such as thinking is single.The polymer nanocomposites that a kind of cyclodextrin functionalized graphene base nano-hybrid material is filler is provided.
Another object of the present invention is that simulation GO is lip-deep containing oxygen functional group, by improving intermolecular and intramolecular interfacial interaction, improves nano ZnO.And provide the preparation method in many oxy radicals molecule introducing GO, the simple method for preparing of polymer nanocomposites and the preparation method of polymer composites thereof that a kind of cyclodextrin functionalized graphene base nano-hybrid material is filler are provided.
The technical solution that realizes the object of the invention is: a kind of polymer nanocomposites, and described matrix material is take cyclodextrin functionalized graphene base nano-hybrid material as filler, and by filler is filled in polymkeric substance and is formed, the general structure of its filler is:
Polymkeric substance can be the polymer molecule of water soluble or organic solvent, such as polyvinyl alcohol, polyoxyethylene glycol, polymethylmethacrylate or polystyrene etc.
The nano-hybrid material of the organic covalent chemical functionalization of above-mentioned cyclodextrin graphene oxide is by obtaining oxidation graphite solid by strong natural graphite powder degree of depth oxide treatment, warp is at N again, ultrasonic dispersion in dinethylformamide (DMF), obtain graphene oxide DMF dispersion liquid, after activated carboxylic, the cyclodextrin (CDs) that adds DMF to dissolve, heated and stirred, filtration and dry after, obtain CDs functionalization graphene nano-hybrid material, and then, utilize solvent blending technology, prepare polymer nanocomposites.
A kind of polymer nanocomposites, its concrete technique comprises the following steps:
Step 2, ultrasonic under, prepare graphene oxide DMF suspension, wherein, the ratio of graphite oxide and DMF solvent is 7.5～15mg/mL;
Step 3, prepare the graphene oxide GOCl of activated carboxylic;
The DMF solution of step 4, preparation cyclodextrin (CDs), wherein, CDs is 2～500mg/mL with the ratio of DMF;
Step 5, the GOCl that step 3 is obtained mix with the CDs solution of preparation in step 4, heated and stirred reaction, and wherein, the mass ratio of graphene oxide and CDs is 0.04～2;
Step 6, filtration under diminished pressure, washing, obtain CDs functionalization graphene nano-hybrid material after dry;
Step 7, prepare polymers soln, wherein, polymkeric substance is 0.05～1g/mL with the ratio of solvent;
Step 8, by ultrasonic the nano-hybrid material in step 6, be scattered in solvent, wherein, nano-hybrid material is 0.5～10mg/mL with the ratio of solvent;
Step 9, add in the solution that joins step 7 in the solution obtaining in step 8 stirring reaction.
Step 10, solvent flashing, obtain matrix material.
Oxidation graphite solid described in step 1 adopts the Hummers method preparation after improving.
Ultrasonic time described in step 2 is 3～10h.
Cyclodextrin described in step 3 is any one in alpha-cylodextrin, beta-cyclodextrin or γ-cyclodextrin.
Temperature of reaction described in step 5 is 70～120 ℃.
Polymkeric substance described in step 7 is the polymer molecule of the water solubles such as polyvinyl alcohol, polyoxyethylene glycol, polymethylmethacrylate or polystyrene or organic solvent.
The stirring reaction time described in step 9 is 1～24h.
Compared with prior art, the preparation method of CDs functionalization graphene nano-hybrid material provided by the invention can improve solvent dispersion performance and the thermal stability of graphene-based Nano filling simultaneously.It can only be scattered in water and high polar organic solvent unlike GO, but can be by regulation and control temperature of reaction, almost can be dispersed in the solvent of arbitrary polarity, expand the scope of selecting of polymer molecule, strengthen the application potential of graphite alkenyl nanometer materials.Especially can pass through simple solvent blending technology, the simple and easy polymer nanocomposites of preparing, is very beneficial for large-scale industrialization and produces.The introducing of CDs has improved the thermal stability of GO effectively, improved simultaneously and polymeric matrix between interface compatibility, make it more be conducive to improve the thermal stability of polymer composites as Nano filling and build novel flame retardant resistance nano composite material.Preparation method of the present invention presses close to the requirement of Green Chemistry, and simple to operate, is easy to control, and is conducive to industrialized mass.
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram of the cyclodextrin functionalized graphene base nano-hybrid material of the present invention polymer nanocomposites that is filler.
Fig. 2 is the infrared spectrogram of β-CDs functionalization graphene nano-hybrid material synthetic in the embodiment of the present invention 1 to 6.
Fig. 3 is β-CDs functionalization graphene nano-hybrid material synthetic in the embodiment of the present invention 3 dispersing property photo in solvent.
Fig. 4 is the thermally-stabilised analytic curve of β-CDs functionalization graphene nano-hybrid material synthetic in the embodiment of the present invention 1 to 6.
Fig. 5 is the thermally-stabilised analytic curve of β-CDs functionalization graphene nano-hybrid material synthetic in the embodiment of the present invention 6 PVA based nano composite material that is filler.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail; the present embodiment is implemented under with technical solution of the present invention prerequisite; provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
As shown in Figure 1, the polymer nanocomposites that a kind of cyclodextrin functionalized graphene base nano-hybrid material is filler, the method comprises the following steps:
Step 2, ultrasonic lower 3-10h, prepare graphene oxide DMF suspension, and the ratio of graphite oxide and DMF solvent is 7.5～15mg/mL;
Step 3, by adding excessive thionyl chloride to react at 70 ℃ after one day in graphene oxide DMF suspension, underpressure distillation is to remove unnecessary SOCl
2after obtain the graphene oxide GOCl of activated carboxylic;
The DMF solution of step 4, preparation cyclodextrin (CDs), CDs is 2～500mg/mL with the ratio of DMF; Wherein, cyclodextrin is any one in alpha-cylodextrin, beta-cyclodextrin or γ-cyclodextrin.
Step 5, GOCl that step 3 is obtained mix with the CDs solution of preparation in step 4, heat 70～120 ℃ at stirring reaction 1-3 days.Wherein, the mass ratio of graphene oxide and CDs is 0.04～2;
Step 6, filtration under diminished pressure, washing, obtain CDs functionalization graphene nano-hybrid material (GO-CDs) after dry;
Step 7, prepare polymers soln, polymkeric substance is 0.05～1g/mL with the ratio of solvent; Wherein, polymkeric substance is the polymer molecule of the water solubles such as polyvinyl alcohol, polyoxyethylene glycol, polymethylmethacrylate or polystyrene or organic solvent;
Step 8, by ultrasonic the product in step 6, be scattered in solvent, Nano filling GO-CDs is 0.5～10mg/mL with the ratio of solvent;
Step 9, add in the solution that joins step 7 in the solution obtaining in step 8 stirring reaction 1～24h.
Step 10, solvent flashing, obtain matrix material.
The first step, the preparation of oxidation graphite solid;
At 80 ℃, with the 30mL vitriol oil, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES, by after 20g natural graphite (400 order) preoxidation, be washed to pH=7, Air drying spends the night stand-by;
The 460mL vitriol oil is cooled to 0 ℃ of left and right, then the graphite of 20g preoxidation is joined wherein, slowly add 60g potassium permanganate, make system temperature be no more than 20 ℃, after interpolation, be warmed up to 35 ℃, after stirring 2h, and slowly add 920mL deionized water in batches, make system temperature be no more than 98 ℃, then after stirring 15 minutes, add 2.8L deionized water and 50mL30% hydrogen peroxide.By the glassy yellow suspension decompress filter obtaining, washing.Until there is no sulfate ion in filtrate, and while being neutrality, product is dried in 60 ℃ of vacuum, oxidation graphite solid obtained;
Second step, packs 200mg graphite oxide powder into round-bottomed flask, then adds 15mL DMF (DMF) solvent, after ultrasonic 5h, obtains the suspension of graphene oxide;
The 3rd step adds 40mL thionyl chloride (SOCl in the suspension in second step
2), at 70 ℃, to react after 24h, underpressure distillation is to remove unnecessary SOCl
2obtain the product (GOCl) of activated carboxylic;
The 4th step, takes 4g β-CDs and joins in 22mL DMF, to be stirred to completely and dissolve, preparation β-CDs solution;
The 5th step, the GOCl that the 3rd step is obtained mixes with the solution of the 4th step preparation, regulates temperature of reaction to 70 ℃, constant temperature stirring reaction 2 days;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains β-CDs functionalization graphene nano-hybrid material, is denoted as: GO-CDs
70;
The 7th step, gets 1g PVA and is dissolved in the deionized water of 15mL at 90 ℃ of temperature;
The 8th step, gets the product GO-CDs in the 6th step
7010mg is ultrasonic to be scattered in 5mL water;
The 9th step, under agitation condition, dropwise joins the solution obtaining in the 8th step in the solution of the 7th step stirring reaction 5h.
The tenth step, solvent flashing, obtains polymer nanocomposites.
GO-CDs
70the infrared spectra of filler as shown in Figure 2 c, proves that this nano-hybrid material is successfully synthetic.
β-CDs functionalization graphene nano-hybrid material (GO-CDs
70) thermally-stabilised analytic curve as shown in Figure 4 b, prove that this nano-hybrid material thermal stability has a distinct increment.
Embodiment 2
First to fourth step, with step 1 to four in embodiment 1;
The 5th step, the GOCl that the 3rd step is obtained mixes with the solution of the 4th step preparation, regulates temperature of reaction to 80 ℃, constant temperature stirring reaction 2 days;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains β-CDs functionalization graphene nano-hybrid material, is denoted as: GO-CDs
80;
The the 7th to the tenth step, with step 7 to ten in embodiment 1.
GO-CDs
80the infrared spectra of filler as shown in Figure 3 d, proves that this nano-hybrid material is successfully synthetic.
β-CDs functionalization graphene nano-hybrid material (GO-CDs
80) thermally-stabilised analytic curve as shown in Fig. 4 c, prove that this nano-hybrid material thermal stability has a distinct increment.
Embodiment 3
First to fourth step, with step 1 to four in embodiment 1;
The 5th step, the GOCl that the 3rd step is obtained mixes with the solution of the 4th step preparation, regulates temperature of reaction to 90 ℃, constant temperature stirring reaction 2 days;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains β-CDs functionalization graphene nano-hybrid material, is denoted as: GO-CDs
90;
The the 7th to the tenth step, with step 7 to ten in embodiment 1.
GO-CDs
90the infrared spectra of filler as shown in Figure 3 e, proves that this nano-hybrid material is successfully synthetic.
The dispersing property photo of synthetic β-CDs functionalization graphene nano-hybrid material in solvent as shown in Figure 3, can find that it not only can be dispersed in the solvent of high polarity, even can be dispersed in the solvent of low polarity.
β-CDs functionalization graphene nano-hybrid material (GO-CDs
90) thermally-stabilised analytic curve as shown in Fig. 4 d, prove that this nano-hybrid material thermal stability has a distinct increment.
Embodiment 4
First to fourth step, with step 1 to four in embodiment 1;
The 5th step, the GOCl that the 3rd step is obtained mixes with the solution of the 4th step preparation, regulates temperature of reaction to 100 ℃, constant temperature stirring reaction 2 days;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains β-CDs functionalization graphene nano-hybrid material, is denoted as: GO-CDs
100;
The the 7th to the tenth step, with step 7 to ten in embodiment 1.
GO-CDs
100the infrared spectra of filler, as shown in Fig. 3 f, proves that this nano-hybrid material is successfully synthetic.
β-CDs functionalization graphene nano-hybrid material (GO-CDs
100) thermally-stabilised analytic curve as shown in Fig. 4 e, prove that this nano-hybrid material thermal stability has a distinct increment.
Embodiment 5
First to fourth step, with step 1 to four in embodiment 1;
The 5th step, the GOCl that the 3rd step is obtained mixes with the solution of the 4th step preparation, regulates temperature of reaction to 110 ℃, constant temperature stirring reaction 2 days;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains β-CDs functionalization graphene nano-hybrid material, is denoted as: GO-CDs
110;
The the 7th to the tenth step, with step 7 to ten in embodiment 1.
GO-CDs
110the infrared spectra of filler, as shown in Fig. 3 g, proves that this nano-hybrid material is successfully synthetic.
β-CDs functionalization graphene nano-hybrid material (GO-CDs
110) thermally-stabilised analytic curve as shown in Fig. 4 f, prove that this nano-hybrid material thermal stability has a distinct increment.
Embodiment 6
First to fourth step, with step 1 to four in embodiment 1;
The 5th step, the GOCl that the 3rd step is obtained mixes with the solution of the 4th step preparation, regulates temperature of reaction to 120 ℃, constant temperature stirring reaction 2 days;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains β-CDs functionalization graphene nano-hybrid material, is denoted as: GO-CDs
120;
The the 7th to the tenth step, with step 7 to ten in embodiment 1.
GO-CDs
120the infrared spectra of filler, as shown in Fig. 3 h, proves that this nano-hybrid material is successfully synthetic.
β-CDs functionalization graphene nano-hybrid material (GO-CDs
120) thermally-stabilised analytic curve as shown in Fig. 4 g, prove that this nano-hybrid material thermal stability has a distinct increment.
The thermally-stabilised analytic curve of the PVA based nano composite material that β-CDs functionalization graphene nano-hybrid material is filler as shown in Figure 5.
Embodiment 7
The first step, with step 1 in embodiment 1;
Second step, packs 200mg graphite oxide powder into round-bottomed flask, then adds 14mL DMF (DMF) solvent, after ultrasonic 10h, obtains the suspension of graphene oxide;
The 3rd step, with step 3 in embodiment 1;
The 4th step, takes 100mg α-CDs and joins in 10mL DMF, to be stirred to completely and dissolve, preparation α-CDs solution;
The 5th step, the GOCl that the 3rd step is obtained mixes with the solution of the 4th step preparation, regulates temperature of reaction to 90 ℃, constant temperature stirring reaction 1 day;
The 6th step, with step 6 in embodiment 1;
The 7th step, gets 1g PEG and is dissolved in the chloroform of 1mL at 25 ℃ of temperature;
The 8th step, gets in the ultrasonic 20mL of the being scattered in chloroform of product 10mg in the 6th step;
The 9th step, under agitation condition, dropwise joins the solution obtaining in the 8th step in the solution of the 7th step stirring reaction 24h.
The tenth step, with step 10 in embodiment 1.
Embodiment 8
The first step, with step 1 in embodiment 1;
Second step, packs 200mg graphite oxide powder into round-bottomed flask, then adds 26.6mL DMF (DMF) solvent, after ultrasonic 3h, obtains the suspension of graphene oxide;
The 3rd step, with step 3 in embodiment 1;
The 4th step, takes 500mg γ-CDs and joins in 50mL DMF, to be stirred to completely and dissolve, preparation γ-CDs solution;
The 5th step, the GOCl that the 3rd step is obtained mixes with the solution of the 4th step preparation, regulates temperature of reaction to 110 ℃, constant temperature stirring reaction 3 days;
The 6th step, with step 6 in embodiment 1;
The 7th step, gets 1g PEG and is dissolved in the chloroform of 10mL at 25 ℃ of temperature;
The 8th step, gets in the ultrasonic 20mL of the being scattered in chloroform of product 10mg in the 6th step;
The 9th step, under agitation condition, dropwise joins the solution obtaining in the 8th step in the solution of the 7th step stirring reaction 20h.
The tenth step, with step 10 in embodiment 1.
Embodiment 9
The first to six step, with step 1 to six in embodiment 8;
The 7th step, gets 1g PMMA and is dissolved in the tetrahydrofuran (THF) of 20mL at 25 ℃ of temperature;
The 8th step, gets in the ultrasonic 10mL of the being scattered in tetrahydrofuran (THF) of product 10mg in the 6th step;
The 9th to ten steps, with step 9 to ten in embodiment 1.
Embodiment 10
The first to six step, with step 1 to six in embodiment 1;
The 7th step, gets 1g PS and is dissolved in the chloroform of 10mL at 25 ℃ of temperature;
The 8th step, gets in the ultrasonic 10mL of the being scattered in chloroform of product 10mg in the 6th step;
The 9th to ten steps, with step 9 to ten in embodiment 1.
From above-described embodiment, the preparation method of cyclodextrin functionalized graphene nano-hybrid material provided by the invention is anchored on cyclodextrin showing of graphene oxide dexterously, by intermolecular and molecule inner boundary, interact, thermostability and the solvent dispersion performance of graphene-based Nano filling have effectively been improved, further be conducive to utilize easy solvent blending technology to prepare polymer nanocomposites, and promote the thermal stability of matrix material, this invention is particularly useful for preparing as Nano filling the flame-proof type polyalcohol nano composite material that thermostability strengthens because the introducing of poly-hydroxy cyclodextrin molecular makes this nano material, there is good application prospect and economic benefit and significant industrial applications prospect.
Claims (10)
1. a polymer nanocomposites, is characterized in that described matrix material is take cyclodextrin functionalized graphene base nano-hybrid material as filler, and the general structure of filler is:
2. polymer nanocomposites according to claim 1, is characterized in that in described matrix material, polymkeric substance is the polymer molecule of water soluble or organic solvent.
3. polymer nanocomposites according to claim 1, is characterized in that described polymkeric substance is selected from the one in polyvinyl alcohol, polyoxyethylene glycol, polymethylmethacrylate or polystyrene.
4. a preparation method for polymer nanocomposites, is characterized in that described matrix material is take cyclodextrin functionalized graphene base nano-hybrid material as filler, filler is filled in polymkeric substance and forms, and comprises the following steps:
Step 1, with natural flake graphite powder, prepare oxidation graphite solid;
Step 2, ultrasonic under, prepare graphene oxide DMF suspension, wherein, the ratio of graphite oxide and DMF solvent is 7.5～15mg/mL;
Step 3, prepare the graphene oxide GOCl of activated carboxylic;
The DMF solution of step 4, preparation cyclodextrin, wherein, CDs is 2～500mg/mL with the ratio of DMF;
Step 5, the GOCl that step 3 is obtained mix with the CDs solution of preparation in step 4, heated and stirred reaction, and wherein, the mass ratio of graphene oxide and CDs is 0.04～2;
Step 6, filtration under diminished pressure, washing, obtain CDs functionalization graphene nano-hybrid material after dry;
Step 7, prepare polymers soln, wherein, polymkeric substance is 0.05～1g/mL with the ratio of solvent;
Step 8, by ultrasonic the nano-hybrid material in step 6, be scattered in solvent, wherein, nano-hybrid material is 0.5～10mg/mL with the ratio of solvent;
Step 9, add in the solution that joins step 7 in the solution obtaining in step 8 stirring reaction.
Step 10, solvent flashing, obtain matrix material.
5. the preparation method of polymer nanocomposites according to claim 4, is characterized in that the oxidation graphite solid described in step 1 adopts the Hummers method preparation after improving.
6. the preparation method of polymer nanocomposites according to claim 4, is characterized in that the ultrasonic time described in step 2 is 3～10h.
7. the preparation method of polymer nanocomposites according to claim 4, is characterized in that the cyclodextrin described in step 3 is any one in alpha-cylodextrin, beta-cyclodextrin or γ-cyclodextrin.
8. the preparation method of polymer nanocomposites according to claim 4, is characterized in that the temperature of reaction described in step 5 is 70～120 ℃.
9. the preparation method of polymer nanocomposites according to claim 4, is characterized in that the polymkeric substance described in step 7 is polyvinyl alcohol, polyoxyethylene glycol, polymethylmethacrylate or polystyrene.
10. the preparation method of polymer nanocomposites according to claim 4, is characterized in that the stirring reaction time described in step 9 is 1～24h.
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| CN104592660A (en) * | 2014-09-11 | 2015-05-06 | 南京理工大学 | Multilayer functionalized graphene nanometer hybrid material utilizing polystyrene as hinge and preparation method thereof |
| CN104777207A (en) * | 2015-04-10 | 2015-07-15 | 武汉大学 | Three-dimensional nitrogen-doped graphene composite material as well as preparation method and application thereof |
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| CN105267976A (en) * | 2015-10-14 | 2016-01-27 | 重庆华邦制药有限公司 | Graphene-oxide cyclodextrin compound and preparation method thereof |
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