CN102491316B - Graphite alkenyl supermolecule hybridization material with strengthened heat stability and preparation method thereof - Google Patents
Graphite alkenyl supermolecule hybridization material with strengthened heat stability and preparation method thereof Download PDFInfo
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- CN102491316B CN102491316B CN2011104129060A CN201110412906A CN102491316B CN 102491316 B CN102491316 B CN 102491316B CN 2011104129060 A CN2011104129060 A CN 2011104129060A CN 201110412906 A CN201110412906 A CN 201110412906A CN 102491316 B CN102491316 B CN 102491316B
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Abstract
The invention discloses a graphite alkenyl supermolecule hybridization material with strengthened heat stability and a preparation method thereof. The graphite alkenyl supermolecule hybridization material with strengthened heat stability is in a nanometer structure constructed on the basis of supermolecule self-package technique. The preparation process includes three steps of graphite oxide preparation, reduced graphene oxide preparation and graphite alkenyl supermolecule hybridization material preparation. Relative to unmodified reduced graphene oxide, the hybridization material combined in the method can be easily dispersed in organic solvent with low polarity and the heat stability is greatly improved. Simultaneously, the hybridization material can serve as a nanometer material to improve the heat stability of a polymer composite material. The combining steps are simple and high in efficiency, so that the hybridization material can be prepared in a large amount and has better application prospect and economical benefit.
Description
Technical field
The present invention relates to a kind of supramolecule hybrid material and preparation method thereof, particularly graphene-based supramolecule hybrid material of a kind of thermostability enhancing and preparation method thereof.
Background technology
2004, the graphite that the Geim research group method by mechanically peel has successfully prepared monatomic bed thickness was rare.Due to its excellent physical and chemical performance, make one of its international hot subject that becomes very soon physics, chemistry, materialogy field.As an emerging research system, can significantly improve calorifics, electricity, optics and the mechanical properties of polymkeric substance based on the polymer composites of Graphene.
Yet, the Graphene chemical stability of structural integrity is high, the surface is inert condition, a little less than the interaction of other media (as solvent etc.), stronger interfacial energy makes it that irreversible reunion occur, be difficult to water-soluble and commonly used organic solvent, this has caused great difficulty for further research and the application of Graphene.
Up to the present, the method for macroscopic preparation of graphene based nano-material is chemically still main.In this course, a kind of important presoma of graphene oxide (graphene oxide, GO) Chang Zuowei.Graphene oxide surface and edge contain a large amount of functional groups, as hydroxyl, ehter bond, carbonyl, carboxyl etc.The existence that these contain the oxygen functional groups makes it be more prone to be dispersed in water and high polar organic solvent, but can not be scattered in the organic solvent of low polarity.
For overcoming the above problems, give full play to its advantageous property, improve the dispersiveness in low polar solvent and polymeric matrix, the chemical modification of graphene oxide and functionalization have become focus, are also one of most important and tool work of challenging at present.
Functionalization graphene (functionalized graphene) will provide new opportunity for chemical and Material Field.
At present, adding tensio-active agent and organic functional is the important method of modified graphene oxide.Wherein, organic functional still occupies dominant position, comprises isocyanic ester method, silanization, coupling agent method, nucleophilic substitution and phase transfer of technology etc.Hydrogen bond by these modifications between can disruptive oxidation graphite linings makes the graphene oxide after modification that good dispersion can be arranged in organic solvent.（1.?Sandip?Niyogi,?Elena?Bekyarova,?Mikhail?E.?Itkis,?Jared?L.?McWilliams,?Mark?A.?Hamon,?Robert?C.?Haddon.?Solution?Properties?of?Graphite?and?Graphene.?J.?Am.?Chem.?Soc.,?2006,?128?(24):?7720–7721.?2.?Cao?Y,?Feng?J,?Wu?P.?Alkyl-functionalized?graphene?nanosheets?with?improved?lipophilicity.?Carbon?2010,?48?(5)?:?1683-5..）
In aforesaid method, temperature of reaction is higher (70 ℃ and 140 ℃ etc.) all, and the synthesis step complex operation, are difficult to large-scale industrialization production.
Summary of the invention
The deficiencies such as the temperature of reaction that the present invention is directed to the prior art existence is high, complex operation provide a kind of graphene-based supramolecule hybrid material.
Another object of the present invention is to provide a kind of preparation method of graphene-based supramolecule hybrid material, and the method need not high-temperature operation, need not highly toxic thionyl chloride, isocyanic ester,
N,
NThe coupling agents such as-dicyclohexyl carbimide (DCC).But utilize the supramolecule self-assembling technique, by simple stirring, the routine operations such as filtration at room temperature just can simply prepare, and realize simultaneously high dispersive and thermal stability in low polar organic solvent.
The technical solution that realizes the object of the invention is: by the strong oxide treatment of natural graphite powder is obtained oxidation graphite solid, then through ultra-sonic dispersion, it is dispersed in
N,
NIn-dimethyl formamide (DMF) solvent, add the chloroformic solution of alkylamine, after stirring at room, filtration, obtain graphene-based supramolecule hybrid material.
Concrete technique comprises the following steps:
Hummers method after step 1, employing modification prepares oxidation graphite solid with natural graphite powder;
Step 4, the solution of step 3 is joined in the suspension of step 2 stirring at room;
Namely obtain graphene-based supramolecule hybrid material after step 5, filtration under diminished pressure, washing, drying.
The ratio of the graphite oxide described in step 2 and DMF solvent is 7.5 ~ 15 mg/mL, described preparation condition be ultrasonic under, described ultrasonic time is 6 ~ 10h.
Alkylamine described in step 3 is 12-stearylamine, and described organic solvent is chloroform, and the mass ratio of described alkylamine and graphite oxide is (10-20): 3.
Churning time described in step 4 is 2 ~ 4 days.
Compared with prior art, the preparation method of graphene-based hybrid nano-material provided by the invention need not thionyl chloride, isocyanic ester,
N,
N-dicyclohexyl carbimide (DCC) etc. is with virose organic coupling agent, need not the high temperature operations such as 70 ℃ and 140 ℃.But at room temperature utilize the supramolecule self-assembling technique, by simple stirring, the routine operations such as filtration just can prepare.The graphene-based supramolecule hybrid nano-material of the preparation of the present invention simultaneously can be realized its good distribution in the even nonpolarity solvent of the low polar solvents such as sherwood oil, dimethylbenzene easily, and shown higher thermal stability, be conducive to improve as Nano filling the novel matrix material of thermal stability structure of polymer composites.
Preparation method of the present invention meets the requirement of Green Chemistry, normal temperature condition, and simple operations is conducive to industrialized mass production.
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail.
Description of drawings
Fig. 1 is the preparation process schematic diagram of the graphene-based supramolecule hybrid material for preparing of the present invention.
Fig. 2 is the general structure schematic diagram of the graphene-based supramolecule hybrid material for preparing of the present invention.
Fig. 3 is the dispersing property photo of supramolecule hybrid material in solvent synthetic in the embodiment of the present invention 1, and product title note is done GO-organic molecule (a, GO-stearylamine; B, graphene oxide).
Fig. 4 is infared spectrum (a, the GO-stearylamine of supramolecule hybrid material synthetic in the embodiment of the present invention 1 and embodiment 2; B, the GO-stearylamine; C, graphene oxide; D, stearylamine; E, amino dodecane).
Fig. 5 be supramolecule hybrid material synthetic in the embodiment of the present invention 1 and embodiment 2 thermally-stabilised analytic curve (1, graphene oxide; 2, GO-amino dodecane; 3, GO-stearylamine).
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail; the present embodiment is implemented under with the 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.
A kind of preparation method of graphene-based supramolecule hybrid material, the method following steps:
Hummers method (Modified Hummers method) the preparation oxidation graphite solid of the first step, employing modification;
Under second step, ultrasonic 6 ~ 10h, preparation concentration is the graphene oxide DMF suspension of 7.5 ~ 15 mg/mL;
The 3rd step, preparation concentration are 20% alkylamine chloroformic solution;
The 4th the step, with the 3rd the step solution join in second step suspension, stirring at room 2 ~ 4 days;
Namely obtain graphene-based supramolecule hybrid material after the 5th step, filtration under diminished pressure, washing, drying.
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
The first step, the preparation of oxidation graphite solid;
At 80 ℃, with the 30 mL vitriol oils, 10 g Potassium Persulphates and 10 g Vanadium Pentoxide in FLAKESs with 20 g natural graphites (400 order) preoxidation after, be washed to pH=7, Air drying spends the night stand-by;
The 460 mL vitriol oils are cooled to 0 ℃ of left and right, then the graphite with 20 g preoxidation joins wherein, slowly add 60 g potassium permanganate, make system temperature be no more than 20 ℃, add being warmed up to 35 ℃ after complete, after stirring 2 h, and slowly add 920 mL deionized waters in batches, make system temperature be no more than 98 ℃, then after stirring 15 minutes, add 2.8 L deionized waters and 50 mL 30 % hydrogen peroxide.With the glassy yellow suspension decompress filter that obtains, washing.Until there is no sulfate ion in filtrate, and when being neutrality, product is dried in 60 ℃ of vacuum, oxidation graphite solid obtained;
Second step with the 300 mg graphite oxide powder round-bottomed flask of packing into, then adds 20 mL
N,
N-dimethyl formamide (DMF) solvent after ultrasonic 6 h, obtains the suspension of graphene oxide;
In the 3rd step, 1 g stearylamine molecule (ODA) is dissolved in 5 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 2 days;
The 5th step after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtained graphene-based supramolecule hybrid material with Büchner funnel, and material structure as shown in Figure 2.
The solvent dispersion performance studies show that as shown in Figure 3: this supramolecular materials can better disperse in low polar solvent, and loses dispersiveness in high polar solvent, forms sharp contrast with the graphene oxide material.
Infrared spectra proves that this nano material is successfully synthetic as shown in Fig. 4 a.
Thermostability as shown in Figure 5, the thermal stability of the Graphene of supramolecular functionalization is higher than the graphene oxide of unmodified.
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
First and second step is with step 1 and two in embodiment 1.
In the 3rd step, 1 g amino dodecane molecule (DDA) is dissolved in 5 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 2 days.
In the 5th step, after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtain graphene-based supramolecule hybrid material with Büchner funnel.
Infrared spectra is as shown in Fig. 4 b; Prove that this nano material is successfully synthetic.
Thermostability as shown in Figure 5; The thermal stability of the Graphene of supramolecular functionalization is higher than the graphene oxide of unmodified.
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
First and second step is with step 1 and two in embodiment 1.
The 3rd the step, with 1 g amino dodecane molecular melting in 5 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 3 days.
In the 5th step, after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtain graphene-based supramolecule hybrid material with Büchner funnel.
Embodiment 4
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
First and second step is with step 1 and two in embodiment 1.
In the 3rd step, 1 g pentadecyl amine molecule (PDA) is dissolved in 5 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 2 days.
In the 5th step, after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtain graphene-based supramolecule hybrid material with Büchner funnel.
Embodiment 5
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
The first step is with step 1 in embodiment 1.
Second step with the 1.5 g graphite oxide powder round-bottomed flask of packing into, then adds 100 mL
N,
N-dimethyl formamide (DMF) solvent after ultrasonic 10h, obtains the suspension of graphene oxide;
The 3rd the step, with 5 g stearylamine molecular meltings in 25 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 4 days.
In the 5th step, after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtain graphene-based supramolecule hybrid material with Büchner funnel.
Embodiment 6
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
The first step is with step 1 in embodiment 1.
Second step with the 1.5 g graphite oxide powder round-bottomed flask of packing into, then adds 150 mL
N,
N-dimethyl formamide (DMF) solvent after ultrasonic 10 h, obtains the suspension of graphene oxide;
The 3rd the step, with 5 g amino dodecane molecular meltings in 25 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 3 days.
In the 5th step, after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtain graphene-based supramolecule hybrid material with Büchner funnel.
Embodiment 7
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
The first step is with step 1 in embodiment 1.
Second step with the 600 mg graphite oxide powder round-bottomed flask of packing into, then adds 40 mL
N,
N-dimethyl formamide (DMF) solvent after ultrasonic 8 h, obtains the suspension of graphene oxide;
The 3rd the step, with 2 g amino dodecane molecular meltings in 10 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 4 days.
In the 5th step, after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtain graphene-based supramolecule hybrid material with Büchner funnel.
Embodiment 8
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
The first step is with step 1 in embodiment 1.
Second step with the 300 mg graphite oxide powder round-bottomed flask of packing into, then adds 20 mL
N,
N-dimethyl formamide (DMF) solvent after ultrasonic 6 h, obtains the suspension of graphene oxide;
In the 3rd step, 1.5 g tetradecy lamine molecules (NTA) are dissolved in 7.5 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 2 days.
In the 5th step, after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtain graphene-based supramolecule hybrid material with Büchner funnel.
Embodiment 9
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
The first step is with step 1 in embodiment 1.
Second step with the 300 mg graphite oxide powder round-bottomed flask of packing into, then adds 30 mL
N,
N-dimethyl formamide (DMF) solvent after ultrasonic 6 h, obtains the suspension of graphene oxide;
The 3rd the step, with 2 g stearylamine molecular meltings in 5 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 2 days.
In the 5th step, after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtain graphene-based supramolecule hybrid material with Büchner funnel.
Embodiment 10
As shown in Figure 1, the described preparation method of the present embodiment comprises the following steps:
The first step is with step 1 in embodiment 1.
Second step with the 300 mg graphite oxide powder round-bottomed flask of packing into, then adds 40 mL
N,
N-dimethyl formamide (DMF) solvent after ultrasonic 6 h, obtains the suspension of graphene oxide;
The 3rd the step, with 2 g amino dodecane molecular meltings in 5 mL chloroform solvents;
In the 4th step, the 3rd step solution is joined in second step suspension stirring at room 4 days.
In the 5th step, after reaction is completed, after filtration under diminished pressure, washing, 60 ℃ of vacuum-drying, namely obtain graphene-based supramolecule hybrid material with Büchner funnel.
Claims (6)
1. the preparation method of the graphene-based supramolecule hybrid material that strengthens of a thermostability is characterized in that said method comprising the steps of:
Hummers method after step 1, employing modification prepares oxidation graphite solid with natural graphite powder;
Step 2, ultrasonic lower preparation graphene oxide DMF suspension, the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/mL;
Step 3, preparation alkylamine organic solution, the mass ratio of alkylamine molecule and graphite oxide is (10-20): 3, alkylamine is 12-stearylamine;
Step 4, the solution of step 3 is joined in the suspension of step 2 stirring at room 2 ~ 4 days;
Namely obtain graphene-based supramolecule hybrid material after step 5, filtration under diminished pressure, washing, drying.
2. the preparation method of the graphene-based supramolecule hybrid material of thermostability enhancing according to claim 1, is characterized in that the ultrasonic time described in step 2 is 6 ~ 10h.
3. the preparation method of the graphene-based supramolecule hybrid material of thermostability enhancing according to claim 1, is characterized in that the organic solvent described in step 3 is chloroform.
4. the graphene-based supramolecule hybrid material that strengthens of a thermostability is characterized in that described material prepares according to the following steps:
Hummers method after step a, employing modification prepares oxidation graphite solid with natural graphite powder;
Step b, ultrasonic lower preparation graphene oxide DMF suspension, the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/mL;
Step c, preparation alkylamine organic solution, the mass ratio of alkylamine molecule and graphite oxide is (10-20): 3, alkylamine is 12-stearylamine;
Steps d, step c solution is joined in step b suspension stirring at room 2 ~ 4 days;
Namely obtain graphene-based supramolecule hybrid material after step e, filtration under diminished pressure, washing, drying.
5. the graphene-based supramolecule hybrid material of thermostability enhancing according to claim 4, is characterized in that the ultrasonic time described in step b is 6 ~ 10h.
6. the graphene-based supramolecule hybrid material of thermostability enhancing according to claim 4, is characterized in that the organic solvent described in step c is chloroform.
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| CN103241735B (en) * | 2013-05-17 | 2014-11-05 | 南京理工大学 | Hybrid nanomaterial of melamine chemically-modified graphene oxide and preparation method of hybrid nanomaterial |
| CN103342903B (en) * | 2013-07-05 | 2015-02-25 | 南京理工大学 | Heat-stability-enhanced melamine covalent functionalized graphene-based nanoscale hybrid material |
| CN103408004B (en) * | 2013-08-02 | 2015-02-25 | 南京理工大学 | Hydrophobic functional graphene oxide nano hybrid material with higher thermal stability and preparation method of hydrophobic functional graphene oxide nano hybrid material |
| CN103950920B (en) * | 2014-04-16 | 2015-08-19 | 同济大学 | A kind of preparation method of graphene nano hybrid material of photosynthesis-carbon dioxide response |
| CN104231624B (en) * | 2014-08-22 | 2016-05-11 | 南京信息职业技术学院 | A kind of modified cyanic acid ester resin heat-conductive composite material and preparation method thereof |
| CN104610572B (en) * | 2015-01-26 | 2017-12-12 | 南京理工大学 | Amino polystyrene functionalization graphene nano material and preparation method thereof |
| CN104730121A (en) * | 2015-02-02 | 2015-06-24 | 南京理工大学 | Multi-wall carbon nano-tube bridged 3D graphene conductive network and preparation method thereof |
| CN107385887B (en) * | 2017-07-28 | 2020-06-23 | 江西昌硕户外休闲用品有限公司 | Active graphene and preparation method and application thereof |
| CN107963671B (en) * | 2017-12-21 | 2019-06-21 | 南京大学盐城环保技术与工程研究院 | Support type composite and its preparation method and application |
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