CN107652204A - A kind of epoxides grafting hydrazine reduction prepares and the method for dispersed graphite alkene - Google Patents
A kind of epoxides grafting hydrazine reduction prepares and the method for dispersed graphite alkene Download PDFInfo
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- CN107652204A CN107652204A CN201710914084.3A CN201710914084A CN107652204A CN 107652204 A CN107652204 A CN 107652204A CN 201710914084 A CN201710914084 A CN 201710914084A CN 107652204 A CN107652204 A CN 107652204A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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Abstract
The present invention relates to graphene reduction and dispersion technology field, and in particular to a kind of epoxides grafting hydrazine reduction prepares and the method for dispersed graphite alkene.Comprise the following steps：Step 1:Prepared by epoxides grafting hydrazine, step 2:Prepared by graphene oxide, step 3:Epoxides is grafted hydrazine redox graphene.Epoxides of the present invention grafting hydrazine has that reproducibility is strong, good dispersion concurrently, technique is simple, the advantages that cheap, by the graphene that the inventive method obtains because surface modification contains hydroxyl and nonpolar alkyl segment, Π Π in regulation and control graphene solvent-dispersible at the same time it can also graphene after effectively preventing reduction reaction from occurring accumulate problem, enable after reduction graphene fine dispersion in a solvent, prevent irreversible reunion, ultra-thin layer graphene is made.
Description
Technical field
The present invention relates to graphene reduction and dispersion technology field, and in particular to prepared by a kind of epoxides grafting hydrazine reduction
And the method for dispersed graphite alkene.
Background technology
University of Manchester in 2004（University of Manchester）Geim professor group use glue for the first time
Band, which to graphite repeatedly peel off, obtains the graphene of individual layer, but this preparation method is because it is difficult to produce graphite on a large scale
Alkene and be restricted.Graphite is laid in abundant in nature, and how people from cheap graphite obtains stone if progressively exploring
Black alkene, being just currently known the method for preparing graphene that is existing and having confirmed has：Mechanical stripping method [K. S.
Novoselovl, A. K. Geiml, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I.
V.Grigorieva, A. A. Firsov, Electric Field Effect in Atomically Thin Carbon
Films, Science, 2004,306:666-669], crystal epitaxy method [Choi J. Lee H. Kim S.
Atomic-Scale Investigation of Epitaxial Graphene Grown on 6H-SiC (0001) Using
Scanning Tunneling Microscopy and Spectroscopy[J] .Journals of Physical
Chemistry C, 2010,114:13344-13348], vapour deposition process [P. W. Sutter, J. Flege, E. A.
Sutter, Epitaxial graphene on ruthenium, Nature Materials,2008, 7: 406-411]、
Organic synthesis method [Wu J S, Pisula W, Mullen K. Graphenes as potential material for
electronics. Chem. Rev,2007,107:718-747], chemistry redox method [Stankovich S, Dikin D
A, Piner R D, et al. Synthesis of graphene-based nanosheet via chemical
reduction of exfoliated graphene oxide [J]. Carbon, 2007,45:1558-1568], carbon nanometer
Pipe patterning method [D. V. Kosynkin, A. L.Higginbotham, A. Sinitskil, J. R. Lomeda, A.
Dimiev, B. K. Price, J. M.Tour, Longitudinal unzipping of carbon nanotubes to
form graphene nanoribbons, Nature, 2009,458:872-876] and thermal reduction [Schniepp, H.
C.; Li, J.-L.; McAllister, M. J.; Sai, H.; Herrera-Alonso, M.; Adamson, D.
H.; Prud'homme, R. K.; Car, R.; Saville, D. A.; Aksay, I. A., Functionalized
single graphene sheets derived from splitting graphite oxide. J Phys Chem B
2006,110, (17), 8535-8539] etc. preparation method.
Chemistry redox method is that laboratory prepares a kind of the most frequently used method of graphene, it is considered to be is most hopeful to realize
Method [Fan X B, the Peng W C.Li Y. Deoxygenation of Exfoliated of commercial quantities metaplasia production
Graphene Oxide under Alkaline Conditions: A Green Route to Graphene
Preparation [J]. Advanced Materals, 2008,20: 4490-4493].There is this method raw material to be easy to get,
Cost is relatively low, technique is simple, the advantages that graphene number of plies is less is made thus prepares the most frequently used side of graphene as laboratory
Method.Chemistry redox method prepares graphene and mainly includes three phases：First, oxidation processes are carried out to graphite using oxidant
Graphite oxide is prepared, then graphite oxide is dispersed in water and handled using ultrasonic echography, finally by selection electronation
Agent carries out electronation to graphene oxide so as to be made graphene, and Roff prime reports in 2007 are carried out to graphene oxide
Reduction can select hydrazine hydrate as reducing agent.Hereafter researcher is found that successively many prepares graphene available for reduction
Reducing agent, such as sodium borohydride [Si Y, Samulski ET. Synthesis of water soluble graphene
[J]. Nano Letters, 2008, 8:1679-1682], hydroquinones [Wang G, Yang J, Park J, et
al. Facile synthesis and characterization of graphene nanosheets [J]. Journal
of Physical Chemistry C, 2008,112:8192-8195], octadecylamine [Li W, Tang X-Z, Zhang H-
B, et al. Simultaneous surface functionalization and reduction of graphene
oxide with octadecylamine for electrically conductive polystyrene
compositites [J]. Carbon, 2011,49:4724-4730], formaldehyde [Tang X Z, Cao Z W, Zhang H
B, et al. Growth of silver nanocrystals on graphene by simultaneous reduction
of graphene oxide and silver ions with a rapid and efficient one-step
approach[J]. Chemical Communications, 2011,47:3084-3086] etc. also have preferably reduction imitate
Fruit.The Guo of Shanghai Communications University is preferable by the use of vitamin as reducing agent, reduction effect；Zhang[Fan X, Peng W, Li
Y, et al. Deoxygenation of Exfoliated Graphite Oxide under Alkaline
Conditions: A Green Route to Graphene Preparation[J]. Advanced Materials,
2008,20:4490-4493] also graphene oxide is reduced using the NaOH under alkaline environment；Additionally someone's profit
Graphene oxide is reduced with glucose, and achieves preferable reduction effect, somebody is also by graphene oxide heat
Hydrogen reducing, verified and feasible [Wu, the Z. S. of this method are used after expansion; Ren, W.; Gao, L.; Liu,
B.; Jiang, C.; Cheng, H.-M., Synthesis of high-quality graphene with a pre-
determined number of layers. Carbon 2009,47(2),:493-499.], C/O numerical value exists after reduction
10.8-14.9.Chemistry redox method while having many advantages, such as, there is also prepare graphene reduction it is insufficient,
Easily stack, produce the problems such as defect, the conventional method that solves problems is that a small amount of be beneficial to point is added in reduction process
Dissipate surfactant [Stankovich, the S. of function; Dikin, D. A.; Piner, R. D.; Kohlhaas, K.
A.; Kleinhammes, A.; Jia, Y.; Wu, Y.; Nguyen, S. T.; Ruoff, R. S., Synthesis
of graphene-based nanosheets via chemical reduction of exfoliated graphite
oxide. Carbon 2007, 45(7),:1558-1565.].Although the stacking for alleviating graphene to a certain extent is asked
Topic, but be not sufficiently stable, the graphene redispersibility after reduction is poor, if by surface-active functional group with reducing passing through of functional group
Be bonded to one-component, it is possible to graphene sheet layer on a molecular scale scattered is realized, so this project uses a kind of ring
Oxide is grafted hydrazine reductant, for preparing the ultra-thin layer graphene of high degree of dispersion.
It is of the invention then be by hydrazo compound grafted epoxy group compound, as the reducing agent of graphene oxide, so
While diazanyl redox graphene can be relied on, make epoxy functional compounds coat or intercalation graphene molecules face it
Between, the Π-Π of graphene molecules can be avoided to accumulate rendezvous problem, ultra-thin layer graphene is made, realizes graphene in molecular water
Dispersiveness on flat.The reducing process is simple, and cost is low, in grapheme material preparation field, be with a wide range of applications and
Huge market prospects.
The content of the invention
The present invention is directed to propose a kind of epoxides grafting hydrazine reduction prepares and the method for dispersed graphite alkene.
Technical program of the present invention lies in：
1. a kind of epoxides grafting hydrazine reduction prepares and the method for dispersed graphite alkene, it is characterised in that：Comprise the following steps：
Step 1:It is prepared by epoxides grafting hydrazine：
A certain amount of solvent is added in reactor, hydrazo compound is added, catalyst, after stirring, adds epoxy
The solution of group compound or epoxy functional compounds, stirring reaction for a period of time, then cools down under certain temperature and pressure
To room temperature, epoxides grafting hydrazine is made, the reducing agent as graphene oxide uses, and epoxides grafting hydrazine preparation principle is such as
Shown in Fig. 1, wherein R, R ' it is C1-C20Alkyl, aryl or with ester group, double bond, alcoxyl silicon substrate, nitro or halogen functional group
Alkyl or aryl, n 1-10；
Step 2:It is prepared by graphene oxide：
Graphite oxide is prepared using improved Hummers methods, or directly uses commercially available graphene oxide product；
Step 3:Epoxides is grafted hydrazine redox graphene：
Certain mass graphene oxide product is taken to be added in good solvent, ultrasonic wave disperses, and then adds ring made from step 1
Oxide is grafted hydrazine, back flow reaction certain time, then washed with absolute ethyl alcohol and deionized water to neutrality at a certain temperature, adopts
Solvent is removed with centrifugation, freeze-drying or heating evaporation mode, graphene is made.
A kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, and it is special
Sign is described epoxy functional compounds, refers to oxirane, expoxy propane, epoxy chlorine（Fluorine, chlorine, bromine）Propane, epoxy
（C4-C18）Alkane, epoxy（C4-C18）Alkene, alkyl（C4-C18）Glycidyl ether, alkenyl（C4-C18）Glycidyl ether, ester group
（C4-C18）Glycidyl ether, GMA, γ-(2,3- the third oxygen of epoxy) propyl-triethoxysilicane,
γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, (3- glycidoxypropyl groups）Methyldiethoxysilane, 3- are (complete
Fluorine n-octyl) -1,2- expoxy propane, 3- (2,2,3,3- tetrafluoro propoxyl group) -1,2- propylene oxides, the hexafluoro nonyl of glycidol ether ten
Base ether, 3- (n-perfluoro-octyl) -1,2- expoxy propane, 3- (perfluor n-hexyl) -1,2- expoxy propane, three（4- hydroxy phenyls）First
The expoxy propane base ether of alkane three, 1,2- epoxy -3,3,3- trifluoro propane, neopentyl glycol diglycidyl ether, butyl glycidyl ether,
2,2- double (4- glycidoxies phenyl) propane, 1 in 2,2- double-(the sweet amine oxygen benzene of 4-) propane or bisphenol A diglycidyl ether
Kind or 2-4 kind mixtures.
A kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, and it is special
Sign refers to hydrazine hydrate, Dimethylhydrazine, 2- diazanyl -5- trifluoromethyl arsenic pyridines, hexamethylene in the hydrazo compound in described step one
Base hydrazine, phenylhydrazine, phenyl hydrazine-p-sulfonic acid, 2- methoxyl group phenylhydrazines, halo phenylhydrazine, polyhalo phenylhydrazine, nitrophenyl hydrazine, more nitrophenyl hydrazines,
5- methylthiophenes [2,3-d] pyrimidine -4- hydrazines or 4-（Difluoro-methoxy）Benzyl] a kind or 2-4 kind mixture in hydrazine.
A kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, and it is special
Sign is that the solvent described in step 1 refers to water, methanol, ethanol, ethylene glycol, glycerine, tirethylene glycol, triethylene Glycol, N,
Dinethylformamide, a kind or the mixture of 2-4 kinds in DMA, dioxane, tetrahydrofuran, diazanyl
Mass concentration scope of the compound in these solvents is 1-99.9%.
A kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, and it is special
Sign is the solution of epoxy functional compounds described in step 1, and its solvent for use refers to water, methanol, ethanol, ethylene glycol, the third three
Alcohol, tirethylene glycol, triethylene Glycol, DMF, DMA, dioxane, tetrahydrofuran
In a kind or 2-4 kinds mixture, mass concentration scope of the epoxy compounds in these solvents is 1-99.9%, can also
Not solubilizer, it is directly added into pure epoxy compound and is reacted.
A kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, and it is special
Sign is that the reaction temperature of the hydrazine grafted epoxy group compound described in step 1 is 0-150 DEG C, can be under 0.1-10MPa pressure
Carry out, the reaction time is 0.5-10 hours, and the molar ratio range for reacting epoxide epoxy group group and hydrazo compound is 0.1-20.
A kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, and it is special
Sign is the graphene dispersing solution described in step 3, and solvent for use refers to water, ethanol, ethylene glycol, glycerine, tirethylene glycol, three
Condensed ethandiol, DMF, a kind or the mixture of 2-4 kinds in DMA, graphene oxide exist
Mass concentration scope in these solvents is 1-50%.
A kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, and it is special
Sign is 20-250 DEG C in the reduction temperature scope of the graphene dispersing solution in described step 3 and epoxides grafting hydrazine, instead
It is 0.5-10 h between seasonable, the quality of graphene oxide and hydrazo compound is 0.1-10 than scope in reaction.
A kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, and it is special
The catalyst that sign is described in step 1 refers to sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, 1 in potassium hydroxide or calcium hydroxide
Kind or 2-3 kind mixtures, dosage are the 0.1-20% of hydrazine quality, can also be not added with catalyst.
Patent accompanying drawing
Fig. 1 epoxides is grafted hydrazine preparation principle；
Fig. 2 GO（a）、N-GO（b）、NO-GO（c）Solvent-dispersible photo；
Fig. 3 GO（a）、N-GO（b）、NO-GO（c）Electron-microscope scanning picture（SEM）；
Fig. 4 GO（a）、N-GO（b）、NO-GO（c）Thermogravimetric curve（TG）；
Fig. 5 GO（a）、N-GO（b）、NO-GO（c）XPS spectrum figure；
Fig. 6 GO（a）, N-GO (b) and NO-GO (c) IR spectrograms.
Embodiment
A kind of grafting hydrazine reduction of 1. epoxides of embodiment prepares and the method for dispersed graphite alkene, comprises the following steps：
Step 1:It is prepared by epoxides grafting hydrazine：
600 grams of water are added in autoclave, add 400 grams of hydrazine hydrates（80%）, after stirring, add 800 grams of epoxies third
Alkane, it is 90 DEG C to keep reaction temperature, and stirring reaction 4h, is subsequently cooled to room temperature under 0.8MPa, and epoxides grafting hydrazine is made
（NO）, the reducing agent as graphene oxide uses.
Step 2:It is prepared by graphene oxide：
Graphite oxide is prepared using improved Hummers methods, the 230 mL concentrated sulfuric acids are placed in 1000 mL three-necked flasks, followed
0 ~ 4 DEG C is cooled in the bath of ring low-temp reaction, the natural flake graphite that 2 g are added under strong stirring is dispersed to the concentrated sulfuric acid；Point
It is a small amount of repeatedly to add 12g potassium permanganate（KMnO4) and 2 g sodium nitrate（NaNO3)；Controlling reaction temperature is 10 ~ 15 DEG C.Magnetic force stirs
2 h are mixed, then three-necked flask is placed in 30 DEG C of thermostat water baths, continue magnetic agitation 30min, now mixture in three-necked flask
For taupe viscous pasty state.And 360 mL distilled water is slowly added in backward there-necked flask, controlling reaction temperature at 70 DEG C, after
The continuous min of magnetic agitation 30.Reaction solution is transferred in 2000 mL beaker, adds 6mL 5% H2O2, diluted with deionized water
To 1500 mL, now reaction solution is brown color.Filter while hot, brown color thing, detection filter are washed with 5% hydrochloric acid and deionized water
Liquid is until without SO4 2-Untill.Obtain graphene oxide product（GO）.
Step 3:Epoxides is grafted hydrazine redox graphene：
Quality is taken to be added to for 100 mg graphene oxide products in 50mL solvent, the min of ultrasonic echography 30 obtains aoxidizing stone
The dispersion liquid of black alkene, epoxides grafting hydrazine made from 100mg step 1 is then added, flow back 4 h at 100 DEG C, heating
Evaporation of solvent, the reduced graphene of dispersant-coated is made（NO-GO）, and detection sign is carried out to it.
The hydrazine hydrate reduction graphene oxide of comparative example 1.：
According to the method described in step 3 in embodiment 1, hydrazine hydrate reduction graphene oxide is utilized：
Quality is taken to be added to for 100 mg graphene oxide products in 50mL solvent, the min of ultrasonic echography 30 obtains aoxidizing stone
The dispersion liquid of black alkene, the hydrazine hydrate containing 100mg is then added, flow back 4 h at 100 DEG C, and heating evaporation removes solvent, system
Obtain hydrazine reduced graphene（N-GO）, and detection sign is carried out to it.
Solvent-dispersible can detect as shown in Fig. 2 Fig. 2 is GO（Graphene oxide）、N-GO（Hydrazine reduced graphene）、NO-
GO（Epoxides is grafted hydrazine reduced graphene）The picture for standing 5 days after being ultrasonically treated in different solvents.From Fig. 2（a）In can
To observe that dispersion effects of the GO in water is fine, without obvious sedimentation phenomenon, after hydrazine hydrate and epoxides grafting hydrazine reduction,
Graphene almost sedimentation completely in water, because reduction causes most of oxy radical in GO to be removed, polar functional
Group is reduced, and the part pi bond of graphene is recovered, and hydrophily weakens；Fig. 2（b）It is GO, N-GO, NO-GO in ethanol scattered
Situation, as can be seen that the dispersion effect of GO, N-GO, NO-GO in ethanol is undesirable from picture, but N-GO is in ethanol
Dissolubility it is relatively preferable because in ultrasonic procedure, ethanol is difficult that infiltration is intercalation between graphene oxide layer, is led
Cause particle to be mixed well with solvent, easily reunite, and polar functional figure is reduced after hydrazine reduction, can be with alcohol solvent pole
Property match, dissolubility is slightly good, and after being grafted hydrazine NO reduction with epoxides, and the nonpolar increase of system is dispersed in ethanol
Decline, but dispersiveness improves in the less DMAc solution of polarity；Such as Fig. 2（c）Dispersion effects of the shown, NO-GO in DMAC
Very well, and GO, N-GO dispersion effect are then poor, reunion sedimentation phenomenon is obvious, this phenomenon absolutely prove epoxides be grafted hydrazine
Reduction can adjust the solvent-dispersible of graphene.
SEM（SEM）For characterizing graphene pattern, the color and surface folding of SEM image can be substantially
Reflect the thickness of graphene.Fig. 3 show GO, N-GO, NO-GO SEM image, corresponds to a, b, c respectively.From Fig. 3（a）Can be with
Find out, GO surface is more coarse, and lamella accumulation is serious, has lost the metallic luster of graphite surface, and can be clearly apparent it
The stepped pattern at edge, and because ultrasound peel off come off under many graphene oxide sheets not of uniform size.Through hydrazine hydrate and
After epoxides grafting hydrazine reduction, such as Fig. 3（b）、（c）Shown, most of oxy radical is removed so that N-GO, NO-GO piece
Thickness degree reduces, and fold occurs in graphenic surface and Gibbs free energy reduces, more stable.Fig. 3（b）With（c）Compare, N-
GO surface relative smooth is clean and tidy, and NO-GO surface folding is then more obvious, and lamellar spacing is smaller, illustrates epoxidation
The graphene sheet layer of thing grafting hydrazine reduction is evenly distributed without Π-Π packing phenomenons, lamellar spacing, good dispersion.
Fig. 4 show graphene oxide（GO）, hydrazine hydrate reduction graphene oxide（N-GO）, epoxides grafting hydrazine reduction
Graphene oxide（NO-GO）TG curves.From Fig. 4（a）In as can be seen that GO occur in Range of measuring temp it is obvious twice
Mass loss.Absorption water in room temperature to the mass loss occurred in the range of 100 DEG C mainly due to surface of graphene oxide
Caused by heated volatilization；In the range of 100 DEG C~300 DEG C, mass loss is about 50%, and this is due to containing for graphene oxide
Caused by oxygen groups are thermally decomposed, CO is generated2、H2O etc..Through hydrazine hydrate and epoxides grafting hydrazine be reduced into graphene it
Afterwards, such as Fig. 4（b）、（c）Shown, the slight mass loss below 100 DEG C in scope is the heated volatilization of a small amount of absorption water in surface
Caused by；In the range of 100 DEG C~200 DEG C, NO-GO and N-GO TG curve ratio GO curves loss are obvious to be reduced, because
The two does not contain the unstable group such as carboxyl, hydroxyl, and in the range of 200 DEG C~800 DEG C, NO-GO mass loss is relatively large,
This is due to caused by containing surface-active polyether chain in NO-GO, there is surface-assembled after illustrating epoxides grafting hydrazine reduction GO
Antisiludging surface active ingredient.
That Fig. 5 is represented is GO（a）、N-GO（b）、NO-GO（c）The full spectrograms of XPS.XPS is analysis of material surface chemistry group
Into a kind of effective ways, from Fig. 5（a）In it can be seen that GO in combination can be the obvious power spectrum of 285eV and 533eV places appearance
Peak, it is known from literature that the two peaks correspond to C respectively1SAnd O1S, illustrate that surface of graphene oxide contains abundant oxy radical；Through
XPS spectrum figure such as Fig. 5 of N-GO and NO-GO after hydrazine hydrate and epoxides grafting hydrazine reduction（b）、（c）It is shown, can be with from figure
Find out that C/O ratio is far above the ratio in GO, illustrate that the addition of hydrazine hydrate and epoxides grafting two kinds of reducing agents of hydrazine removes
GO surfaces substantial amounts of oxy radicals, and generate new carbon-carbon bond.
It is illustrated in figure 6 graphene oxide（GO）, hydrazine hydrate reduction graphene oxide（N-GO）, hydrazine hydrate grafted epoxy third
Alkane redox graphene（NO-GO）FT-IR phenograms.From fig. 6 it can be seen that GO is in 3383.1cm-1Place absorbs
Peak, the peak belong to the O-H hydrogen bond associations peak of-OH and-COOH in graphene oxide, substantially disappear or drop after hydrazine hydrate reduction
Low, epoxides grafting hydrazine reduction ratio hydrazine hydrate reduction is more abundant；1725 cm-1The absworption peak at place is due on carboxyl or carbonyl
- C=O stretching vibration caused by；Substantially reduced after hydrazine hydrate and epoxides grafting hydrazine reduction；1619cm-1 The C of aromatic hydrocarbon
=C skeletal vibrations, after hydrazine hydrate reduction hydrocarbylation, basket moves to 1547.9cm-1；Reduction hydrocarbylation through epoxides grafting hydrazine
Afterwards, basket moves to 1560.1cm-1 ,It is also likely to be N-H deformation vibration modes；- the CH of aromatic side chain-COOH reduction generations2-, in its face
Flexural vibrations absworption peak：1454.1 and 1456.0cm-1；1220.3cm-1Shaken for the C-O in aromatic carboxylic, phenol or alcohol is flexible
Dynamic, after the reduction hydrocarbylation of hydrazine hydrate, basket moves to 1189.4cm-1For C-N stretching vibration absworption peaks；It is grafted through epoxides
After the reduction hydrocarbylation of hydrazine, basket moves to 1190.8cm-1For C-N stretching vibration absworption peaks；1126.6 flexible shake for the C-O-C of ether
Dynamic absworption peak, substantially disappears after hydrazine hydrate reduction；Substantially reduced after epoxides grafting hydrazine reduction；1048.6 cm-1Primary alconol
Middle O-C stretching vibration absworption peaks, substantially disappeared after hydrazine hydrate or epoxides grafting hydrazine reduction are eliminated or epoxides is grafted；
Part generation alkene=C-H out-of-plane deformation vibration absorption peak is respectively 988.7 and 1006.1cm-1, it is also possible to aromatic ether
R-O stretching vibration absworption peaks；855.5cm-1 The C-H out-of-plane bending vibrations of aromatic ring, hydrazine hydrate and epoxides grafting hydrazine reduce it
Still exist afterwards.FT- IR collection of illustrative plates sign further demonstrates surface of graphene oxide and contains abundant oxy radical.Through hydration
After hydrazine and epoxides grafting hydrazine reduction, graphene can be prepared.
A kind of grafting hydrazine reduction of 2. epoxides of embodiment prepares and the method for dispersed graphite alkene, comprises the following steps：
Step 1:It is prepared by epoxides grafting hydrazine：
60 grams of water are added in three-necked flask, add 80 grams of hydrazine hydrates（80%）, after stirring, add 220 grams of epoxy chlorine
Propane, it is 40 DEG C to keep reaction temperature, and stirring reaction 4h, is subsequently cooled to room temperature at this temperature, and epoxides grafting is made
Hydrazine, the reducing agent as graphene oxide use.
Step 2:It is prepared by graphene oxide：
Graphite oxide is prepared using improved Hummers methods, the 230 mL concentrated sulfuric acids are placed in 1000 mL three-necked flasks, followed
4 DEG C are cooled in the bath of ring low-temp reaction.The natural flake graphite that 3g is added under strong stirring is dispersed to the concentrated sulfuric acid；Divide few
Amount repeatedly adds 20 g potassium permanganate and 2g sodium nitrate；Controlling reaction temperature is 15 DEG C, the h of magnetic agitation 2, then by three-necked flask
It is placed in 25 DEG C of thermostat water baths, continues magnetic agitation 30min, now mixture is taupe viscous pasty state in three-necked flask.
And 360 mL distilled water is slowly added in backward there-necked flask, controlling reaction temperature continues the min of magnetic agitation 30 at 80 DEG C,
Reaction solution is transferred in 2000 mL beaker, adds 6mL 5% H2O2, 1500 mL are diluted to deionized water, are now reacted
Liquid is brown color, is filtered while hot, washs brown color thing with 5% hydrochloric acid and deionized water, detection filtrate is until without SO4 2-Untill.
Obtain graphene oxide product.
Step 3:Epoxides is grafted hydrazine redox graphene：
Quality is taken to be added to for 100 mg graphene oxide products in 50mL solvent, the min of ultrasonic echography 30 obtains aoxidizing stone
The dispersion liquid of black alkene, epoxides grafting hydrazine made from 150mg step 1 is then added, flow back 4 h at 100 DEG C, centrifugation
Washing is multiple, then freeze-drying is separated off solvent, and the reduced graphene of dispersant-coated is made.
A kind of grafting hydrazine reduction of 3. epoxides of embodiment prepares and the method for dispersed graphite alkene, comprises the following steps：
Step 1:It is prepared by epoxides grafting hydrazine：
500 grams of water and 100 grams of ethylene glycol are added in autoclave, add 1200 grams of DNPHs, after stirring,
1800 grams of expoxy propane are added, it is 100 DEG C to keep reaction temperature, and stirring reaction 5h, is subsequently cooled to room under 1.0MPa
Temperature, is made epoxides grafting hydrazine, and the reducing agent as graphene oxide uses.
Step 2:It is prepared by graphene oxide：
Graphite oxide is prepared using improved Hummers methods, the 200 mL concentrated sulfuric acids are placed in 1000 mL three-necked flasks, followed
0 DEG C is cooled in the bath of ring low-temp reaction.The natural flake graphite that 1g is added under strong stirring is dispersed to the concentrated sulfuric acid；Divide few
Amount repeatedly adds 25 g potassium permanganate and 3 g sodium nitrate；Controlling reaction temperature is 15 DEG C.The h of magnetic agitation 2, then three mouthfuls are burnt
Bottle is placed in 25 DEG C of thermostat water baths, continues magnetic agitation 30min, and now mixture is that taupe is thick in three-necked flask
State.And 460 mL distilled water is slowly added in backward there-necked flask, controlling reaction temperature continues magnetic agitation 30 at 80 DEG C
min.Reaction solution is transferred in 2000 mL beaker, adds 9mL 5% H2O2, 1500 mL are diluted to deionized water, now
Reaction solution is brown color.Filter while hot, wash brown color thing with 5% hydrochloric acid and deionized water, detection filtrate is until without SO4 2-For
Only.Obtain graphene oxide product.
Step 3:Epoxides is grafted hydrazine redox graphene：
Quality is taken to be added to for 100 mg graphene oxide products in 50mL solvent, the min of ultrasonic echography 30 obtains aoxidizing stone
The dispersion liquid of black alkene, epoxides grafting hydrazine made from 250mg step 1 is then added, flow back 4 h at 180 DEG C, centrifugation
Washing separation is multiple, reheats evaporation of solvent, and the reduced graphene of dispersant-coated is made.
A kind of grafting hydrazine reduction of 4. epoxides of embodiment prepares and the method for dispersed graphite alkene, comprises the following steps：
Step 1:It is prepared by epoxides grafting hydrazine：
500 grams of water, 500 grams of ethylene glycol/1 gram sulfuric acid are added in quartz reaction kettle, add 800 grams of DNPHs
（80%）, after stirring, 1200 grams of expoxy propane are added, it is 100 DEG C to keep reaction temperature, is stirred in this temperature range
8h is reacted, is subsequently cooled to room temperature, epoxides grafting hydrazine is made, the reducing agent as graphene oxide uses.
Step 2:It is prepared by graphene oxide：
Graphite oxide is prepared using improved Hummers methods, the 230 mL concentrated sulfuric acids are placed in 1000 mL three-necked flasks, followed
3 DEG C are cooled in the bath of ring low-temp reaction.The natural flake graphite that 5 g are added under strong stirring is dispersed to the concentrated sulfuric acid；Divide few
Amount repeatedly adds 25 g potassium permanganate and 4 g sodium nitrate；Controlling reaction temperature is 15 DEG C.The h of magnetic agitation 2, then three mouthfuls are burnt
Bottle is placed in 35 DEG C of thermostat water baths, continues magnetic agitation 30min, and now mixture is that taupe is thick in three-necked flask
State.And 360 mL distilled water is slowly added in backward there-necked flask, controlling reaction temperature continues magnetic agitation 30 at 70 DEG C
min.Reaction solution is transferred in 2000 mL beaker, adds 6mL 5% H2O2, 1500 mL are diluted to deionized water, now
Reaction solution is brown color.Filter while hot, wash brown color thing with 5% hydrochloric acid and deionized water, detection filtrate is until without SO4 2-For
Only.Obtain graphene oxide product.
Step 3:Epoxides is grafted hydrazine redox graphene：
Quality is taken to be added to for 100 mg graphene oxide products in 50mL solvent, the min of ultrasonic echography 30 obtains aoxidizing stone
The dispersion liquid of black alkene, epoxides grafting hydrazine made from 50mg step 1 is then added, flowed back 5 h at 200 DEG C, and heating is steamed
Hair removes solvent, and the reduced graphene of dispersant-coated is made.
A kind of grafting hydrazine reduction of 5. epoxides of embodiment prepares and the method for dispersed graphite alkene, comprises the following steps：
Step 1:It is prepared by epoxides grafting hydrazine：
60 grams of water are added in autoclave, add 60 grams of hydrazine hydrates（60%）, after stirring, add 50 grams of metering systems
Acid glycidyl ester, it is 100 DEG C to keep reaction temperature, and stirring reaction 4h, is subsequently cooled to room temperature under 0.6MPa, and ring is made
Oxide is grafted hydrazine, and the reducing agent as graphene oxide uses.
Step 2:It is prepared by graphene oxide：
Graphite oxide is prepared using improved Hummers methods, the 200 mL concentrated sulfuric acids are placed in 1000 mL three-necked flasks, followed
4 DEG C are cooled in the bath of ring low-temp reaction.The natural flake graphite that 4 g are added under strong stirring is dispersed to the concentrated sulfuric acid；Point
It is a small amount of repeatedly to add 25 g potassium permanganate and 4 g sodium nitrate；Controlling reaction temperature is 15 DEG C.The h of magnetic agitation 2, then by three mouthfuls
Flask is placed in 35 DEG C of thermostat water baths, continues magnetic agitation 30min, and now mixture is that taupe is sticky in three-necked flask
State.And 460 mL distilled water is slowly added in backward there-necked flask, controlling reaction temperature continues magnetic agitation 30 at 90 DEG C
min.Reaction solution is transferred in 2000 mL beaker, adds 5-10mL 5% H2O2, 1500 mL are diluted to deionized water,
Now reaction solution is brown color.Filter while hot, wash brown color thing with 5% hydrochloric acid and deionized water, detection filtrate is until nothing
SO4 2-Untill.Obtain graphene oxide product.
Step 3:Epoxides is grafted hydrazine redox graphene：
Quality is taken to be added to for 100 mg graphene oxide products in 50mL solvent, the min of ultrasonic echography 30 obtains aoxidizing stone
The dispersion liquid of black alkene, epoxides grafting hydrazine made from 350mg step 1 is then added, flow back 8 h at 100 DEG C, heating
Evaporation of solvent, the reduced graphene of dispersant-coated is made.
A kind of grafting hydrazine reduction of 6. epoxides of embodiment prepares and the method for dispersed graphite alkene, comprises the following steps：
Step 1:It is prepared by KH560 epoxides grafting hydrazine：
60 grams of water are added in three-necked flask, add 60 grams of hydrazine hydrates（80%）, after stirring, add 50 grams of γ-(2,
The oxygen of 3- epoxies third) propyl-triethoxysilicane, it is 80 DEG C to keep reaction temperature, stirring reaction 4h, is subsequently cooled to room temperature, is made
Epoxides grafting hydrazine is obtained, the reducing agent as graphene oxide uses.
Step 2:It is prepared by graphene oxide：
Graphite oxide is prepared using improved Hummers methods, the 230 mL concentrated sulfuric acids are placed in 1000 mL three-necked flasks, followed
4 DEG C are cooled in the bath of ring low-temp reaction.The natural flake graphite that 5 g are added under strong stirring is dispersed to the concentrated sulfuric acid；Divide few
Amount repeatedly adds 25 g potassium permanganate and 3g sodium nitrate；Controlling reaction temperature is 15 DEG C.The h of magnetic agitation 2, then by three-necked flask
It is placed in 30 DEG C of thermostat water baths, continues magnetic agitation 30min, now mixture is taupe viscous pasty state in three-necked flask.
And 400 mL distilled water is slowly added in backward there-necked flask, controlling reaction temperature continues the min of magnetic agitation 30 at 80 DEG C.
Reaction solution is transferred in 2000 mL beaker, adds 10mL 5% H2O2, 1500 mL are diluted to deionized water, now instead
It is brown color to answer liquid.Filter while hot, wash brown color thing with 5% hydrochloric acid and deionized water, detection filtrate is until without SO4 2-For
Only.Obtain graphene oxide product.
Step 3:Epoxides is grafted hydrazine redox graphene：
Quality is taken to be added to for 100 mg graphene oxide products in 50mL solvent, the min of ultrasonic echography 30 obtains aoxidizing stone
The dispersion liquid of black alkene, epoxides grafting hydrazine made from 450mg step 1 is then added, flow back 5 h at 100 DEG C, heating
Evaporation of solvent, the reduced graphene of dispersant-coated is made.
Claims (9)
1. a kind of epoxides grafting hydrazine reduction prepares and the method for dispersed graphite alkene, it is characterised in that：Comprise the following steps：
Step 1:It is prepared by epoxides grafting hydrazine：
A certain amount of solvent is added in reactor, hydrazo compound is added, catalyst, after stirring, adds pure ring
The solution of oxygen groups compound or epoxy functional compounds, under certain temperature and pressure stirring reaction for a period of time, Ran Houleng
But to room temperature, epoxides grafting hydrazine is made, the reducing agent as graphene oxide uses, epoxides grafting hydrazine preparation principle
As shown in figure 1, wherein R, R ' it is C1-C20Alkyl, aryl or with ester group, double bond, alcoxyl silicon substrate, nitro or halogen function
The alkyl or aryl of group, n 1-10；
Step 2:It is prepared by graphene oxide：
Graphite oxide is prepared using improved Hummers methods, or directly uses commercially available graphene oxide product；
Step 3:Epoxides is grafted hydrazine redox graphene：
Certain mass graphene oxide product is taken to be added in good solvent, ultrasonic wave disperses, and then adds ring made from step 1
Oxide is grafted hydrazine, back flow reaction certain time, then washed with absolute ethyl alcohol and deionized water to neutrality at a certain temperature, adopts
Solvent is removed with centrifugation, freeze-drying or heating evaporation mode, graphene is made.
2. a kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, its feature
It is described epoxy functional compounds, refers to oxirane, expoxy propane, epoxy chlorine（Fluorine, chlorine, bromine）Propane, epoxy（C4-
C18）Alkane, epoxy（C4-C18）Alkene, alkyl（C4-C18）Glycidyl ether, alkenyl（C4-C18）Glycidyl ether, ester group（C4-
C18）Glycidyl ether, GMA, γ-(2,3- the third oxygen of epoxy) propyl-triethoxysilicane, γ-
(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, (3- glycidoxypropyl groups）Methyldiethoxysilane, (perfluor is just by 3-
Octyl group) -1,2- expoxy propane, 3- (2,2,3,3- tetrafluoro propoxyl group) -1,2- propylene oxides, the hexafluoro nonyl of glycidol ether ten
Ether, 3- (n-perfluoro-octyl) -1,2- expoxy propane, 3- (perfluor n-hexyl) -1,2- expoxy propane, three（4- hydroxy phenyls）Methane
Three expoxy propane base ethers, 1,2- epoxy -3,3,3- trifluoro propane, neopentyl glycol diglycidyl ether, butyl glycidyl ether, 2,
Double (the 4- glycidoxies phenyl) propane of 2-, a kind in 2,2- double-(the sweet amine oxygen benzene of 4-) propane or bisphenol A diglycidyl ether
Or 2-4 kind mixtures.
3. a kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, its feature
Refer to hydrazine hydrate, Dimethylhydrazine, 2- diazanyl -5- trifluoromethyl arsenic pyridines, cyclohexyl in the hydrazo compound in described step one
Hydrazine, phenylhydrazine, phenyl hydrazine-p-sulfonic acid, 2- methoxyl group phenylhydrazines, halo phenylhydrazine, polyhalo phenylhydrazine, nitrophenyl hydrazine, more nitrophenyl hydrazines, 5-
Methylthiophene [2,3-d] pyrimidine -4- hydrazines or 4-（Difluoro-methoxy）Benzyl] a kind or 2-4 kind mixture in hydrazine.
4. a kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, its feature
It is that the solvent described in step 1 refers to water, methanol, ethanol, ethylene glycol, glycerine, tirethylene glycol, triethylene Glycol, N, N-
Dimethylformamide, a kind or the mixture of 2-4 kinds in DMA, dioxane, tetrahydrofuran, diazanyl
Mass concentration scope of the compound in these solvents is 1-99.9%.
5. a kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, its feature
Be the solution of the epoxy functional compounds described in step 1, its solvent for use refer to water, methanol, ethanol, ethylene glycol, glycerine,
Tirethylene glycol, triethylene Glycol, DMF, in DMA, dioxane, tetrahydrofuran
1 kind or the mixture of 2-4 kinds, mass concentration scope of the epoxy compounds in these solvents is 1-99.9%, can also be not added with
Solvent, it is directly added into pure epoxy compound and is reacted.
6. a kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, its feature
The reaction temperature for being the hydrazine grafted epoxy group compound described in step 1 is 0-150 DEG C, can be entered under 0.1-10MPa pressure
OK, the reaction time is 0.5-10 hours, and the molar ratio range for reacting epoxide epoxy group group and hydrazo compound is 0.1-20.
7. a kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, its feature
It is the graphene dispersing solution described in step 3, solvent for use refers to water, ethanol, ethylene glycol, glycerine, tirethylene glycol, three contractings
Ethylene glycol, DMF, a kind or the mixture of 2-4 kinds in DMA, graphene oxide is at this
Mass concentration scope in a little solvents is 1-50%.
8. a kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, its feature
It is 20-250 DEG C in the reduction temperature scope of the graphene dispersing solution in described step 3 and epoxides grafting hydrazine, reaction
Time is 0.5-10 h, and the quality of graphene oxide and hydrazo compound is 0.1-10 than scope in reaction.
9. a kind of epoxides grafting hydrazine reduction according to claim 1 prepares and the method for dispersed graphite alkene, its feature
It is that the catalyst described in step 1 refers to sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, a kind in potassium hydroxide or calcium hydroxide
Or 2-3 kind mixtures, dosage are the 0.1-20% of hydrazine quality, can also be not added with catalyst.
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| CN101654243A (en) * | 2009-08-28 | 2010-02-24 | 青岛大学 | Preparation method of functional nano-graphene |
| CN102015655A (en) * | 2008-05-09 | 2011-04-13 | 詹森药业有限公司 | Trisubstituted pyrazoles as acetylcholine receptor modulators |
| US20150344311A1 (en) * | 2012-11-14 | 2015-12-03 | Sogang University Research Foundation | Method for manufacturing reduced graphene oxide using solid hydrazine derivative |
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| CN102015655A (en) * | 2008-05-09 | 2011-04-13 | 詹森药业有限公司 | Trisubstituted pyrazoles as acetylcholine receptor modulators |
| CN101654243A (en) * | 2009-08-28 | 2010-02-24 | 青岛大学 | Preparation method of functional nano-graphene |
| US20150344311A1 (en) * | 2012-11-14 | 2015-12-03 | Sogang University Research Foundation | Method for manufacturing reduced graphene oxide using solid hydrazine derivative |
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