CN105503581B - A kind of water-soluble nano graphenic surface activating agent and its synthetic method and application - Google Patents
A kind of water-soluble nano graphenic surface activating agent and its synthetic method and application Download PDFInfo
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- 0 *C(COc1cc2c(C3=CC(O*)=C(*)CC3c(c3c4)c5c(c6c(C(C7)C8=CC(*)=C7O)c(cc(c(OCC(O)=O)c7)OCC(O)=*)c7c(CC(C7=C*9)=CC(O*)=C9O*)c66)c8c3c*([U]CC(O)=O)c4OCC(O)=O)c5c6c7c2cc1OC*(O)=O)=O Chemical compound *C(COc1cc2c(C3=CC(O*)=C(*)CC3c(c3c4)c5c(c6c(C(C7)C8=CC(*)=C7O)c(cc(c(OCC(O)=O)c7)OCC(O)=*)c7c(CC(C7=C*9)=CC(O*)=C9O*)c66)c8c3c*([U]CC(O)=O)c4OCC(O)=O)c5c6c7c2cc1OC*(O)=O)=O 0.000 description 2
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- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
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Abstract
The invention discloses a kind of water-soluble nano graphenic surface activating agent and its synthetic method and application, the structural formula of the surfactant isM in formula+Represent Li+、Na+、K+、NH4 +、N(CH3)4 +Or N (C2H5)4 +, R represents C1~C12Alkyl, the surfactant is that, with 3,4 two (ethoxycarbonylmethoxy) benzaldehydes and 1,3,5 three ((3,4 dialkoxy) phenyl methyl) benzene are raw material, utilize Ac2O/FeCl3/CH3NO2" one pot " of system occurs after Friedel-Crafts reaction and cyclisation oxidative dehydrogenation, is prepared from through hydrolysis and acid-base neutralization, and raw materials used cheap and easy to get, reaction condition is gentle, and product yield is higher.Water-soluble nano graphenic surface activating agent of the present invention can be used for peeling off graphite, prepare the preferable individual layer of surface topography or few layer graphene, and the concentration height of obtained graphene dispersing solution is peeled off, provide a kind of feasible method for the excellent graphene of extensive processability.
Description
Technical field
The invention belongs to carbon material preparing technical field, and in particular to a kind of water-soluble nano graphenic surface activating agent
And its synthetic method, and application of the surfactant in preparing graphite alkene is efficiently peeled off.
Background technology
Graphene has special two-dimensional structure, and the planar carbon atom arranged by honeycomb-patterned ordered is stacked and formed.Graphene
There is outstanding Electronic Performance, hot property and mechanical performance because of its special structure and high specific surface area, be expected in electronics
The fields such as device, the energy, machinery, chemical industry, special material and medical treatment obtain extensive use.Therefore the preparation of extensive high-efficiency and economic
Graphene turns into one of study hotspot of scientific worker.
At present, the preparation method of graphene mainly have mechanical stripping method, epitaxial growth method, chemical vapour deposition technique (CVD),
Oxidation-reduction method and liquid phase graphite stripping method.Mechanical stripping method and epitaxial growth method are not suitable for big due to low-yield and high cost
Large-scale production graphene；Although CVD can be produced, area is larger, the less graphene of defect, its low yield and energy disappears
Consumption is big；Oxidation-reduction method can largely prepare redox graphene, but this method destroys the lattice structure of graphene
Cause the poor-performing of redox graphene.Liquid phase stripping method is proved that low defect graphene can be prepared recently, different
Solvent or surfactant to stripping have different effects.
Liquid phase peel off graphene be usually under ultrasonic wave added, with appropriate surfaces can organic solvent (such as DMF,
NMP) or in the aqueous solution of special surface activating agent carry out.Organic solvent is due to higher boiling, high price and highly toxic
Feature, and it is unable to large-scale application.Therefore, it is largely to prepare the one of graphene to be peeled off in the aqueous solution containing surfactant
Individual better method.
Coleman research groups (ACS Nano, 2010,4 (6), 3155-3162) report adds sodium taurocholate in aqueous phase
Salt, ultrasound more than 400 hours, finally gives 0.3mg/mL graphene dispersing solution, wherein 20% or so graphene is individual layer
Graphene.Liu Jun research groups (ACS Nano, 2014,8 (7), 6663-6670) synthesize be connected with ion cluster electron deficient π be total to
Molecular conjugate, 1.2~5mg/mL is brought up to by ultrasonic stripping method by the concentration of graphene dispersing solution, the side reported with Coleman
Method is compared, and substantially increases the efficiency for preparing graphene, but single-layer graphene only accounts for 6%.
The content of the invention
Technical problem solved by the invention is to overcome business efficiency present in existing graphene preparation low and production
There is provided a kind of water-soluble nano graphenic surface activity that can be used for efficiently peeling off preparing graphite alkene for the problems such as quality is poor
Agent, and the surfactant preparation method and application.
The technical scheme that solution above-mentioned technical problem is used is the structure of the water-soluble nano graphenic surface activating agent
Formula is as follows：
The synthetic route of above-mentioned water-soluble nano graphenic surface activating agent is as follows：
In above-mentioned 1~formula of formula 4, M+Represent Li+、Na+、K+、NH4 +、N(CH3)4 +、N(C2H5)4 +In any one, R represent
C1~C12Alkyl.
Its specific synthetic method is made up of following step：
1st, ring closure reaction
Using dry methylene chloride as solvent, by 1 shown in formula 1,3,5- tri- ((3,4- dialkoxy) phenyl methyl) benzene with
3,4- bis- (ethoxycarbonylmethoxy) benzaldehyde, acetic anhydride shown in formula 2 are 1 in molar ratio:3~4.5:12~25, room temperature is stirred
Mix 6~24 hours, after under ice-water bath, argon gas protection, the nitromethane solution of ferric trichloride is added dropwise, wherein 1,3,5- tri- ((3,
4- dibutoxies) phenyl methyl) mol ratio of benzene and ferric trichloride is 1:12~20, react at room temperature 6~12 hours, add methanol
Reaction is quenched, product is isolated and purified, the compound of formula 3 is obtained.
2nd, hydrolysis
It is 1 in molar ratio by the compound of formula 3 and NaOH or potassium hydroxide using the mixture of second alcohol and water as solvent:6
~10 back flow reactions 2~5 hours, adjust pH value to 2~3 with watery hydrochloric acid, isolate and purify product, obtain the compound of formula 4.
3rd, acid-base reaction
In the aqueous solution that the compound of formula 4 is added to alkali, wherein the compound of formula 4 and the mol ratio of alkali are 1:5~10, it is described
Alkali is any one in lithium carbonate, NaOH, potassium hydroxide, ammoniacal liquor, TMAH, tetraethyl ammonium hydroxide,
It is stirred at room temperature 30~60 minutes, is spin-dried for, obtains water-soluble nano graphenic surface activating agent.
In above-mentioned steps 1, preferably 1,3,5- tri- ((3,4- dialkoxy) phenyl methyl) benzene and (the carbethoxyl group first of 3,4- bis-
Epoxide) benzaldehyde, acetic anhydride, ferric trichloride mol ratio be 1:3.3:20:16.
In above-mentioned steps 2, the compound of preferred formula 3 is 1 with the mol ratio of NaOH or potassium hydroxide:6.
In above-mentioned steps 3, the mol ratio of the compound of preferred formula 4 and alkali is 1:6.
Purposes of the water-soluble nano graphenic surface activating agent of the present invention in preparing graphite alkene is peeled off, specific method
It is as follows：
It is 1 in mass ratio by graphite powder and water-soluble nano graphenic surface activating agent:1 adds in deionized water, in ice
Ultrasonic disperse 30~90 minutes in water-bath, centrifuge, obtain graphene dispersing solution.
Beneficial effects of the present invention are as follows：
1st, the simple synthetic method of water-soluble nano graphenic surface activating agent of the present invention, raw materials used cheap and easy to get, instead
Mild condition is answered, easy-to-operate, product yield is higher.
2nd, water-soluble nano graphenic surface activating agent of the present invention is used for the efficiency high for peeling off preparing graphite alkene, peels off
The graphene obtained afterwards is mainly the preferable individual layer of surface topography or few layer graphene, and the stone peeled off and obtained is calculated using difference assay
The concentration of black alkene dispersion liquid is 5mg/mL or so.Prove to peel off successfully through XRD, SEM, tem analysis and surface topography is preferable, be big
The superior graphene of scale processability provides a kind of feasible method.
Brief description of the drawings
Fig. 1 is 325 mesh graphite and peels off 325 mesh graphite using the water-soluble nano graphenic surface activating agent of embodiment 1
The X-ray diffractogram of the graphene obtained afterwards.
Fig. 2 peels off the graphene obtained after 325 mesh graphite using the water-soluble nano graphenic surface activating agent of embodiment 1
Scanning electron microscope diagram.
Fig. 3 is that the graphite obtained after 325 mesh graphite is peeled off using the water-soluble nano graphenic surface activating agent of embodiment 1
The SEM enlarged drawing of alkene.
Fig. 4 is that the graphite obtained after 325 mesh graphite is peeled off using the water-soluble nano graphenic surface activating agent of embodiment 1
The transmission electron microscope figure of alkene.
Fig. 5 is that the graphite obtained after 325 mesh graphite is peeled off using the water-soluble nano graphenic surface activating agent of embodiment 1
The transmission electron microscope enlarged drawing of alkene.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in more detail, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
By taking the following water-soluble nano graphenic surface activating agent of composite structure formula as an example, specific synthetic method is：
1st, ring closure reaction
((3,4- dibutoxies) the phenyl first of 1.22g (1.56mmol) 1,3,5- tri- is sequentially added into 250mL there-necked flasks
Base) benzene, (ethoxycarbonylmethoxy) benzaldehydes of 1.60g (5.15mmol) 3,4- bis-, 3.00mL (31.70mmol) acetic anhydride,
The dichloromethane that 0.10g (0.62mmol) ferric trichlorides and 150mL are dried, is stirred at room temperature 24 hours, is protected in ice-water bath, argon gas
Under, the nitromethane solution that 20mL is dissolved with 4.02g (24.96mmol) ferric trichloride is added dropwise, drips rear room temperature and continues to stir
Reaction 6 hours, adds methanol and is quenched reaction, and reaction solution washs 3 times with saturated sodium-chloride water solution, deionized water successively, then
Dichloromethane is removed through anhydrous sodium sulfate drying, filtering, rotary evaporation, then with dichloromethane and ethyl acetate volume ratio 20:1
Mixed liquor makees eluant, eluent column chromatography for separation, obtains the following (carbethoxyl group of yellow solid 2,3,10,11,18,19- six of structural formula
Methoxyl group) -6, [a, d, g, j, m, p] guans, its yield are 82.5% to the benzo of 7,14,15,22,23- six butoxy six.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and
MALDI-TOF mass spectrographs (Germany, Burker Daltonics) are characterized, and characterize data is as follows：
1H NMR (400MHz, CDCl3+TMS)δ(ppm)：8.73 (s, 2H), 8.63 (s, 2H), 4.98 (s, 4H), 4.55-
4.19 (m, 12H), 2.01-1.96 (m, 4H), 1.67-1.62 (m, 4H) 1.35-1.33 (t, 6H), 1.32-1.05 (t, 6H)；13C
NMR (100MHz, CDCl3+TMS)δ(ppm)：168.79,149.03,147.21,125.95,125.09,123.83,120.40,
113.20,110.92,69.28,66.97,61.54,31.60,19.47,14.27,14.07；MALDI-TOF-MS：m/z
(C96H108O24) theoretical value 1045.70, measured value 1045.72.
2nd, hydrolysis
(the ethoxycarbonylmethyloxies of 0.60g (0.36mmol) 2,3,10,11,18,19- six are added in 100mL single-necked flasks
Base) six butoxy of -6,7,14,15,22,23-, six benzo [a, d, g, j, m, p] guans, 0.10g (2.52mmol) NaOH,
50mL ethanol, 10mL deionized waters, back flow reaction 3 hours, rotary evaporation remove most of ethanol, add 100mL deionized waters,
Resulting solution mass fraction adjusts pH value to 2~3, a large amount of thick precipitations of generation, through ether for 10% aqueous hydrochloric acid solution
Extraction, anhydrous sodium sulfate drying, suction filtration, filtrate rotary evaporation obtain the following yellow powder Liu Ben Bing guan derivatives of structural formula
Hexacarboxylic acid, its yield is 90%.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and
MALDI-TOF mass spectrographs (Germany, Burker Daltonics) are characterized, and characterize data is as follows：
1H NMR (400MHz, DMSO-d6+TMS)δ(ppm)：8.60 (s, 2H), 8.57 (s, 2H), 5.08-4.98 (m,
4H), 4.44-4.24 (m, 4H), 1.90-1.87 (m, 4H), 1.61-1.54 (m, 4H), 1.03-1.00 (t, 6H)；MALDI-
TOF-MS：m/z(C84H84O24) theoretical value 1476.53, measured value 1476.82.
3rd, acid-base reaction
0.50g (0.34mmol) Liu Ben Bing guan derivatives hexacarboxylic acid, 30mL are added into 50mL single-necked flasks and contains 0.08g
The aqueous solution of (2.04mmol) NaOH, is stirred at room temperature 30 minutes, is spin-dried for, and obtains water-soluble nano graphenic surface activity
Agent.
Products therefrom is characterized with Maxis high resolution mass spectrometers (Germany, Bruker companies), and characterize data is as follows：
UHRMS-ESI：m/z(C84H78Na6O24) theoretical value 1608.4269, measured value 781.2231 ([M-2Na]2-)、
513.1534([M-3Na]3-)、379.1174([M-4Na]4-)、620.5815([2M-5Na]5-)。
Embodiment 2
By taking the following water-soluble nano graphenic surface activating agent of composite structure formula as an example, specific synthetic method is：
In the step 3 of embodiment 1,0.50g (0.34mmol) six benzene and guan derivative are added into 50mL single-necked flasks
Hexacarboxylic acid, 30mL contain the aqueous solution of 0.12g (2.04mmol) potassium hydroxide, are stirred at room temperature 30 minutes, other steps and embodiment 1
It is identical, obtain water-soluble nano graphenic surface activating agent.
Products therefrom is characterized with Maxis high resolution mass spectrometers (Germany, Bruker companies), and characterize data is as follows：
UHRMS-ESI：m/z(C84H78K6O24) theoretical value 1704.2705, measured value 813.1725 ([M-2K]2-)、
529.1274([M-3K]3-)、387.1042([M-4K]4-)、542.0336([2M-5K]5-)。
Embodiment 3
By taking the following Liu Ben Bing guan derivative hexacarboxylic acid sodium salts of composite structure formula as an example, specific synthetic method is：
1st, ring closure reaction
In step 1 in embodiment 1, used 1,3,5- tri- ((3,4- diethoxy) phenyl methyl) benzene equimolars
1,3,5- tri- ((3,4- dimethoxy) phenyl methyl) benzene of amount are replaced, and other steps are same as Example 1, obtain structural formula such as
Under the benzo of (the ethoxycarbonylmethoxy) -6,7,14,15,22,23- of yellow solid 2,3,10,11,18,19- six hexa methoxies six
[a, d, g, j, m, p] guans, its yield are 81%.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and
MALDI-TOF mass spectrographs (Germany, Burker Daltonics) are characterized, and characterize data is as follows：
1H NMR (400MHz, CDCl3+TMS)δ(ppm)：8.72 (s, 2H), 8.60 (s, 2H), 5.01-4.91 (s, 4H),
4.37-4.31 (s, 4H), 4.21 (s, 6H), 1.34-1.32 (t, 6H)；13C NMR (100MHz, CDCl3+TMS)δ(ppm)：
168.90,148.84,147.39,129.91,125.87,124.95,123.76,120.28,108.89,66.75,61.49,
56.20,13.98；MALDI-TOF-MS：m/z(C78H72O24) theoretical value 1392.44, measured value 1392.93.
2nd, hydrolysis
(the ethoxycarbonylmethyloxies of 0.50g (0.36mmol) 2,3,10,11,18,19- six are added in 100mL single-necked flasks
Base) six benzo of -6,7,14,15,22,23- hexa methoxies [a, d, g, j, m, p] guans, 0.10g (2.52mmol) NaOH,
50mL ethanol, 10mL deionized waters, back flow reaction 3 hours, rotary evaporation remove most of ethanol, add 100mL deionized waters,
Resulting solution mass fraction adjusts pH value to 2~3, a large amount of thick precipitations of generation, through ether for 10% aqueous hydrochloric acid solution
Extraction, anhydrous sodium sulfate drying, suction filtration, filtrate rotary evaporation obtain the following yellow powder Liu Ben Bing guan derivatives of structural formula
Hexacarboxylic acid, its yield is 91.5%.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and
MALDI-TOF mass spectrographs (Germany, Burker Daltonics) are characterized, and characterize data is as follows：
1H NMR (400MHz, DMSO-d6+TMS)δ(ppm)：8.59 (s, 2H), 8.55 (s, 2H) 5.12-5.00 (s, 4H),
4.11 (s, 6H)；MALDI-TOF-MS：m/z(C66H48O24) theoretical value 1224.25, measured value 1224.80.
3rd, acid-base reaction
0.42g (0.34mmol) Liu Ben Bing guan derivatives hexacarboxylic acid, 30mL are added into 50mL single-necked flasks and contains 0.08g
The aqueous solution of (2.04mmol) NaOH, is stirred at room temperature 30 minutes, is spin-dried for, and obtains water-soluble nano graphenic surface activity
Agent.
Products therefrom is characterized with Maxis high resolution mass spectrometers (Germany, Bruker companies), and characterize data is as follows：
UHRMS-ESI：m/z(C84H78Na6O24) theoretical value 1356.1452, measured value 655.0830 (M-2Na]2-)、
429.0588([M-3Na]3-)、316.0476([M-4Na]4-)、19.6690([2M-5Na]5-)。
Embodiment 4
The purposes of water-soluble nano graphenic surface activating agent prepared by embodiment 1 in preparing graphite alkene is peeled off,
Specifically used method is as follows：
The mesh graphite powders of 0.2g 325,0.2g water-soluble nanos graphenic surface activity are added in 10mL glass sample bottles
Agent, 8mL deionized waters, use ultrasonic cleaner ultrasonic disperse 60 minutes in ice-water bath, are then centrifuged under 5000 revs/min
30 minutes, take supernatant liquor as graphene dispersing solution.Graphite in the graphene dispersing solution peeled off is calculated using difference assay
The concentration of alkene is 5mg/mL or so.
Characterized, as a result seen to peeling off front and rear sample using RagukuD/Max2550 (Japan) type X-ray diffractometers
Fig. 1.By analyzing Fig. 1, graphite is graphite features absworption peak, the graphite obtained after stripping in the sharp peak of 26 ° or so appearance
Alkene occurs wide and weak graphene characteristic absorption peak at 23 ° then without this peak, illustrates that graphite is successfully peeled off and obtains graphene.
Using Quantan200 (Holand) type environmental scanning electron microscopes and JEM-2100 type transmission electron microscopes
(Jeol Ltd.) carries out morphology characterization to obtained graphene, as a result sees Fig. 2~5.As seen from the figure, obtained after stripping
Graphene be mainly the preferable individual layer of surface topography or few layer graphene.
Claims (7)
1. a kind of water-soluble nano graphenic surface activating agent, it is characterised in that the structural formula of the surfactant is as follows：
M in formula+Represent Li+、Na+、K+In any one, R represents C1~C12Alkyl.
2. the synthetic method of the water-soluble nano graphenic surface activating agent described in claim 1, it is characterised in that it is by following
Step is constituted：
(1) ring closure reaction
Using dry methylene chloride as solvent, by 1 shown in formula 1,3,5- tri- ((3,4- dialkoxy) phenyl methyl) benzene and the institute of formula 2
3,4- bis- (ethoxycarbonylmethoxy) benzaldehyde for showing, acetic anhydride are 1 in molar ratio:3~4.5:12~25, it is stirred at room temperature 6~
24 hours, after ice-water bath, argon gas protection under, be added dropwise ferric trichloride nitromethane solution, wherein 1,3,5- tri- ((3,4- bis-
Butoxy) phenyl methyl) mol ratio of benzene and ferric trichloride is 1:12~20, react at room temperature 6~12 hours, add methanol and be quenched
Reaction, isolates and purifies product, obtains the compound of formula 3；
R represents C in formula1~C12Alkyl；
(2) hydrolysis
It is 1 in molar ratio by the compound of formula 3 and NaOH or potassium hydroxide using the mixture of second alcohol and water as solvent:6~10
Back flow reaction 2~5 hours, adjusts pH value to 2~3 with watery hydrochloric acid, isolates and purifies product, obtain the compound of formula 4；
(3) acid-base reaction
In the aqueous solution that the compound of formula 4 is added to alkali, wherein the compound of formula 4 and the mol ratio of alkali are 1:5~10, described alkali is
Any one in lithium carbonate, NaOH, potassium hydroxide, is stirred at room temperature 30~60 minutes, is spin-dried for, obtain water-soluble nano stone
Black alkene surfactant.
3. the synthetic method of water-soluble nano graphenic surface activating agent according to claim 2, it is characterised in that：It is described
In step (1), 1,3,5- tri- ((3,4- dialkoxy) phenyl methyl) benzene and 3,4- bis- (ethoxycarbonylmethoxy) benzaldehyde, second
Acid anhydrides, the mol ratio of ferric trichloride are 1:3.3:20:16.
4. the synthetic method of water-soluble nano graphenic surface activating agent according to claim 2, it is characterised in that：It is described
In step (2), the compound of formula 3 is 1 with the mol ratio of NaOH or potassium hydroxide:6.
5. the synthetic method of water-soluble nano graphenic surface activating agent according to claim 2, it is characterised in that：It is described
In step (3), the mol ratio of the compound of formula 4 and alkali is 1:6.
6. application of the water-soluble nano graphenic surface activating agent in preparing graphite alkene is peeled off described in claim 1.
7. water-soluble nano graphenic surface activating agent according to claim 6 answering in preparing graphite alkene is peeled off
With, it is characterised in that：It is 1 in mass ratio by the water-soluble nano graphenic surface activating agent described in graphite powder and claim 1:
1 adds in deionized water, and ultrasonic disperse 30~90 minutes in ice-water bath centrifuge, obtain graphene dispersing solution.
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