CN102351174A - Preparation method of dispersible silane functionalized graphene - Google Patents
Preparation method of dispersible silane functionalized graphene Download PDFInfo
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Abstract
The invention provides a preparation method of dispersible silane functionalized graphene. The method comprises the steps of: conducting ultrasonic dispersion to graphene oxide in absolute ethyl alcohol so as to form a uniform graphene oxide dispersion solution, then adjusting the pH value to 3-4, or under the protection of an inert atmosphere, adding silane into the dispersing solution for modification, with silane and graphene oxide in a mass ratio of 0.1:1-5:1, continuing the reaction for 12h-48h at a temperature ranging from normal temperature to 78DEG C, carrying out centrifugation, then adding hydrazine hydrate to the obtained solid, performing heating reduction, and filtering the reaction solution, then washing and drying the filter cake, thus obtaining dispersible silane functionalized grapheme. The method of the invention is simple and practicable, and the obtained silane functionalized grapheme has good dispersibility in solvents like absolute ethyl alcohol, acetone, toluene, ethyl acetate, butyl acetate, and tetrahydrofuran (THF), etc.
Description
Technical field
The present invention relates to the preparation of Graphene, be specifically related to a kind of dispersibility silane-functionalized preparation method of graphene.
Background technology
Graphene is the carbonaceous material by the tightly packed individual layer bi-dimensional cellular shape structure that forms of carbon atom, can be regarded as the basic structural unit that makes up soccerballene, carbon nanotube, graphite.Graphene has high Young's modulus (about 1100Gpa), thermal conductivity (about 5000J/ (mKs)), room temperature carrier mobility (2 * 10 because of it
5Cm
2/ (Vs)) and specific surface area (calculated value 2630m
2/ g), also have quantum hall effect and quantum and wear effect etc. then, be expected to be widely used in nano composite material, liquid crystal material and the energy storage material.Yet the neither hydrophilic also oleophylic not of Graphene, chemical reaction is inertia in addition, has hindered research and application to it, but thereby the preparation stable dispersion will promote its application and development greatly in the Graphene of certain solvent.
But in order to obtain the graphene suspension of stable dispersion, improve the consistency of Graphene and other matrixes, need effectively modify with surface-functionalized Graphene.Through containing a large amount of hydroxyls, epoxy group(ing), carbonyl and carboxyl isoreactivity group and other molecule carries out chemical reaction in the precursor graphene oxide surface of Graphene, realize that Graphene covalent linkage functionalization is the important channel.The most frequently used functional modification agent at present mainly contains isocyanates, silane coupling agent, organic amine.Stankovich (Stankovich S; Piner R D; Nguyen S T; Et al.Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide.Carbon; 2006,44 (15): 3342-3347) grade is utilized the reaction of the hydroxyl and the carboxyl of isocyanic ester and graphene oxide, has changed the surface property of graphene oxide; Make it stable dispersion at N, in the dinethylformamide organic solvents such as (DMF).Marvin's stone (Marvin's stone; Zhou Junwen; Lin Xiaodan. the preparation of thanomin functionalization graphene and sign. chemical journal .2011; 1463 ~ 1468) etc. 69 (12): the employing thanomin carries out modification, reduction to the precursor graphene oxide of Graphene; Increased the graphene film interlamellar spacing, make it to be scattered in water, ethanol, acetone, DMF and with the mixed solvent of water in.Wang(WangGX; ShenXP; WangB; Etal.Synthesisandcharacterisationofhydrophilicandorganop hilicgraphenenanosheets.Carbon; 2009; 47(5): 1359-1364) etc. the employing octadecylamine carries out modification to the predecessor graphene oxide of Graphene; But the Graphene stable dispersion that is obtained is in oxolane (THF), DMF organic solvent; This method also is applicable to the organic amine (NethravathiC of different chain length; ViswanathB; ShivakumaraC; Etal.Theproductionofsmectiteclay/graphenecompositesthrou ghdelaminationandco-stacking.Carbon.2008,46:1773-1781).Application number is that 2010102879852 patent application document carries out modification through amino silicane coupling agent to Graphene; And then enhancing silica gel; It has good dispersiveness (Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences in water, ethanol, tetrahydrofuran (THF), methyl-sulphoxide equal solvent; Patent of invention; Application number: 2010102879852); Yet this patent application document only is described containing amino silicane coupling agent, non-amino silicane coupling agent one type of silane is not studied.In fact; With regard to the monolithic graphene oxide; Also contain many same or different active function groups; When it being carried out chemical modification with polyfunctional group silane; Between graphene oxide sheet and the graphene oxide sheet chemically crosslinked takes place very easily often; Cause final Graphene to reunite, lump, it is undesirable to be difficult to dispersion or dispersion effect.
Summary of the invention
In order to solve the problem that prior art exists, the invention provides a kind of dispersibility silane-functionalized preparation method of graphene, it may further comprise the steps:
Step 1: graphene oxide is dissolved in the dehydrated alcohol; Ultra-sonic dispersion forms uniform dispersion liquid; Regulate the pH value then and be 3～4 or under inert atmosphere protection; Adding is the silane of 0.1:1～5:1 with the graphene oxide mass ratio in dispersion liquid, and ℃ following reaction 12h～48h carries out centrifugation then in normal temperature～78; Remove supernatant liquor; Following clear liquid is neutral with dehydrated alcohol and deionized water wash to scrub raffinate, obtains solid product, promptly silane-modified graphene oxide;
Step 2: above-mentioned silane-modified graphene oxide is scattered in the dehydrated alcohol; Ultra-sonic dispersion becomes uniform dispersion liquid; And then adding Hydrazine Hydrate 80; In 60 ℃～78 ℃ following reduction reaction 12h～24h; Suction filtration reaction solution then; Suction filtration gained solid is neutral with dehydrated alcohol and deionized water wash to scrub raffinate, is the silane-functionalized Graphene after the oven dry of gained solid.
For further realizing the object of the invention, said silane is 0.5:1～1:1 with the quality of graphene oxide than optimum range.
Said silane is more than one in a chlorosilane, monoisocyanates base propyl silane, mono amino silane, single aniline alkyl silane, single mercapto propyl silane or the monoalkoxy silane.
Further, said monoalkoxy silane is mono methoxy silane or monosubstituted ethoxy silane.
For further realizing the object of the invention, a said chlorosilane is trimethylchlorosilane, chlorotriethyl silane, phenyl dimethylchlorosilane, diphenyl methyl chloro silane or vinyl-dimethyl oxygen base chlorosilane.
For further realizing the object of the invention, said monoisocyanates base propyl silane is trimethylammonium isocyanate group propyl silane, triethyl isocyanate group propyl silane, phenyl dimethyl isocyanate group propyl silane, diphenyl methyl isocyanate group propyl silane or vinyl-dimethyl based isocyanate base propyl silane.
Said mono amino silane is aminopropyl trimethyl silane, aminopropyl triethyl silicane, aminopropyl diphenylmethylsilane, aminopropyl phenyl dimethylsilane, aminopropyl vinyl-dimethyl base silane, phenylamino oxypropyl trimethyl silane, phenylamino propyl-triethylsilicane alkane, phenylamino propyl group phenyl dimethylsilane or phenylamino propyl group diphenylmethylsilane.
Be further to realize that the object of the invention, said single mercapto propyl silane are that mercapto oxypropyl trimethyl silane, mercapto propyl-triethylsilicane alkane, mercapto propyl group phenyl dimethylsilane, mercapto propyl group diphenylmethylsilane obtain mercapto propyl ethylene base dimethoxy silane.
For further realizing the object of the invention, said mono methoxy silane is trimethylammonium methoxy silane, triethyl methoxy silane, phenyl dimethyl methyl TMOS, diphenylmethyl methoxylsilane or vinyl-dimethyl methoxylsilane; Said monosubstituted ethoxy silane is trimethylethoxysilane, triethyl-ethoxy-silicane alkane, phenyl dimethylethoxysilane, diphenyl methyl Ethoxysilane or vinyl-dimethyl base oxethyl silane.
Compared with prior art, the present invention has the following advantages:
(1) technical process of the present invention is simple, mild condition, and lower to the conversion unit requirement, used silane modifier is nontoxic to be easy to get, and cost is low;
(2) the prepared silane-functionalized Graphene number of plies of the present invention is less, in dehydrated alcohol, acetone, toluene, ethyl acetate, butylacetate, tetrahydrofuran (THF) equal solvent, has good dispersiveness.
Description of drawings
Fig. 1 is the afm scan figure of the trimethylammonium methoxy silane functionalization graphene of embodiment 1 preparation;
Fig. 2 is the microgram of afm scan figure of the trimethylammonium methoxy silane functionalization graphene of embodiment 1 preparation.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated, but is not limited to following instance.
Embodiment 1
The preparation of trimethylammonium methoxy silane functionalization graphene:
Step 1: get the 100mg graphite oxide and be dissolved in the 100ml dehydrated alcohol, form the homodisperse liquid of 1mg/ml behind the ultra-sonic dispersion 1h, using dilute hydrochloric acid to regulate dispersion liquid pH is 3; Be the ratio adding trimethylammonium methoxy silane of 1:0.5 then according to graphene oxide and trimethylammonium methoxy silane mass ratio; Behind 60 ℃ of reaction 24h; Centrifugation; Remove supernatant liquor; Following clear liquid with dehydrated alcohol and deionized water wash repeatedly; Remove unreacted trimethylammonium methoxy silane fully, to neutral, obtain silane-modified graphene oxide until washings.
Step 2: above-mentioned silane-modified graphene oxide is scattered in the 100ml dehydrated alcohol behind the ultrasonic 1h; Become uniform and stable modified oxidized Graphene dispersion liquid; Add the 1g Hydrazine Hydrate 80 then; Behind reduction 48h under 60 ℃; Suction filtration reaction solution then; The gained filter cake is neutral with dehydrated alcohol and deionized water wash to scrub raffinate again, and then places vacuum drying oven dry under 60 ℃ filter cake, obtains the trimethyl silane functionalization graphene.
This silane-functionalized Graphene can be dispersed in the organic solvents such as ethanol, acetone, toluene, ethyl acetate, butylacetate, tetrahydrofuran (THF).
Fig. 1 and Fig. 2 are atomic force microscope (AFM) scintigram of prepared trimethylammonium methoxy silane functionalization graphene, from figure, can find out that its thickness is about 1～2nm.
Triethyl methoxy silane, phenyl dimethyl methyl TMOS, diphenylmethyl methoxylsilane, vinyl-dimethyl methoxylsilane, trimethylethoxysilane, triethyl-ethoxy-silicane alkane, phenyl dimethylethoxysilane, diphenyl methyl Ethoxysilane, vinyl-dimethyl base oxethyl silane replace the trimethylammonium methoxy silane, and remaining is with embodiment 1.
Embodiment 3
The preparation of trimethylchlorosilane functionalization graphene:
Step 1: get the 100mg graphite oxide and be dissolved in the 10ml dehydrated alcohol, form the homodisperse liquid of 1mg/ml behind the ultra-sonic dispersion 1h; According to graphene oxide and trimethylchlorosilane mass ratio down the ratio adding trimethylchlorosilane of 1:1 in nitrogen atmosphere protection then; At 60 ℃ of reaction 24h; Centrifugation; Remove supernatant liquor; Use dehydrated alcohol and deionized water wash then repeatedly; Remove unreacted trimethylchlorosilane fully, and make washings, obtain silane-modified graphene oxide to neutral;
Step 2: above-mentioned silane-modified graphene oxide is scattered in the 100ml dehydrated alcohol behind the ultrasonic 1h; Become uniform and stable modified oxidized Graphene dispersion liquid; Add the 1g Hydrazine Hydrate 80 then; Behind 60 ℃ of following reductase 12 4h; Suction filtration reaction solution then; Till the gained filter cake was neutrality with dehydrated alcohol and deionized water wash reduction reaction products therefrom to scrub raffinate again, the gained solid placed 60 ℃ of dryings of vacuum drying oven, obtains the trimethyl silane functionalization graphene.
This silane-functionalized Graphene can be dispersed in the organic solvents such as ethanol, acetone, toluene, ethyl acetate, butylacetate, tetrahydrofuran (THF).
Substitute trimethylchlorosilane with chlorotriethyl silane, phenyl dimethylchlorosilane, diphenyl methyl chloro silane, vinyl-dimethyl oxygen base chlorosilane, remaining is with embodiment 3.
Embodiment 5
The preparation of trimethylammonium isocyanate group propyl silane functionalization graphene:
Step 1: get the 100mg graphite oxide and be dissolved in the 100ml anhydrous ethyl acetate, form the homodisperse liquid of 1mg/ml behind the ultra-sonic dispersion 1h; According to graphene oxide and trimethylammonium isocyanate group propyl silane mass ratio down the ratio adding trimethylammonium isocyanate group propyl silane of 1:0.2 in nitrogen atmosphere protection then; Behind 60 ℃ of continuation reaction 12h; Centrifugation; Remove supernatant liquor; Following clear liquid with dehydrated alcohol and deionized water wash repeatedly; Remove unreacted silane coupling agent fully, to neutral, obtain silane-modified graphene oxide until washings;
Step 2: above-mentioned silane-modified graphene oxide is scattered in the 100ml dehydrated alcohol behind the ultrasonic 1h; Become uniform and stable modified oxidized Graphene dispersion liquid; Add the 1g Hydrazine Hydrate 80 then; Behind reduction 35h under 78 ℃; Suction filtration reaction solution then; The gained filter cake is neutral with dehydrated alcohol and deionized water wash reduction reaction products therefrom to scrub raffinate again, and the gained solid places vacuum drying oven dry under 70 ℃, obtains trimethylammonium isocyanate group propyl silane functionalization graphene.This silane-functionalized Graphene can be dispersed in the organic solvents such as ethanol, acetone, toluene, ethyl acetate, butylacetate, tetrahydrofuran (THF).
Substitute trimethylammonium isocyanate group propyl silane with triethyl isocyanate group propyl silane, phenyl dimethyl isocyanate group propyl silane, diphenyl methyl isocyanate group propyl silane, vinyl-dimethyl based isocyanate base propyl silane, remaining is with embodiment 5.
Embodiment 7
The preparation of aminopropyl trimethyl silane functionalization graphene:
Step 1: get the 100mg graphite oxide and be dissolved in the 100ml dehydrated alcohol, form the homodisperse liquid of 1mg/ml behind the ultra-sonic dispersion 0.5h, the pH value of using dilute hydrochloric acid to regulate dispersion liquid then is 4; According to graphene oxide and aminopropyl trimethyl silane mass ratio is the ratio adding aminopropyl trimethyl silane of 1:5; Behind 78 ℃ of reaction 12h; Centrifugation; Remove supernatant liquor; Following clear liquid with dehydrated alcohol and deionized water wash repeatedly; Remove unreacted silane coupling agent fully, to neutral, the gained solid is the graphene oxide of aminopropyl trimethyl silane modification until scrub raffinate;
Step 2: above-mentioned silane-modified graphene oxide is scattered in the 100ml dehydrated alcohol behind the ultrasonic 1h; Become uniform and stable modified oxidized Graphene dispersion liquid; Add the 1g Hydrazine Hydrate 80 then; Behind reduction 12h under 65 ℃; Suction filtration reaction solution then; The gained filter cake is neutral with dehydrated alcohol and deionized water wash reduction reaction products therefrom to scrub raffinate again, and the gained solid places 60 ℃ of dryings of vacuum drying oven, obtains aminopropyl trimethyl silane functionalization graphene.This silane-functionalized Graphene can be dispersed in the organic solvents such as ethanol, acetone, toluene, ethyl acetate, butylacetate, tetrahydrofuran (THF).
Substitute the aminopropyl trimethyl silane with aminopropyl triethyl silicane, aminopropyl diphenylmethylsilane, aminopropyl phenyl dimethylsilane, aminopropyl vinyl-dimethyl base silane, phenylamino oxypropyl trimethyl silane, phenylamino propyl-triethylsilicane alkane, phenylamino propyl group phenyl dimethylsilane, phenylamino propyl group diphenylmethylsilane, phenylamino propyl ethylene base dimethylsilane, remaining is with embodiment 7.
Embodiment 9
The preparation of mercapto oxypropyl trimethyl silane functionality fossil China ink alkene:
Step 1: get the 100mg graphite oxide and be dissolved in the 100ml dehydrated alcohol, form the homodisperse liquid of 1mg/ml behind the ultra-sonic dispersion 1h; According to graphene oxide and mercapto oxypropyl trimethyl silane mass ratio down the ratio adding mercapto oxypropyl trimethyl silane of 1:3 in nitrogen atmosphere protection then; Continue reaction 48h at 60 ℃; Centrifugation; Remove supernatant liquor; Following clear liquid with dehydrated alcohol and deionized water wash repeatedly; Remove unreacted mercapto oxypropyl trimethyl silane fully, to neutral, obtain silane-modified graphene oxide until washings;
Step 2: above-mentioned silane-modified graphene oxide is scattered in the 100ml dehydrated alcohol behind the ultrasonic 1h; Become uniform and stable modified oxidized Graphene dispersion liquid; Add the 1g Hydrazine Hydrate 80 then; Behind 78 ℃ of following reduction reaction 18h; Suction filtration reaction solution then, the gained filter cake is used dehydrated alcohol and deionized water wash reduction reaction products therefrom again, is neutral to scrub raffinate; The gained solid places 60 ℃ of dryings of vacuum drying oven, obtains mercapto oxypropyl trimethyl silane functionality fossil China ink alkene.This silane-functionalized Graphene can be dispersed in the organic solvents such as ethanol, acetone, toluene, ethyl acetate, butylacetate, tetrahydrofuran (THF).
Substitute mercapto oxypropyl trimethyl silane with mercapto propyl-triethylsilicane alkane, mercapto propyl group phenyl dimethylsilane, mercapto propyl group diphenylmethylsilane, mercapto propyl ethylene base dimethoxy silane, remaining is with embodiment 9.
Claims (10)
1. dispersibility silane-functionalized preparation method of graphene is characterized in that step is following:
Step 1: graphene oxide is dissolved in the dehydrated alcohol; Ultra-sonic dispersion forms uniform dispersion liquid; Regulate the pH value then and be 3～4 or under inert atmosphere protection; Adding is the silane of 0.1:1～5:1 with the graphene oxide mass ratio in dispersion liquid, and ℃ following reaction 12h～48h carries out centrifugation then in normal temperature～78; Remove supernatant liquor; Following clear liquid is neutral with dehydrated alcohol and deionized water wash to scrub raffinate, obtains solid product, promptly silane-modified graphene oxide;
Step 2: above-mentioned silane-modified graphene oxide is scattered in the dehydrated alcohol; Ultra-sonic dispersion becomes uniform dispersion liquid; And then adding Hydrazine Hydrate 80; In 60 ℃～78 ℃ following reduction reaction 12h～24h; Suction filtration reaction solution then; Suction filtration gained solid is neutral with dehydrated alcohol and deionized water wash to scrub raffinate, is the silane-functionalized Graphene after the oven dry of gained solid.
2. preparation method according to claim 1, the mass ratio that it is characterized in that said silane and graphene oxide is 0.5:1～1:1.
3. preparation method according to claim 1 and 2 is characterized in that said silane is more than one in a chlorosilane, monoisocyanates base propyl silane, mono amino silane, single aniline alkyl silane, single mercapto propyl silane or the monoalkoxy silane.
4. preparation method according to claim 3 is characterized in that said monoalkoxy silane is mono methoxy silane or monosubstituted ethoxy silane.
5. preparation method according to claim 3 is characterized in that a said chlorosilane is trimethylchlorosilane, chlorotriethyl silane, phenyl dimethylchlorosilane, diphenyl methyl chloro silane or vinyl-dimethyl oxygen base chlorosilane.
6. preparation method according to claim 3 is characterized in that said monoisocyanates base propyl silane is trimethylammonium isocyanate group propyl silane, triethyl isocyanate group propyl silane, phenyl dimethyl isocyanate group propyl silane, diphenyl methyl isocyanate group propyl silane or vinyl-dimethyl based isocyanate base propyl silane.
7. preparation method according to claim 3 is characterized in that said mono amino silane is aminopropyl trimethyl silane, aminopropyl triethyl silicane, aminopropyl diphenylmethylsilane, aminopropyl phenyl dimethylsilane, aminopropyl vinyl-dimethyl base silane, phenylamino oxypropyl trimethyl silane, phenylamino propyl-triethylsilicane alkane, phenylamino propyl group phenyl dimethylsilane or phenylamino propyl group diphenylmethylsilane.
8. preparation method according to claim 3 is characterized in that said single mercapto propyl silane is mercapto oxypropyl trimethyl silane, mercapto propyl-triethylsilicane alkane, mercapto propyl group phenyl dimethylsilane, mercapto propyl group diphenylmethylsilane or mercapto propyl ethylene base dimethoxy silane.
9. preparation method according to claim 4 is characterized in that said mono methoxy silane is trimethylammonium methoxy silane, triethyl methoxy silane, phenyl dimethyl methyl TMOS, diphenylmethyl methoxylsilane or vinyl-dimethyl methoxylsilane.
10. preparation method according to claim 4 is characterized in that said monosubstituted ethoxy silane is trimethylethoxysilane, triethyl-ethoxy-silicane alkane, phenyl dimethylethoxysilane, diphenyl methyl Ethoxysilane or vinyl-dimethyl base oxethyl silane.
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