CN104445137A - Method for preparing dichlorocarbene functional carbon nano tube - Google Patents
Method for preparing dichlorocarbene functional carbon nano tube Download PDFInfo
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- CN104445137A CN104445137A CN201410480688.8A CN201410480688A CN104445137A CN 104445137 A CN104445137 A CN 104445137A CN 201410480688 A CN201410480688 A CN 201410480688A CN 104445137 A CN104445137 A CN 104445137A
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Abstract
The invention discloses a method for preparing a dichlorocarbene functional carbon nano tube, belonging to the field of research of carbon nano tubes. The method comprises the following steps: removing the water absorbed by the carbon nano tube; performing ultrasonic dispersion treatment on the dried carbon nano tube in a chloroform solvent, thereby obtaining carbon nano tube/chloroform suspension; adding a low-temperature alkali/tetrahydrofuran mixed solution into the suspension; removing other chemical substances by using water and tetrahydrofuran respectively; and finally, drying, thereby obtaining the dichlorocarbene functional carbon nano tube. According to the method disclosed by the invention, the dichlorocarbene is generated by a one-step reaction only and stably exists in an anhydrous solvent, an addition reaction is carried out between the dichlorocarbene and carbon-carbon double bonds on the tube wall of the carbon nano tube, a cyclopropane derivative is generated, and the solubility of the carbon nano tube in acrylonitrile, normal hexane, chloroform, dichloromethane, methylbenzene and other organic solvents can be obviously improved.
Description
Technical field
The invention belongs to field of carbon nanotubes, be specifically related to a kind of preparation method of dichlorocarbene's functionalized carbon nano-tube.
Background technology
Since Iijima in 1991 finds carbon nanotube, carbon nanotube is subject to extensive concern because of the tubular structure of its uniqueness and excellent performance, and becomes the focus of material, the research of physics and chemistry circle.Meanwhile, carbon nanotube has good application prospect in matrix material, microelectronics, biological and chemical sensor.But due to the unreactiveness on its surface, not modified carbon nanotube is insoluble in organic solvent and water, then limit its application.Therefore the many scientists in the world have carried out a large amount of exploratory developments to the solubility issues of carbon nanotube.
At present, the approach improving carbon nanotube solubility mainly carries out chemically modified to carbon nanotube, modifying method mainly contains: 1. directly and carbon nano tube surface react, comprise carbon nanotube is fluoridized, hydrogenation, aryl diazonium salts electrochemical reaction, Cabbeen (dichlorocarbene) functionalization etc.; 2. the carboxylic acid reaction of logical superacidulated carbon tube-surface, the hydroxy-acid group mainly utilizing the defect of carbon nanotube to produce, introduces other functional small molecules or macromole long-chain.
Cabbeen functionalization is wherein a kind of functionalization means, clearly can improve the solvability of carbon nanotube in many organic solvents and water.Coleman etc. (non-patent literature 1 J. Am. Chem. Soc., 2003,125:8722-8723) use carbene reaction modification Single Walled Carbon Nanotube (SWNTs).SWNTs and the 2-methyl sulphur ethanol generation transesterification reaction of modification, the SWNTs of sulfhydrylation can complexing gold colloid.The gold colloid of the upper load of SWNTs demonstrates the generation of carbene reaction.Hu etc. (non-patent literature 2 J. Am. Chem. Soc., 2003,125:14893-14900) will be dissolved in dichlorobenzene after the SWNTs chloride successively of HNO3 cutting, amination, add PhHgCCl2Br and carry out thermolysis, the dichlorocarbene of generation and SWNTs are obtained by reacting dichlorocarbene's functionalized carbon nano-tube.Add dichlorocarbene's presoma PhHgCCl2Br of different amount, the degree of SWNTs functionalization can be different.This patent is the effective way of the another kind synthesis Cabbeen functionalized carbon nano-tube being different from above non-patent literature.
Summary of the invention
For the problem that the reaction process preparing Cabbeen functionalized carbon nano-tube method is at present comparatively complicated, the invention provides a kind of preparation method that can generate the simple efficient economy safety of dichlorocarbene's functionalized carbon nano-tube by means of only single step reaction.
Technical scheme of the present invention is as follows:
A preparation method for dichlorocarbene's functionalized carbon nano-tube, adopts following steps:
The first step: by the carbon nanotube moisture that dry removing carbon nanotube absorbs at 100 ~ 120 DEG C, be that the chloroform solvent that 1:100 ~ 1:150 puts into adopts ultrasonication 1 ~ 2h by the carbon nanotube of drying according to mass ratio, obtain abundant finely dispersed carbon nanotube/chloroform suspension;
Second step: be that 1:2 ~ 1:4 is placed in tetrahydrofuran (THF) according to mol ratio by alkali, stir and obtain alkali and tetrahydrofuran (THF) mixed solution, and alkali and tetrahydrofuran (THF) mixed solution being cooled to-80 ~-50 DEG C to reduce reaction severe degree, in alkali and the first step, the consumption of chloroform is 1:1 ~ 1:5 according to mol ratio;
3rd step: carbon nanotube/chloroform suspension that the first step makes dropwise is joined in the alkali of second step cooling and the mixed solution of tetrahydrofuran (THF), obtain mixture, mixture is poured in ice, wherein alkali metal chloride and oxyhydroxide is removed with water cleaning, be the ethanol purge 2 ~ 3 times of 99.99 % again by purity, then by tetrahydrofuran (THF) removing other chemical substances wherein, at 100 ~ 120 DEG C, drying removes wherein organic solvent and moisture, can obtain the carbon nanotube of dichlorocarbene's functionalization.
As a kind of optimal way: the alkali in second step is one or several the mixture in potassium tert.-butoxide, sodium tert-butoxide, potassium hydroxide, sodium hydroxide.
As a kind of optimal way: described carbon nanotube is any one in Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes.
The invention has the beneficial effects as follows: the preparation method of a kind of dichlorocarbene's functionalized carbon nano-tube that the present invention proposes, produces dichlorocarbene by means of only single step reaction, and reactions steps is simple, low raw-material cost is easy to obtain, and the required device of synthesis is simple, economic security.Dichlorocarbene is stable existence in anhydrous solvent, with carbon-carbon double bond generation addition reaction on carbon nanotube tube wall, generate cyclopropane derivative, the solubleness of carbon nanotube in the organic solvents such as vinyl cyanide, normal hexane, chloroform, methylene dichloride, toluene can be significantly improved.
Embodiment
The invention will be further described below.
Embodiment 1
A preparation method for dichlorocarbene's functionalized carbon nano-tube, adopts following steps:
1) by 89mg Single Walled Carbon Nanotube powder dry 8h at 110 DEG C, the moisture that removing carbon nanotube absorbs; The carbon nanotube of drying is placed in 6ml chloroform solvent, and adopt processor for ultrasonic wave process 1h, processing power is 40W, obtains abundant finely dispersed carbon nanotube/chloroform suspension;
2) 41.9g potassium tert.-butoxide is placed in 71.8ml tetrahydrofuran (THF), stirs and obtain potassium tert.-butoxide/tetrahydrofuran (THF) mixed solution; With dry ice/ethanolic soln, potassium tert.-butoxide/tetrahydrofuran (THF) mixed solution is cooled to-75 DEG C;
3) carbon nanotube/chloroform suspension is dropwise joined in the potassium tert.-butoxide/tetrahydrofuran (THF) mixed solution of cooling, obtain mixture; Mixture is poured into the ice (ice that water-setting is formed, mixture can give out heat, directly putting into water can make water seethe with excitement, cause danger) in, the Repone K and potassium hydroxide that remove wherein is cleaned with water, be the ethanol purge 2 times of 99.99 % again by purity, then by tetrahydrofuran (THF) removing butanols wherein and other chemical substances, obtain carbon nanotube powder; By carbon nanotube powder dry 24h at 100 DEG C, the carbon nanotube of dichlorocarbene's functionalization can be obtained.
Embodiment 2
A preparation method for dichlorocarbene's functionalized carbon nano-tube, adopts following steps:
1) by 108mg multi-walled carbon nano-tubes powder dry 10h at 105 DEG C, the moisture that removing carbon nanotube absorbs; The carbon nanotube of drying is placed in 8ml chloroform solvent, and adopt processor for ultrasonic wave process 1h, processing power is 50W, obtains abundant finely dispersed carbon nanotube/chloroform suspension;
2) 38.2g sodium tert-butoxide is placed in 51.0ml tetrahydrofuran (THF), stirs and obtain sodium tert-butoxide/tetrahydrofuran (THF) mixed solution; With dry ice/ethanolic soln, sodium tert-butoxide/tetrahydrofuran (THF) mixed solution is cooled to-60 DEG C;
3) carbon nanotube/chloroform suspension is dropwise joined in the sodium tert-butoxide/tetrahydrofuran (THF) mixed solution of cooling, obtain mixture; Being poured into by mixture in ice, with water cleaning removing sodium-chlor and sodium hydroxide, then is the ethanol purge 3 times of 99.99 % by purity, then by tetrahydrofuran (THF) removing butanols wherein and other chemical substances, obtains carbon nanotube powder; By carbon nanotube powder dry 24h at 105 DEG C, the carbon nanotube of dichlorocarbene's functionalization can be obtained.
Embodiment 3
A preparation method for dichlorocarbene's functionalized carbon nano-tube, adopts following steps:
1) 111mg single wall carbon is received carbon nanotube dust dry 8h at 120 DEG C, the moisture that removing carbon nanotube absorbs; The carbon nanotube of drying is placed in 9ml chloroform solvent, and adopt processor for ultrasonic wave process 1.5h, processing power is 60W, obtains abundant finely dispersed carbon nanotube/chloroform suspension;
2) 18.8g potassium hydroxide is placed in 43.0ml tetrahydrofuran (THF), stirs and obtain potassium hydroxide/tetrahydrofuran (THF) mixed solution; With dry ice/ethanolic soln, potassium hydroxide/tetrahydrofuran (THF) mixed solution is cooled to-60 DEG C;
3) carbon nanotube/chloroform suspension is dropwise joined in the potassium hydroxide/tetrahydrofuran (THF) mixed solution of cooling, obtain mixture; Mixture is poured in ice, remove wherein Repone K and potassium hydroxide with water cleaning, then be the ethanol purge 2 times of 99.99 % by purity, then remove other chemical substances wherein with tetrahydrofuran (THF), obtain carbon nanotube powder; By carbon nanotube powder dry 20h at 110 DEG C, the carbon nanotube of dichlorocarbene's functionalization can be obtained.
Embodiment 4
A preparation method for dichlorocarbene's functionalized carbon nano-tube, adopts following steps:
1) by 99mg double-walled carbon nano-tube powder dry 10h at 100 DEG C, the moisture that removing carbon nanotube absorbs; The carbon nanotube of drying is placed in 10ml chloroform solvent, and adopt processor for ultrasonic wave process 2h, processing power is 70W, obtains abundant finely dispersed carbon nanotube/chloroform suspension;
2) mixture (its mol ratio is 1:1) of 6.0g sodium hydroxide and potassium hydroxide is placed in 31.9ml tetrahydrofuran (THF), stirs and obtain sodium hydroxide/tetrahydrofuran (THF) mixed solution; With dry ice/ethanolic soln, sodium hydroxide and potassium hydroxide mixture/tetrahydrofuran (THF) mixed solution are cooled to-50 DEG C;
3) carbon nanotube/chloroform suspension is dropwise joined in the sodium hydroxide/tetrahydrofuran (THF) mixed solution of cooling, obtain mixture; Mixture is poured in ice, with water cleaning removing sodium-chlor wherein, Repone K, sodium hydroxide and potassium hydroxide, then be the ethanol purge 2 times of 99.99 % by purity, then remove other chemical substances with tetrahydrofuran (THF), obtain carbon nanotube powder; By carbon nanotube powder dry 20h at 120 DEG C, the carbon nanotube of dichlorocarbene's functionalization can be obtained.
Claims (3)
1. a preparation method for dichlorocarbene's functionalized carbon nano-tube, is characterized in that, preparation process comprises the following steps:
The first step: by the carbon nanotube moisture that dry removing carbon nanotube absorbs at 100 ~ 120 DEG C, be that the chloroform liquid that 1:100 ~ 1:150 puts into adopts ultrasonication 1 ~ 2h according to mass ratio, obtain abundant finely dispersed carbon nanotube/chloroform suspension;
Second step: be that 1:2 ~ 1:4 is placed in tetrahydrofuran (THF) according to mol ratio by alkali, stir and obtain the mixed solution of alkali and tetrahydrofuran (THF), and alkali and tetrahydrofuran (THF) mixed solution being cooled to-80 ~-50 DEG C to reduce reaction severe degree, in alkali and the first step, the consumption of chloroform is 1:1 ~ 1:5 according to mol ratio;
3rd step: the carbon nanotube the first step obtained/chloroform suspension dropwise joins in the alkali and tetrahydrofuran (THF) mixed solution cooled in second step, obtain mixture, mixture is poured in ice, wherein alkali metal chloride and oxyhydroxide is removed with water cleaning, be the ethanol purge 2 ~ 3 times of 99.99 % again by purity, then with tetrahydrofuran (THF) cleaning 2 ~ 3 times, finally at 100 ~ 120 DEG C, drying removes wherein organic solvent and moisture, can obtain the carbon nanotube of dichlorocarbene's functionalization.
2. the preparation method of a kind of dichlorocarbene's functionalized carbon nano-tube according to claim 1, is characterized in that: the alkali in second step is one or several the mixture in potassium tert.-butoxide, sodium tert-butoxide, potassium hydroxide, sodium hydroxide.
3. according to the preparation method of claim 1 or a kind of dichlorocarbene's functionalized carbon nano-tube according to claim 2, it is characterized in that: described carbon nanotube is any one in Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6187823B1 (en) * | 1998-10-02 | 2001-02-13 | University Of Kentucky Research Foundation | Solubilizing single-walled carbon nanotubes by direct reaction with amines and alkylaryl amines |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6187823B1 (en) * | 1998-10-02 | 2001-02-13 | University Of Kentucky Research Foundation | Solubilizing single-walled carbon nanotubes by direct reaction with amines and alkylaryl amines |
Non-Patent Citations (2)
| Title |
|---|
| K. KAMARAS ET AL.: "Covalent Bond Formation to a Carbon Nanotube Metal", 《SCIENCE》 * |
| YU JINGANG ET AL.: "Preparation and Characterization of Dichlorocarbene Modified Multiple-walled Carbon Nanotubes", 《CHEMICAL RESEARCH IN CHINESE UNIVERSITY》 * |
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