CN101177260A - Method for preparing primary amine carbon nano tube - Google Patents
Method for preparing primary amine carbon nano tube Download PDFInfo
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- CN101177260A CN101177260A CNA2006101182873A CN200610118287A CN101177260A CN 101177260 A CN101177260 A CN 101177260A CN A2006101182873 A CNA2006101182873 A CN A2006101182873A CN 200610118287 A CN200610118287 A CN 200610118287A CN 101177260 A CN101177260 A CN 101177260A
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Abstract
The invention relates to a preparation method for primary amine modified carbon nano-tubes (CNT). Firstly, the carbon nano-tubes (CNT) with carboxyl at surface are obtained after acid treatment of the carbon nano-tubes (CNT). Carboxyl carbon nano-tubes (CNT), di-tert-butyl dicarbonate and sodium azide are reacted under the composite catalysis of phase-transfer metal catalyst and Lewis acid to obtain the carbon nano-tubes (CNT) with carbamic tert-butyl. Then the tert-butyl group is lost in hydrochloric ethyl acetate solution to generate the carbon nano-tubes (CNT) with primary amine group. Compared with other methods, the carbon nano-tubes (CNT) prepared with the invention has higher primary amine level, and can be used as an important reaction intermediate as well as be compounded with polymers to obtain composite materials with high performance.
Description
Technical field
The present invention relates to belong to the material field, relate to carbon nanotube, especially the method on the carbon nano-tube modified surface of chemical method.
Background technology
Since Lijima in 1991 found carbon nanotube, just because of its particular structure, good electrical properties and mechanical property were the focuses of Recent study to carbon nanotube.Carbon nanotube has nanometer grade diameter micron order length, and length-to-diameter ratio can reach 100～1000, and intensity is high, has the ideal Young's modulus, is a kind of perfect filamentary material, and its performance is better than current any fiber.Therefore can be used as super fiber, be used for the enhancing body of advanced composite materials; Because carbon nanotube combines the quantum rule of the semi-metal character of graphite and energy level and electronic wave, and has nano level yardstick, makes it also boundless in the application prospect of person in electronics; The huge specific surface area of carbon nanotube and the adsorbable a large amount of hydrogen of the pore texture that has, so carbon nanotube has also become the focus of research as best hydrogen storage material; Owing to the vestibule structure and the absorption property of carbon nanotube uniqueness, therefore can be used as the carrier of catalyzer, the katalysis that improves catalyzer has to greatest extent also shown good prospects for application aspect catalysis.
Carbon nanotube directly used as material have certain difficulty, as not finding at present suitable solvent as yet, dispersed bad or the like in other materials.The chemically modified modified carbon nano-tube can change the state and the structure of carbon nano tube surface, changes or improve the dispersiveness of carbon nanotube in some solvent or other materials thereby reach.
Up to the present, there have been many investigators to carry out the carbon nano-tube modified Research on surface of chemical method.Method comprises: direct fluoridation, acidification reaction, Cabbeen addition, free radical reaction, electrochemical reaction or thermal chemical reaction, 1,3 moment of dipole cycloaddition reaction, azide reaction, electrophilic addition reaction and force-chemical reaction etc.
[1～5]About amination is carbon nano-tube modified report arranged also at present, as Weglikowska
[6]Deng having prepared the single-walled nanotube that phenylenediamine is modified with chloride method.Stevens
[7]Deng having prepared the fluorizated Single Walled Carbon Nanotube earlier, modify with diamine then, on Single Walled Carbon Nanotube, introduced amino group.Saito
[8]And Cao Chunhua
[9]Deng being equipped with the carbon nanotube that diamine is modified with the condensing agent legal system.But these methods all have a common shortcoming, are exactly that because two amine of diamines is active identical, this kind method can not guarantee that the amino of modifying one is decided to be primary amino group with the diamine reaction.The present invention is converted into the carboxylamine base tert-butyl ester with the carboxyl above the carboxylated carbon nanotube through single step reaction and then is converted into the reaction of primary amino, and this reaction has overcome above reaction shortcoming, has not yet to see report.
Summary of the invention
The present invention will overcome in the existing carbon nano tube modified technology, severe reaction conditions, and the shortcoming of step complexity especially solves present method and can not guarantee that the amino of modifying one is decided to be the problem of primary amino.The object of the invention is to provide a kind of method for preparing primary amine carbon nano tube, and this primary amine carbon nano tube can be used as important intermediate, further reacts, and satisfies different research work and Application Areas.
The present invention also will solve the preparation method of this carbon nanotube.
For solving the problems of the technologies described above, the present invention is performed such: by molecular designing, preparation earlier has the modified carbon nano-tube of carboxyl, then with this carboxyl carbon nanotube and the two dimethyl dicarbonate butyl ester (BOC of containing
2O) and sodium azide under transition metal composite and Lewis acid catalysis, react, obtain having the carbon nanotube of t-butyl carbamate.In the hydrochloric acid dioxane solution, slough the formic acid tertiary butyl then, obtain having the carbon nanotube of primary aminoization.Concrete preparation method is as follows:
1. carbon nanometer tube material is mixed with acid with strong oxidizing property with 0.1～100 weight ratio, with ultrasonic 0.1～100h post-heating of at room temperature handling below the 100kHz, temperature of reaction is between 20～200 ℃, reaction times is between 0.5～100h, with the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube after the vacuum-drying.Wherein acid with strong oxidizing property is selected from 0.1～70wt% nitric acid, 0.1～100wt% sulfuric acid, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixture, 1/100～100/1 mol ratio potassium permanganate and hydrochloric acid mixture, 1/100～100/1 mol ratio potassium permanganate and nitrate mixture, 1/100～100/1 mol ratio H
2O
2With sulfuric acid mixed solution, 1/100～100/1 mol ratio H
2O
2With hydrochloric acid mixed solution or 1/100～100/1 mol ratio H
2O
2With the nitric acid mixing solutions.This is carboxylated carbon nanotube.
2. get above-mentioned carboxylated carbon nanotube 1 weight part, two dimethyl dicarbonate butyl esters, 1～100 weight part, sodium azide 1-100 weight part, account for the 15mol% of carbon nanotube carboxyl amount phase-transfer catalyst, account for Lewis acid composite catalyst and 1～200 weight part tetrahydrofuran (THF) (THF) solvent of the 3.3mol% of carbon nanotube carboxyl amount, 40 ℃ ultrasonic 0～10 hour, reflux to stir 16-24h at 40 ℃ again.Filter repetitive scrubbing and remove unreacted reactant.Obtain having the carbon nanotube of t-butyl carbamate.
Will more than have carbon nanotube 1 weight part and acid solution 1～100 weight part of t-butyl carbamate, react 1～10h at normal temperatures, ultrasonic reaction 0～10 hour at room temperature simultaneously, filtration is also washed after drying with THF.Obtain having the carbon nanotube of primary aminoization.
The used carbon nanotube of the present invention comprises the single wall [SWNT] of catalytic pyrolysis, arc-over, template, chemical Vapor deposition process and the preparation of laser evaporation method, double-walled and multi-walled carbon nano-tubes [MWNT].
The used catalyzer of reaction is a kind of in tetramethyl ammonium chloride, 4 bromide, tetraethylammonium bromide, etamon chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, methyl triethyl ammonium chloride, the benzyl tributyl brometo de amonio in the step 2 of the present invention, with a kind of mixed catalytic in Lewis acid zinc chloride, zinc bromide, trifluoromethanesulfonic acid zinc, zinc fluoride, the zinc iodide.
Acid solution used in the step 3 of the present invention can be the dioxane solution of hydrochloric acid, the ethyl acetate solution of hydrochloric acid, the acetic acid mixed solution of hydrochloric acid, trifluoroacetic dichloromethane solution.
Mild condition of the present invention, step is simple, its surface that provides has the carbon nanotube of primary aminoization, its surperficial primary amine bond energy further reacts, thereby can introduce other polymkeric substance or functional group in the carbon nano tube surface design very easily, thereby obtain to have the functionalized carbon nano-tube of special construction and performance and relevant nano composite material.For the preparation high performance material provides a kind of reactive behavior high intermediate, have a wide range of applications.
Description of drawings
Fig. 1 is the embodiment of the invention 1 a chemical reaction step synoptic diagram
The infrared spectrogram of the carbon nanotube of the carboxyl modified that Fig. 2 obtains for embodiment 1 the first step
The infrared spectrogram of the carbon nanotube that the primary amine groups that Fig. 3 obtains for embodiment 1 the 3rd goes on foot is modified
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.Carbon nanotube used among the embodiment is all available from the organic institute in Chinese Academy of Sciences Chengdu.
Embodiment 1
As shown in Figure 1: the first step: with 500mg SWNT (diameter 1～2nm, purity is greater than 90%) and 150ml H
2SO
4With HNO
3Mixing solutions (98%H
2SO
4: 68%HNO
3=3: 1vol/vol) mix, back flow reaction is 4 hours under 35～40 ℃ and 50kHz ultra-sonic oscillation condition.Be the vinylidene membrane filtration of 0.45 μ m with the aperture then, be washed to pH and be neutral.Product places vacuum drying oven, 40 ℃ of following vacuum-drying 24h.With above-mentioned carboxylated and clean after product place H
2SO
4With H
2O
2Mixing solutions (98%H
2SO
4: 30%H
2O
2=4: 1vol/vol) in 70 ℃ of following backflow 2h.Be the vinylidene membrane filtration of 0.45 μ m with the aperture then, be washed to pH and be neutral.Product places vacuum drying oven, 40 ℃ of following vacuum-drying 24h.The infrared spectra of product as shown in Figure 2.
Second step: get above-mentioned carboxylated carbon nanotube 85mg and place reaction flask, add two dimethyl dicarbonate butyl ester 120mg, sodium azide 114mg, Tetrabutyl amonium bromide 24mg, zinc chloride 2mg, tetrahydrofuran (THF) 100ml, 40 ℃ of following stirring and refluxing 24h.Filter and wash with THF, and thorough drying.Obtain having the carbon nanotube of t-butyl carbamate.
The 3rd step: the carbon nanotube 50mg that will have t-butyl carbamate, join in the mixing solutions of 10ml hydrochloric acid and 20ml ethyl acetate, stir, reacted at normal temperatures 2 hours, stopped reaction is the vinylidene membrane filtration of 0.45 μ m with the aperture, uses the deionized water thorough washing again, with the aperture is the Fibrous membrane filtration of 0.45 μ m, obtains black powder.Be the carbon nanotube of uncle's ammonification.Its infrared spectra as shown in Figure 3.
Embodiment 2
The first step goes on foot referring to embodiment 1, the second: get above-mentioned acidifying carbon nanotube 85mg and place reaction flask, add two dimethyl dicarbonate butyl ester 120mg, sodium azide 114mg, Tetrabutyl amonium bromide 24.15mg, zinc bromide 7.425mg, tetrahydrofuran (THF) 100ml, 40 ℃ of following stirring and refluxing 24h.Filter and wash for several times with THF.Obtain having the carbon nanotube of t-butyl carbamate.
The 3rd step: the carbon nanotube 50mg that will have t-butyl carbamate, join in the mixing solutions of 10ml hydrochloric acid and 20ml ethyl acetate, stir, reacted at normal temperatures 2 hours, stopped reaction is the vinylidene membrane filtration of 0.45 μ m with the aperture, washes with water again, with the aperture is the Fibrous membrane filtration of 0.45 μ m, obtains black powder.
Embodiment 3
The first step goes on foot referring to embodiment 1, the second: get above-mentioned acidifying carbon nanotube 85mg and place reaction flask, add two dimethyl dicarbonate butyl ester 120mg, sodium azide 114mg, Tetrabutyl amonium bromide 24.15mg, trifluoromethanesulfonic acid zinc 12mg, tetrahydrofuran (THF) 100ml, 40 ℃ of following stirring and refluxing 24h.Filter and wash for several times with THF.Obtain having the carbon nanotube of t-butyl carbamate.
The 3rd step: the carbon nanotube 50mg that will have t-butyl carbamate, join in the mixing solutions of 10ml hydrochloric acid and 20ml ethyl acetate, stir, reacted at normal temperatures 2 hours, stopped reaction is the vinylidene membrane filtration of 0.45 μ m with the aperture, washes with water again, with the aperture is the Fibrous membrane filtration of 0.45 μ m, obtains black powder.
Embodiment 4
The first step is referring to embodiment 1, second step: get above-mentioned acidifying carbon nanotube 85mg and place reaction flask, add two dimethyl dicarbonate butyl ester 120mg, sodium azide 114mg, Tetrabutyl amonium bromide 24.15mg, trifluoromethanesulfonic acid zinc 12mg, tetrahydrofuran (THF) 100ml, 40 ℃ were descended stirring and refluxing 24h ultrasonic 2 hours.Filter and wash for several times with THF.Obtain having the carbon nanotube of t-butyl carbamate.
The 3rd step: the carbon nanotube 50mg that will have t-butyl carbamate, join in the mixing solutions of 10ml hydrochloric acid and 20ml ethyl acetate, stir, reacted at normal temperatures 2 hours, stopped reaction is the vinylidene membrane filtration of 0.45 μ m with the aperture, washes with water again, with the aperture is the Fibrous membrane filtration of 0.45 μ m, obtains black powder.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Reference
[1]Ya-Ping?Sun，Weijie?Huang，Yi?Lin，Kefu?Fu，Alex?Kitaygorodskiy，Lance?A.Riddle，Y.Joy?Yu，and?David?L.Carroll.Soluble?Dendron-Functionalized?Carbon?Nanotubes：Preparation，Characterization，and?Properties?Chem.Mater.2001，13：2864-2869.
[2]Yi?Lin，Bing?Zhou，K.A.Shiral?Fernando，Ping?Liu，Lawrence?F.Allard，and?Ya-Ping?Sun.Polymeric?Carbon?Nanocomposites?from?Carbon?Nanotubes?Functionalized?with?Matrix?Polymer.Macromolecules?2003，36，7199-7204.
[3]Weijie?Huang，Yi?Lin，Shelby?Taylor，Jay?Gaillard，Apparao?M.Rao，and?Ya-Ping?Sun.Sonication-Assisted?Functionalization?and?Solubilization?of?Carbon?Nanotubes?Nano?Lett.2002，2，231-234.
[4]K.A.Shiral?Fernando，Yi?Lin，and?Ya-Ping?Sun.High?Aqueous?Solubility?of?FunctionalizedSingle-Walled?Carbon?Nanotubes?Langmuir?2004，20，4777-4778.
[5]Weijie?Huang，Shiral?Fernando，Yi?Lin，Bing?Zhou，Lawrence?F.Allard，andYa-PingSun.Preferential?Solubilization?of?Smaller?Single-Walled?Carbon?Nanotubes?in?SequentialFunctionalization?Reactions.Langmuir?2003，19：7084-7088.
[6]Dettlaff-Weglikowska?U，Benoit?J?M，Chiu?P?W.et?al.Chemical?functionalization?of?singlewalled?carbon?nanotubes[J].Current?Applyied?physics，2002，2(6)：497～501.
[7]Stevens?J?V，Huang?A?Y，Peng?H?Q.et?al.Sidewall?Amino-Functionalization?of?Single-WalledCarbon?Nanotubes?through?Fluorination?and?Subsequent?Reactions?with?Terminal?Diamines[J].Nano?letters，2003，3(3)：331～336.
[8]Saito?T，Matsushige?K，Tanaka?K.et?al.Chemical?treatment?and?modification?of?multi-walledcarbon?nanotubes[J].Physica?B，2002，323(1-4)：280～283.
[9] Cao Chunhua, Li Jialin, Jia Zhijie etc. on carbon nanotube, introduce the research [J] of amine groups with diamines. new carbon, 2004,19 (2): 137-140.
Claims (7)
1. one kind is carried out the method that surperficial primary amine groups is modified to carbon nanotube, comprise the steps: that carboxylic carbon nano-tube and two dimethyl dicarbonate butyl esters and sodium azide react under phase-transfer catalyst and Lewis acid composite catalyzing, obtain having the carbon nanotube of t-butyl carbamate, this carbon nanotube is sloughed the formic acid tertiary butyl in acid solution then, obtains having the carbon nanotube of primary aminoization.
2. method according to claim 1, its concrete preparation process is as follows:
A, carbon nanotube is mixed with 0.1～100 weight ratio with acid with strong oxidizing property, handle 0.1～100h post-heating with 0～100kHz is ultrasonic at 35～40 ℃, temperature of reaction is between 20～200 ℃, reaction times is between 0.5～100h, with the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains carboxylated carbon nanotube after the vacuum-drying;
B, above-mentioned carboxylated carbon nanotube 1 weight part, two dimethyl dicarbonate butyl esters, 1～100 weight part, sodium azide 1-100 weight part, the phase-transfer catalyst that accounts for the 15mol% of carbon nanotube carboxyl amount, Lewis acid composite catalyst and 1～200 weight part tetrahydrofuran (THF) that accounts for the 3.3mol% of carbon nanotube carboxyl amount are mixed, 40 ℃ ultrasonic 0～10 hour, reflux to stir 16-24h again; Filter and wash with tetrahydrofuran (THF); Obtain having the carbon nanotube of t-butyl carbamate;
C, will more than have carbon nanotube 1 weight part and acid solution 1～100 weight part of t-butyl carbamate, react 1～10h at normal temperatures, ultrasonic reaction is 0～10 hour simultaneously, obtains the carbon nanotube of surperficial primary amino modification behind the washing membrane filtration.
3. method according to claim 2, wherein acid with strong oxidizing property is selected from 0.1～70wt% nitric acid, 0.1～100wt% sulfuric acid, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixture, 1/100～100/1 mol ratio potassium permanganate and hydrochloric acid mixture, 1/100～100/1 mol ratio potassium permanganate and nitrate mixture, 1/100～100/1 mol ratio H
2O
2With sulfuric acid mixed solution, 1/100～100/1 mol ratio H
2O
2With hydrochloric acid mixed solution or 1/100～100/1 mol ratio H
2O
2With wherein a kind of of nitric acid mixing solutions.
4. method according to claim 2 is characterized in that used carbon nanotube comprises single wall, double-walled and the multi-walled carbon nano-tubes of catalytic pyrolysis, arc-over, template, chemical Vapor deposition process and the preparation of laser evaporation method.
5. method according to claim 2 is characterized in that the used phase-transfer catalyst of reaction comprises tetramethyl ammonium chloride, 4 bromide, tetraethylammonium bromide, etamon chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, methyl triethyl ammonium chloride, benzyl tributyl brometo de amonio in second step.
6. method according to claim 2 is characterized in that the used Lewis acid of reaction comprises zinc chloride, zinc bromide, trifluoromethanesulfonic acid zinc, zinc fluoride, zinc iodide in second step.
7. method according to claim 2 is characterized in that acid solution used in the three-step reaction comprises the hydrochloric acid dioxane solution, hydrochloric ethyl acetate solution, the mixing solutions of hydrochloric acid acetate, trifluoroacetic dichloromethane solution of 10: 20 vol/vol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102689893A (en) * | 2012-05-11 | 2012-09-26 | 上海上大瑞沪微系统集成技术有限公司 | Mass carbon nano-tube surface modification method |
| CN103276593A (en) * | 2013-05-28 | 2013-09-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for enhancing carbon nano tube fiber by utilizing fluorine-removing cross-linking reaction |
| CN107892290A (en) * | 2017-12-13 | 2018-04-10 | 西安医学院 | A kind of preparation method and applications of PEOz modifications single-walled carbon nanotube |
| CN108400076A (en) * | 2018-01-30 | 2018-08-14 | 华东师范大学 | A method of vacuum filtration improves field emission performance of carbon nano tube film |
-
2006
- 2006-11-10 CN CN200610118287A patent/CN100586845C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102689893A (en) * | 2012-05-11 | 2012-09-26 | 上海上大瑞沪微系统集成技术有限公司 | Mass carbon nano-tube surface modification method |
| CN103276593A (en) * | 2013-05-28 | 2013-09-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for enhancing carbon nano tube fiber by utilizing fluorine-removing cross-linking reaction |
| CN103276593B (en) * | 2013-05-28 | 2015-08-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Utilize the method for going fluorine cross-linking reaction to strengthen carbon nano-tube fibre |
| CN107892290A (en) * | 2017-12-13 | 2018-04-10 | 西安医学院 | A kind of preparation method and applications of PEOz modifications single-walled carbon nanotube |
| CN108400076A (en) * | 2018-01-30 | 2018-08-14 | 华东师范大学 | A method of vacuum filtration improves field emission performance of carbon nano tube film |
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