CN100590068C - Method for preparing primary amine carbon nano tube - Google Patents
Method for preparing primary amine carbon nano tube Download PDFInfo
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- CN100590068C CN100590068C CN200610118286A CN200610118286A CN100590068C CN 100590068 C CN100590068 C CN 100590068C CN 200610118286 A CN200610118286 A CN 200610118286A CN 200610118286 A CN200610118286 A CN 200610118286A CN 100590068 C CN100590068 C CN 100590068C
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- fluorenylmethyloxycarbonyl
- carbon nanotube
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- tertbutyloxycarbonyl
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Abstract
The invention relates to a preparation method for primary amine modified carbon nano-tubes (CNT), firstly, the hydroxyl of hydroxyl carbon nano-tube (CNT) and the hydroxyl of amino acid protected withfluorenyl methoxy carbonyl or di-tert-butyl dicarbonate are reacted to obtain carbon nano-tubes (CNT) with carbamic fluorenylmethyl or carbamic tert-butyl; then fluorenylmethyl group or tert-butyl group is lost in acid solution to generate the primary amine modified carbon nano-tubes (CNT). The primary amine modification degree of the primary amine modified carbon nano-tubes (CNT) is higher thanthat of products prepared with the prior art, which allows the generated carbon nano-tubes (CNT) to work as an important reaction intermediate to graft other materials to the outer surface of the carbon nano-tubes (CNT) via chemical reactions and to realize functional design and application of the carbon nano-tubes (CNT). The generated carbon nano-tubes (CNT) can also be compounded with polymers to obtain composite materials with high performance.
Description
Technical field
The invention belongs 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.About amination is carbon nano-tube modified report arranged also at present
[1～4]Utilize carboxyl carbon nanotube and reacting ethylenediamine if any the people, obtain amido modified carbon nanotube, but because two amine of quadrol active identical, this kind method can not guarantee that the amino of modifying one is decided to be primary amino group.
The present invention is with the hydroxyl of hydroxyl carbon nanotube and the amino acid whose carboxyl or and the two dimethyl dicarbonate butyl ester (BOC of fluorenylmethyloxycarbonyl (Fmoc) protection
2O) Bao Hu the amino acid whose carboxyl reaction carbon nanotube that can obtain having the carbon nanotube of carboxylamine fluorenes methyl esters or have t-butyl carbamate.Slough formic acid fluorenes methoxycarbonyl or t-butyl formate base then in acid solution, just obtain having the carbon nanotube of primary aminoization, this reaction has overcome above reaction shortcoming, has not yet to see report.
Summary of the invention
The existing carbon nanotube that the present invention will solve shows in the modification technique, severe reaction conditions, step complicated problems.Purpose is to provide a kind of method for preparing the higher carbon nanotube of primary amine groups degree, and this primary amine carbon nano tube can be used as important intermediate, further reacts, and satisfies different research work and Application Areas.
For solving the problems of the technologies described above, the present invention is performed such: by molecular designing, earlier with the hydroxyl of hydroxyl carbon nanotube and the amino acid whose carboxyl or and the two dimethyl dicarbonate butyl ester (BOC of fluorenylmethyloxycarbonyl (Fmoc) protection
2O) Bao Hu amino acid whose carboxyl or and the amino acid whose carboxyl reaction of the carbobenzoxy-(Cbz) protection carbon nanotube that can obtain having the carbon nanotube of carboxylamine fluorenes methyl esters or have t-butyl carbamate.In acid solution, go protection then, slough formic acid fluorenes methoxycarbonyl or t-butyl formate base, obtain having the carbon nanotube of primary amine groups.Concrete preparation method is as follows:
1. with the amino acid or and the two dimethyl dicarbonate butyl ester (BOC of hydroxylated carbon nanotube 1 weight part, fluorenylmethyloxycarbonyl (Fmoc) protection
2O) Bao Hu amino acid/11～100 weight parts, catalyzer 0.1～5 weight part, 1～200 parts by weight solvent mix, and 0～40 ℃ of ultrasonic 0～10h down refluxes down at 50-150 ℃ then and stirs 12～48h.Filter and with tetrahydrofuran (THF) (THF) repetitive scrubbing, filtration, vacuum-drying, the carbon nanotube that obtains having the carbon nanotube of carboxylamine fluorenes methyl esters or have t-butyl carbamate.
2. get above-mentioned carbon nanotube 1 weight part and acid solution 1～100 weight part that has the carbon nanotube of carboxylamine fluorenes methyl esters or have t-butyl carbamate, ultrasonic 0～10h under 0～40 ℃, react 1～10h at normal temperatures, obtain having the carbon nanotube of primary amine groupsization.
The used carbon nanotube of the present invention comprises single wall, double-walled and multi-walled carbon nano-tubes.
The amino acid or the two dimethyl dicarbonate butyl ester (BOC of fluorenylmethyloxycarbonyl (Fmoc) protection that the present invention is used
2O) Bao Hu amino acid comprises:
The N-tert-butoxycarbonyl-l-alanine, N-tertbutyloxycarbonyl-L-aspartic acid, N-tertbutyloxycarbonyl-altheine, N-tertbutyloxycarbonyl-L-phenylalanine, N-tertbutyloxycarbonyl-L-L-glutamic acid, N-tertbutyloxycarbonyl-L-glutaminate, N-tertbutyloxycarbonyl-glycine, N-tertbutyloxycarbonyl-L-leucine, the N-tert-butoxy-oxo-L-isoleucine, N-tertbutyloxycarbonyl-L-methionine(Met), N-tertbutyloxycarbonyl-L-proline(Pro), N-tertbutyloxycarbonyl-L-Serine, the N-tert-butoxycarbonyl-l-l-tryptophan, N-tertbutyloxycarbonyl-L-Xie Ansuan;
N-fluorenylmethyloxycarbonyl-L-L-Ala, N-fluorenylmethyloxycarbonyl-L-aspartic acid, N-fluorenylmethyloxycarbonyl-altheine, N-fluorenylmethyloxycarbonyl-L-arginine, N-fluorenylmethyloxycarbonyl-L-Threonine, N-fluorenylmethyloxycarbonyl-L-glutaminate, N-fluorenylmethyloxycarbonyl-glycine, N-fluorenylmethyloxycarbonyl-L-phenylalanine, N-fluorenylmethyloxycarbonyl-L-leucine, N-fluorenylmethyloxycarbonyl-L-Isoleucine, N-fluorenylmethyloxycarbonyl-L-methionine(Met), N-fluorenylmethyloxycarbonyl-L-proline(Pro), N-fluorenylmethyloxycarbonyl-L-Serine, N-fluorenylmethyloxycarbonyl-L-tryptophane, N-fluorenylmethyloxycarbonyl-L-Xie Ansuan.
The used solvent of the present invention is organic solvent, particularly dimethylbenzene, acetone, N, dinethylformamide, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide, tetrahydrofuran (THF), butanone, benzene, toluene, chlorinated benzene.
The used catalyzer of reaction is tosic acid, the vitriol oil, Phenylsulfonic acid, boric acid, phosphoric acid, sodium phosphite, phosphorous acid amine, metal iodide, Quilonum Retard, tricresyl phosphite nonylbenzene ester, triphenyl phosphite, tricresyl phosphite (2 in the step 1 of the present invention, 4-two trimethylphenylmethane bases) ester, sulphur, 4,4-two (a 6-tertiary butyl-tolyl) thiophenol, nonyl phenyl dithiol oligopolymer, uncle's penta phenyl dithiol oligopolymer, nickel dibutyl dithiocarbamate.
Acid solution used in the step 2 of the present invention comprises 1: the mixing solutions of 1vol/vol hydrochloric acid dioxane solution, hydrochloric ethyl acetate solution, hydrochloric acid acetate, trifluoroacetic dichloromethane solution.
The invention provides the carbon nano-tube modified method of a kind of primary amine groupsization, it is exactly that the primary amine carbon nano tube that obtains of prior art may contain the secondary amino group carbon nanotube that the primary amine carbon nano tube that obtains is compared with the prior art remarkable advantages, and the present invention obtains is pure primary amine groups carbon nanotube, and the primary amine bond energy that the surface that provides has the carbon nano tube surface of primary aminoization further reacts, thereby the polymkeric substance that can introduce 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 a chemical reaction process synoptic diagram of the present invention
Fig. 2 is the infrared spectrogram of the carbon nanotube of the hydroxyl modified that uses of embodiment 1
Fig. 3 is the infrared spectrogram of the carbon nanotube modified of the primary amine groups of embodiment 1 preparation
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.Hydroxylated carbon nanotube used in the present invention is all available from the organic institute in Chengdu, and diameter is less than 8nm, and purity is greater than 90%, and hydroxy radical content is about 5.58%, and its infared spectrum directly uses as shown in Figure 2.Amino acid is all available from Shanghai traditional Chinese medicines group company, analytical pure.
Embodiment 1
Step as shown in Figure 1: the first step: with hydroxylated carbon nanotube 100mg, two dimethyl dicarbonate butyl ester (BOC
2O) Bao Hu phenylalanine 400mg, phosphatase 11 00mg mix with the 50mL dichlorobenzene solution.Ultrasonic 2h under 40 ℃ refluxes down at 120 ℃ then and stirs 24h.Filter, use the THF repetitive scrubbing, filtration, vacuum-drying obtains having the carbon nanotube of t-butyl carbamate.
Second step: get the above-mentioned carbon nanotube 90mg that has t-butyl carbamate and mix with hydrochloric acid 10mL, dioxane 10mL, 40 ℃ of time ultrasonic 2h, stirring reaction 2h at normal temperatures obtains the carbon nanotube of primary aminoization after water and the tetrahydrofuran (THF) filtration washing drying.The infared spectrum that obtains product as shown in Figure 3.The as can be seen from the figure success of its primary amine modification.
Embodiment 2
The first step: with hydroxylated carbon nanotube 100mg and two dimethyl dicarbonate butyl ester (BOC
2O) Bao Hu phenylalanine 800mg, tosic acid 80mg, in the 60mL xylene solution, 40 ℃ of following ultrasonic 3h reflux down at 120 ℃ then and stir 24h.Filter, use the THF repetitive scrubbing, filtration, vacuum-drying obtains having the carbon nanotube of t-butyl carbamate.
Second step: get the above-mentioned carbon nanotube 90mg that has t-butyl carbamate, hydrochloric acid 10mL, ethyl acetate 10mL, 40 ℃ of following ultrasonic 2h, stirring reaction 2h at normal temperatures obtains the carbon nanotube of primary aminoization.
Embodiment 3
The first step: with the phenylalanine 500mg of hydroxylated carbon nanotube 100mg and fluorenylmethyloxycarbonyl (Fmoc) protection, sodium phosphite 50mg, 40 ℃ of ultrasonic 2h down, then in the 80mL toluene solution, 80 ℃ are refluxed down and stir 24h.Filter, use the THF repetitive scrubbing, filtration, vacuum-drying obtains having the carbon nanotube of carboxylamine fluorenes methyl esters.
Second step: get the above-mentioned carbon nanotube 90mg that has carboxylamine fluorenes methyl esters, hydrofluoric acid 10mL, ethyl acetate 10mL, 40 ℃ of following ultrasonic 2h, stirring reaction 2h at normal temperatures obtains the carbon nanotube of primary aminoization.
Embodiment 4
The first step: with the glycine 500mg of hydroxylated carbon nanotube 100mg and fluorenylmethyloxycarbonyl (Fmoc) protection, Phenylsulfonic acid 40mg, 40 ℃ of ultrasonic 2h down, then in the 100mL dichlorobenzene solution, 120 ℃ are refluxed down and stir 24h.Filter, use the THF repetitive scrubbing, filtration, vacuum-drying obtains having the carbon nanotube of carboxylamine fluorenes methyl esters.
Second step: get the above-mentioned carbon nanotube 90mg that has carboxylamine fluorenes methyl esters, hydrofluoric acid 10mL, ethyl acetate 10mL, 40 ℃ of following ultrasonic 2h, stirring reaction 2h at normal temperatures obtains the carbon nanotube of primary aminoization.
Embodiment 5
The first step: with the phenylalanine 800mg of hydroxylated carbon nanotube 100mg and fluorenylmethyloxycarbonyl (Fmoc) protection, tosic acid 40mg, 40 ℃ of ultrasonic 2h down, then at 100mLN, in the N-dimethylformamide solution, 120 ℃ are refluxed down and stir 24h.Filter, use the THF repetitive scrubbing, filtration, vacuum-drying obtains having the carbon nanotube of carboxylamine fluorenes methyl esters.
Second step: get the above-mentioned carbon nanotube 90mg that has carboxylamine fluorenes methyl esters, hydrofluoric acid 10mL, ethyl acetate 10mL, 40 ℃ of following ultrasonic 2h, stirring reaction 2h at normal temperatures obtains having the carbon nanotube of primary aminoization.
Embodiment 6
The first step: with the L-Ala 800mg of hydroxylated carbon nanotube 100mg and carbobenzoxy-(Cbz) protection, tosic acid 40mg, 40 ℃ of ultrasonic 2h down, then at 100mLN, in the N-dimethylformamide solution, 120 ℃ are refluxed down and stir 24h.Filter, use the THF repetitive scrubbing, filtration, vacuum-drying obtains having the carbon nanotube of carboxylamine fluorenes methyl esters.
Second step: get the above-mentioned carbon nanotube 90mg that has carboxylamine fluorenes methyl esters, hydrofluoric acid 10mL, ethyl acetate 10mL, 40 ℃ of following ultrasonic 2h, stirring reaction 2h at normal temperatures obtains having the carbon nanotube of primary aminoization.
The invention provides the carbon nano-tube modified method of a kind of primary amine groupsization, it is exactly that the primary amine carbon nano tube that obtains of prior art may contain the secondary amino group carbon nanotube that the primary amine carbon nano tube that obtains is compared with the prior art remarkable advantages, is pure primary amine groups carbon nanotube and the present invention obtains.
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]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
[2]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
[3]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
[4] 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 (6)
1, a kind of method for preparing the carbon nanotube of primary amine groups modification, comprise the steps: that the hydroxyl of hydroxylation carbon nanotube and the amino acid whose carboxyl of fluorenylmethyloxycarbonyl protection or the amino acid whose carboxyl of two dimethyl dicarbonate butyl esters protection react, and obtain having the carbon nanotube of carboxylamine fluorenes methyl esters or the carbon nanotube of t-butyl carbamate under catalyzer; Slough formic acid fluorenes methoxycarbonyl or t-butyl formate base then in acid solution, obtain primary amine carbon nano tube, its concrete preparation process is as follows:
The first step, with the amino acid/11～100 weight parts protection of hydroxylation carbon nanotube 1 weight part and fluorenylmethyloxycarbonyl or the protection of two dimethyl dicarbonate butyl esters, catalyzer 0.1～5 weight part, in 1～200 parts by weight solvent, ultrasonic 2～10h under 0～40 ℃ refluxes down at 50～150 ℃ then and stirs 12～48h; Reaction finishes after-filtration and uses tetrahydrofuran (THF) repetitive scrubbing, filtration, vacuum-drying, obtains having the carbon nanotube of carboxylamine fluorenes methyl esters or t-butyl carbamate;
Second goes on foot, gets above-mentioned carbon nanotube 1 weight part and acid solution 1～100 weight part that has carboxylamine fluorenes methyl esters or t-butyl carbamate, ultrasonic 2～10h under 0～40 ℃, react 1～10h at normal temperatures, obtain the carbon nanotube of primary amine groupsization after filtration, washing, the drying.
2, method according to claim 1, the amino acid of used fluorenylmethyloxycarbonyl protection or the amino acid of two dimethyl dicarbonate butyl esters protection comprise:
The N-tert-butoxycarbonyl-l-alanine, N-tertbutyloxycarbonyl-L-aspartic acid, N-tertbutyloxycarbonyl-altheine, N-tertbutyloxycarbonyl-L-phenylalanine, N-tertbutyloxycarbonyl-L-L-glutamic acid, N-tertbutyloxycarbonyl-L-glutaminate, N-tertbutyloxycarbonyl-glycine, N-tertbutyloxycarbonyl-L-leucine, the N-tert-butoxy-oxo-L-isoleucine, N-tertbutyloxycarbonyl-L-methionine(Met), N-tertbutyloxycarbonyl-L-proline(Pro), N-tertbutyloxycarbonyl-L-Serine, the N-tert-butoxycarbonyl-l-l-tryptophan, N-tertbutyloxycarbonyl-L-Xie Ansuan;
N-fluorenylmethyloxycarbonyl-L-L-Ala, N-fluorenylmethyloxycarbonyl-L-aspartic acid, N-fluorenylmethyloxycarbonyl-altheine, N-fluorenylmethyloxycarbonyl-L-arginine, N-fluorenylmethyloxycarbonyl-L-Threonine, N-fluorenylmethyloxycarbonyl-L-glutaminate, N-fluorenylmethyloxycarbonyl-glycine, N-fluorenylmethyloxycarbonyl-L-phenylalanine, N-fluorenylmethyloxycarbonyl-L-leucine, N-fluorenylmethyloxycarbonyl-L-Isoleucine, N-fluorenylmethyloxycarbonyl-L-methionine(Met), N-fluorenylmethyloxycarbonyl-L-proline(Pro), N-fluorenylmethyloxycarbonyl-L-Serine, N-fluorenylmethyloxycarbonyl-L-tryptophane, N-fluorenylmethyloxycarbonyl-L-Xie Ansuan.
3, method according to claim 1 is characterized in that used hydroxylation carbon nanotube comprises single wall and multi-walled carbon nano-tubes.
4, method according to claim 1 is characterized in that used solvent comprises dimethylbenzene, acetone, N, dinethylformamide, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide, tetrahydrofuran (THF), butanone, benzene, toluene, chlorinated benzene.
5, method according to claim 1, it is characterized in that the used catalyzer of reaction comprises tosic acid, the vitriol oil, Phenylsulfonic acid, boric acid, phosphoric acid, sodium phosphite, phosphorous acid amine, metal iodide, Quilonum Retard, tricresyl phosphite nonylbenzene ester, triphenyl phosphite, tricresyl phosphite (2 in the first step, 4-two trimethylphenylmethane bases) ester, sulphur, 4,4-two (a 6-tertiary butyl-tolyl) thiophenol, nonyl phenyl dithiol oligopolymer, uncle's penta phenyl dithiol oligopolymer, nickel dibutyl dithiocarbamate.
6, method according to claim 1 is characterized in that used acid solution comprises 1 in the reaction of second step: the mixing solutions of 1vol/vol hydrochloric acid dioxane solution, hydrochloric ethyl acetate solution, hydrochloric acid acetate, trifluoroacetic dichloromethane solution.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6426134B1 (en) * | 1998-06-30 | 2002-07-30 | E. I. Du Pont De Nemours And Company | Single-wall carbon nanotube-polymer composites |
| US20040071624A1 (en) * | 2001-01-29 | 2004-04-15 | Tour James M. | Process for derivatizing carbon nanotubes with diazonium species and compositions thereof |
| JP2004168570A (en) * | 2002-11-18 | 2004-06-17 | Japan Science & Technology Agency | Method for manufacturing soluble carbon nanotube |
| CN1733602A (en) * | 2005-06-17 | 2006-02-15 | 吉林大学 | Highly water-soluble carbon nanometer tube preparation method |
| CN1830768A (en) * | 2006-03-31 | 2006-09-13 | 中国科学院长春应用化学研究所 | Aminatel single wall nanometer carbon pipe and its preparation method |
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2006
- 2006-11-10 CN CN200610118286A patent/CN100590068C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6426134B1 (en) * | 1998-06-30 | 2002-07-30 | E. I. Du Pont De Nemours And Company | Single-wall carbon nanotube-polymer composites |
| US20040071624A1 (en) * | 2001-01-29 | 2004-04-15 | Tour James M. | Process for derivatizing carbon nanotubes with diazonium species and compositions thereof |
| JP2004168570A (en) * | 2002-11-18 | 2004-06-17 | Japan Science & Technology Agency | Method for manufacturing soluble carbon nanotube |
| CN1733602A (en) * | 2005-06-17 | 2006-02-15 | 吉林大学 | Highly water-soluble carbon nanometer tube preparation method |
| CN1830768A (en) * | 2006-03-31 | 2006-09-13 | 中国科学院长春应用化学研究所 | Aminatel single wall nanometer carbon pipe and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Dispersion and alignment of carbon nanotubes in polymermatrix: A review. xie xl et al.materials science & engineering reports,Vol.49 No.4. 2005 * |
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