CN101700880A - Carbon nano tube surface modification method - Google Patents
Carbon nano tube surface modification method Download PDFInfo
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- CN101700880A CN101700880A CN200910220116A CN200910220116A CN101700880A CN 101700880 A CN101700880 A CN 101700880A CN 200910220116 A CN200910220116 A CN 200910220116A CN 200910220116 A CN200910220116 A CN 200910220116A CN 101700880 A CN101700880 A CN 101700880A
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Abstract
The invention provides a carbon nano tube surface modification method, relating to the surface modification technology of material; an organic-functional group is led on the surface of the carbon nano tube to improve the interface affinity of the carbon nano tube and polymer, a dispersed system which is composed of the carbon nano tube and organic molecule monomers with active double bonds can be directly radiated by high-energy rays, so as to initiate grafting reaction of the organic molecules on the carbon nano tube, the organic-functional group is led on the surface of the carbon nano tube, so as to realize surface modification of the carbon nano tube. The carbon nano tube has wide application prospect in the field such as nanometer electronic devices, catalyst carriers, electrochemistry material, super-strength composite material and hydrogen storage material; a simple and effective carbon nano tube surface modification method is provided by the invention, so as to promote the development of the high-performance structural material or functional material.
Description
Technical field
The present invention relates to a kind of process for modifying surface of material, particularly a kind of process for modifying surface of carbon nanotube utilizes the energetic ray irradiation to cause the organic molecule monomer and at the graft reaction of carbon nano tube surface carbon nanotube is carried out modification.
Background technology
Carbon nanotube can be divided into Single Walled Carbon Nanotube (SWNT) and multi-walled carbon nano-tubes (MWNT).Carbon nanotube is the curling seamless hollow tubular thing that forms of hexagon reticulated structure by class graphite, has the diameter of nano-scale and length can reach tens of microns, it is the monodimension nanometer material of foot sign, because it has particular structure, excellent physical and chemical property, has caused the extensive concern of scientific circles.Carbon nanotube nano electron device, support of the catalyst, electrochemical material,, numerous areas such as super-strength matrix material, hydrogen storage material all has wide practical use.But because the huge specific surface area of carbon nanotube, between the tube and tube of carbon nanotube adsorption very strong, carbon nanotube is easy to the bunchy of reuniting, and is difficult to disperse, and has limited the application of carbon nanotube in every field greatly.So that it is used well in more field, the modification of carbon nanotube becomes the focus of research for the own character of improving carbon nanotube.
The semisphere that the termination of carbon nanotube is made up of the five-ring and the six-ring of carbon by acid treatment, can produce the end group defective or cause the carbon pipe to be prescinded, thus on CNT surface or the terminal carboxylation of the CNT that prescinds enough carboxylation positions are provided.(Liu J such as Smalley, Rinzler A G, Dai H J, et a1.Science, 1998,280:1253) at first using volume ratio is that the nitration mixture of 3: 1 the vitriol oil and concentrated nitric acid " is cut into " short tube of 100～300nm with carbon nanotube, then is 4: 1 the vitriol oil and 30% hydrogen peroxide oxidation sodium again with volume ratio, obtains the Single Walled Carbon Nanotube that end group is a carboxyl.On this basis, Haddon etc. (HamonM A, Chen J, Hu H, et al.Adv Mater, 1999,11:834) carboxyl is become acyl chlorides, increase reactive behavior, and then with the alkylamine of long-chain, obtain the Single Walled Carbon Nanotube of solubility.Except forming amido linkage, also can introduce lipotropy, hydrophilic radical by esterification, increased carbon nanotube solubleness.Hamwi etc. (Hamwi A, Alevergnat H, et al.Carbon, 1997,35:723), formed carbon fluoride nano-tube by carbon nanotube and fluorine generation addition reaction, control different temperature of reaction, can control the fluorizated degree.The C-F key is easy to be subjected to nucleophilic reagent attacks such as RLi, RMgX or RONa, thereby can further carry out surface-functionalized to carbon nanotube.Jnrewicz (Jnrewicz K, Delpeux S, Bertagna V, et al.Chem Phys Lett, 2001,347:36) reported and utilize the big p key of carbon nano tube surface height delocalized and other macromolecular compounds that contain conjugated system to carry out that p-p is non-covalent to be combined, polymer is coated on the carbon nanotube, thereby can obtain surface tissue and character is not all destroyed, structure is maintained functional modification carbon nanotube.Ying (Ying Y M, Saini R K, Liang F, et al.Org Lett, 2003,5 (9): 1471-1473) and Umek (Umek P, Seo J W, Hernadi K, et al.Chem Mater.2003,47514755) etc. 15 (25): finding that peroxide breakdown produces carbon radicals can be carbon nano-tube modified, and the radical modification of carbon nanotube is a kind of feasible and simple modifying method, and CNT goes up the group of modifying and provides prerequisite for miscellaneous other further modification reaction again.Elder generations such as Guo Jinxue carry out the energetic ray irradiation to carbon nanotube, and then itself and organism mixed exposure handled, thereby make its modification that obtains organising, their experimental study explanation high-energy ray irradiation can make carbon nano tube surface produce textural defect, helps the surface modification of carbon nanotube.
Summary of the invention
The object of the present invention is to provide a kind of process for modifying surface of carbon nanotube, adopt high-energy ray irradiation, by introducing organo-functional group in carbon nano tube surface, to improve the interface affinity of CNT (carbon nano-tube) and polymkeric substance, utilize the direct irradiation of energetic ray by CNT (carbon nano-tube) and the monomeric dispersion system of organic molecule that contains activity double key, cause the graft reaction of organic molecule, introduce organo-functional group, thereby realize surface modification carbon nanotube in carbon nano tube surface in carbon nano tube surface.
The objective of the invention is to be achieved through the following technical solutions:
A kind of surface modifying method of carbon nanotube, the dispersion system that utilizes the direct irradiation of energetic ray to be made of CNT (carbon nano-tube) and organic molecule monomer causes the graft reaction of organic molecule in carbon nano tube surface, introduces organo-functional group in carbon nano tube surface.
The surface modifying method of described a kind of carbon nanotube, the organic molecule monomer that is adopted are the organic molecules that maleic anhydride one class has unsaturated double-bond.
The surface modifying method of described a kind of carbon nanotube, carbon nanotube are dispersed in and carry out the energetic ray irradiation in the solution of organic molecule, make to cause the organic molecule free radical that produces on the spot directly in the generation graft modification reaction of carbon nano tube surface.
The surface modifying method of described a kind of carbon nanotube, the energetic ray that is adopted is a gamma-radiation.
The invention has the beneficial effects as follows: a kind of method of carrying out surface modification of carbon nanotube simply and effectively is provided, promotes the exploitation of high performance structures material or functional materials, thereby produce remarkable economic efficiency and social benefit.
Embodiment
Carbon nanotube of the present invention can be Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes.The plane that is similar to graphite that carbon nanotube is made up of the carbon six-ring, by the nano level tubular structure that certain way curls and forms, wherein each carbon atom passes through SP
2Hydridization and 3 carbon atom bondings on every side form a large amount of height delocalization p electronics, have the ability of capturing free radical.
Organic molecule monomer of the present invention can be a maleic anhydride, and methacrylic acid (ester), vinylformic acid (ester) etc. has the organic molecule of unsaturated double-bond.This organic micromolecule is easy to living radical under high-energy ray irradiation.Free radical has not atom, molecule or the atomic group of sharing electron, and they are neutral, neutral.Free radical is very active, has strong addition performance and oxidation susceptibility, can attack the p electron pair of carbon tube-surface delocalizationization, realizes chemical Functionalization of Carbon Nanotubes.
Among the present invention, carbon nanotube can directly mix with organic molecule or be dispersed in and carries out the energetic ray irradiation in the solution of organic molecule, cause the organic molecule monomer form free radical on the spot with the carbon nanotube effect, directly in the generation graft modification reaction of carbon nano tube surface.Energetic ray of the present invention can be gamma-radiation or high energy electron ray.High-energy ray irradiation dosage is unsuitable too high, because heavy dose of energetic ray has destruction to carbon nanotube structure, can cause the decay of aspect performances such as the mechanical strength of carbon nanotube itself and electroconductibility.
Be example with the multi-walled carbon nano-tubes among the embodiment, but the carbon nanotube that the present invention was suitable for is not limited to multi-walled carbon nano-tubes, the organic molecule that is adopted is the More Malay acid anhydrides, but the organic molecule that the present invention was suitable for is not limited to maleic anhydride.
Embodiment 1:
50mg puts into small beaker with multi-walled carbon nano-tubes, behind the adding acetone soln ultra-sonic dispersion 3h, adds the 20g maleic anhydride again and continues ultra-sonic dispersion 6h; solution in the beaker is packed in the test tube; charge into nitrogen protection, place gamma-radiation irradiation then, irradiation dose is 100KGy.Sample carries out high speed centrifugation cleaning, room temperature vacuum-drying 24h then behind the irradiation.The comprehensive thermal analyzer of STA449C that adopts the anti-instrument Manufacturing Co., Ltd of speeding of Germany to produce carries out thermogravimetic analysis (TGA) to carbon nanotube.Experimental result shows: when irradiation dose is 100KGy, be 8.3% through the carbon nanotube of the gamma-radiation radiation treatment rate of weight loss during at 450 ℃, do not decompose at carbon nanotube below 450 ℃ that weightlessness can be owing to due to the organic decomposition.This explanation gamma-radiation has caused maleic anhydride and the graft modification reaction has taken place carbon nanotube, in the carbon nano tube surface grafting organo-functional group.
The comparative example 1:
Used carbon nanotube is identical with embodiment 1, just without the gamma-radiation radiation treatment.To showing without the thermogravimetic analysis (TGA) experimental result of gamma-radiation radiation treatment carbon nanotube: without the rate of weight loss of gamma-radiation irradiation carbon nanotube 450 ℃ the time is 3.9%, can be owing to due to the decomposition of a small amount of organo-functional group of introducing in the purge process.
Claims (4)
1. the surface modifying method of a carbon nanotube, it is characterized in that the dispersion system that utilizes the direct irradiation of energetic ray to constitute by CNT (carbon nano-tube) and organic molecule monomer, cause the graft reaction of organic molecule, introduce organo-functional group in carbon nano tube surface in carbon nano tube surface.
2. the surface modifying method of a kind of carbon nanotube according to claim 1 is characterized in that the organic molecule monomer that is adopted is the organic molecule that maleic anhydride one class has unsaturated double-bond.
3. the surface modifying method of a kind of carbon nanotube according to claim 1, it is characterized in that carbon nanotube is dispersed in carries out the energetic ray irradiation in the solution of organic molecule, make to cause the organic molecule free radical that produces on the spot directly in the generation graft modification reaction of carbon nano tube surface.
4. the surface modifying method of a kind of carbon nanotube according to claim 1 is characterized in that the energetic ray that is adopted is a gamma-radiation.
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| CN200910220116A CN101700880A (en) | 2009-11-24 | 2009-11-24 | Carbon nano tube surface modification method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169838A (en) * | 2011-03-15 | 2011-08-31 | 上海大学 | Manufacturing method of carbon nano-tube micro-channel cooler system |
| CN108532287A (en) * | 2018-03-30 | 2018-09-14 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano-tube fibre |
| CN109777153A (en) * | 2019-03-12 | 2019-05-21 | 中国工程物理研究院核物理与化学研究所 | A kind of method of modifying of inorganic nano-particle |
| CN115594887A (en) * | 2022-12-13 | 2023-01-13 | 广东粤港澳大湾区黄埔材料研究院（Cn） | Preparation method of modified carbon nanotube and application of modified carbon nanotube in tire tread rubber |
-
2009
- 2009-11-24 CN CN200910220116A patent/CN101700880A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169838A (en) * | 2011-03-15 | 2011-08-31 | 上海大学 | Manufacturing method of carbon nano-tube micro-channel cooler system |
| CN102169838B (en) * | 2011-03-15 | 2013-04-03 | 上海大学 | Manufacturing method of carbon nano-tube micro-channel cooler system |
| CN108532287A (en) * | 2018-03-30 | 2018-09-14 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano-tube fibre |
| CN109777153A (en) * | 2019-03-12 | 2019-05-21 | 中国工程物理研究院核物理与化学研究所 | A kind of method of modifying of inorganic nano-particle |
| CN115594887A (en) * | 2022-12-13 | 2023-01-13 | 广东粤港澳大湾区黄埔材料研究院（Cn） | Preparation method of modified carbon nanotube and application of modified carbon nanotube in tire tread rubber |
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