CN103350993A - Method for chemical modification of carbon nano-tubes - Google Patents
Method for chemical modification of carbon nano-tubes Download PDFInfo
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- CN103350993A CN103350993A CN2013101517504A CN201310151750A CN103350993A CN 103350993 A CN103350993 A CN 103350993A CN 2013101517504 A CN2013101517504 A CN 2013101517504A CN 201310151750 A CN201310151750 A CN 201310151750A CN 103350993 A CN103350993 A CN 103350993A
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Abstract
The invention provides a method for chemical modification of carbon nano-tubes. The method comprises the following steps: adding carbon nano-tubes to a mixing solution comprising an alkali and a surfactant, carrying out a reaction at a temperature of 100-300 DEG C, and purifying. The method has characteristics of simple and reliable process, mild reaction conditions, easy operation, low cost, clear preparation process mechanism and good repeatability.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of method of carbon nanometer tube with chemical decoration, more specifically relate to a kind of method of utilizing hydrothermal method to carry out simply, quickly carbon nanometer tube with chemical decoration.
Background technology
1991, when Iijima utilizes the formed cathode deposit of electron microscope observation graphic discharge, the multi-walled carbon nano-tubes that found diameter 4～30nm, reach micron dimension, tube wall presents graphite-structure has worldwide started the research boom of one carbon nanotube immediately.Along with the character of carbon nanotube is slowly understood by common people, its various advantageous properties are found one by one, have caused immediately the great attention of science all circles.
Carbon nanotube has many premium propertiess, but it is dissolved in any solvent hardly; Simultaneously, because it has huge surface energy, very easily reunites, hindered it has been carried out Molecular level study and operational applications, also be difficult to include it in the bio-medical system, therefore greatly limited carbon nanotube application in every respect.It is water-soluble carbon nanometer tube that carbon nanotube is carried out chemically modified, makes it to dissolve or to be dispersed in solvent especially in the water, has become a requisite step that it is applied to the bio-medical field.
Existing method to carbon nano tube chemical decoration mainly comprises two kinds of physical adsorption method and chemical bonding methods.
The physical adsorption method makes the carbon nanotube acquisition water-soluble thereby namely utilize soluble substance to be adsorbed on carbon nano tube surface formation self-assembled structures, such as encapsulated dye on carbon nanotube (Yu Haihu etc., Chinese Journal of Chemical Physics, 2005; 18 (6): 1039; Hu CG, et al., Electrochem.Commun., 2007; 128), polyacrylic acid (Liu AH, et al., Biosens.Bioelectron., 2,006 9 (1):; 22 (5): 694; Nanotechnology, 2006; 2845), polyoxyethylene glycol (Nakayama-Ratchford N, et al., J.Am.Chem.Soc., 2,007 17 (12):; 2448) etc. 129 (9): obtain water miscible carbon nanotube.Chinese invention patent ZL200410064123.8 is wrapped in the self-assembled materials such as upper layer protein or upper layer protein subunit on the carbon nanotube, has obtained water-soluble carbon nanometer tube.But the relative method of chemical bonding, stable, the destroyed not risk of self-assembled structures is larger, might lose after self-assembled structures is destroyed in application process that it is water-soluble.
The chemical bonding method makes the carbon nanotube acquisition water-soluble thereby namely connect the solubility group with covalent linkage on carbon nanotube, as connecting with carboxyl (Arrais A et al., Fuller.Nanotub.Carbon Nanostruct., 2004 at carbon nanotube; 12 (4): 789; Yu HH, et al., Sens.Actuator B-Chem., 2006; 119 (2): 512; Guo Lihua etc., chemical journal 2005; 63 (20): 1936; Miller AJ, et al.Appl.Phys.Lett., 2006; 89 (12)), amino (Lacerda L, et al., Adv.Funct.Mater., 2006; 16 (14): 1839; Isobe H, et al., Angew.Chem.-Int.Edit., 2006; 6676), sulfonic group (Zhao B, et al., J.Am.Chem.Soc., 2,005 45 (40):; 8197) 127 (22): material or polyoxyethylene glycol (Chattopadhyay J, et al., Chem.Mat., 2006 of group such as; 18 (25): 5864; Sun YP, et al., Chem.Mat., 2001; 13 (9): 2864; Della Negra F, et al., Fuller.Nanotub.Carbon Nanostruct., 2003; 25), polypropylene amine (Kim JB, et al., Macromol.Rapid Commun., 2,007 11 (1):; 276), polyvinyl alcohol (Paiva MC, et al., Carbon2004 28 (3):; 2849) even albumen (Fu KF, et al., J.Nanosci.Nanotechnol., 2,002 42 (14):; 2 (5): 457; Huang WJ et al., Nano Lett., 2002; 311), enzyme (Asuri P, et al., Biotechnol.Bioeng., 2,006 2 (4):; 804), Phosphorylcholine (Zhang T.et al., Carbon, 2,008 95 (5):; 46 (13): 1782-1791; Zhang T.et al., Chin.Chem.Lett., 2008,19 (1): 105-109) etc.Chinese patent 02104528.3 discloses the carbon nanotube after purifying and the chloride and the primary amine that contains polyglycol ether or secondary amine reaction, obtains water-soluble carbon nanometer tube.Chinese patent ZL200310109072.1 discloses and will make its surface with specific initiating group after the carbon nanotube processing, then cause (methyl) tert-butyl acrylic ester monomer polymerization with atom transition free radical polymerization reaction, again to the processing that is hydrolyzed of poly-(methyl) tert-butyl acrylic ester, make it to slough tertiary butyl, generate carboxyl, thereby become water miscible poly-(methyl) vinylformic acid, obtain the water-soluble carbon nanometer tube of more carboxyl polymer grafting.Chinese patent ZL200310121617.0 discloses and will make its surface with specific initiating group after the carbon nanotube processing, then contain two key responsive to temperature type polymerisation with the atom transition free radical polymerization reaction initiation, obtain Temperatur esensitire type water soluble carbon nano pipe.Chinese patent ZL200310121619.X discloses and will make its surface with specific initiating group after the carbon nanotube processing, then cause vinylbenzenesulfonic acid sodium monomer polymerization with atom transition free radical polymerization reaction, obtain the water-soluble carbon nanometer tube of poly-sulfonated phenylethylene grafting.Above patented method all is to connect at carbon nanotube to have water miscible polymer segment to give carbon nanotube water-soluble.Chinese patent ZL200510016888.9 discloses behind the carbon nanotube of acidifying purifying and chloride, by chemically modified Methionin is grafted on carbon nanotube tube wall and the port, thereby gives carbon nanotube high water soluble and biocompatibility.Chinese patent ZL200710023165.0 discloses in the carbon nano tube surface grafting Phosphorylcholine structure and has made it have water-soluble and have good biocompatibility.Above-mentioned chemical bonding method has adopted acidulated condition to make the irregularity structure oxidation of carbon nano tube surface obtain carboxylic group before carrying out various chemically modifieds more, further modifies take carboxylic group as starting point again.Its building-up process need to use strong acid (sulfuric acid, nitric acid) and heat, ultrasonic etc., danger is larger in the process, and spent acid also causes serious environmental pollution, building-up process is also more loaded down with trivial details.
(Imasaka K, et al., Nanotechnology, 2006 such as Imasaka; 17 (14): 3421; Nanotechnology.2007; 18 (33): 7) reported with pulse streamer discharge and the plasma method of being connected and connect the method for hydroxyl group sites in carbon nano tube surface, but need to use special high voltage installation, still be difficult to realize and extensive popularization and application.
Summary of the invention
Goal of the invention: the method that the purpose of this invention is to provide a kind of simple to operate, carbon nanometer tube with chemical decoration that reaction conditions is gentle.
Technical scheme: the method for a kind of carbon nanometer tube with chemical decoration provided by the invention may further comprise the steps: carbon nanotube is added comprise in the mixing solutions of alkali and tensio-active agent, 100-300 ° of C reaction is behind the purifying and get final product.
As preferably, described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
Preferred as another kind, in the described mixing solutions, the weight percent concentration of alkali is 1% to its saturation concentration, and preferably its concentration is 1%-40%, and the weight percent concentration of tensio-active agent is 0.1%～5%, is preferably 1%～3%; The mass ratio of carbon nanotube and mixing solutions is 1:(200～280).
Preferred as another kind, described alkali is one or more the mixing in the oxyhydroxide of IA family basic metal and IIA family alkaline-earth metal in the periodic table of elements; Be preferably one or more the mixing in potassium hydroxide, sodium hydroxide, lithium hydroxide, magnesium hydroxide, the calcium hydroxide.
Preferred as another kind, described tensio-active agent is the composition of composition, cationic surfactant and the nonionic surface active agent of aniorfic surfactant, cats product, nonionic surface active agent, aniorfic surfactant and nonionic surface active agent.
Preferred as another kind, described anion surfactant is one or more in long chain alkyl sulfates, long-chain alkyl benzene sulfonate, chain alkyl carboxylate salt, sulfuric acid and the anionic polyacrylamide, is preferably one or more in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and the soap.
Preferred as another kind, described cats product is one or more in quaternary ammonium salt, fatty amine salt, polyethylene polyamine salt, heterocyclic cats product and the cationic polyacrylamide; One or more in cetyl trimethylammonium bromide, dodecyl alkyl trimethyl ammonium chloride, octadecyl dimethyl benzyl aliquat and the 2-alkylamino ethyl imidazol(e) quinoline preferably.
Preferred as another kind, described nonionogenic tenside is one or more among polyoxyethylene, glycerin fatty acid ester and the polyalcohols water soluble surfactant active, is preferably one or more in alkylphenol polyoxyethylene, high-carbon fatty alcohol polyoxyethylene ether, fatty acid methyl ester ethoxylate, sorbitan ester and the glyceryl monostearate.
Preferred as another kind, temperature of reaction is 180-250 ° of C, and the reaction times is 1-24 hour, is preferably 12-24 hour.
Preferred as another kind, purification step is: reaction solution is centrifugal, the gained washing of precipitate, be drying to obtain.
Preferred as another kind, after the carbon nanotube adding comprised the mixing solutions of alkali and tensio-active agent, supersound process made to mix.
Beneficial effect: method simple and reliable process, the reaction conditions of carbon nanometer tube with chemical decoration provided by the invention is gentle, easy to operate, with low cost, preparation process mechanism clear and definite, good reproducibility.
The carbon nanometer tube with chemical decoration that adopts method provided by the invention to make makes to connect the hydroxyl reaction site on the carbon nanotube, for condition has been created in the further modification of carbon nanotube.Utilize the hydroxyl reaction site that connects on the carbon nanotube, further Atom Transfer Radical Polymerization, with isocyanic ester, with carboxyl, further carbon nanotube is modified with the classical chemical reaction of acid chloride groups etc., thereby make hydroxyl become a site of carbon nanometer tube with chemical decoration.
Description of drawings
Fig. 1 is the x-ray photoelectron power spectrum of the hydroxylation carbon nanotube that makes of embodiment 1.
Fig. 2 is the thermogravimetric analysis figure of the hydroxylation carbon nanotube that makes of the embodiment of the invention 1 to 10.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described concrete material proportion of embodiment, processing condition and result thereof only are used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
Embodiment 1
Get the 0.1g multi-walled carbon nano-tubes, sodium hydroxide solution 20mL, adding cetyl trimethylammonium bromide and polyoxyethylene nonylphenol ether (OP-10) composition (1:1) with weight percent 10%, making its concentration is 1%, and mixing, supersound process got dispersion liquid with dispersing Nano carbon tubes in 10 minutes.
Pour dispersion liquid into 25mL with teflon-lined stainless steel autoclave, reaction 12 hours under 210 ° of C after the sealing, during the multiple oscillation reactor make that material fully mixes in the still.Reaction is cooled to room temperature after finishing.Product is through centrifugation, after deionized water is washed till filtrate PH=7, cleans the salt that adheres to removal for 2 times, tensio-active agent etc. with dehydrated alcohol again.Leach thing dry 4 hours of 60 ° of C in vacuum drying oven.Obtain the multi-wall carbon nano-tube pipe powder of the hydroxyl modified of black, thermogravimetic analysis (TGA) shows percentage of grafting 5.61%.
Embodiment 2
Identical with embodiment 1, but employed alkali is potassium hydroxide, can obtain percentage of grafting and be 5.45% multi-walled carbon nano-tubes.
Embodiment 3
Identical with embodiment 1, but employed carbon nanotube is Single Walled Carbon Nanotube, can obtain percentage of grafting and be 3.65% Single Walled Carbon Nanotube.
Embodiment 4
Identical with embodiment 1, but temperature of reaction is 180 ° of C, can obtain percentage of grafting and be 3.63% multi-walled carbon nano-tubes.Embodiment 5
Identical with embodiment 1, but the tensio-active agent that adopts is Sodium dodecylbenzene sulfonate (SDBS), can obtain percentage of grafting and be 5.83% multi-walled carbon nano-tubes.
Embodiment 6
Identical with embodiment 5, but the temperature of reaction that adopts is 250 ° of C, can obtain percentage of grafting and be 6.68% multi-walled carbon nano-tubes.
Embodiment 7
Identical with embodiment 6, be 40% potassium hydroxide solution but the alkali that adopts is mass percent concentration, can obtain percentage of grafting and be 5.22% multi-walled carbon nano-tubes.
Embodiment 8
Identical with embodiment 6, be 40% sodium hydroxide solution but the alkali that adopts is mass percent concentration, can obtain percentage of grafting and be 7.87% multi-walled carbon nano-tubes.
Embodiment 9
Identical with embodiment 8, but what adopt is to be 24 hours in the reaction times, can obtain percentage of grafting and be 8.65% multi-walled carbon nano-tubes.
Embodiment 10
Identical with embodiment 9, but adopt be the Pluronic F68 of concentration 2% as tensio-active agent, can obtain percentage of grafting and be 10.8% multi-walled carbon nano-tubes.
Embodiment 11
Get the 0.1g Single Walled Carbon Nanotube, add the mixing solutions 20mL of alkali and tensio-active agent, mixing, supersound process 10 minutes get dispersion liquid; Wherein, described alkali is lithium hydroxide, and described tensio-active agent is high-carbon fatty alcohol polyoxyethylene ether, and mixing solutions is the saturated solution of lithium hydroxide, and wherein the mass percent concentration of tensio-active agent is 0.1%.
Pour dispersion liquid into 25mL with teflon-lined stainless steel autoclave, reaction 24 hours under 100 ° of C after the sealing, during the multiple oscillation reactor make that material fully mixes in the still.Reaction is cooled to room temperature after finishing.Product is through centrifugation, after deionized water is washed till filtrate PH=7, cleans the salt that adheres to removal for 2 times, tensio-active agent etc. with dehydrated alcohol again; Leach thing dry 4 hours of 60 ° of C in vacuum drying oven.Obtain the Single Walled Carbon Nanotube powder of the hydroxyl modified of black, thermogravimetic analysis (TGA) shows percentage of grafting 5.55%.
Embodiment 12
Get the 0.1g multi-walled carbon nano-tubes, add the mixing solutions 20mL of alkali and tensio-active agent, mixing, supersound process 10 minutes get dispersion liquid; Wherein, described alkali is magnesium hydroxide, and described tensio-active agent is sodium lauryl sulphate, and the mass percent concentration of alkali is 1%, and the mass percent concentration of tensio-active agent is 3%.
Pour dispersion liquid into 25mL with teflon-lined stainless steel autoclave, reaction 1 hour under 300 ° of C after the sealing, during the multiple oscillation reactor make that material fully mixes in the still.Reaction is cooled to room temperature after finishing.Product is through centrifugation, after deionized water is washed till filtrate PH=7, cleans the salt that adheres to removal for 2 times, tensio-active agent etc. with dehydrated alcohol again; Leach thing dry 4 hours of 60 ° of C in vacuum drying oven.Obtain the multi-wall carbon nano-tube pipe powder of the hydroxyl modified of black, thermogravimetic analysis (TGA) shows percentage of grafting 7.62%.
Embodiment 13
Get the 0.1g multi-walled carbon nano-tubes, add the mixing solutions 20mL of alkali and tensio-active agent, mixing, supersound process 10 minutes get dispersion liquid; Wherein, described alkali is calcium hydroxide, and described tensio-active agent is the mixing of sodium lauryl sulphate and fatty acid methyl ester ethoxylate (2:1), and the mass percent concentration of alkali is 5%, and the mass percent concentration of tensio-active agent is 5%.
Pour dispersion liquid into 25mL with teflon-lined stainless steel autoclave, reaction 16 hours under 230 ° of C after the sealing, during the multiple oscillation reactor make that material fully mixes in the still.Reaction is cooled to room temperature after finishing.Product is through centrifugation, after deionized water is washed till filtrate PH=7, cleans the salt that adheres to removal for 2 times, tensio-active agent etc. with dehydrated alcohol again; Leach thing dry 4 hours of 60 ° of C in vacuum drying oven.Obtain the multi-wall carbon nano-tube pipe powder of the hydroxyl modified of black, thermogravimetic analysis (TGA) shows percentage of grafting 6.10%.
Embodiment 14
Substantially the same manner as Example 13, difference only is: the tensio-active agent that adopts is the mixing of sorbitan ester and glyceryl monostearate (1:1), can obtain percentage of grafting and be 6.85% multi-walled carbon nano-tubes.
Embodiment 15
Substantially the same manner as Example 13, difference only is: the tensio-active agent that adopts is the mixing of octadecyl dimethyl benzyl aliquat and 2-alkylamino ethyl imidazol(e) quinoline (1:2), can obtain percentage of grafting and be 7.29% multi-walled carbon nano-tubes.
Embodiment 16
Substantially the same manner as Example 13, difference only is: the tensio-active agent that adopts is soap, can obtain percentage of grafting and be 6.17% multi-walled carbon nano-tubes.
Claims (10)
1. the method for a carbon nanometer tube with chemical decoration is characterized in that: may further comprise the steps: carbon nanotube is added comprise in the mixing solutions of alkali and tensio-active agent, 100-300 ° of C reaction is behind the purifying and get final product.
2. the method for a kind of carbon nanometer tube with chemical decoration according to claim 1, it is characterized in that: described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
3. the method for a kind of carbon nanometer tube with chemical decoration according to claim 1 is characterized in that: in the described mixing solutions, the weight percent concentration of alkali is 1% to its saturation concentration, and the weight percent concentration of tensio-active agent is 0.1%～5%; The mass ratio of carbon nanotube and mixing solutions is 1:(200～280).
4. the method for a kind of carbon nanometer tube with chemical decoration according to claim 1 is characterized in that: described alkali is one or more the mixing in the oxyhydroxide of IA family basic metal and IIA family alkaline-earth metal in the periodic table of elements.
5. the method for a kind of carbon nanometer tube with chemical decoration according to claim 1, it is characterized in that: described tensio-active agent is the composition of composition, cationic surfactant and the nonionic surface active agent of aniorfic surfactant, cats product, nonionic surface active agent, aniorfic surfactant and nonionic surface active agent.
6. the method for a kind of carbon nanometer tube with chemical decoration according to claim 6, it is characterized in that: described anion surfactant is one or more in long chain alkyl sulfates, long-chain alkyl benzene sulfonate, chain alkyl carboxylate salt, sulfuric acid and the anionic polyacrylamide.
7. the method for a kind of carbon nanometer tube with chemical decoration according to claim 6, it is characterized in that: described cats product is one or more in quaternary ammonium salt, fatty amine salt, polyethylene polyamine salt, heterocyclic cats product and the cationic polyacrylamide.
8. the method for a kind of carbon nanometer tube with chemical decoration according to claim 1, it is characterized in that: described nonionogenic tenside is one or more among polyoxyethylene, glycerin fatty acid ester and the polyalcohols water soluble surfactant active.
9. the method for a kind of carbon nanometer tube with chemical decoration according to claim 1, it is characterized in that: temperature of reaction is 180-250 ° of C, and the reaction times is 1-24 hour, is preferably 12-24 hour.
10. the method for a kind of carbon nanometer tube with chemical decoration according to claim 1, it is characterized in that: purification step is: reaction solution is centrifugal, the gained washing of precipitate, be drying to obtain.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103754900A (en) * | 2014-01-17 | 2014-04-30 | 天津城建大学 | Preparation method and application of monodisperse magnesium hydroxide nanoparticles based on carbon nanotube carrier |
| CN114702059A (en) * | 2021-12-30 | 2022-07-05 | 南京大学 | Binary hydroxide nanotube with composite structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843904A (en) * | 2006-03-30 | 2006-10-11 | 复旦大学 | Method for conducting modification of surface hydroxy group of carbon nanotube |
| CN101049926A (en) * | 2007-05-15 | 2007-10-10 | 浙江大学 | Method for dispersing Nano carbon tubes |
| CN102180458A (en) * | 2011-03-25 | 2011-09-14 | 深圳市贝特瑞纳米科技有限公司 | Nano-carbon material dispersion liquid and preparation method and equipment thereof |
-
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- 2013-04-26 CN CN2013101517504A patent/CN103350993A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843904A (en) * | 2006-03-30 | 2006-10-11 | 复旦大学 | Method for conducting modification of surface hydroxy group of carbon nanotube |
| CN101049926A (en) * | 2007-05-15 | 2007-10-10 | 浙江大学 | Method for dispersing Nano carbon tubes |
| CN102180458A (en) * | 2011-03-25 | 2011-09-14 | 深圳市贝特瑞纳米科技有限公司 | Nano-carbon material dispersion liquid and preparation method and equipment thereof |
Non-Patent Citations (1)
| Title |
|---|
| 袁婕等: "表面活性剂分散碳纳米管的进展", 《化工时刊》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103754900A (en) * | 2014-01-17 | 2014-04-30 | 天津城建大学 | Preparation method and application of monodisperse magnesium hydroxide nanoparticles based on carbon nanotube carrier |
| CN103754900B (en) * | 2014-01-17 | 2015-08-12 | 天津城建大学 | A kind of single dispersing magnesium hydroxide nano-particle preparation method based on carbon nanotube carrier and application |
| CN114702059A (en) * | 2021-12-30 | 2022-07-05 | 南京大学 | Binary hydroxide nanotube with composite structure and preparation method thereof |
| CN114702059B (en) * | 2021-12-30 | 2023-06-06 | 南京大学 | Binary hydroxide nanotube with composite structure and preparation method thereof |
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Application publication date: 20131016 |