CN1246218C - Carbon nanometer tube with initiating group on surface and its preparation method - Google Patents
Carbon nanometer tube with initiating group on surface and its preparation method Download PDFInfo
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- CN1246218C CN1246218C CN 200310108932 CN200310108932A CN1246218C CN 1246218 C CN1246218 C CN 1246218C CN 200310108932 CN200310108932 CN 200310108932 CN 200310108932 A CN200310108932 A CN 200310108932A CN 1246218 C CN1246218 C CN 1246218C
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Abstract
The present invention relates to a carbon nanotube with initiating groups on the surface, and a preparation method thereof. The method comprises the steps as follows: acidifying and acidylating a carbon nanotube, and making the carbon nanotube to react with polyalcohol or polyamine so as to carry about hydroxy or amino on the surface of the carbon nanotube; making the carbon nanotube to react with alpha-halogen acyl halide to prepare a carbon nanotube with initiating groups on the surface. The prepared carbon nanotube has good activity, and can initiate the reaction of in-situ polymerization in a monomer body or a solution, and thus, the prepared carbon nanotube can be used as important raw material for preparing various carbon nanotubes with in-situ forming graft polymers; the prepared carbon nanotube can conveniently realize the structure design of a polymer on the surface of the carbon nanotube so as to prepare various carbon nanotubes with special structure and performance and related nanometer components.
Description
Technical field: the present invention relates to a kind of preparation method of functionalized carbon nano-tube, particularly the surface has carbon nanotube of initiating group and preparation method thereof.
Background technology: carbon nanotube (Cabon Nanotube is called for short CNT) is just found a kind of novel carbon structure in 1991, is the body that is rolled into by the Graphene lamella that carbon atom forms.Carbon nanotube be divided into Single Walled Carbon Nanotube (Single-wall Nanotube, SWNT) and multi-walled carbon nano-tubes (Multi-wall Nanotube, MWNT).Its preparation method mainly contains catalyse pyrolysis, arc-over, template and laser evaporation etc.
Because diameter is very little, length-to-diameter ratio is big, carbon nanotube is regarded as quasi-one-dimensional nanometer material.Confirmed now that carbon nanotube has peculiar electric property, superpower mechanical property, good adsorption property, thereby caused very big attention in the material field.The transistor and the indicating meter that have now had carbon nanotube to make come out.
Along with the development of nano science and technology, various carbon nanotubes with specified property cause people's interest gradually.The acid treatment that people such as Richard E.Smalley scrutinized carbon nanotube in 1998, obtained the products distribution situation under the different treatment condition, this has laid good basis (Science, 1998,280 (22): 1253-1255) for further studying later on.Afterwards, various modified carbon nano-tubes and composite structure thereof are produced out.Such as carbon nanotube with solvent solubility, have carbon nano tube device of molecular detection function or the like.
On the other hand, Sawamoto and Matyjaszewski have almost simultaneously found that independently transition metal-catalyzed " activity " controllable free-radical polymerisation of a kind of usefulness is atom transfer radical polymerization (ATRP).This method becomes the research focus of polymer chemistry in the world soon, and is described as " the recent studies on method of 21 century ".This method is to the control of target product with keep and be better than traditional polymerization greatly aspect the lower molecular weight distributing index, also avoided in the traditional method the harsh requirement to the polymerization environment.Simultaneously, because the popularity of initiator, especially, can in product, introduce functional group easily, also can synthesize multiple block polymer with the participation of the initiator of functional group.
Along with science and technology development, have the nanostructure of unique texture and function and the attention that nano-device has obtained people gradually, the annual report that a large amount of this respects are all arranged.Utilize perfect structure of carbon nanotube and excellent performance, exploitation is that the nanostructure and the nano-device of matrix just seems particularly necessary with the carbon nanotube.Utilize the advantage of ATRP method, the combined carbon nanotube just can synthesize various carbon nano tube devices with ad hoc structure, and the application that this can expand above method and material greatly promotes the development of this science and technical field.
Summary of the invention: the objective of the invention is to pass through chemical reaction, make the compound that has initiating group be connected to carbon nano tube surface, preparation surface has the carbon nanotube of initiating group, thereby can cause reaction such as atom transfer radical polymerization, satisfies the needs in different application field.
Technical scheme of the present invention is as follows:
By molecular designing,, with the reaction of alpha-halogen carboxylic acid halides, obtain the carbon nanotube that the surface has initiating group again with making its surface be with hydroxyl or amido with polyvalent alcohol or polyamine reaction after carbon nanotube acidifying and the acidylate.
The concrete preparation method of carbon nanotube that surface of the present invention has initiating group is as follows:
Step (a): 1 weight part exsiccant carbon nanometer tube material and 0.1～100 weight part acid with strong oxidizing property, behind 0～100kHz ultrasonication, 0.1～100hr, be heated to 20～200 ℃, reaction 0.5～100hr, with the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube behind 0～180 ℃ of vacuum-drying 10～30hr;
Step (b): add step (a) gained acidifying carbon nanotube 1 weight part and acylating agent 1～100 weight part, behind 0～100kHz ultrasonication, 10～1000min, be heated to 20～200 ℃, reaction 0.5～100hr down stirs and refluxes, suction filtration and repetitive scrubbing are removed acylating agent, obtain acylated carbon nano-tube;
Step (c): add step (b) gained acidylate carbon nanotube 1 weight part and polyvalent alcohol or polyamine 1～50 weight part, sealing, take out inflated with nitrogen repeatedly three times, behind 0～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has hydroxyl or amido;
Step (d): add carbon nanotube 1 weight part and alpha-halogen carboxylic acid halides 1～50 weight part that step (c) gained surface has hydroxyl or amido, sealing, take out inflated with nitrogen repeatedly three times, behind 0～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is after the washing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has the needed initiating group of radical living polymerization.
Used carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template or the preparation of laser evaporation method in the inventive method step (a).
The used acid with strong oxidizing property of the inventive method step (a) is selected from 0.1～70% weight acid concentration nitric acid, 0.1～100% weight acid concentration 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 mixed solution, 1/100～100/1 mol ratio potassium permanganate and hydrochloric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 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.
Used acylating agent is selected from phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide in the inventive method step (b).
Polyvalent alcohol or polyamine used in the inventive method step (c) are selected from ethylene glycol, quadrol, glycerol, third triamine, 1, the 2-propylene glycol, 1,2-propylene diamine, 1, ammediol, 1,3-propylene diamine, 1,4-butyleneglycol, 1,4-butanediamine, 1,2-butyleneglycol, 1,2-butanediamine, 1,3 butylene glycol, 1,3-butanediamine, trihydroxybutane, fourth triamine, polyoxyethylene glycol or polyethyene diamine.
Used alpha-halogen carboxylic acid halides is selected from alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride or alpha-chloro propionyl chloride in the inventive method step (d).
Do not use solvent among the inventive method step (c), (d) or with dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine, dimethylamino pyridine are that solvent or the mixed solvent that contains these solvents are reaction medium.
Carbon nanotube provided by the invention has good activity, can in monomer body or solution, cause home position polymerization reaction, thereby prepare the carbon nanotube that multiple original position generates polymer graft as important material, and can realize the polymer architecture design in carbon nano tube surface easily, thereby obtain various carbon nanotube and relevant nano-devices, have a wide range of applications with special construction and performance.
Description of drawings:
Fig. 1: the surface has the heat decomposition curve of the carbon nanotube of initiating group
Fig. 2: polymethylmethacrylate grafted carbon nanotube
1H NMR figure
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: the multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is initial raw material, and is acidified, after the acidylate, connects ethylene glycol, with alpha-brominated isobutyryl bromine reaction, obtains the carbon nanotube that the surface has initiating group again.Step (a): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add 2g exsiccant carbon nanometer tube material and 20mL 60% weight acid concentration concentrated nitric acid, behind 40kHz ultrasonication 30min, be heated to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain the acidifying carbon nanotube behind 80 ℃ of vacuum-drying 24hr with the deionized water repetitive scrubbing;
Step (b): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add step (a) gained acidifying carbon nanotube 1.5g and thionyl chloride 8g, behind 40kHz ultrasonication 30min, be heated to 60 ℃, reaction 24hr down stirs and refluxes, suction filtration and repetitive scrubbing are removed thionyl chloride, obtain acylated carbon nano-tube;
Step (c): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add step (b) gained acidylate carbon nanotube 1.3g and ethylene glycol 25g, seal with the turned welt soft rubber ball, take out inflated with nitrogen repeatedly three times, behind 40kHz ultrasonication 30min, react 24hr down at 100 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, with behind the deionized water wash, 80 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has hydroxyl repeatedly;
Step (d): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, adding step (c) gained surface has the carbon nanotube 1.1g and the alpha-brominated isobutyl acylbromide 1g of hydroxyl, seal with the turned welt soft rubber ball, take out inflated with nitrogen repeatedly three times, behind 40kHz ultrasonication 30min, at 20 times reaction 1～20hr, suction filtration is removed unreacted reactant and byproduct of reaction, with behind the deionized water wash, 80 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has initiating group repeatedly.
Fig. 1 is the surperficial heat decomposition curve that has the carbon nanotube of initiating group, and two steps are respectively the decomposition (600 ℃) of initiating group (300 ℃) and carbon nanotube itself.
Embodiment 2: have the carbon nanotube of initiating group with the surface of embodiment 1 preparation, be raw material, with atom transition free radical polymerization reaction grafting polymethylmethacrylate (PMMA).
Step: in the single neck round-bottomed flask of the 50mL that the magnetic agitation rotor is housed, add 0.6g CuBr, 0.7g part PMDETA (pentamethyl--diethyl triamine), the surface that adds embodiment 1 gained again has the carbon nanotube 1g of initiating group, and solvent DMF 10mL fills N after the sealing
210min adds methyl methacrylate monomer 10mL, continues inflated with nitrogen 10min, react 20hr down at 100 ℃, after viscosity was significantly increased, stopped reaction was after the chloroform dilution, suction filtration, washing is removed unreacted monomer and catalyzer etc., 80 ℃ of vacuum-dryings, obtain polymethylmethacrylate grafted carbon nanotube, obtain material 2.8g;
Fig. 2 is a polymethylmethacrylate grafted carbon nanotube
1H NMR figure, the corresponding result of characteristic peak as shown in the figure.
Claims (7)
1. the surface has the preparation method of the carbon nanotube of initiating group, it is characterized in that concrete preparation method is as follows:
Step (a): 1 weight part exsiccant carbon nanometer tube material and 0.1～100 weight part acid with strong oxidizing property, behind 0～100kHz ultrasonication, 0.1～100hr, be heated to 20～200 ℃, reaction 0.5～100hr, with the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube behind 0～180 ℃ of vacuum-drying 10～30hr;
Step (b): add step (a) gained acidifying carbon nanotube 1 weight part and acylating agent 1～100 weight part, behind 0～100kHz ultrasonication, 10～1000min, be heated to 20～200 ℃, reaction 0.5～100hr down stirs and refluxes, suction filtration and repetitive scrubbing are removed acylating agent, obtain acylated carbon nano-tube;
Step (c): add step (b) gained acidylate carbon nanotube 1 weight part and polyvalent alcohol or polyamine 1～50 weight part, sealing, take out inflated with nitrogen repeatedly three times, behind 0～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has hydroxyl or amido;
Step (d): add carbon nanotube 1 weight part and alpha-halogen carboxylic acid halides 1～50 weight part that step (c) gained surface has hydroxyl or amido, sealing, take out inflated with nitrogen repeatedly three times, behind 0～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is after the washing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has the needed initiating group of radical living polymerization.
2. surface according to claim 1 has the preparation method of the carbon nanotube of initiating group, it is characterized in that carbon nanotube used in the step (a) is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template or the preparation of laser evaporation method.
3. surface according to claim 1 has the preparation method of the carbon nanotube of initiating group, it is characterized in that the used acid with strong oxidizing property of step (a) is selected from 0.1～70% weight acid concentration nitric acid, 0.1～100% weight acid concentration 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 mixed solution, 1/100～100/1 mol ratio potassium permanganate and hydrochloric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 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.
4. surface according to claim 1 has the preparation method of the carbon nanotube of initiating group, it is characterized in that used acylating agent is selected from phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide in the step (b).
5. surface according to claim 1 has the preparation method of the carbon nanotube of initiating group, it is characterized in that polyvalent alcohol used in the step (c) or polyamine are selected from ethylene glycol, quadrol, glycerol, third triamine, 1,2-propylene glycol, 1,2-propylene diamine, 1, ammediol, 1,3-propylene diamine, 1,4-butyleneglycol, 1,4-butanediamine, 1,2-butyleneglycol, 1,2-butanediamine, 1,3-butyleneglycol, 1,3-butanediamine, trihydroxybutane, fourth triamine, polyoxyethylene glycol or polyethyene diamine.
6. surface according to claim 1 has the preparation method of the carbon nanotube of initiating group, it is characterized in that used alpha-halogen carboxylic acid halides is selected from alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride or alpha-chloro propionyl chloride in the step (d).
7. surface according to claim 1 has the preparation method of the carbon nanotube of initiating group, it is characterized in that not using among step (c), (d) solvent or with dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine or dimethylamino pyridine are that solvent or the mixed solvent that contains these solvents are reaction medium.
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| CN100357346C (en) * | 2006-03-14 | 2007-12-26 | 同济大学 | Process for preparing multifunctional carbon nanotube for epoxy resin nano composites |
| CN101104668B (en) * | 2006-07-12 | 2010-12-01 | 同济大学 | Method for preparing functional carbon nano-tube and application thereof |
| CN101104512B (en) * | 2006-07-14 | 2010-12-08 | 同济大学 | Method for preparing macromolecule modified carbon nano-tube and application thereof |
| CN101104511B (en) * | 2006-07-14 | 2010-12-08 | 同济大学 | Method for preparing functional carbon nano-tube and application thereof |
| CN100439241C (en) * | 2006-08-25 | 2008-12-03 | 昆明贵金属研究所 | Preparation method of mercapto carbon nanometer pipe |
| CN101394712B (en) | 2007-09-21 | 2010-08-25 | 清华大学 | Hole blackening solution and preparation thereof |
| TWI408003B (en) * | 2007-09-28 | 2013-09-11 | Hon Hai Prec Ind Co Ltd | Solution for preparing the through hole walls for electroplating and method of making the same |
| CN103626152B (en) * | 2013-11-27 | 2015-02-11 | 广东电网公司电力科学研究院 | Modification method of carbon nano tube |
| CN106587013B (en) * | 2016-12-06 | 2019-03-01 | 江南大学 | A kind of switching mode Carbon nano-tube dispersant |
| CN107197543A (en) * | 2017-05-31 | 2017-09-22 | 华东师范大学 | A kind of preparation method of the low dimensional nano-sized carbon electric heating film of Nano Silver surface modification |
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