CN1546545A - Multi-carboxyl polymer grafted water-soluble carbon nanometer tube and preparation method thereof - Google Patents
Multi-carboxyl polymer grafted water-soluble carbon nanometer tube and preparation method thereof Download PDFInfo
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Abstract
The invention provides an in-situ process for preparing multi-carboxyl polymer grafted water-soluble carbon nanometer tube which comprises, processing the carbon tubes to obtain the surface with initiation group, then employing atom transfer free radical polymerization reaction to ignite (methyl) butyl acrylate monomer polarization, carrying out hydrolysis processing to poly (methyl) butyl acrylate, removing butyl and preparing carboxyl group, which becomes water-soluble poly (methyl) acroleic acid, through which multi-carboxyl polymer grafted water-soluble carbon nanometer tube is obtained.
Description
Technical field: the present invention relates to a kind of preparation method of water-soluble carbon nanometer tube, particularly more carboxyl polymer grafted water-soluble carbon nanometer tube 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 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 utilize methods such as atom transfer radical polymerization by molecular designing, preparation more carboxyl polymer grafted water-soluble carbon nanometer tube satisfies the needs in different application field.
Technical scheme of the present invention is as follows:
By molecular designing, carbon nano tube surface is handled, make it to have the required active group of ATRP polyreaction, thereby can cause the polymerization that contains double bond monomer; At first in the presence of catalyzer and part, cause the special butyl ester monomer polymerization of (methyl) vinylformic acid, gathered the special butyl ester grafted of (methyl) vinylformic acid carbon nanotube with atom transition free radical polymerization reaction; To gather the special butyl ester grafted of (methyl) vinylformic acid carbon nanotube, then in the presence of catalyzer to the processing that is hydrolyzed of the special butyl ester of poly-(methyl) vinylformic acid, make it to slough tertiary butyl, generate carboxyl, thereby become water miscible poly-(methyl) vinylformic acid, then obtain more carboxyl polymer grafted water-soluble carbon nanometer tube.
The concrete preparation method of more carboxyl polymer grafted water-soluble carbon nanometer tube of the present invention is as follows:
Step (a): 1 weight part exsiccant carbon nanometer tube material and 0.1～100 weight part acid with strong oxidizing property, with 0～100kHz ultrasonication, 0.1～100hr post-heating to 20～200 ℃, reaction 0.5～100hr, use 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 initiating group;
Step (e): add 0.01～1 weight part catalyzer, 0.01～5 weight part part, the surface that adds step (d) gained again has carbon nanotube 1 weight part of initiating group, and solvent 0～50 weight part fills Ar or N after the sealing
21～100min, add the special butyl ester monomer of (methyl) vinylformic acid 0.01～80 weight part, continue inflated with nitrogen or argon gas 1～100min, react 0.01～1000hr down at 0～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in poor solvent, and the gained precipitation heavily is dissolved in good solvent, suction filtration, washing, 0～180 ℃ of vacuum-drying is gathered the special butyl ester grafted of (methyl) vinylformic acid carbon nanotube;
Step (f): add the special butyl ester grafted of poly-(methyl) vinylformic acid of step (e) gained carbon nanotube 1 weight part, solvent 0.01～100 weight part, catalyzer 0.01～100 weight part, airtight back is reacted 0.01～1000hr down at 0～100 ℃, solvent and catalyzer are removed, obtained more carboxyl polymer grafted water-soluble carbon nanometer tube.
Used carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template and 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) comprises 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, 1/100～100/1 mol ratio H
2O
2With the nitric acid mixing solutions.
Used acylating agent comprises phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide, thionyl bromide in the inventive method step (b).
Polyvalent alcohol or polyamine material used in the inventive method step (c) comprise 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, polyethyene diamine.
Used alpha-halogen carboxylic acid halides comprises alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride, 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.
Catalyst system therefor is the metallic compound that contains Cu (I), Fe (II), Mo (V), Re (V), Ru (II), Ni (I), Pb (II) such as cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, ReO in the inventive method step (e)
2I (PPh
3)
2, RuCl
2, Ni (NCN) Br, Pd (OAc)
2Used part is 2-dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine, tri-n-butyl phosphine; Solvent for use is dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or contain the mixture of these solvents.
Be that solvent or the mixed solvent that contains these solvents are reaction medium with water, methyl alcohol, ethanol, methylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine, dimethylamino pyridine in the inventive method step (f); With hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, trifluoroacetic acid and composition thereof as catalyzer.
Preparation method provided by the invention is simple, and controllability is strong; Gained more carboxyl polymer grafted water-soluble carbon nanometer tube shows good solubility owing to have a large amount of wetting ability carboxylic groups in water; This solvability has been improved the workability of carbon nanotube greatly, can be used as the specialist additive of water-soluble high-molecular material; Owing to its nano level size, can be used as the nano-device of specific function simultaneously, construct specific quantum structure; Also can be used as the carrier of material transfer and transfer between different system, realize specific purpose; Thereby have purposes widely at nano science, Materials science and biomedical aspects, wide application prospect is arranged.
Description of drawings:
Fig. 1: more carboxyl polymer grafted water-soluble carbon nanometer tube
1H NMR spectrogram
Fig. 2: more carboxyl polymer grafted water-soluble carbon nanometer tube infrared spectrum
Fig. 3: the solvability photo of more carboxyl polymer grafted water-soluble carbon nanometer tube in water and chloroform
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 an initial raw material; acidified; after the acidylate, connect ethylene glycol, again with alpha-brominated isobutyryl bromine reaction; with the special butyl ester PtBA of ATRP method grafted polyacrylic acid); then in the presence of catalyzer to processings that be hydrolyzed of the special butyl ester of polyacrylic acid, make it to slough tertiary butyl, the generation carboxyl; thereby become water miscible polyacrylic acid, then obtain more carboxyl polymer grafted water-soluble carbon nanometer tube.
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 ratio concentration concentrated nitric acid, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain 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;
Step (e): 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 step (d) gained again has the carbon nanotube 1g of initiating group, and solvent DMF 10mL fills N after the sealing
210min adds the special butyl ester monomer of vinylformic acid 10mL, continues to fill N
210min reacts 20hr down at 100 ℃, after viscosity is significantly increased, and stopped reaction, after the chloroform dilution, suction filtration, unreacted monomer and catalyzer etc. are removed in washing, and 80 ℃ of vacuum-dryings obtain the special butyl ester grafted of polyacrylic acid carbon nanotube, obtain material 2.8g;
Step (f): add the special butyl ester grafted of step (e) gained polyacrylic acid carbon nanotube 1g, methylene dichloride 10mL, CF
3COOH 0.5g, airtight after stirring reaction 24hr at room temperature, wait the generation post precipitation, solvent and catalyzer are removed, obtain more carboxyl polymer grafted water-soluble carbon nanometer tube 0.7g.
Fig. 1 has provided product more carboxyl polymer grafted water-soluble carbon nanometer tube
1H NMR spectrogram, main polymer chain (CH
2-: δ=2.7～2.9ppm;-CH-: δ=2.0～2.3ppm) and reactive hydrogen (proof of COOH: δ=9.1～9.4ppm) polyacrylic structure.The infrared spectrum of product (Fig. 2) has clearly proved carbonyl (～1730cm
-1) and reactive hydrogen (3200～3700cm
-1).Fig. 3 has provided the solvability photo of product more carboxyl polymer grafted water-soluble carbon nanometer tube in water and chloroform, can find out intuitively that from figure product can well dissolve in water and disperse, and can not dissolve in organic solvent.
Claims (10)
1. more carboxyl polymer grafted water-soluble carbon nanometer tube and preparation method thereof 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, with 0～100kHz ultrasonication, 0.1～100hr post-heating 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 initiating group;
Step (e): add 0.01～1 weight part catalyzer, 0.01～5 weight part part, the surface that adds step (d) gained again has carbon nanotube 1 weight part of initiating group, and solvent 0～50 weight part fills Ar or N after the sealing
21～100min, add the special butyl ester monomer of (methyl) vinylformic acid 0.01～80 weight part, continue inflated with nitrogen or argon gas 1～100min, react 0.01～1000hr down at 0～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in poor solvent, and the gained precipitation heavily is dissolved in good solvent, suction filtration, washing, 0～180 ℃ of vacuum-drying is gathered the special butyl ester grafted of (methyl) vinylformic acid carbon nanotube;
Step (f): add the special butyl ester grafted of poly-(methyl) vinylformic acid of step (e) gained carbon nanotube 1 weight part, solvent 0.01～100 weight part, catalyzer 0.01～100 weight part, airtight back is reacted 0.01～1000hr down at 0～100 ℃, solvent and catalyzer are removed, obtained more carboxyl polymer grafted water-soluble carbon nanometer tube.
2. more carboxyl polymer grafted water-soluble carbon nanometer tube according to claim 1 and preparation method thereof 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 and the preparation of laser evaporation method.
3. more carboxyl polymer grafted water-soluble carbon nanometer tube according to claim 1 and preparation method thereof is characterized in that the used acid with strong oxidizing property of step (a) comprises nitric acid, sulfuric acid, nitric acid and sulfuric acid mixing acid, is added with potassium permanganate or H in addition
2O
2Hydrochloric acid, nitric acid, sulfuric acid and mixing acid thereof.
4. more carboxyl polymer grafted water-soluble carbon nanometer tube according to claim 1 and preparation method thereof is characterized in that used acylating agent comprises phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide, thionyl bromide in the step (b).
5. more carboxyl polymer grafted water-soluble carbon nanometer tube according to claim 1 and preparation method thereof, it is characterized in that polyvalent alcohol used in the step (c) or polyamine material comprise 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-butyleneglycol, 1,3-butanediamine, trihydroxybutane, fourth triamine, polyoxyethylene glycol, polyethyene diamine.
6. more carboxyl polymer grafted water-soluble carbon nanometer tube according to claim 1 and preparation method thereof is characterized in that used alpha-halogen carboxylic acid halides comprises alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride, alpha-chloro propionyl chloride in the step (d).
7. more carboxyl polymer grafted water-soluble carbon nanometer tube according to claim 1 and preparation method thereof, 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, dimethylamino pyridine are that solvent or the mixed solvent that contains these solvents are reaction medium.
8. more carboxyl polymer grafted water-soluble carbon nanometer tube according to claim 1 and preparation method thereof is characterized in that catalyst system therefor in the step (e) is the metallic compound that contains Cu (I), Fe (II), Mo (V), Re (V), Ru (II), Ni (I), Pb (II) such as cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, ReO
2I (PPh
3)
2, RuCl
2, Ni (NCN) Br, Pd (OAc)
2Used part is 2-dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine, tri-n-butyl phosphine; Solvent for use is dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or contain the mixture of these solvents.
9. more carboxyl polymer grafted water-soluble carbon nanometer tube according to claim 1 and preparation method thereof is characterized in that in the step (f) with water, methyl alcohol, ethanol, methylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine, dimethylamino pyridine being that solvent or the mixed solvent that contains these solvents are reaction medium; With hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, trifluoroacetic acid and composition thereof as catalyzer.
10. more carboxyl polymer grafted water-soluble carbon nanometer tube is characterized in that the more carboxyl polymer grafted water-soluble carbon nanometer tube that adopts the described preparation method of claim 1-9 to obtain.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100395274C (en) * | 2006-04-25 | 2008-06-18 | 东华大学 | Prepn process of carbon nanotube epoxy resin curing agent |
| CN101461944B (en) * | 2009-01-09 | 2011-05-04 | 复旦大学附属华山医院 | Magnetic polyacrylic acid modified carbon nano-tube medicament carrier |
| CN102675802A (en) * | 2011-12-22 | 2012-09-19 | 河南科技大学 | Modified carbon nanotube-reinforced polydicyclopentadiene compound material and method for preparing same |
| CN102942708A (en) * | 2012-11-26 | 2013-02-27 | 东南大学 | Preparation method for medical polypropylene material with hydrophilic surface |
| CN103173041A (en) * | 2013-03-08 | 2013-06-26 | 北京化工大学 | Method for making core-shell polyhedral oligomeric silsesquioxane (POSS) coated multi-walled carbon nanotube (MWNT) |
| CN109179379A (en) * | 2018-11-01 | 2019-01-11 | 中山大学 | A kind of Specific surface area carbon material and its preparation method and application with carbon nanotube core@amorphous carbon shell unit |
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2003
- 2003-12-04 CN CN 200310109072 patent/CN1234746C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100395274C (en) * | 2006-04-25 | 2008-06-18 | 东华大学 | Prepn process of carbon nanotube epoxy resin curing agent |
| CN101461944B (en) * | 2009-01-09 | 2011-05-04 | 复旦大学附属华山医院 | Magnetic polyacrylic acid modified carbon nano-tube medicament carrier |
| CN102675802A (en) * | 2011-12-22 | 2012-09-19 | 河南科技大学 | Modified carbon nanotube-reinforced polydicyclopentadiene compound material and method for preparing same |
| CN102942708A (en) * | 2012-11-26 | 2013-02-27 | 东南大学 | Preparation method for medical polypropylene material with hydrophilic surface |
| CN103173041A (en) * | 2013-03-08 | 2013-06-26 | 北京化工大学 | Method for making core-shell polyhedral oligomeric silsesquioxane (POSS) coated multi-walled carbon nanotube (MWNT) |
| CN103173041B (en) * | 2013-03-08 | 2014-06-04 | 北京化工大学 | Method for making core-shell polyhedral oligomeric silsesquioxane (POSS) coated multi-walled carbon nanotube (MWNT) |
| CN109179379A (en) * | 2018-11-01 | 2019-01-11 | 中山大学 | A kind of Specific surface area carbon material and its preparation method and application with carbon nanotube core@amorphous carbon shell unit |
| CN109179379B (en) * | 2018-11-01 | 2021-11-30 | 中山大学 | Carbon material with nano-network structure and carbon nanotube core @ functional amorphous carbon shell unit, and preparation method and application thereof |
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