CN1232590C - Poly (methyl) tert-butyl acrylic ester grafted carbon nanometer tube and its preparation method - Google Patents
Poly (methyl) tert-butyl acrylic ester grafted carbon nanometer tube and its preparation method Download PDFInfo
- Publication number
- CN1232590C CN1232590C CN 200310109071 CN200310109071A CN1232590C CN 1232590 C CN1232590 C CN 1232590C CN 200310109071 CN200310109071 CN 200310109071 CN 200310109071 A CN200310109071 A CN 200310109071A CN 1232590 C CN1232590 C CN 1232590C
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- methyl
- poly
- preparation
- weight part
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention provides an in-situ generated poly (methyl) tert-butyl acrylic ester grafted carbon nano tube and a preparation method thereof. After the carbon nano tube is processed, the surface of the carbon nano tube is provided with specific initiating radical groups. Then, (methyl) tert-butyl acrylic ester monomer polymerization is initiated by atom transfer radical polymerization reaction to obtain the poly (methyl) tert-butyl acrylic ester grafted carbon nano tube. The preparation method has the advantages of simplicity, practicability and easy control. The obtained product can be dissolved in various kinds of organic solvent and is provided with specific tert-butyls which can be easily hydrolyzed and decomposed on the structure. The poly (methyl) tert-butyl acrylic ester grafted carbon nano tube has wide application to the field of constructing the polymer composite nano structure of the nano tube, such as amphipathy nucleocapsid nano structures and nano elements.
Description
Technical field: the present invention relates to a kind of preparation method of water-soluble carbon nanometer tube, the special butyl ester grafted of particularly poly-(methyl) vinylformic acid carbon nanotube 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 utilize methods such as atom transfer radical polymerization by molecular designing, the special butyl ester grafted of poly-(methyl) vinylformic acid of preparation carbon nanotube 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 (ATRP); 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 gathered the special butyl ester grafted of (methyl) vinylformic acid carbon nanotube.
The concrete preparation method of the special butyl ester grafted of poly-(methyl) vinylformic acid of the present invention carbon nanotube 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, 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 0～1000hr 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;
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, 1/10-100/1 mol ratio H
20
2With sulfuric acid mixed solution, 1/100～100/1 mol ratio H
20
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.
Preparation method provided by the invention is simple, be easy to control, products obtained therefrom can be dissolved in multiple organic solvent, and structurally have the special tertiary butyl that is easy to hydrolysis and decomposition, have widely in structure carbon nanotube polymer composite nanostructure such as amphipathic core-shell nano structure and field of nanometer devices and use.
Description of drawings:
Fig. 1: the special butyl ester grafted of polyacrylic acid carbon nanotube
1H NMR spectrogram
Fig. 2: the special butyl ester grafted of polyacrylic acid carbon nanotube infrared spectrum
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 Transfer Radical Polymerization grafted polyacrylic acid, obtain the special butyl ester grafted of polyacrylic acid carbon nanotube.
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 20mL60% weight acid 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 2.4g.
Fig. 1 has provided the special butyl ester grafted of polyacrylic acid carbon nanotube
1H NMR spectrogram, characteristic peak is respectively :-CH
2-(δ=2.0～2.3ppm) ,-CH-(1.6～1.8ppm) ,-CH
3(δ=1.3～1.6ppm).Fig. 2 is the infrared spectrum of product, and carbonyl peak appears at wave number 1720～1730cm
-1About.
Claims (9)
1. the preparation method of the special butyl ester grafted of poly-(methyl) vinylformic acid carbon nanotube 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, 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 cuprous chloride, cuprous bromide, iron protochloride or ferrous bromide, 0.01～5 weight part Tetramethyl Ethylene Diamines, pentamethyl--diethyl triamine or hexamethyl-triethyl tetramine, the surface that adds step (d) gained again has carbon nanotube 1 weight part of initiating group, 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 0～1000hr 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.
2. the preparation method of the special butyl ester grafted of poly-(methyl) vinylformic acid according to claim 1 carbon nanotube 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. the preparation method of the special butyl ester grafted of poly-(methyl) vinylformic acid according to claim 1 carbon nanotube is characterized in that the used acid with strong oxidizing property of step (a) is selected from nitric acid, sulfuric acid, nitric acid and sulfuric acid mixing acid, is added with potassium permanganate or H
2O
2Hydrochloric acid, nitric acid, sulfuric acid or its mixing acid.
4. the preparation method of the special butyl ester grafted of poly-(methyl) vinylformic acid according to claim 1 carbon nanotube 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. the preparation method of the special butyl ester grafted of poly-(methyl) vinylformic acid according to claim 1 carbon nanotube 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. the preparation method of the special butyl ester grafted of poly-(methyl) vinylformic acid according to claim 1 carbon nanotube 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. the preparation method of the special butyl ester grafted of poly-(methyl) vinylformic acid according to claim 1 carbon nanotube, 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. the preparation method of the special butyl ester grafted of poly-(methyl) vinylformic acid according to claim 1 carbon nanotube, it is characterized in that solvent for use is selected from dimethyl sulfoxide (DMSO), N in the step (e), 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. the special butyl ester grafted of poly-(methyl) vinylformic acid carbon nanotube is characterized in that the special butyl ester grafted of poly-(methyl) vinylformic acid carbon nanotube that adopts each described preparation method of claim 1-8 to obtain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109071 CN1232590C (en) | 2003-12-04 | 2003-12-04 | Poly (methyl) tert-butyl acrylic ester grafted carbon nanometer tube and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109071 CN1232590C (en) | 2003-12-04 | 2003-12-04 | Poly (methyl) tert-butyl acrylic ester grafted carbon nanometer tube and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1546577A CN1546577A (en) | 2004-11-17 |
| CN1232590C true CN1232590C (en) | 2005-12-21 |
Family
ID=34335013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310109071 Expired - Fee Related CN1232590C (en) | 2003-12-04 | 2003-12-04 | Poly (methyl) tert-butyl acrylic ester grafted carbon nanometer tube and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1232590C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386373C (en) * | 2004-12-10 | 2008-05-07 | 中国科学院长春应用化学研究所 | In situ polymerization preparing method for carbon nano tube and polytene composite material |
| CN1331899C (en) * | 2005-12-15 | 2007-08-15 | 上海交通大学 | Method for preparing carbon nano tube/polymer nano composite material |
| CN101177261B (en) * | 2007-11-08 | 2010-05-19 | 上海交通大学 | Method for preparing biocompatible cellulose functionalized carbon nano tube |
| CN111234141A (en) * | 2020-03-19 | 2020-06-05 | 山东科技大学 | Method for synthesizing high-molecular carbon nano tube composite material by free radical polymerization |
| CN112795027B (en) * | 2021-01-13 | 2023-03-14 | 玉林师范学院 | Preparation method of temperature-controllable separated nano material with surface activity |
-
2003
- 2003-12-04 CN CN 200310109071 patent/CN1232590C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1546577A (en) | 2004-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1207186C (en) | Super-branched polymer grafted carbon nanotube and its prepn process | |
| CN1246356C (en) | Prepn process of in-situ polymerized polymer grafted carbon nanotube | |
| CN101058418A (en) | Poly(glycidyl methacrylate), carbon nano-tube modified by derivative of the same and preparation method thereof | |
| CN101092739A (en) | Method for preparing high water soluble Nano carbon tube grafted by super branched polymer | |
| CN1246218C (en) | Carbon nanometer tube with initiating group on surface and its preparation method | |
| CN1209382C (en) | Preparation method of block polymer grafted earbon nano-pipe | |
| CN1232590C (en) | Poly (methyl) tert-butyl acrylic ester grafted carbon nanometer tube and its preparation method | |
| JP5676170B2 (en) | Ionic hyperbranched polymer and carbon nanomaterial dispersant | |
| CN1218978C (en) | Polysulfonated styrene grafted water soluble carbon nano pipe and its preparation method | |
| CN1326770C (en) | Carbon nanometer tube with surface connected with magnetic nanometer particle and its preparation method | |
| CN1234746C (en) | Multi-carboxyl polymer grafted water-soluble carbon nanometer tube and preparation method thereof | |
| CN1260308C (en) | Material of luminescent nano carbon tube and preparation method | |
| CN1243061C (en) | Inner hydrophilic external oleophibic type nuclear shell carbon nano pipe and its preparation method | |
| CN1254514C (en) | Nano carbon tube grafted with super branched polymer synthesized in situ and preparation method | |
| CN1218979C (en) | Ultrabranching poly parachloro methyl benzene etthylene grafted carbon nano pipe and its preparation method | |
| CN1284728C (en) | Temperatur esensitire type water soluble carbon nano pipe and its preparation method | |
| Choi et al. | Graft polymerization of styrene from single-walled carbon nanotube using atom transfer radical polymerization | |
| CN1257944C (en) | Core-shell type lipophilic-hydrophilic carbon nanometer tube and its preparation method | |
| CN1304284C (en) | Surface adsorption semi-conductor nanocrystalline carbon tube and its preparation method | |
| CN101181988A (en) | Preparation method of carbon-nano tube-phosphorylcholine polymer composite material for blood environment | |
| Carson et al. | Synthesis, characterization and stability of chitosan and poly (methyl methacrylate) grafted carbon nanotubes | |
| Lee et al. | Formation of carbon nanotube/glucose-carrying polymer hybrids by surface-initiated, atom transfer radical polymerization | |
| KR101051969B1 (en) | Compatibilizer for Polyamide / Carbon Nanotube Nanocomposites and Polyamide / Carbon Nanotube Composites Comprising the Same | |
| CN1246219C (en) | New type material of nano carbon tube in hydrophile/oleophylic type nucleocapsid and preparation method | |
| CN1546579A (en) | Polymer thin layer coated carbon nanometer tube and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |