CN101249957A - Carbon nano-tube having quaternary amines group on surface and preparation thereof - Google Patents
Carbon nano-tube having quaternary amines group on surface and preparation thereof Download PDFInfo
- Publication number
- CN101249957A CN101249957A CNA2008100340116A CN200810034011A CN101249957A CN 101249957 A CN101249957 A CN 101249957A CN A2008100340116 A CNA2008100340116 A CN A2008100340116A CN 200810034011 A CN200810034011 A CN 200810034011A CN 101249957 A CN101249957 A CN 101249957A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- quaternary amines
- preparation
- weight part
- mixture
- 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.)
- Pending
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a carbon nanotube with a surface provided with quaternary ammonium groups and a process for preparation thereof. The surface of the carbon nanotube is modified via strong acid oxidant to obtain the carbon nanotube with the surface provided with carboxyl, and the carbon nanotube with the surface provided with carboxyl reacts to halogenating agent to obtain the carbon nanotube with the surface chained with acyl halide groups. Diamine reacts to the acyl halide groups on the surface of the carbon nanotube to obtain the carbon nanotube with the surface provided with amine-terminated group, and then the amine-terminated group on the carbon nanotube reacts to alkylating agents to obtain the carbon nanotube with the surface provided with the quaternary ammonium groups. The obtained carbon nanotube with the surface provided with the quaternary ammonium groups is structurally similar to cation surface active agent, which has strong dispersing and dissolving property in polar solvent, particularly in water. The carbon nanotube with the surface provided with the quaternary ammonium groups of the invention is beneficial for performing wet operations in the post processing process of the carbon nanotube and creates conditions for large-scale application of the carbon nanotube.
Description
Technical field
The present invention relates to a kind of surface functional group carbon nano tube and preparation method thereof, particularly the surface has carbon nanotube of quaternary amines and preparation method thereof.
Background technology
The class graphite linings structure of the single or multiple lift tubular that carbon nanotube is made up of carbon atom.The carbon nanotube diameter is little, length-to-diameter ratio is big, is a kind of quasi-one-dimensional nanometer material.Carbon nanotube is because its nano-scale and unique bond structure that becomes make it have many special physical propertiess.For example special mechanical properties, chemical property, field emission performance etc.Though carbon nanotube has a good application prospect and huge using value, up to the present, it also is not widely used in industrial and agricultural production and people's life.The reason that checks the carbon nanotube large-scale application is many-sided, and wherein the strong Van der Waals force between the carbon nanotube is one of major reason.Strong Van der Waals force cause carbon nanotube often tens even up to a hundred flock together, exist with the state of nanotube bundle.This nanotube bundle lacks solvability in solvent, and in the course of processing operational difficulty because many courses of processing require " wet method " operation.
In order to solve this stubborn problem, the various countries scientist has carried out unremitting effort.At present the method that adopted of bibliographical information mainly is to link some organic molecule group or organic polymers in carbon nano tube surface, and the processable by these organic groups drives carbon nanotube to be disperseed in solvent.For example: Bullups, W.E. etc. receive various alkane on the single armed carbon nano tube surface, make it that certain dissolubility (NANO LETTERS, 2004,4 (7): 1257-1260) can be arranged in chloroform, methylene dichloride and dimethyl formamide; Adronov, A. etc. pass through the surface grafting polystyrene of the method for living polymerization in Single Walled Carbon Nanotube, and products therefrom can be dissolved in chloroform, methylene dichloride, tetrahydrofuran (THF) etc., and (Macromolecules 2005,38 (4): 1172-1179).But, use the method for present bibliographical information, the solvability of carbon nanotube (the particularly solvability in water) still can not reach practical requirement.
Quaternary amine belongs to the organism of ionic, and it can dissociate into quaternary ammonium cation and halide anion in water, and they all can combine with water, forms hydrated ion.Owing to these reasons, cause quaternary amine soluble in water especially.It is usually as solubility promoter, tensio-active agent etc., impels material (for example vegetables oil, whiteruss etc.) originally not soluble in water stable dispersion, dissolving in water.Here, we are linked to quaternary amines on the carbon nanotube, utilize the high resolution of quaternary amines in water on the one hand, impel carbon nanotube to dissolve in water; On the other hand, the quaternary amines that is linked at nanotube surface is dissociated into quaternary ammonium cation in water, and they are electrically identical, just can repel mutually, makes the carbon nanotube that is scattered in the water be difficult for reuniting bunchy again, has increased the long dispersion stability of nanotube solution.The subsequent operations of nanotube is carried out in the aqueous solution, i.e. wet processes, this has solved the problem of the difficulties in dispersion that runs in the operating process of nanotube post-treatment, for the large-scale application of carbon nanotube has been created condition.
Summary of the invention
Technical problem to be solved by this invention provides a kind of surface and has carbon nanotube of quaternary amine functional group and preparation method thereof, to overcome the problem of the difficulties in dispersion that runs in the operating process of nanotube post-treatment in the prior art.
As a kind of important intermediate nano material, the carbon nanotube that the surface has a quaternary amine functional group has extremely strong water-soluble, can make post-treatment process wet method operation in the aqueous solution of nanotube, for the large-scale application of carbon nanotube has been created condition.
The technical solution used in the present invention: the surface has the preparation method of the carbon nanotube of quaternary amines, comprises the following steps:
A. the carbon nanometer tube material of 0.1～20 weight part is mixed with the strong acid oxygenant of 5～300 weight parts, at 10～70 ℃ of following supersound process 0.5～5h, be heated to 80～200 ℃ of reaction 0.5～50h then, membrane filtration, the water repetitive scrubbing repeatedly is neutral to filtrate, vacuum-drying then obtains the carbon nanotube that the surface has carboxyl;
B. above-mentioned processed carbon nanotubes 0.1～20 weight part is mixed with acylating agent 10～500 weight parts, ultra-sonic dispersion 0.5～5h is heated to 20～100 ℃, and reaction 2～50h down stirs and reflux, suction filtration and repeatedly washing obtain the carbon nanotube that acyl halide group is contained on the surface;
Carbon nanotube 0.1～20 weight part that c contains the surface that obtains among the step b acid chloride groups is put into the organic solvent of 10～100 weight parts with diamine 0.1～50 weight part, ultra-sonic dispersion 0.5～5h, temperature is 10～50 ℃, stirring reaction 0.5～30h, suction filtration and washing obtain the carbon nanotube that amido is contained on the surface;
Carbon nanotube 0.1～20 weight part and alkylating reagent 0.1～200 weight part, solvent 0～1000 weight part that d contains amido with the surface that obtains among the step c mix, ultra-sonic dispersion 0.5～5h, be heated to 30～150 ℃, under agitation react 0.5～50h, suction filtration and washing obtain the carbon nanotube that quaternary amines is contained on the surface.
Carbon nanotube described in the step a is selected from Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes, cage modle carbon nanotube, slub type carbon nanotube or their mixture, and described strong acid oxygenant is the vitriol oil, concentrated nitric acid and vitriol oil mixture, hydrogen peroxide, the vitriol oil and potassium permanganate mixture.
Acylating agent described in the step b is selected from sulfur oxychloride, SULPHURYL CHLORIDE, thionyl bromide, phosphorus trichloride or phosphorus pentachloride.
Organic solvent is selected from cyanobenzene, dimethyl sulfoxide (DMSO), N among the step c, the mixture of dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, dioxane, chloroform, tetrahydrofuran (THF), ethyl acetate acetonitrile, butanone, benzene, toluene, oil of mirbane, chlorinated benzene, dichlorobenzene one of them or more than one.
Diamine described in the step c is selected from quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine or their mixture.
Alkylating reagent described in the steps d is selected from methyl chloride, monobromethane, methyl iodide, oxyethane, monochloroethane, monobromethane, iodoethane, epoxy chloropropane etc.
Solvent described in the steps d is selected from Virahol, tetrahydrofuran (THF), N, the mixture of dinethylformamide, N,N-dimethylacetamide, dioxane one of them or more than one.
Beneficial effect of the present invention: the present invention is carbon nanotube strong acid oxidizer treatment, makes its surface produce carboxyl, and then carboxylic acid halidesization, amination, alkylation, obtains the modified carbon nano-tube that the surface has quaternary amines.This surperficial chain is connected to the carbon nanotube of quaternary amines, have the structure that is similar to cats product, also have and its similar performance: especially in water, have extremely strong dispersiveness, solvability (solubleness surpasses 10mg/mL in water) at polar solvent.
The modified carbon nano-tube that the present invention obtains can be finished various wet processes in the aqueous solution.For example, blend, grafting, making nano-device etc., for carbon nanotube early large-scale application created condition.
Description of drawings
Fig. 1 is the atomic force microscope photo of the surface Single Walled Carbon Nanotube that has quaternary amines.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
With the multi-walled carbon nano-tubes is raw material, through the strong acid oxidation, again with the sulfur oxychloride reaction, obtains the carbon nanotube of chloride; It and propylene diamine react, and obtain aminated carbon nanotube; With the methyl iodide effect, obtain quaternary ammoniated carbon nanotube then.
A. the 1g multi-walled carbon nano-tubes is mixed with the concentrated nitric acid of 30mL,, be heated to 130 ℃ of reaction 6h then at 25 ℃ of following supersound process 1h, use the polyester membrane filtration, water washing, this process repeated multiple times is to filtrate neutrality, 50 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has carboxyl then;
B. above-mentioned processed carbon nanotubes 0.5g is mixed with sulfur oxychloride 20g, ultra-sonic dispersion 1h is heated to 50 ℃, the reaction 24h down that stirs and reflux, and suction filtration and repeatedly washing obtain the carbon nanotube that acid chloride groups is contained on the surface;
The carbon nanotube 0.5g that c contains the surface that obtains among the step b acid chloride groups puts into 25mL exsiccant tetrahydrofuran (THF) with propylene diamine 5mL, ultra-sonic dispersion 1h is heated to 50 ℃, stirs reaction 24h down, suction filtration and washing obtain the carbon nanotube that amido is contained on the surface;
Carbon nanotube 0.5g and methyl iodide 5g, Virahol 50mL that d contains amido with the surface that obtains among the step c mix, ultra-sonic dispersion 1h is heated to 90 ℃, under agitation reacts 48h, suction filtration and washing obtain the multi-walled carbon nano-tubes that quaternary amines is contained on the surface.
Embodiment 2
With the multi-walled carbon nano-tubes is raw material, with the hexanediamine reaction, obtains aminated carbon nanotube after its carboxylic acidization; With the methyl iodide effect, obtain surperficial quaternary ammoniated multi-walled carbon nano-tubes then.
Step a, b, d are with embodiment 1; Step c changes hexanediamine 8mL into, and other is constant.Because the link arm between quaternary amines and the nanotube is longer at this moment, quaternary amines can reach in the solvent and go.
Embodiment 3
With the Single Walled Carbon Nanotube is raw material, with the hexanediamine reaction, obtains aminated carbon nanotube after its carboxylic acidization; With the monobromethane effect, obtain surperficial quaternary ammoniated Single Walled Carbon Nanotube then.
Step b, c are with embodiment 1; Step a changes the 1g Single Walled Carbon Nanotube into to be mixed with the concentrated nitric acid of 100mL; Steps d changes monobromethane 10g, dimethyl formamide 100mL into, and other is constant.Obtain the surface and contain the Single Walled Carbon Nanotube of quaternary amines.
Embodiment 4
Step b, c, d are with embodiment 1; Step a changes the 0.1g Single Walled Carbon Nanotube into to be mixed with the vitriol oil of 5g, at 70 ℃ of following supersound process 0.5h, is heated to 200 ℃ of reaction 0.5h then, membrane filtration, the water repetitive scrubbing repeatedly is neutral to filtrate, and 50 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has carboxyl then.
Embodiment 5
Step b, c, d are with embodiment 1; The multi-walled carbon nano-tubes that step a changes into 20g mixes with the concentrated nitric acid of 300g, at 10 ℃ of following supersound process 5h, is heated to 80 ℃ of reaction 50h then, membrane filtration, the water repetitive scrubbing repeatedly is neutral to filtrate, and 50 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has carboxyl then.
Embodiment 6
Step a, c, d are with embodiment 1; Step b changes into carboxylated carbon nanotube 0.1g is mixed with sulfur oxychloride 10g, ultra-sonic dispersion 0.5h, and 20 ℃ of following stirring reaction 50h, suction filtration and repeatedly washing obtain the carbon nanotube that acyl halide group is contained on the surface.
Embodiment 7
Step a, c, d are with embodiment 1; Step b changes into carboxylated carbon nanotube 20g is mixed with phosphorus pentachloride 500g, and ultra-sonic dispersion 5h is heated to 100 ℃, the reaction 2h down that stirs and reflux, and suction filtration and repeatedly washing obtain the carbon nanotube that acyl halide group is contained on the surface.
Embodiment 8
Step a, b, d are with embodiment 1; Step c changes carbon nanotube 0.1g that acid chloride groups is contained on the surface into and puts into the tetrahydrofuran (THF) of 10g with propylene diamine 0.1g, ultra-sonic dispersion 5h, and temperature is 10 ℃, stirring reaction 0.5h, suction filtration and washing obtain the carbon nanotube that amido is contained on the surface.
Embodiment 9
Step a, b, d are with embodiment 1; Step c changes carbon nanotube 20g that acid chloride groups is contained on the surface into and puts into the dichlorobenzene of 100g with hexanediamine 50g, ultra-sonic dispersion 0.5h, and temperature is 50 ℃, stirring reaction 30h, suction filtration and washing obtain the carbon nanotube that amido is contained on the surface.
Embodiment 10
Step a, b, c are with embodiment 1; Steps d changes carbon nanotube 0.1g and monobromethane 0.1g that amido is contained on the surface into and mixes, and ultra-sonic dispersion 5h is heated to 30 ℃, under agitation reacts 50h, and suction filtration and washing obtain the carbon nanotube that quaternary amines is contained on the surface.
Embodiment 11
Step a, b, c are with embodiment 1; Steps d changes carbon nanotube 20g and pyridine 200g, Virahol 1000g that amido is contained on the surface into and mixes, and ultra-sonic dispersion 0.5h is heated to 150 ℃, under agitation reacts 0.5h, and suction filtration and washing obtain the carbon nanotube that quaternary amines is contained on the surface.
The functionalizing carbon nanotube that the present invention obtains has high solvability in the aqueous solution, above 10mg/mL, and can steady in a long-termly exist and not reunite, and this provides condition for the operation of the wet method in the carbon nanotube post-treatment process.
Claims (7)
1. a surface has the preparation method of the carbon nanotube of quaternary amines, it is characterized in that comprising the following steps:
A. the carbon nanometer tube material of 0.1～20 weight part is mixed with the strong acid oxygenant of 5～300 weight parts, at 10～70 ℃ of following supersound process 0.5～5h, be heated to 80～200 ℃ of reaction 0.5～50h then, membrane filtration, the water repetitive scrubbing repeatedly is neutral to filtrate, 50 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has carboxyl then;
B. above-mentioned processed carbon nanotubes 0.1～20 weight part is mixed with acylating agent 10～500 weight parts, ultra-sonic dispersion 0.5～5h is heated to 20～100 ℃, and reaction 2～50h down stirs and reflux, suction filtration and repeatedly washing obtain the carbon nanotube that acyl halide group is contained on the surface;
Carbon nanotube 0.1～20 weight part that c contains the surface that obtains among the step b acid chloride groups is put into the solvent of 10～100 weight parts with diamine 0.1～50 weight part, ultra-sonic dispersion 0.5～5h, temperature is 10～50 ℃, stirring reaction 0.5～30h, suction filtration and washing obtain the carbon nanotube that amido is contained on the surface;
Carbon nanotube 0.1～20 weight part and alkylating reagent 0.1～200 weight part, solvent 0～1000 weight part that d contains amido with the surface that obtains among the step c mix, ultra-sonic dispersion 0.5～5h, be heated to 30～150 ℃, under agitation react 0.5～50h, suction filtration and washing obtain the carbon nanotube that quaternary amines is contained on the surface.
2. the surperficial according to claim 1 preparation method who has the carbon nanotube of quaternary amines, it is characterized in that: the carbon nanotube described in the step a is selected from Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes, cage modle carbon nanotube, slub type carbon nanotube or their mixture; Strong acid oxygenant described in the step a is: the vitriol oil, concentrated nitric acid and vitriol oil mixture, hydrogen peroxide, the vitriol oil and potassium permanganate mixture.
3. the surperficial according to claim 1 preparation method who has the carbon nanotube of quaternary amines, it is characterized in that: the acylating agent described in the step b is selected from sulfur oxychloride, SULPHURYL CHLORIDE, thionyl bromide, phosphorus trichloride or phosphorus pentachloride.
4. the surperficial according to claim 1 preparation method who has the carbon nanotube of quaternary amines, it is characterized in that: organic solvent is selected from cyanobenzene, dimethyl sulfoxide (DMSO), N among the step c, the mixture of dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, dioxane, chloroform, tetrahydrofuran (THF), ethyl acetate, acetonitrile, butanone, benzene, toluene, oil of mirbane, chlorinated benzene, dichlorobenzene one of them or more than one.
5. the surperficial according to claim 1 preparation method who has the carbon nanotube of quaternary amines, it is characterized in that: diamine described in the step c is selected from quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine or their mixture.
6. the surperficial according to claim 1 preparation method who has the carbon nanotube of quaternary amines, it is characterized in that: alkylating reagent described in the steps d is selected from methyl chloride, monobromethane, methyl iodide, oxyethane, monochloroethane, monobromethane, iodoethane, epoxy chloropropane etc.
7. the surperficial according to claim 1 preparation method who has the carbon nanotube of quaternary amines, it is characterized in that: solvent described in the steps d is selected from Virahol, tetrahydrofuran (THF), N, the mixture of dinethylformamide, N,N-dimethylacetamide, dioxane one of them or more than one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100340116A CN101249957A (en) | 2008-02-28 | 2008-02-28 | Carbon nano-tube having quaternary amines group on surface and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100340116A CN101249957A (en) | 2008-02-28 | 2008-02-28 | Carbon nano-tube having quaternary amines group on surface and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101249957A true CN101249957A (en) | 2008-08-27 |
Family
ID=39953581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100340116A Pending CN101249957A (en) | 2008-02-28 | 2008-02-28 | Carbon nano-tube having quaternary amines group on surface and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101249957A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702549A (en) * | 2012-06-01 | 2012-10-03 | 哈尔滨工业大学 | Preparation method for composite film material of oxazole ring structured polyimide/carbon nano tube |
| CN103196983A (en) * | 2013-02-26 | 2013-07-10 | 浙江大学 | Method for simultaneous determination of methotrexate and calcium folinate |
| CN104987478A (en) * | 2015-07-16 | 2015-10-21 | 哈尔滨工业大学 | Preparation method and degradation method of carbon nanotube/aminal dynamic covalent network structured compound |
| CN105368030A (en) * | 2015-11-23 | 2016-03-02 | 上海中镭新材料科技有限公司 | Antistatic pc/abs alloy and preparation method thereof |
| CN106750539A (en) * | 2017-01-20 | 2017-05-31 | 青岛科技大学 | A kind of modified carbon nano-tube and preparation method thereof |
| CN109354008A (en) * | 2018-09-26 | 2019-02-19 | 福建新峰二维材料科技有限公司 | Non-close multi-walled carbon nanotube material preparation method and its electrode and battery of preparation |
| CN110615427A (en) * | 2018-06-19 | 2019-12-27 | 哈尔滨工业大学 | Preparation method of high-flexibility self-crosslinking carbon nanotube film |
| CN112811413A (en) * | 2021-03-30 | 2021-05-18 | 无锡零一未来新材料技术研究院有限公司 | Modification method of carbon nano tube, modified carbon nano tube and application thereof |
| CN117457846A (en) * | 2023-10-20 | 2024-01-26 | 宇锵新材料(湖北)有限公司 | Lithium battery electrode plate containing conductive coating and manufacturing method thereof |
-
2008
- 2008-02-28 CN CNA2008100340116A patent/CN101249957A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702549A (en) * | 2012-06-01 | 2012-10-03 | 哈尔滨工业大学 | Preparation method for composite film material of oxazole ring structured polyimide/carbon nano tube |
| CN103196983A (en) * | 2013-02-26 | 2013-07-10 | 浙江大学 | Method for simultaneous determination of methotrexate and calcium folinate |
| CN104987478A (en) * | 2015-07-16 | 2015-10-21 | 哈尔滨工业大学 | Preparation method and degradation method of carbon nanotube/aminal dynamic covalent network structured compound |
| CN104987478B (en) * | 2015-07-16 | 2017-03-22 | 哈尔滨工业大学 | Degradation method of carbon nanotube/aminal dynamic covalent network structured compound |
| CN105368030A (en) * | 2015-11-23 | 2016-03-02 | 上海中镭新材料科技有限公司 | Antistatic pc/abs alloy and preparation method thereof |
| CN105368030B (en) * | 2015-11-23 | 2017-03-29 | 上海中镭新材料科技有限公司 | Antistatic PC/ABS and preparation method thereof |
| CN106750539A (en) * | 2017-01-20 | 2017-05-31 | 青岛科技大学 | A kind of modified carbon nano-tube and preparation method thereof |
| CN110615427A (en) * | 2018-06-19 | 2019-12-27 | 哈尔滨工业大学 | Preparation method of high-flexibility self-crosslinking carbon nanotube film |
| CN110615427B (en) * | 2018-06-19 | 2021-01-05 | 哈尔滨工业大学 | Preparation method of high-flexibility self-crosslinking carbon nanotube film |
| CN109354008A (en) * | 2018-09-26 | 2019-02-19 | 福建新峰二维材料科技有限公司 | Non-close multi-walled carbon nanotube material preparation method and its electrode and battery of preparation |
| CN112811413A (en) * | 2021-03-30 | 2021-05-18 | 无锡零一未来新材料技术研究院有限公司 | Modification method of carbon nano tube, modified carbon nano tube and application thereof |
| CN112811413B (en) * | 2021-03-30 | 2023-09-26 | 无锡零一未来新材料技术研究院有限公司 | Modification method of carbon nano tube, modified carbon nano tube and application thereof |
| CN117457846A (en) * | 2023-10-20 | 2024-01-26 | 宇锵新材料(湖北)有限公司 | Lithium battery electrode plate containing conductive coating and manufacturing method thereof |
| CN117457846B (en) * | 2023-10-20 | 2024-05-24 | 宇锵新材料(湖北)有限公司 | Lithium battery electrode plate containing conductive coating and manufacturing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101249957A (en) | Carbon nano-tube having quaternary amines group on surface and preparation thereof | |
| Lin et al. | Chemistry of carbon nanotubes | |
| CN101264881B (en) | Cyclodextrin-carbon nano tube derivatives and preparation method thereof | |
| CN101104668B (en) | Method for preparing functional carbon nano-tube and application thereof | |
| CN104845381B (en) | A kind of preparation method of modified multiwalled carbon nanotube material | |
| CN101230211B (en) | Method for preparing small-molecule imide modified carbon nano-tube | |
| CN101092739A (en) | Method for preparing high water soluble Nano carbon tube grafted by super branched polymer | |
| CN101381464B (en) | Method for preparing sulfonated polyaniline grafted multi-wall carbon nanotube | |
| DE60223374D1 (en) | FIBERS FROM ALIGNED CARBON NANOTUBES AND MANUFACTURING METHOD | |
| CN1326770C (en) | Carbon nanometer tube with surface connected with magnetic nanometer particle and its preparation method | |
| CN101177261B (en) | Method for preparing biocompatible cellulose functionalized carbon nano tube | |
| CN102220027A (en) | Grapheme/electroconductive polymer composite and preparation method thereof | |
| CN1718614A (en) | In situ synthesis polyimide grafted carbon nano-tube and its preparation method | |
| CN1486927A (en) | Super-branched polymer grafted carbon nanotube and its prepn process | |
| Agrawalla et al. | Solvothermal synthesis of a polyaniline nanocomposite-a prospective biosensor electrode material | |
| CN101215361A (en) | Method for preparing graft polymer containing carbon nano-tube | |
| CN106032273A (en) | Amido reinforced graphene film, nitrogen doped graphene film and preparation method thereof | |
| CN101195709B (en) | Method for producing high decentrality amido carbon nano-tube/nylon 66 composite material | |
| CN103172048A (en) | Preparation method of water-soluble carbon nanotube | |
| CN101565180A (en) | Method for preparing functionalized carbon nanotube based on polyethyleneimine | |
| CN100457610C (en) | Method of modifying multiwall carbon nano-tube | |
| CN101214948A (en) | Method for preparing carbon nano-tube with polyethylene polyamine group connected at surface thereof | |
| CN101709112B (en) | Preparation method of bismaleimide block polymer containing carbon nanotubes | |
| CN102145885A (en) | Method for preparing surface phosphorylated water-soluble carbon nanotube and prepared carbon nanotube | |
| CN101457019B (en) | Carbon nanotube/polysulfonamide nano composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20080827 |