CN1284727C - Method for carbon nanometer tube with chemical decoration - Google Patents
Method for carbon nanometer tube with chemical decoration Download PDFInfo
- Publication number
- CN1284727C CN1284727C CN 200310113304 CN200310113304A CN1284727C CN 1284727 C CN1284727 C CN 1284727C CN 200310113304 CN200310113304 CN 200310113304 CN 200310113304 A CN200310113304 A CN 200310113304A CN 1284727 C CN1284727 C CN 1284727C
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- nano tube
- carbon nanotubes
- carbon
- acid
- 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 belongs to the field of carbon nanotubes, particularly to a simple method of chemical modified carbon nanotubes. The simple method of chemical modified carbon nanotubes comprises the following steps: purifying and cutting the carbon nanotubes by oxidizing acid; then, reacting the obtained methyloic carbon nanotubes with alkaline water solution to generate corresponding salt; further, reacting with alkyl halide under the action of a phase transfer catalyst to obtain corresponding modified carbon nanotubes. The present invention does not need converting carboxylic acid into acyl chloride, and the carboxylic acid is directly reacted with inorganic base; intermediate products do not need to be separated, and the next reaction is made directly, so the steps are simple; the present invention can be completely reacted in a short time, and efficiency is high.
Description
Technical Field
The invention belongs to the field of carbon nanotubes, and particularly relates to a simple method for chemically modifying carbon nanotubes.
Background
The carbon nano tube is a novel nano material discovered by professor Iijima of Japanese scientists in 1991, and has good application prospect in a plurality of fields such as hydrogen storage materials, field emission materials, battery materials, stealth materials, reinforcing materials, sensor materials, catalyst materials and the like. However, carbon nanotubes have insolubility and insolubility, and studies on carbon nanotubes have been conducted in the solid state for a long time, so that application studies of carbon nanotubes have been greatly affected. For example, when preparing a carbon nanotube-polymer composite, the compatibility of the carbon nanotube and the polymer cannot be solved well due to the insolubility of the carbon nanotube, which greatly affects the application and development of the carbon nanotube. Chemical modification of carbon nanotubes by covalent or non-covalent methods is an effective way to overcome the above difficulties and has achieved good results.
Haddon et al (Science, 282, 95, 1998; U.S. Pat. No. 6,187,823B 1) in the U.S. states the preparation of soluble single-walled carbon nanotubes (SWNTs). The method comprises the steps of firstly purifying SWNTs, then cutting and polishing the surface of the purified carbon nano tube, converting the carbon nano tube into acyl chloride, and then reacting the acyl chloride with primary amine such as octadecylamine to obtain the single-wall carbon nano tube which can be dissolved in an organic solvent. Tangben faithfulness (Macromolecules, 32, 2569, 1999) of hong Kong utilizes an in-situ polymerization method to catalyze and polymerize multi-walled carbon nanotubes (MWNTs) and phenylacetylene to obtain polyphenylacetylene-coated MWNTs which can be dissolved in organic solvents such as tetrahydrofuran, toluene, chloroform and the like. U.S. Margrave and Smalley (chem.Phys.Lett., 296, 188, 1998; chem.Phys.Lett., 310, 367, 1999; J.Phys.chem.B, 103, 4318, 1999) studied the fluorination of SWNTs at different temperatures. Fluorine tubes (fluorotubes) with fluorine-containing side walls were obtained. The fluorine tube can react with alkyl lithium (such as hexyl lithium) or alkyl magnesium bromide under the action of ultrasonic waves to obtain fluorinated SWNTs containing alkyl chains, and the fluorinated SWNTs can be dissolved in various organic solvents such as chloroform, tetrahydrofuran and the like. Sun and CarroII (J.Am.chem.Soc., 122, 5879, 2000, USA) also yielded soluble carbon nanotubes by reacting poly- (propionyl-ethylene-co-ethylene) with cleaved carbon nanotubes.
The inventor utilizes secondary amine to react with carbon nano-tubes to obtain fat-soluble carbon nano-tubes (Chinese patent application No. 02104527.5); polyethylene glycol reacts with the carbon nano-tube to obtain the water-soluble carbon nano-tube (Chinese patent application number: 02104528.5); the inventors have also developed the Haddon process to produce soluble carbon nanotubes on a large scale (Chinese patent application No.: 03138282.7).
However, the preparation method of the soluble carbon nanotube has certain limitations due to long reaction time and complicated process.
Disclosure of Invention
The invention aims to provide a simple method for chemically modifying a carbon nano tube. The method can carry out chemical modification on the carbon nano tube in a short time by a simple method, and the post-treatment is relatively simple.
The inventor firstly uses oxidizing acid to purify and cut the carbon nano tube, then uses the obtained carbon nano tube containing carboxyl to react with the aqueous solution of alkali such as sodium hydroxide and the like to generate corresponding salt, and further reacts with halogenated hydrocarbon under the action of a phase transfer catalyst to obtain the corresponding modified carbon nano tube. The reaction is schematically as follows:
wherein the carbon nanotube is a single-walled carbon nanotube or a multi-walled carbon nanotube prepared by various methods (chemical gas deposition, arc, laser, etc.). The alkali is sodium hydroxide, potassium hydroxide, ammonia water, other alkaline substances or any mixture thereof, etc. The halogenated hydrocarbon is chloro-, bromo-or iodo-substituted hydrocarbon (which refers to straight-chain or branched-chain hydrocarbon group with 5-50 carbon atoms and can include halogenated olefin group or halogenated alkynyl group) and other compounds connected with halogen, and the catalyst is quaternary ammonium salt, quaternary phosphonium salt, tertiary amine, crown ether, cryptate ether and other transfer catalysts or any mixture thereof.
The method comprises the following steps:
(1) purification of carbon nanotubes
Heating and refluxing or ultrasonically treating 1 part by weight of carbon nano tube and 5-50 parts by weight of nitric acid with the concentration of 30-70 wt% or mixed acid of concentrated nitric acid and concentrated sulfuric acid (preferably the volume ratio is 1: 3) for 5-48 hours; centrifuging to remove acid liquor, washing the solid with water until the pH value of the water phase is 4-7, and drying the solid in vacuum to obtain a purified and cut carbon nano tube;
(2) preparation of carbon nanotube carboxylates
Carrying out ultrasonic treatment, oscillation or stirring on 1 weight part of the carbon nano tube purified in the step (1) in 1-5 parts of dilute solution of alkali for 2-60 minutes to obtain uniform black suspension, wherein the pH value is 8-11 to obtain carboxylate of the carbon nano tube;
(3) preparation of soluble carbon nanotubes
Adding 1-10 parts by weight of phase transfer catalyst and 1-10 parts by weight of halogenated hydrocarbon into 1 part by weight of the aqueous suspension of the carbon nanotube carboxylate in the step (2), reacting at 80-120 ℃ for 2-24 hours, adding an organic solvent into the reaction mixture, transferring the mixture into a separating funnel, oscillating and standing; and separating an organic layer, filtering, concentrating the filtrate, precipitating in ethanol, washing the obtained solid with ethanol, and drying to obtain the chemically modified carbon nano tube.
The alkali is sodium hydroxide, potassium hydroxide, ammonia water and other alkaline substances or any mixture thereof.
The catalyst is quaternary ammonium salt, quaternary phosphonium salt, tertiary amine, crown ether, cryptate, etc. transfer catalyst or any mixture thereof.
The halogenated hydrocarbon is chloro-, bromo-or iodo-substituted hydrocarbon (which refers to straight-chain or branched-chain hydrocarbon with 5-50 carbon atoms, and may include halogenated alkylene or halogenated alkynyl) and other compounds connected with halogen.
The organic solvent is chloroform, dichloromethane, ether, toluene, xylene, chlorobenzene, o-dichlorobenzene, carbon tetrachloride or carbon disulfide, etc.
The concentrated nitric acid and the concentrated sulfuric acid are commercial products.
The invention has the advantages that:
1. the method does not need to convert carboxylic acid into acyl chloride, directly reacts with inorganic base, does not need to separate intermediate products, directly carries out the next reaction, and has simple steps.
2. The method is carried out in a water phase, can reduce pollution and is relatively environment-friendly.
3. The invention can complete the reaction in a short time and has high efficiency.
Detailed Description
Example 1
1g of raw material multi-walled carbon nano-tube is heated and refluxed for 24 hours in 100ml of concentrated nitric acid with the concentration of 65 wt%, the solid after centrifugation is dried in a vacuum oven after being washed for many times by water, added into 100ml of 0.01M sodium hydroxide solution, ultrasonically treated for 5 minutes, then added with 2g of tetraoctylammonium bromide and 2ml of bromohexadecane, heated to 80 ℃ and stirred for reaction for 6 hours. The product was cooled, 100ml of chloroform was added, and the mixture was sufficiently shaken and then transferred to a separatory funnel and allowed to stand. The organic layer was separated and filtered, and the filtrate was concentrated to about 10ml on a rotary evaporator and then precipitated by dropwise addition to 200ml of ethanol. The precipitate was collected by centrifugation and washed with ethanol several times and dried to obtain about 0.8g of the product.
Example 2
Heating and refluxing 5g of raw material multi-walled carbon nano-tube in 500ml of 65% concentrated nitric acid for 24 hours, washing the solid after centrifugation with water for multiple times, drying in a vacuum oven, adding the washed solid into 300ml of 0.01M potassium hydroxide solution, carrying out ultrasonic treatment for 5 minutes, then adding 5g of tetraoctylammonium bromide and 10ml of bromododecane, heating to 80 ℃, and stirring for reacting for 6 hours. The product was cooled, 300ml of chloroform was added, and after sufficient shaking, the mixture was transferred to a separatory funnel and allowed to stand. The organic layer was separated and filtered, and the filtrate was concentrated to 30ml on a rotary evaporator and then precipitated by dropwise addition to 300ml of ethanol. The precipitate was collected by centrifugation and washed with ethanol several times and dried to give about 3g of the product.
Example 3
1g of raw material single-walled carbon nanotube is ultrasonically treated for 5 hours in 100ml of mixed acid (volume ratio is 1: 3) of 65% concentrated nitric acid and 98% concentrated sulfuric acid, the solid is washed by water for a plurality of times after the centrifugal treatment, then is dried in a vacuum oven, is added into 100ml of 0.01M sodium hydroxide solution, is ultrasonically treated for 5 minutes, then is added with 1g of tetraoctylammonium bromide and 2ml of bromohexadecane, and is heated to 80 ℃ to be stirred and reacted for 6 hours. The product was cooled, 100ml of chloroform was added, and the mixture was sufficiently shaken and then transferred to a separatory funnel and allowed to stand. The organic layer was separated and filtered, and the filtrate was concentrated to 10ml on a rotary evaporator and then precipitated by dropwise addition to 200ml of ethanol. The precipitate was collected by centrifugation and washed with ethanol several times and dried to obtain about 0.8g of the product.
Example 4
5g of raw material multi-walled carbon nano-tube is ultrasonically treated for 5 hours in 500ml of mixed acid (volume ratio is 1: 3) of 65% concentrated nitric acid and 98% concentrated sulfuric acid, the solid is washed by water for a plurality of times after the centrifugal treatment, then is dried in a vacuum oven, is added into 300ml of 0.01M ammonia water solution, is stirred for 15 minutes, then is added with 5g of hexadecyl trimethyl ammonium bromide and 10ml of chloro tetradecane, is heated to 80 ℃ and is stirred for reaction for 12 hours. The product was cooled, 300ml of chloroform was added, and after sufficient shaking, the mixture was transferred to a separatory funnel and allowed to stand. The organic layer was separated and filtered, and the filtrate was concentrated to 30ml on a rotary evaporator and then precipitated by dropwise addition to 300ml of ethanol. The precipitate was collected by centrifugation and washed with ethanol several times and dried to give about 3g of the product.
Example 5
1g of raw material multi-walled carbon nano-tube is ultrasonically treated for 5 hours in 100ml of mixed acid (volume ratio is 1: 3) of concentrated nitric acid with concentration of 65% and concentrated sulfuric acid with concentration of 98%, the solid after centrifugation is dried in a vacuum oven after being repeatedly washed by water, added into 100ml of sodium hydroxide solution with concentration of 0.01M, ultrasonically treated for 5 minutes, then added with 1g of tetraoctyl ammonium bromide and 2ml of iodohexane, heated to 80 ℃ and stirred for reaction for 2 hours. The product was cooled, 100ml of chloroform was added, and the mixture was sufficiently shaken and then transferred to a separatory funnel and allowed to stand. The organic layer was separated and filtered, and the filtrate was concentrated to 10ml on a rotary evaporator and then precipitated by dropwise addition to 200ml of ethanol. The precipitate was collected by centrifugation and washed with ethanol several times and dried to obtain about 0.8g of the product.
Example 6
Heating and refluxing 1g of raw material single-walled carbon nanotube in 100ml of 65% concentrated nitric acid for 24 hours, washing the solid after centrifugation with water for multiple times, drying in a vacuum oven, adding the washed solid into 100ml of 0.01M sodium hydroxide solution, carrying out ultrasonic treatment for 5 minutes, then adding 2g of crown ether (18 crown 6) and 2ml of bromohexadecane, heating to 80 ℃, and stirring for reacting for 6 hours. The product was cooled, 100ml of chloroform was added, and the mixture was sufficiently shaken and then transferred to a separatory funnel and allowed to stand. The organic layer was separated and filtered, and the filtrate was concentrated to about 10ml on a rotary evaporator and then precipitated by dropwise addition to 200ml of ethanol. The precipitate was collected by centrifugation and washed with ethanol several times and dried to obtain about 0.8g of the product.
Example 7
5g of raw material multi-wall carbon nano tube is ultrasonically treated for 5 hours in 500ml of mixed acid (volume ratio is1: 3) of 65% concentrated nitric acid and 98% concentrated sulfuric acid, the solid is washed by water for a plurality of times after the centrifugal treatment, then is dried in a vacuum oven, is added into the mixed solution of 150ml of 0.01M aqueous ammonia and 150ml of 0.01M sodium hydroxide, is stirred for 15 minutes, then is added with 5g of hexadecyl trimethyl ammonium bromide and 10ml of chloro tetradecane, is heated to 80 ℃ and is stirred for reaction for 12 hours. The product was cooled, 300ml of chloroform was added, and after sufficient shaking, the mixture was transferred to a separatory funnel and allowed to stand. The organic layer was separated and filtered, and the filtrate was concentrated to 30ml on a rotary evaporator and then precipitated by dropwise addition to 300ml of ethanol. The precipitate was collected by centrifugation and washed with ethanol several times and dried to give about 3g of the product.
Example 8
1g of raw material multi-walled carbon nano-tube is heated and refluxed for 24 hours in 100ml of concentrated nitric acid with the concentration of 65 percent, the solid after the centrifugation of the product is dried in a vacuum oven after being washed by water for many times, the product is added into 100ml of sodium hydroxide solution with the concentration of 0.01M, the ultrasonic treatment is carried out for 5 minutes, then 1g of hexadecyl trimethyl ammonium bromide, 1g of crown ether (18 crown 6) and 2ml of bromohexadecane are added, and the mixture is heated to 80 ℃ and stirred for reaction for 6 hours. The product was cooled, 100ml of chloroform was added, and the mixture was sufficiently shaken and then transferred to a separatory funnel and allowed to stand. The organic layer was separated and filtered, and the filtrate was concentrated to about 10ml on a rotary evaporator and then precipitated by dropwise addition to 200ml of ethanol. The precipitate was collected by centrifugation and washed with ethanol several times and dried to obtain about 0.8g of the product.
Example 9
1g of raw material single carbon nano tube is heated and refluxed for 24 hours in 100ml of concentrated nitric acid with the concentration of 65 wt%, the solid after the centrifugation is dried in a vacuum oven after being washed for many times by water, the product is added into 100ml of sodium hydroxide solution with the concentration of 0.01M, the ultrasonic treatment is carried out for 5 minutes, then 2g of triethylamine and 2ml of bromohexadecane are added, the mixture is heated to 80 ℃ and stirred for reaction for 6 hours. The product was cooled, 100ml of chloroform was added, and the mixture was sufficiently shaken and then transferred to a separatory funnel and allowed to stand. The organic layer was separated and filtered, and the filtrate was concentrated to about 10ml on a rotary evaporator and then precipitated by dropwise addition to 200ml of ethanol. The precipitate was collected by centrifugation and washed with ethanol several times and dried to obtain about 0.8g of the product.
Claims (9)
1. A method for chemically modifying carbon nanotubes, comprising: the carbon nano tube is purified and cut by using oxidizing acid, then the obtained carbon nano tube containing carboxyl is reacted with an aqueous solution of alkali to generate corresponding salt, and the corresponding salt is further reacted with halogenated hydrocarbon under the action of a phase transfer catalyst to obtain the corresponding modified carbon nano tube.
2. The method of claim 1, further comprising: the purification of the carbon nano tube is that 1 weight part of the carbon nano tube and 5 to 50 weight parts of mixed acid of concentrated nitricacid and concentrated sulfuric acid or nitric acid are heated and refluxed or ultrasonically treated; removing acid liquor, washing the solid with water until the pH value of the water phase is 4-7, and drying the solid in vacuum to obtain a purified carbon nano tube;
the concentration of the nitric acid is 30-70 wt%.
3. The method of claim 1, further comprising: the preparation of the carbon nano tube carboxylate is that 1 part by weight of purified carbon nano tube is subjected to ultrasonic treatment, oscillation or stirring in 1-5 parts of diluted alkali solution to obtain uniform black suspension, and the pH value is 8-11 to obtain the carbon nano tube carboxylate.
4. The method of claim 1, further comprising: the reaction with the halogenated hydrocarbon under the action of the phase transfer catalyst is to add 1 to 10 weight parts of the phase transfer catalyst and 1 to 10 weight parts of the halogenated hydrocarbon into 1 weight part of the water suspension of the carbon nano tube carboxylate, react at the temperature of 80 to 120 ℃, and add an organic solvent into a reaction mixture; and separating an organic layer, filtering, concentrating the filtrate, precipitating in ethanol, washing the obtained solid with ethanol, and drying to obtain the chemically modified carbon nano tube.
5. The method of claim 2, further comprising: the ultrasonic treatment time is 5-48 hours.
6. A method as claimed in claim 1 or 3, characterized by: the alkali is sodium hydroxide, potassium hydroxide, ammonia water or any mixture thereof.
7. The method of claim 1 or 4, wherein: the catalyst isquaternary ammonium salt, quaternary phosphonium salt, tertiary amine, crown ether, cryptand phase transfer catalyst or any mixture thereof.
8. The method of claim 1 or 4, wherein: the halogenated hydrocarbon is straight-chain or branched-chain chlorinated, brominated or iodinated hydrocarbon with 5-50 carbon atoms.
9. The method of claim 4, wherein: the organic solvent is chloroform, dichloromethane, diethyl ether, toluene, xylene, chlorobenzene, o-dichlorobenzene, carbon tetrachloride or carbon disulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310113304 CN1284727C (en) | 2003-11-07 | 2003-11-07 | Method for carbon nanometer tube with chemical decoration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310113304 CN1284727C (en) | 2003-11-07 | 2003-11-07 | Method for carbon nanometer tube with chemical decoration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1613755A CN1613755A (en) | 2005-05-11 |
| CN1284727C true CN1284727C (en) | 2006-11-15 |
Family
ID=34759886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310113304 Expired - Fee Related CN1284727C (en) | 2003-11-07 | 2003-11-07 | Method for carbon nanometer tube with chemical decoration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1284727C (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391832C (en) * | 2005-09-29 | 2008-06-04 | 上海交通大学 | Surface chemical modification for carbon nanometer tubes |
| CN100334003C (en) * | 2005-09-29 | 2007-08-29 | 华南理工大学 | Nanometer alpha-nickel hydroxide and its prepn |
| CN1962428B (en) * | 2005-11-10 | 2010-11-10 | 鸿富锦精密工业（深圳）有限公司 | Nanometer carbon tube modification process |
| CN100439241C (en) * | 2006-08-25 | 2008-12-03 | 昆明贵金属研究所 | Preparation method of mercapto carbon nanometer pipe |
| CN101177257B (en) * | 2006-11-10 | 2010-04-14 | 同济大学 | Method for preparing hydrophilic carbon nano tube |
| CN101458606B (en) * | 2007-12-12 | 2012-06-20 | 清华大学 | Touch screen, method for producing the touch screen, and display device using the touch screen |
| CN102348635B (en) * | 2009-03-12 | 2014-07-23 | 独立行政法人科学技术振兴机构 | Process for producing organically modified carbon nanotube |
| US9725603B2 (en) * | 2012-06-21 | 2017-08-08 | Tesla Nanocoatings, Inc. | Process for preparing anticorrosive coatings comprising functionalized graphite materials |
| CN102703936B (en) * | 2012-06-28 | 2015-06-03 | 华南理工大学 | Carbon nano tube/cobalt composite coating and preparation method thereof |
| CN102805103A (en) * | 2012-08-13 | 2012-12-05 | 同济大学 | Synthesis method of carbon nanotube based sterilizing material |
| 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 |
| CN105368406A (en) * | 2015-10-11 | 2016-03-02 | 浙江百纳橡塑设备有限公司 | Fused salt and functional carbon nanotube composite material and preparation method thereof |
| CN106540663B (en) * | 2016-12-09 | 2019-06-11 | 南华大学 | A kind of preparation method of the crown ether modified carbon nano tube tube material for adsorption uranium |
| CN110527243B (en) * | 2019-09-17 | 2020-12-18 | 河南大学 | Polyethyleneimine functionalized carbon nanotube modified polyformaldehyde composite material and preparation method thereof |
-
2003
- 2003-11-07 CN CN 200310113304 patent/CN1284727C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1613755A (en) | 2005-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1284727C (en) | Method for carbon nanometer tube with chemical decoration | |
| KR100775878B1 (en) | Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof and use of derivatized nanotubes | |
| Lin et al. | Chemistry of carbon nanotubes | |
| US7514063B1 (en) | Method for the purification of semiconducting single walled carbon nanotubes | |
| US20110017587A1 (en) | Production of chemically functionalized nano graphene materials | |
| CN1308230C (en) | Highly water-soluble carbon nanometer tube preparation method | |
| US11220433B2 (en) | Process for modification of carbon surfaces | |
| CN111151302B (en) | Preparation method of covalent organic framework material doped rod-shaped cadmium sulfide composite photocatalyst | |
| CN101058418A (en) | Poly(glycidyl methacrylate), carbon nano-tube modified by derivative of the same and preparation method thereof | |
| JPH11502494A (en) | Functionalized nanotubes | |
| CN106117065A (en) | A kind of Preparation method and use of modified graphene oxide | |
| CN101264881A (en) | Cyclodextrin-carbon nano tube derivatives and preparation method thereof | |
| CN101428786A (en) | Functional carbon material synthesized with one-step reaction and method for producing the same | |
| Yu et al. | Synthetic possibility of polystyrene functionalization based on hydroxyl groups of graphene oxide as nucleophiles | |
| CN1436721A (en) | Prepn of water soluble carbon nanotube | |
| Yu et al. | The covalently organic functionalization of graphene: methodologies and protocols | |
| CN109174049B (en) | Preparation method and application of imprinted porous lithium/rubidium ion adsorption material | |
| CN106582533A (en) | Amino and thiol-modified graphene/carbon nanotube composite material and preparation method therefor | |
| US7879940B2 (en) | Polymerization initated at sidewalls of carbon nanotubes | |
| CN1687192A (en) | Method for preparing material of Nano carbon tube grafted by azobenzene in light responsibility | |
| CN1218978C (en) | Polysulfonated styrene grafted water soluble carbon nano pipe and its preparation method | |
| CN1830768A (en) | Aminatel single wall nanometer carbon pipe and its preparation method | |
| CN1552620A (en) | Method for preparing carbon nanometer tube in large-scale | |
| CN101224884A (en) | Preparation method of benzene sulfochloride substituted carbon nano-tube and grafting modification method initiated thereby | |
| CN111100255B (en) | Carbon nano tube-styrene derivative compound, preparation method and application |
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 |