CN1760269B - Electric polymer and preparation method - Google Patents
Electric polymer and preparation method Download PDFInfo
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- CN1760269B CN1760269B CN 200410067112 CN200410067112A CN1760269B CN 1760269 B CN1760269 B CN 1760269B CN 200410067112 CN200410067112 CN 200410067112 CN 200410067112 A CN200410067112 A CN 200410067112A CN 1760269 B CN1760269 B CN 1760269B
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- carbon nanotube
- conductive polymers
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Abstract
An electrical conducting polymer is prepared from carbon nanotubes and polymer in weight ratio of 1: (2-1000) through preparing carbon nanotube suspension, preparing polymer solution, mixing and moulding.
Description
Technical field
The present invention relates to a kind of conductive polymers and preparation method thereof, relate in particular to conductive polymers of a kind of carbon nanotubes and preparation method thereof.
Background technology
Carbon nanotube is a kind of novel carbon structure material, specifically, is several approximately nanometers of a kind of diameter, and length is several microns tubular structure material approximately.Because its particular structure makes it have the unrivaled many excellent properties of other material, as the conductor or the semi-conductor electroconductibility of uniqueness, high physical strength, hydrogen storage ability and microwave absorption capacity etc.
Fast development along with modern technologies, the electromagnetism wave amplitude is penetrated harm and potential hazard that the mankind are caused and is strengthened day by day, the high-performance conductive polymkeric substance can improve electronics and resist electromagnetic interference, suppress electromagnetic radiation, realize the EMI electromagnetic wave shielding, it is widely used in the plastic casing or the cabinet inside of electronicss such as mobile telephone, computer, Medical Instruments, information household appliances and aerospace.
From the latter stage eighties, begun research work, but because the condition restriction of each side there are not yet so far the technology of the suitable market requirement and product to come out to the conductive polymers aspect.After carbon nanotube was invented, the someone began to utilize its excellent conductivity that it is developed in the application aspect the conductive polymers as additive.At present, in some scientific researches, use hot fusion method that polymer materials is processed usually, but owing to adopted mechanical stirring, make the carbon nanotube that inserts be easy to be fractureed, especially when the hot melt macromolecular material becomes thickness by heating, with regard to easier carbon nanotube is fractureed during stirring, and the carbon nanotube after fractureing will lose its excellent conductivity.
Summary of the invention
Purpose of the present invention is exactly to provide conductive polymers that a kind of product conducts electricity very well, preparation technology is simple, cost is low and preparation method thereof for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of conductive polymers is characterized in that, this conductive polymers comprises carbon nanotube, polymer materials, and the weight ratio of described carbon nanotube and polymer materials is 1: 2～1000.
Described carbon nanotube is selected from one or both the mixture in Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes.
Described polymer materials comprises one or more the mixture that is selected from polycarbonate-based, polyacrylate(s) and the polyethylene copolymerization superpolymer.
The structural formula of described polycarbonate polymer material is:
Described
R
1＝-H；-F；
R
2＝-CH
3；-CH
2CH
3；-CH
2CH
2CH
3；-CH(CH
3)CH
3；
n＝100～4000。
The structural formula of described polyacrylate polymers material is:
Described
R
1，R
2＝-H；
R
3＝-H；-CH
3；-CH
2CH
3；
R
4＝-CH
3；-CH
2CH
3；-CH
2CH
2CH
3；-CH(CH
3)CH
3；-CH
2C
6H
5；
n＝100～10000。
The structural formula of described polyethylene copolymerization superpolymer is:
Described
R
1，R
2，R
3，R
5，R
6，R
7＝-H；
R
4，R
8＝-C
6H
5；-CN；-Cl；-COOCH
3；-COOCH
2CH
3
n＝100～10000；
m＝100～10000。
A kind of preparation method of conductive polymers is characterized in that, this preparation method may further comprise the steps:
(1) with mean diameter 1.0～10nm, the carbon nanotube more than the length 1 μ m is dissolved in the organic solvent with the concentration of 0.1～10mg/ml, and dispersed with stirring is made unit for uniform suspension A;
(2) be that the polymer materials of 1～15mm adds that the concentration with 5～200mg/ml is mixed with homogeneous solution B in the organic solvent with median size;
(3) above-mentioned suspending liquid A is sneaked in the solution B, the weight ratio of carbon nanotube and polymer materials is 1: 2～1000, pours die for molding behind the uniform mixing into, makes a kind of conductive polymers.
Described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, 1,1, ammediol, glycerol, methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride, 1,1-ethylene dichloride, 1, acetate, propionic acid, butyric acid, Succinic Acid, valeric acid, acetone, propione, cyclopentanone, ring ethyl ketone, methyl acetate, ethyl acetate, propyl acetate, ether, dioxane, tetrahydrofuran (THF), sherwood oil, pentane, ethane, hexanaphthene, heptane, methane amide, ethanamide, N, dinethylformamide, benzene, toluene, dimethylbenzene, pyridine, pyrroles, the mixture of one or more in the pyrazoles.
The present invention adopts dissolution method to prepare conductive polymers, promptly, by adding organic solvent, make macromolecule polymer material reduce toughness, when adding carbon nanotube in macromolecule polymer material, this carbon nanotube is difficult for destroyed, thereby makes a kind of conductive polymers of carbon nanotubes of excellent performance, its conductive capability improves greatly, has opened up application prospects.
Compared with prior art, the present invention has the following advantages:
What (1) greatly reduce conductive polymers oozes out threshold value (Percolatian Threshold).This value adds to advance polymkeric substance relevant with shape additive, and length-to-diameter ratio is big more, and the P value is low more; Below the P value, insulated with material, more than the P value, material begins conduction; Additive is the ball-type structure, and the P value appears at about 20%～30% place of weight content.When additive was tubular structure, the P value appeared at weight content＜1% o'clock in theory, in fact about about 1%.The P value is low more, and material property is good more, because the original character of impact polymer material less, and additive is many more, reprocesses also difficult more.
(2) having added the conductive polymers performance behind the carbon nanotube uses the conductive polymers of other additive high more at present, usually the additive that adopts is a carbon black etc. at present, has used the conducting polymer ability behind the carbon nanotube to use carbon black to improve three orders of magnitude.Simultaneously, the product that adopts the inventive method (dissolution method) to obtain, its electric conductivity is more high than the product that existing employing hot fusion method obtains.
(3) use carbon nanotube to use other material easier, damage little grinding tool as the conducting polymer materials processing of additive as the conducting polymer materials of additive.When using the polymkeric substance hand set machine shell that steel fiber makes as additive, very big to the damage intensity of grinding tool such as, processing.
(4) use carbon nanotube to use the matrix material of steel fiber much even, can carry out precision sizing to it like this, thereby open application prospect in person in electronics as the matrix material of additive.
(5) preparation technology is simpler than hot fusion method, and handling ease, and cost is low.
Embodiment
Embodiment 1
1. (diameter of Single Walled Carbon Nanotube is about 1.0 nanometers to take by weighing 40 milligrams of Single Walled Carbon Nanotube with analytical balance, length is about 2.5 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of methylene dichloride organic solvents, use ultrasonic oscillation, form 20 milliliters of finely dispersed methylene dichloride suspension that contain carbon nanotube.
2. take by weighing 200 milligrams of poly bisphenol carbonic ethers with analytical balance and be loaded on 20 milliliters having in the cover glass container, add 5 milliliters of methylene dichloride organic solvent dissolutions, it is fully dissolved form transparent methylene dichloride poly bisphenol carbonate solution.Accurately shift 1.0 milliliters of finely dispersed methylene dichloride suspension that contain carbon nanotube in transparent methylene dichloride poly bisphenol carbonate solution with transfer pipet, use magnetic agitation and ultrasonic oscillation number minute successively, it is mixed.
3. uncap makes its volatile fraction solvent, to residue during 5.0 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and poly bisphenol carbonic ether weight ratio and be 1/100 polymeric film.
4. the specific conductivity with four probe method measure sample film is 5.8 * 10
-4(blank assay is surveyed the specific conductivity of pure poly bisphenol carbonic ether film less than 10 to S/cm
-6S/cm).
Embodiment 2
1. (diameter of Single Walled Carbon Nanotube is about 1.0 nanometers to take by weighing 40 milligrams of Single Walled Carbon Nanotube with analytical balance, length is about 2.5 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of methylene dichloride organic solvents, use ultrasonic oscillation, form 20 milliliters of finely dispersed methylene dichloride suspension that contain carbon nanotube.
2. take by weighing 200 milligrams of poly bisphenol carbonic ethers with analytical balance and be loaded on 20 milliliters having in the cover glass container, add 5 milliliters of methylene dichloride organic solvent dissolutions, it is fully dissolved form transparent methylene dichloride poly bisphenol carbonate solution.In transparent methylene dichloride poly bisphenol carbonate solution, use magnetic agitation and ultrasonic oscillation number minute with the finely dispersed methylene dichloride suspension that contains carbon nanotube of the accurate transferase 12 .0 of transfer pipet milliliter successively, it is mixed.
3. uncap makes its volatile fraction solvent, to residue during 5.0 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and poly bisphenol carbonic ether weight ratio and be 1/50 polymeric film.
4. the specific conductivity with four probe method measure sample film is 1.3 * 10
-2(blank assay is surveyed the specific conductivity of pure poly bisphenol carbonic ether film less than 10 to S/cm
-6S/cm).
Embodiment 3
1. (diameter of Single Walled Carbon Nanotube is about 1.0 nanometers to take by weighing 40 milligrams of Single Walled Carbon Nanotube with analytical balance, length is about 2.5 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of methylene dichloride organic solvents, use ultrasonic oscillation, form 20 milliliters of finely dispersed methylene dichloride suspension that contain carbon nanotube.
2. take by weighing 100 milligrams of poly bisphenol carbonic ethers with analytical balance and be loaded on 20 milliliters having in the cover glass container, add 3 milliliters of methylene dichloride organic solvent dissolutions, it is fully dissolved form transparent methylene dichloride poly bisphenol carbonate solution.In transparent methylene dichloride poly bisphenol carbonate solution, use magnetic agitation and ultrasonic oscillation number minute with the finely dispersed methylene dichloride suspension that contains carbon nanotube of the accurate transferase 45 .0 of transfer pipet milliliter successively, it is mixed.
3. uncap makes its volatile fraction solvent, to residue during 4.5 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and poly bisphenol carbonic ether weight ratio and be 1/10 polymeric film.
4. the specific conductivity with four probe method measure sample film is 7.63 * 10
-1(blank assay is surveyed the specific conductivity of pure poly bisphenol carbonic ether film less than 10 to S/cm
-6S/cm).
Embodiment 4
1. (diameter of Single Walled Carbon Nanotube is about 1.0 nanometers to take by weighing 40 milligrams of Single Walled Carbon Nanotube with analytical balance, length is about 2.5 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of methylene dichloride organic solvents, use ultrasonic oscillation, form 20 milliliters of finely dispersed methylene dichloride suspension that contain carbon nanotube.
2. take by weighing 50 milligrams of poly bisphenol carbonic ethers with analytical balance and be loaded on 20 milliliters having in the cover glass container, add 2 milliliters of methylene dichloride organic solvent dissolutions, it is fully dissolved form transparent methylene dichloride poly bisphenol carbonate solution.In transparent methylene dichloride poly bisphenol carbonate solution, use magnetic agitation and ultrasonic oscillation number minute with the finely dispersed methylene dichloride suspension that contains carbon nanotube of the accurate transferase 45 .0 of transfer pipet milliliter successively, it is mixed.
3. uncap makes its volatile fraction solvent, to residue during 3.5 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and poly bisphenol carbonic ether weight ratio and be 1/5 polymeric film.
4. the specific conductivity with four probe method measure sample film is that (blank assay is surveyed the specific conductivity of pure poly bisphenol carbonic ether film less than 10 to 1.56S/cm
-6S/cm).
Embodiment 5
1. (diameter of Single Walled Carbon Nanotube is about 1.4 nanometers to take by weighing 40 milligrams of Single Walled Carbon Nanotube with analytical balance, length is about 6.0 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of trichloromethane organic solvents, use ultrasonic oscillation, form 20 milliliters of finely dispersed trichloromethane suspension that contain carbon nanotube 2.0 mg/ml.
2. take by weighing 400 milligrams of polymethylmethacrylates with analytical balance and be loaded on 20 milliliters having in the cover glass container, add 8 milliliters of trichloromethane organic solvent dissolutions, it is fully dissolved form transparent trichloromethane polymethyl methacrylate solution.In transparent trichloromethane polymethyl methacrylate solution, use magnetic agitation and ultrasonic oscillation number minute with the finely dispersed trichloromethane suspension that contains carbon nanotube of the accurate transferase 10 .2 of transfer pipet milliliter successively, it is mixed
3. uncap makes its volatile fraction solvent, to residue during 8.0 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and polymethylmethacrylate weight ratio and be 1/1000 polymeric film.
4. the specific conductivity with four probe method measure sample film is 1.4 * 10
-6(blank assay is surveyed the specific conductivity of pure polymethyl methacrylate film less than 10 to 5/cm
-6S/cm).
Embodiment 6
1. (diameter of Single Walled Carbon Nanotube is about 1.4 nanometers to take by weighing 40 milligrams of Single Walled Carbon Nanotube with analytical balance, length is about 6.0 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of trichloromethane organic solvents, use ultrasonic oscillation, form 20 milliliters of finely dispersed trichloromethane suspension that contain carbon nanotube 2.0 mg/ml.
2. take by weighing 200 milligrams of polymethylmethacrylates with analytical balance and be loaded on 20 milliliters having in the cover glass container, add 5 milliliters of trichloromethane organic solvent dissolutions, it is fully dissolved form transparent trichloromethane polymethyl methacrylate solution.In transparent trichloromethane polymethyl methacrylate solution, use magnetic agitation and ultrasonic oscillation number minute with the finely dispersed trichloromethane suspension that contains carbon nanotube of the accurate transferase 10 .2 of transfer pipet milliliter successively, it is mixed
3. uncap makes its volatile fraction solvent, to residue during 5.0 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and polymethylmethacrylate weight ratio and be 1/500 polymeric film.
4. the specific conductivity with four probe method measure sample film is 6.7 * 10
-6(blank assay is surveyed the specific conductivity of pure polymethyl methacrylate film less than 10 to S/cm
-6S/cm).
Embodiment 7
1. (diameter of Single Walled Carbon Nanotube is about 1.4 nanometers to take by weighing 40 milligrams of Single Walled Carbon Nanotube with analytical balance, length is about 6.0 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of trichloromethane organic solvents, use ultrasonic oscillation, form 20 milliliters of finely dispersed trichloromethane suspension that contain carbon nanotube 2.0 mg/ml.
2. take by weighing 100 milligrams of polymethylmethacrylates with analytical balance and be loaded on 20 milliliters having in the cover glass container, add 3 milliliters of trichloromethane organic solvent dissolutions, it is fully dissolved form transparent trichloromethane polymethyl methacrylate solution.In transparent trichloromethane polymethyl methacrylate solution, use magnetic agitation and ultrasonic oscillation number minute with the finely dispersed trichloromethane suspension that contains carbon nanotube of the accurate transferase 12 .5 of transfer pipet milliliter successively, it is mixed.
3. uncap makes its volatile fraction solvent, to residue during 4.0 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and polymethylmethacrylate weight ratio and be 1/20 polymeric film.
4. the specific conductivity with four probe method measure sample film is 8.8 * 10
-2(blank assay is surveyed the specific conductivity of pure polymethyl methacrylate film less than 10 to S/cm
-6S/cm).
Embodiment 8
1. (diameter of Single Walled Carbon Nanotube is about 1.4 nanometers to take by weighing 40 milligrams of Single Walled Carbon Nanotube with analytical balance, length is about 6.0 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of trichloromethane organic solvents, use ultrasonic oscillation, form 20 milliliters of finely dispersed trichloromethane suspension that contain carbon nanotube 2.0 mg/ml.
2. take by weighing 50 milligrams of polymethylmethacrylates with analytical balance and be loaded on 20 milliliters having in the cover glass container, add 2 milliliters of trichloromethane organic solvent dissolutions, it is fully dissolved form transparent trichloromethane polymethyl methacrylate solution.In transparent trichloromethane polymethyl methacrylate solution, use magnetic agitation and ultrasonic oscillation number minute with the finely dispersed trichloromethane suspension that contains carbon nanotube of the accurate transferase 45 .0 of transfer pipet milliliter successively, it is mixed
3. uncap makes its volatile fraction solvent, to residue during 3.5 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and polymethylmethacrylate weight ratio and be 1/5 polymeric film.
4. the specific conductivity with four probe method measure sample film is that (blank assay is surveyed the specific conductivity of pure polymethyl methacrylate film less than 10 to 3.48S/cm
-6S/cm).
Embodiment 9
1. (diameter of multi-walled carbon nano-tubes is about 20 nanometers to take by weighing 40 milligrams of multi-walled carbon nano-tubes with analytical balance, length is about 15 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of DMF (N, dinethylformamide) organic solvent, use ultrasonic oscillation, form 20 milliliters of finely dispersed DMF suspension that contain carbon nanotube 2.0 mg/ml.
2. take by weighing 200 milligrams of polystyrene acrylonitrile multipolymer (SAN with analytical balance; Styrene AcrylnitrileCopolymer) is loaded on 20 milliliters have in the cover glass container, adds 5 milliliters of DMF organic solvent dissolutions, it is fully dissolved form transparent DMF polystyrene acrylonitrile copolymer solution.Accurately shift 1.0 milliliters of finely dispersed DMF suspension that contain carbon nanotube in transparent DMF polystyrene acrylonitrile copolymer solution with transfer pipet, use magnetic agitation and ultrasonic oscillation number minute successively, it is mixed.
3. uncap makes its volatile fraction solvent, to residue during 5.0 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and polystyrene acrylonitrile multipolymer weight ratio and be 1/100 polymeric film.
4. the specific conductivity with four probe method measure sample film is 1.9 * 10
-4(blank assay is surveyed the specific conductivity of pure polystyrene acrylonitrile copolymer film less than 10 to S/cm
-6S/cm).
Embodiment 10
1. (diameter of multi-walled carbon nano-tubes is about 20 nanometers to take by weighing 40 milligrams of multi-walled carbon nano-tubes with analytical balance, length is about 15 microns) be loaded in 50 milliliters of Glass Containerss with cover that accurate calibration arranged, add 20 milliliters of DMF (N, dinethylformamide) organic solvent, use ultrasonic oscillation, form 20 milliliters of finely dispersed DMF suspension that contain carbon nanotube 2.0 mg/ml.
2. take by weighing 50 milligrams of polystyrene acrylonitrile multipolymer (SAN with analytical balance; Styrene AcrylnitrileCopolymer) is loaded on 20 milliliters have in the cover glass container, adds 2 milliliters of DMF organic solvent dissolutions, it is fully dissolved form transparent DMF polystyrene acrylonitrile copolymer solution.In transparent DMF polystyrene acrylonitrile copolymer solution, use magnetic agitation and ultrasonic oscillation number minute with the finely dispersed DMF suspension that contains carbon nanotube of the accurate transferase 45 .0 of transfer pipet milliliter successively, it is mixed.
3. uncap makes its volatile fraction solvent, to residue during 3.5 milliliters of liquid, the mixed solution of sample is injected mould, is placed on the air drying moulding, obtains carbon nanotube and polystyrene acrylonitrile multipolymer weight ratio and be 1/5 polymeric film.
4. the specific conductivity with four probe method measure sample film is that (blank assay is surveyed the specific conductivity of pure polystyrene acrylonitrile copolymer film less than 10 to 1.28S/cm
-6S/cm).
Claims (5)
1. conductive polymers, it is characterized in that, this conductive polymers comprises carbon nanotube, polymer materials, the weight ratio of described carbon nanotube and polymer materials is 1: 2～1000, and the structural formula that described polymer materials is selected from polyacrylate(s), described polyacrylate polymers material is:
Wherein,
R
1，R
2＝-H；
R
3=-H;-CH
3Or-CH
2CH
3
R
4=-CH
2CH
3-CH
2CH
2CH
3-CH (CH
3) CH
3Or-CH
2C
6H
5
n＝100～10000。
2. a kind of conductive polymers according to claim 1 is characterized in that: described carbon nanotube is selected from one or both the mixture in Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes.
3. conductive polymers as claimed in claim 1 is characterized in that, described conductive polymers is made by the method that comprises the steps:
(1) with mean diameter 1.0～10nm, the carbon nanotube more than the length 1 μ m is dispersed in the organic solvent with the concentration of 0.1～10mg/ml, and dispersed with stirring is made unit for uniform suspension A;
(2) be that the polymer materials of 1～15mm adds that the concentration with 5～200mg/ml is mixed with homogeneous solution B in the described organic solvent with median size;
(3) above-mentioned suspending liquid A is sneaked in the solution B, the weight ratio of carbon nanotube and polymer materials is 1: 2～1000, pours die for molding behind the uniform mixing into, makes a kind of conductive polymers.
4. the preparation method of a kind of conductive polymers according to claim 1 is characterized in that, this preparation method may further comprise the steps:
(1) with mean diameter 1.0～10nm, the carbon nanotube more than the length 1 μ m is dispersed in the organic solvent with the concentration of 0.1～10mg/ml, and dispersed with stirring is made unit for uniform suspension A;
(2) be that the polymer materials of 1～15mm adds that the concentration with 5～200mg/ml is mixed with homogeneous solution B in the organic solvent with median size;
(3) above-mentioned suspending liquid A is sneaked in the solution B, the weight ratio of carbon nanotube and polymer materials is 1: 2～1000, pours die for molding behind the uniform mixing into, makes a kind of conductive polymers.
5. the preparation method of a kind of conductive polymers according to claim 4, it is characterized in that: described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, 1,1, ammediol, glycerol, methylene dichloride, trichloromethane, tetracol phenixin, 1, the 2-ethylene dichloride, 1,1-ethylene dichloride, 1,1,1-trichloroethane, acetate, propionic acid, butyric acid, Succinic Acid, valeric acid, acetone, propione, cyclopentanone, ring ethyl ketone, methyl acetate, ethyl acetate, propyl acetate, ether, dioxane, tetrahydrofuran (THF), sherwood oil, pentane, ethane, hexanaphthene, heptane, methane amide, ethanamide, N, dinethylformamide, benzene, toluene, dimethylbenzene, pyridine, pyrroles, the mixture of one or more in the pyrazoles.
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|---|---|---|---|
| CN 200410067112 CN1760269B (en) | 2004-10-13 | 2004-10-13 | Electric polymer and preparation method |
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| CN1760269B true CN1760269B (en) | 2010-06-09 |
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| CN100434478C (en) * | 2006-09-28 | 2008-11-19 | 同济大学 | Medium temperature proton conductive mateiral basedon hydrophilic carbon nano tube and its preparing method |
| CN104194007B (en) * | 2014-09-28 | 2016-08-24 | 中国科学院理化技术研究所 | Polymer base micro-/ nano filling modifier compound premix preparation method of granules |
| CN106189164A (en) * | 2016-06-30 | 2016-12-07 | 嘉兴市高正高分子材料有限公司 | A kind of preparation method of PC/ carbon nanotube conducting master batch |
| CN108117725A (en) * | 2017-12-27 | 2018-06-05 | 张万虎 | A kind of preparation method of high-strength high conductivity carbon nanomaterial/fluoropolymer resin composite membrane |
| CN107987550A (en) * | 2017-12-27 | 2018-05-04 | 江苏飞博尔新材料科技有限公司 | A kind of preparation method of conducing composite material |
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|---|---|---|---|---|
| US20030077515A1 (en) * | 2001-04-02 | 2003-04-24 | Chen George Zheng | Conducting polymer-carbon nanotube composite materials and their uses |
| CN1569939A (en) * | 2004-04-26 | 2005-01-26 | 东华大学 | Carbon nanotube electrically conductive fibre and method for making same |
| CN1813314A (en) * | 2003-06-27 | 2006-08-02 | 通用电气公司 | Electrically conductive compositions comprising carbon nanotubes and method of manufacture thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030077515A1 (en) * | 2001-04-02 | 2003-04-24 | Chen George Zheng | Conducting polymer-carbon nanotube composite materials and their uses |
| CN1813314A (en) * | 2003-06-27 | 2006-08-02 | 通用电气公司 | Electrically conductive compositions comprising carbon nanotubes and method of manufacture thereof |
| CN1569939A (en) * | 2004-04-26 | 2005-01-26 | 东华大学 | Carbon nanotube electrically conductive fibre and method for making same |
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