CN100344652C - Polymer/carbon mano-tube composite film and its preparation method - Google Patents
Polymer/carbon mano-tube composite film and its preparation method Download PDFInfo
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- CN100344652C CN100344652C CNB200410096856XA CN200410096856A CN100344652C CN 100344652 C CN100344652 C CN 100344652C CN B200410096856X A CNB200410096856X A CN B200410096856XA CN 200410096856 A CN200410096856 A CN 200410096856A CN 100344652 C CN100344652 C CN 100344652C
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Abstract
The present invention discloses a high molecular / carbon nanotube composite membrane and a preparation process thereof. The high molecular / carbon nanotube composite membrane of the present invention contains a high molecular base and carbon nanotubes, and the weight part proportion of the high molecular base and the carbon nanotubes is 10 to 500/1. The carbon nanotubes have defined orientation in the high molecule base. The preparation process comprises the following steps: 1) adding the carbon nanotubes into ionic surfactant solution of which the concentration is 0.01 to 1 mol/L to be dispersed in ultrasonic way to form stable suspending liquid; 2), regulating the temperature of the stable suspending liquid to 0 to 25 DEG C, and adding high molecular monomers to be dispersed in an ultrasonic way; 3), regulating the temperature of the liquid obtained by the second step to-10 to 25 DEG C, and regulating the pH valve to 3.5 to 7.5 by adding acid; 4), using the mixed liquid obtained by the third step as electrolytic liquid to make electrochemical polymerization and obtain the high molecular / carbon nanotube composite membrane. The high molecular / carbon nanotube composite membrane can be widely used for (electric) chemical sensors, field emitting devices, etc.
Description
Technical field
The present invention relates to polymer composite and preparation method thereof, particularly relate to a kind of polymer/carbon mano-tube composite film and preparation method thereof.
Background technology
Carbon nanotube (perhaps CNT (carbon nano-tube)) is just found a kind of novel carbon structure in 1991, and it is seamless, the hollow tube body that is rolled into by the graphene film that carbon atom forms, and generally can be divided into Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes.Because the diameter of carbon nanotube is very little, length-to-diameter ratio is big, so the visual one-dimensional material that is as the criterion.Theoretical prediction and experimental study result show that the electronic band structure of carbon nanotube is special, and wave vector is defined to axially, quantum effect is obvious, have the emission threshold value low, emission is big, the field emission performance of stable high excellence can be used for making the high-performance flat-panel monitor; Test finds that also Single Walled Carbon Nanotube is real quantum lead, can be used for making nano electron devices such as transistor.The structure of carbon nanotube is complete Graphene grid, and its theoretical strength approaches the intensity of carbon-carbon bond.Its intensity of theoretical prediction is approximately 100 times of steel, and density has only 1/6 of steel, and has good flexible, therefore be called as super fiber, the enhancing body that can be used for advanced composite materials is made lightweight, high-strength space hawser, exhibits one's skill to the full in high-tech sectors such as Aeronautics and Astronautics.
At present, along with the realization of carbon nanotube large-scale production, people more and more pay attention to the applied research of carbon nanotube.Wherein, be filled in the polymer as conduction or reinforcing filler, the polymer/carbon mano-tube composite that preparation has ad hoc structure or function is an extremely important application direction of carbon nanotube.For example, add 1% carbon nanotube in industrial Resins, epoxy, its thermal conductivity has increased by 70% and 125% respectively under 40K and room temperature; The Single Walled Carbon Nanotube of adding 1% can improve the mechanical property of polystyrene greatly and make external load transfer on the carbon nanotube effectively in polystyrene; The adding carbon nanotube can improve the electric property of polyaniline etc. greatly in polyaniline.The complex method that has developed at present has multiple, as adopting polymer is joined solution mixing method in the organic solution of carbon nanotube, carbon nanotube directly is distributed to polymer melts melting mixing method in the body, carbon nanotube is grafted to grafting method on the macromolecular chain, situ aggregation method in the presence of carbon nanotube and electrochemical method etc.Yet, adopt these conventional complex methods that carbon nanotube is orientated in macromolecule matrix in order, this has limited the excellent properties of having given play to carbon nanotube in matrix material to greatest extent to a great extent.
In order to realize the orderly orientation of carbon nanotube in macromolecule matrix, method commonly used at present has: 1) adopt the carbon nanotube (carbon nano pipe array) that is orientated in advance directly to carry out in-situ polymerization, this method needs the synthetic and transfer techniques of carbon nano pipe array; 2) adopt cut mechanically induced carbon nanotube orientation, although this method has realized the orientation of carbon nanotube, what obtain is destructive matrix material; 3) adopt electrospinning silk technology, the conjugated fibre often that obtains; 4) utilize the auxiliary method in magnetic field, this method needs expensive externally-applied magnetic field equipment, and cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of polymer/carbon mano-tube composite film and preparation method thereof.
Polymer/carbon mano-tube composite film provided by the present invention, containing ratio of weight and number is 10-500: 1 macromolecule matrix and carbon nanotube, described carbon nanotube is ordered arrangement in described macromolecule matrix.
This polymer/carbon mano-tube composite film is prepared according to the following procedure: 1) add carbon nanotube in concentration is the ionogenic surfactant solution of 0.01-1mol/L, ultra-sonic dispersion is to forming steady suspension, and the add-on of described carbon nanotube is 0.1-3mg carbon nanotube/ml solution; 2) regulate suspension temperature between 0-25 ℃, to wherein adding high polymer monomer, ultra-sonic dispersion, the mass ratio of described high polymer monomer and described carbon nanotube are 10-500: 1; 3) regulating step 2) the gained fluid temperature between-10-25 ℃, add acid for adjusting pH 3.5-7.5; 4) be electrolytic solution with step 3) gained mixed solution, carry out electrochemical polymerization, obtain described polymer/carbon mano-tube composite film.
Wherein, described ionogenic surfactant is an anion surfactant, or has the quaternary ammonium cation tensio-active agent of formula I structure,
Wherein, R
1For carbon atom is the alkyl of 8-20; R
2Be methyl or ethyl; R
3Be methyl or ethyl; R
4Be methyl or ethyl; X is a halogen atom.
Anion surfactant commonly used has sulfate type, anion surfactants such as sulfonate type or carboxylic acid type.
When carrying out ultra-sonic dispersion, used ultrasonic power is 600-2400W; Ultrasonic frequency is 19-80KHz.The high polymer monomer that can adopt the inventive method to be prepared as polymer/carbon mano-tube composite film has multiple, and commonly used have aniline, pyrroles, a vinylbenzene etc.
Mixed solution through above-mentioned dispersion treatment can be directly as electrolytic solution, adopt two electrodes or three-electrode system, use continuous current, conventional electrochemical methods such as permanent unit or cyclic voltammetric, at conductor (as gold electrode, inert metal electrodes such as platinum electrode, nickel electrode, conductive glass electrodes such as active metal electrodes such as electrolytic iron or tin indium oxide) or semi-conductor (as p type or n type silicon electrode) electrode surface carries out electropolymerization, and (current potential that is applied or electric current can cause the polymer electropolymerization, and the electrochemical reaction that does not cause electrode itself gets final product), promptly can obtain polymer/carbon mano-tube composite film, carbon nanotube has the orientation perpendicular to electrode surface in composite membrane.
The present invention adopts the method for tensio-active agent aid dispersion, realize the good distribution of carbon nanotube in aqueous medium, and with the supporting electrolyte of tensio-active agent as electrochemical polymerization, can guarantee the homodisperse of carbon nanotube in macromolecule matrix to greatest extent, and, realize the orientations of carbon nanotube in macromolecule matrix in the mode of original position electropolymerization.It is few that the inventive method has a facility investment, characteristics such as technological operation is simple, carbon nanotube in the gained polymer/carbon mano-tube composite film has definite orientation (direction of carbon nanotube is vertical substantially with the electrode surface of film forming direction), can be widely used in aspects such as () chemical sensor, feds.
Description of drawings
Figure 1A is 5000 times of electromicroscopic photographs of complexes membrane of the present invention;
Figure 1B is 30000 times of electromicroscopic photographs of complexes membrane of the present invention;
Fig. 1 C is the spectrogram of thing complexes membrane of the present invention.
Embodiment
Embodiment 1, polypyrrole/single-wall carbon nanotube composite film
1, the preparation of electrolytic solution
In the lauryl sodium sulfate aqueous solution of 35 milliliters of 1mol/L, adding Single Walled Carbon Nanotube makes its concentration reach 0.1mg/ml, ultra-sonic dispersion (power of ultrasonic generator is 2400W, and frequency is 80KHz) obtained finely dispersed carbon nano tube suspension after 4 hours; After this suspension is cooled to 0-5 ℃, adds pyrrole monomer and make its concentration be about 50mg/ml, ultra-sonic dispersion is cooled to 0-5 ℃ once more, regulates its pH value in about 7.5 with the HCl solution of 0.1M.
2, electrochemical polymerization
This mixture adopts the three-electrode electro Chemical device to carry out electrochemical polymerization as the electrolytic solution of follow-up electrochemical polymerization, and working electrode is a gold electrode, and reference electrode is a saturated calomel electrode, and counter electrode is a platinum electrode.Adopt the cyclic voltammetric polymerization methods, the potential scan scope is from-0.2V to+0.8V, and sweep velocity 50mV/s, scanning times depend on the thickness of resultant target complexes membrane, and scanning times is 10 circulations in the present embodiment.After electrochemical polymerization finishes, take out working electrode and wash complexes membrane repeatedly for several times with deionized water and dehydrated alcohol.
3, the detection of composite membrane
Prepared polypyrrole really/carbon nanotube polymer film on the vibrational spectrum data sheet prescribed electrode surface.
Figure 1A and Figure 1B all are electromicroscopic photographs of polypyrrole/carbon mano-tube composite film, and Figure 1A is 5000 times of photos;
Figure 1B is 30000 times of photos, can find out clearly from electromicroscopic photograph, and carbon nanotube has definite orientation in macromolecule matrix.Infrared spectra and the Raman spectrum data of Fig. 1 C show that all the base material of the complexes membrane of gained is the polypyrrole of electropolymerization really.
Embodiment 2, polyaniline/multi-walled carbon nano-tubes complex thin film
1, the preparation of electrolytic solution
In the sodium dodecyl sulfate aqueous solution of 50 milliliters of 0.01mol/L, adding multi-walled carbon nano-tubes makes its concentration reach 3mg/ml, ultra-sonic dispersion (power of ultrasonic generator is 600W, and frequency is 19KHz) obtained finely dispersed carbon nano tube suspension after 3 hours; After this suspension is cooled to 0-5 ℃, adds aniline monomer and make its concentration be about 30mg/ml, ultra-sonic dispersion is cooled to 0-5 ℃ once more, with the H of 1M
2SO
4Solution is regulated its pH value in about 3.5.
2, electrochemical polymerization
This mixture adopts the three-electrode electro Chemical device to carry out electrochemical polymerization as the electrolytic solution of follow-up electrochemical polymerization, and working electrode is the ITO conductive glass electrode, and reference electrode is a saturated calomel electrode, and counter electrode is a platinum electrode.Adopt the constant potential polymerization methods, the polymerization electromotive force is+0.8V that the thickness of complexes membrane depends on the time of electropolymerization under this current potential.Can be observed obvious sedimentary complexes membrane after usually 10 seconds.After electrochemical polymerization finishes, take out working electrode and wash complexes membrane repeatedly for several times with deionized water and dehydrated alcohol.
Embodiment 3, polystyrene/single-wall carbon nanotube composite film
1, the preparation of electrolytic solution
In the Trimethyllaurylammonium bromide aqueous solution of 40 milliliters of 0.5mol/L, adding Single Walled Carbon Nanotube makes its concentration reach 0.5mg/ml, ultra-sonic dispersion (power of ultrasonic generator is 1200W, and frequency is 60KHz) obtained finely dispersed carbon nano tube suspension after 5 hours; After being cooled to this suspension about 15 ℃, adding styrene monomer and make its concentration be about 10mg/ml, ultra-sonic dispersion is cooled to 0-5 ℃ once more, regulates its pH value in about 6.5 with the HCl solution of 0.1M.
2, electrochemical polymerization
This mixture adopts the three-electrode electro Chemical device to carry out electrochemical polymerization as the electrolytic solution of follow-up electrochemical polymerization, and working electrode is the doped silicon electrode, and reference electrode is a saturated calomel electrode, and counter electrode is a platinum electrode.Adopt the continuous current polymerization methods, the polymerization current density is 1mA/cm
2, the thickness of complexes membrane depends on the time of electropolymerization under this current density.Can be observed obvious sedimentary complexes membrane after usually 10 seconds.After electrochemical polymerization finishes, take out working electrode and wash complexes membrane repeatedly for several times with deionized water and dehydrated alcohol.
Claims (5)
1, the preparation carbon nanotube is the method for the polymer/carbon mano-tube composite film of ordered arrangement in macromolecule matrix, comprise the steps: 1) in being the ionogenic surfactant solution of 0.01-1mol/L, concentration adds carbon nanotube, ultra-sonic dispersion is to forming steady suspension, and the add-on of described carbon nanotube is 0.1-3mg carbon nanotube/ml solution; 2) regulate suspension temperature between 0-25 ℃, to wherein adding high polymer monomer, ultra-sonic dispersion, the mass ratio of described high polymer monomer and described carbon nanotube are 10-500: 1; 3) regulating step 2) the gained fluid temperature between-10-25 ℃, add acid for adjusting pH 3.5-7.5; 4) be electrolytic solution with step 3) gained mixed solution, carry out electrochemical polymerization, obtain described polymer/carbon mano-tube composite film.
2, preparation method according to claim 1 is characterized in that: described ionogenic surfactant is anion surfactant or quaternary ammonium cation tensio-active agent with formula I structure;
Wherein, R
1For carbon atom is the alkyl of 8-20; R
2Be methyl or ethyl; R
3Be methyl or ethyl; R
4Be methyl or ethyl; X is a halogen atom.
3, preparation method according to claim 2 is characterized in that: described anion surfactant is a sulfate type, sulfonate type or carboxylic acid type anion surfactant.
4, according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: the used ultrasonic power of described ultra-sonic dispersion is 600-2400W; Ultrasonic frequency is 19-80KHz.
5, according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: described high polymer monomer is aniline, pyrroles or vinylbenzene.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100469691C (en) * | 2006-07-17 | 2009-03-18 | 中国科学院过程工程研究所 | Method of improving chemical activity of carbon nano-tube |
| CN101235193B (en) * | 2008-01-15 | 2010-12-08 | 北京科技大学 | Method for preparing degradable biocompatibility macromolecule/carbon nano-tube composite material |
| CN101659789B (en) * | 2008-08-29 | 2012-07-18 | 清华大学 | Preparation method for carbon nano tube/conducting polymer composite material |
| CN102544501A (en) * | 2012-02-09 | 2012-07-04 | 东南大学 | Method for preparing polypyrrole nanometer wire-graphene composite material |
| CN103093972B (en) * | 2013-01-25 | 2015-08-12 | 中北大学 | Be applied to the preparation method of the compound film electrode material of MEMS supercapacitor |
| CN103273661A (en) * | 2013-06-27 | 2013-09-04 | 中国兵器工业集团第五三研究所 | In-plane oriented carbon nano tube reinforced resin film and preparation method thereof |
| CN111223678A (en) * | 2020-01-08 | 2020-06-02 | 重庆电子工程职业学院 | Method for preparing PPy flexible capacitor film conductor with porous structure |
| CN112409591A (en) * | 2020-11-20 | 2021-02-26 | 复旦大学 | In-situ super-assembling preparation method of high molecular polymer/carbon nano tube compound |
| CN112201795B (en) * | 2020-12-03 | 2021-03-23 | 季华实验室 | Polymer composite coating preparation method, bipolar plate and proton exchange membrane fuel cell |
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| CN1401455A (en) * | 2001-08-24 | 2003-03-12 | 株式会社日立制作所 | Friction stirring joining method |
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| CN1401455A (en) * | 2001-08-24 | 2003-03-12 | 株式会社日立制作所 | Friction stirring joining method |
Non-Patent Citations (3)
| Title |
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| 碳纳米管/导电聚苯胺纳米复合纤维的合成与表征 黄大庆、丁鹤雁、刘俊能，《功能材料》，第34卷第2期 2003 * |
| 碳纳米管-聚合物复合材料的研究进展 沈广霞、庄燕燕、林昌健，《化学进展》，第16卷第1期 2004 * |
| 纳米碳管/聚合物功能复合材料 李莉香、李峰、英哲、杨全红，成会明，《新型炭材料》，第18卷第1期 2003 * |
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