CN102206356A - Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof - Google Patents
Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof Download PDFInfo
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Abstract
Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and a preparation method thereof. The composite particle has a structure that the surface of a polystyrene particle (microballoon) is covered with a casing layer, and precious metal nanoparticles are embed into the casing layer and the surface. The preparation method of the composite particles comprises that dispersing aniline in water through stirring and ultrasonic processing at a temperature below zero and mixing the dispersion and polystyrene emulsion to produce a reaction, after the reaction of the above mixture lasts for a certain time, adding orderly precious metal nanoparticle sol, ammonium persulfate aqueous solution and hydrochloric acid into the reaction products, wherein the hydrochloric acid is added dropwisely into reaction products and the mixture undergoes a reaction for 4 hours; then heating the reaction products to room temperature and making the reaction products undergo a continued reaction for 20 hours, and carrying out filtering separation, washing and drying to obtain powdery Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles.
Description
(1) technical field the invention belongs to the nano-functional material technical field, is specifically related to a kind of polystyrene/(noble metal nano particles @ polyaniline) composite particles and preparation method thereof.
(2) technical background conductive polymers latex nano-complex particle material integrates the functional of the electroconductibility of polymer self and nano particle, and having molecular structure can design, and specific conductivity can be regulated and advantage such as morphological specificity may command.Noble metal nano particles such as gold have unique optical property and good chemical stability, has the polystyrene/noble metal nano composite particles of " Fried Glutinous Rice Balls with Sesame " type structure owing to have very superior catalysis, electricity and optical property, particularly they absorb at the controlled surface plasma body resonant vibration of aqueous phase, all have broad application prospects at numerous areas such as electronics and optics, chemistry and biology transmitter, catalyzer and medical imagings.Noble metal nano particles is introduced conductive polymers latex nano-complex particle, not only can strengthen the combination stability between noble metal nano particles and the substrate, eliminate its dissipation to environment, thereby improve its work-ing life and increase its life cycle, and also be significantly improved for performances such as the catalysis of particle itself, sensings.Secondly, at its functional performance and practical application, the yardstick of noble metal nano particles and controllability thereof are one of very important characteristics, as people such as J. C. Meredith preparation and and then studied the golden nanometer particle yardstick to the influence of ultraviolet light response wavelength moving characteristic (reference 1:
Chemistry of Materials, 2009,21,5654-5663).And when using as catalyzer, then wish noble metal nano particles in this class composite particles reach finer yardstick (reference 2:
Angewandte Chemie International Edition, 2007,46,4151-4154).Therefore, the controllability of raising noble metal nano particles is very important in a composite particles technology of preparing aspect.
Is the composite particles with polymkeric substance-conducting polymer-noble metal nano particles three components of matrix (as polystyrene) for preparation with common polymer, Mangeney proposes a kind of method of static self-assembly: adopt pyrroles and amino-pyrroles surface and copolymerized at polystyrene microsphere, prepare the surface and be rich in amido modified polystyrene/polypyrrole composite particles, add the stable gold particle of Trisodium Citrate then, utilize electrostatic interaction, obtain surface attachment the polystyrene of gold particle/polypyrrole composite particles (reference 3:
Langmuir, 2006,22,10163).Armes etc. have prepared polystyrene/polypyrrole composite particles earlier, utilize the Au(III then) the redox reaction original position that takes place of ion and polypyrrole form golden nanometer particle (reference 4:
J. Mater. Chem., 2001,11,2363).Fujii has reported the building-up process of the pipe/polyhenylethylene nano latex particle that a kind of polypyrrole-palladium coats: adopting with the Polyvinylpyrolidone (PVP) is that the polystyrene particle of stablizer is as substrate, the pyrrole monomer that adds can be enriched on the particle surface in the Polyvinylpyrolidone (PVP) molecular layer, adds presoma PdCl then
2, make it be attached to the polystyrene particle surface by redox reaction, obtain composite particles (reference 5:
Langmuir, 2010,26,6230).Selvan forms vesica with polystyrene-poly divinyl pyridine segmented copolymer in toluene solvant, utilize the surface that hydrochloro-auric acid is enriched in vesica with the electrostatic interaction of poly-divinyl pyridine then, pyrroles of Jia Ruing and hydrochloro-auric acid generation oxidation-reduction reaction subsequently, produced simultaneously golden nanometer particle and conductive polymers form composite structure (reference 6:
Adv. Mater.,1998,10,132).
The characteristics of the preparation process that above-mentioned report adopted are, one adopts the on-the-spot synthetic noble metal nano particles of redox reaction, and size of particles and monodispersity are difficult to effective control usually, and noble metal nano particles is positioned at the surface of composite particles; Secondly, in order to form composite structure effectively, all need matrix surface is designed or functionalization in advance, to improve the interaction between matrix and noble metal nano particles or its precursor.
(3) summary of the invention the objective of the invention is to the preparation method that proposes a kind of polystyrene/(noble metal nano particles @ polyaniline) composite particles and realize this composite structure.
The structure of polystyrene proposed by the invention/(noble metal nano particles polyaniline) composite particles is: on polystyrene particle (microballoon) surface, be covered with the shell of polyaniline, in the polyaniline shell and the surface, be embedded with noble metal nano particles.Among the present invention, noble metal nano particles is gold and silver or Pd nano particle; The weight ratio of noble metal nano particles and polystyrene particle is no more than 3.40; The weight ratio of polyaniline and polystyrene is 1: 2 ~ 1: 20; The number average bead diameter of polystyrene particle (microballoon) is not less than 100 nanometers; The particle diameter ratio of polystyrene particle and noble metal nano particles is not less than 10.
Polystyrene with said structure proposed by the invention/(noble metal nano particles @ polyaniline) composite particles, its preparation method is: aniline monomer is added in the entry, mix with pre-prepd polystyrene emulsion, add pre-prepd monodispersed noble metal nano particles colloidal sol again, after mixing certain hour, add ammonium persulfate aqueous solution, slow dripping hydrochloric acid then, Powdered polystyrene/(the noble metal nano particles @ polyaniline) composite particles that behind the reaction certain hour, can obtain having the said structure feature.Concrete preparation process is as follows:
1. the preparation of particle
The preparation of polystyrene emulsion can be adopted conventional polymerization processs such as dispersion polymerization, as, adopt the polymerization system that comprises monomer, pure medium or alcohol-water blending agent, non-ionic type amphiphilic macromolecular stablizer and oil-soluble initiator; Also can directly select commercially available polystyrene particle (microballoon) for use, water is mixed with polystyrene emulsion.
Monodispersed noble metal nano particles colloidal sol can adopt chemical reduction method, forms redox system by separately precursor and reductive agent, selects different reaction systems and reaction conditions to prepare the different various noble metal nano particles colloidal sols of particle diameter; Also can directly select commercially available monodispersed noble metal nano particles for use, water is mixed with noble metal nano particles colloidal sol.
2. the preparation of composite particles
Aniline is joined weight in its pure water of 100 ~ 1000 times, be cooled to 0 ° of C, stir down that ultra-sonic dispersion added polystyrene emulsion after 10 ~ 20 minutes, ultrasonic and stirred 10 ~ 20 minutes, 0 ° of C continues down to stir 1 ~ 3 hour subsequently.
In above-mentioned system, add noble metal nano particles colloidal sol, under 0 ° of C, stirred 0.5 ~ 1 hour.
The aqueous solution that adds ammonium persulphate in above-mentioned system, dripping hydrochloric acid after dropwising, was reacted 4 hours under 0 ° of C then, rose to room temperature and continued reaction 20 hours.Behind the stopped reaction,, till upper solution becomes colorless,, obtain Powdered composite particles again through centrifugation, vacuum-drying with dilute hydrochloric acid solution centrifuge washing repeatedly.
Among the present invention, noble metal nano particles is gold and silver or Pd nano particle.
Among the present invention, the number average bead diameter of the polystyrene particle of selecting for use (microballoon) is not less than 100 nanometers, and the particle diameter ratio of polystyrene particle and noble metal nano particles is not less than 10.
Among the present invention, the weight ratio of noble metal nano particles and polystyrene particle is no more than 3.40.
Among the present invention, the solid content of polystyrene emulsion is 4 ~ 20 wt%; The solid content of noble metal nano particles colloidal sol is 0.1 ~ 1.0 wt%; The weight ratio of aniline and polystyrene particle is 1: 2～1: 20; The mol ratio of ammonium persulphate and aniline is about 1:1; The mol ratio of HCl and aniline is 1:1 ~ 1:2; The concentration range of hydrochloric acid is 0.25 ~ 1.00 mol/L.
The characteristics of method proposed by the invention are: be matrix with the polystyrene particle 1., need not special surface design or functionalization, whole process of preparation is oversimplified; 2. noble metal nano particles can adopt prior art to prepare in advance, has enlarged its form, the isoparametric adjustable scope of size, thereby is easy to obtain the composite particles of different performance and feature.
(4) embodiment
Embodiment 1
In four-necked bottle, 2.8 g Polyvinylpyrolidone (PVP)s are dissolved in 160 ml Virahols, be warming up to 70 ° of C.Again 0.2 g Diisopropyl azodicarboxylate is dissolved in 20 g styrene monomers, under nitrogen protection, joins in the above-mentioned solution.Mechanical stirring, 24 hours postcooling of isothermal reaction are to room temperature.The gained emulsion is washed respectively 3 times with ethanol and deionized water successively through centrifugation, is scattered in to be made into the polystyrene particle emulsion that solid content is 4.2 wt % in the pure water, and its number average bead diameter is 1800 nm.
Under the room temperature, with 36 ml concentration is that the aqueous solution of chloraurate of 0.122 wt% joins in the 111 ml deionized waters, be warming up to the solution boiling under the magnetic agitation, the 1 wt% citric acid three sodium solution that adds 3 ml, reacted 30 minutes, and obtained claret-colored golden nanometer particle colloidal sol and by centrifugal 20 ml that are concentrated to.Transmission electron microscope shows that it has monodispersity preferably, and particle diameter is about 30 nm.
0.042g aniline is joined in the 10 ml distilled water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring, add 3 g polystyrene particle emulsions, ultrasonic and stir about 15 minutes, close ultrasonic after, add 7 ml distilled water, continued to place ice-water bath 3 hours.Add the golden nanometer particle colloidal sol of 10 ml and continue in the ice-water bath and stirred 1 hour, adding 0.84 ml concentration is the ammonium persulfate aqueous solution of 1 mol/L, stirs after 5 minutes, and slowly dripping 0.45 ml concentration is the hydrochloric acid of 1 mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with dilute hydrochloric acid centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with golden nanometer particle.The particle diameter ratio of polystyrene particle and golden nanometer particle is 60.The weight ratio of golden nanometer particle and polystyrene particle is 0.09, and the weight ratio of polyaniline and polystyrene is 1: 3.75.
Polystyrene emulsion and golden nanometer particle colloidal sol that embodiment 2 adopts in the example 1.
0.010 g aniline is joined in the 10 ml distilled water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring, add 3 g polystyrene particle emulsions, ultrasonic and stir about 15 minutes, close ultrasonic after, add 7 ml distilled water, continued to place ice-water bath 3 hours.Add the golden nanometer particle colloidal sol of 10 ml and continue ice-water bath stirring 1 hour, adding 0.20 ml concentration is the ammonium persulfate aqueous solution of 1 mol/L, stirs after 5 minutes, and slowly dripping 0.11 ml concentration is the hydrochloric acid of 1 mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with dilute hydrochloric acid centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal again with supernatant liquid, after vacuum-drying obtains powdered samples.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with golden nanometer particle.The particle diameter ratio of polystyrene particle and golden nanometer particle is 60.The weight ratio of golden nanometer particle and polystyrene particle is 0.09, and the weight ratio of polyaniline and polystyrene is 1: 12.
The polystyrene emulsion that embodiment 3 adopts in the example 1.
Under the room temperature, with 36 ml concentration is that the aqueous solution of chloraurate of 0.122 wt% joins in the 111 ml deionized waters, be warming up to the solution boiling under the magnetic agitation, the 1 wt% citric acid three sodium solution that adds 3 ml, reacted 30 minutes, and obtained claret-colored golden nanometer particle colloidal sol and by centrifugal 10 ml that are concentrated to.Transmission electron microscope shows that it has monodispersity preferably, and particle diameter is about 30 nm.
0.042g aniline is joined in the 10 ml distilled water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring, add 3 g polystyrene particle emulsions, ultrasonic and stir about 15 minutes, close ultrasonic after, add 7 ml distilled water, continued to place ice-water bath 3 hours.Add the golden nanometer particle colloidal sol of 10 ml and continue in the ice-water bath and stirred 1 hour, adding 0.84 ml concentration is the ammonium persulfate aqueous solution of 1 mol/L, stirs after 5 minutes, and slowly dripping 0.45 ml concentration is the hydrochloric acid of 1 mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with dilute hydrochloric acid centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with golden nanometer particle.The particle diameter ratio of polystyrene particle and golden nanometer particle is 60.The weight ratio of golden nanometer particle and polystyrene particle is 0.15, and the weight ratio of polyaniline and polystyrene is 1: 3.75.
The polystyrene emulsion that embodiment 4 adopts in the example 1.
Under the room temperature, with 36 ml concentration is that the aqueous solution of chloraurate of 0.122 wt% joins in the 113 ml deionized waters, be warming up to the solution boiling under the magnetic agitation, the 1 wt% citric acid three sodium solution that adds 0.84 ml, reacted 30 minutes, and obtained claret-colored golden nanometer particle colloidal sol and by centrifugal 20 ml that are concentrated to.Transmission electron microscope shows that it has monodispersity preferably, and particle diameter is about 80 nm.
0.014 g aniline is joined in the 10 ml distilled water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring, add 3 g polystyrene particle emulsions, ultrasonic and stir about 15 minutes, close ultrasonic after, add 7 ml distilled water, continued to place ice-water bath 3 hours.Add the golden nanometer particle colloidal sol of 10 ml and continue ice-water bath stirring 1 hour, adding 0.28 ml concentration is the ammonium persulfate aqueous solution of 1 mol/L, stirs after 5 minutes, slowly drips the hydrochloric acid that 0.15ml concentration is 1 mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with dilute hydrochloric acid centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with golden nanometer particle.The particle diameter ratio of polystyrene particle and golden nanometer particle is 23.The weight ratio of golden nanometer particle and polystyrene particle is 0.08, and the weight ratio of polyaniline and polystyrene is 1: 9.5.
The polystyrene emulsion that embodiment 5 adopts in the example 1.
Under the room temperature, with 15 ml concentration is that the silver nitrate aqueous solution of 0.216 wt% joins in the 180 ml deionized waters, be warming up to the solution boiling under the magnetic agitation, the 10 wt% citric acid three sodium solutions that add 0.54 ml, reacted 30 minutes, obtain yellowish green Nano silver grain colloidal sol and by centrifugal 10 ml that are concentrated to, transmission electron microscope shows that its particle diameter is about 60 nm.
0.042 g aniline is joined in the 10 ml distilled water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring, add 3 g polystyrene particle emulsions, ultrasonic and stir about 15 minutes, close ultrasonic after, add 7 ml distilled water, continued ice-water bath 3 hours.Add the Nano silver grain colloidal sol of 10 ml and continue ice-water bath stirring 1 hour, adding 0.84 ml concentration is the ammonium persulfate aqueous solution of 1 mol/L, stirs after 5 minutes, and slowly dripping 0.45 ml concentration is the hydrochloric acid of 1 mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with dilute hydrochloric acid centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with Nano silver grain.The particle diameter ratio of polystyrene particle and Nano silver grain is 30.The weight ratio of Nano silver grain and polystyrene particle is 0.10, and the weight ratio of polyaniline and polystyrene is 1: 3.75.
The polystyrene emulsion that embodiment 6 adopts in the example 1.
Adopt the Nano silver grain colloidal sol in the example 5.
0.010 g aniline is joined in the 10 ml distilled water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring, add 3 g polystyrene particle emulsions, ultrasonic and stir about 15 minutes, close ultrasonic after, add 7 ml distilled water, continued ice-water bath 3 hours.Add the Nano silver grain colloidal sol of 10 ml and continue ice-water bath stirring 1 hour, adding 0.20 ml concentration is the ammonium persulfate aqueous solution of 1 mol/L, stirs after 5 minutes, and slowly dripping 0.11 ml concentration is the hydrochloric acid of 1 mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with dilute hydrochloric acid centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with Nano silver grain.The particle diameter ratio of polystyrene particle and Nano silver grain is 30.The weight ratio of Nano silver grain and polystyrene particle is 0.10, and the weight ratio of polyaniline and polystyrene is 1: 12.
Claims (7)
1. polystyrene/(noble metal nano particles polyaniline) composite particles is characterized in that being covered with on polystyrene particle (microballoon) surface shell of polyaniline, in the polyaniline shell and the surface, is embedded with noble metal nano particles; The weight ratio of noble metal nano particles and polystyrene particle is no more than 3.40; The weight ratio of polyaniline and polystyrene is 1: 2 ~ 1: 20; The number average bead diameter of polystyrene particle (microballoon) is not less than 100 nanometers; The particle diameter ratio of polystyrene particle and noble metal nano particles is not less than 10.
2. according to the described polystyrene of claim 1/(noble metal nano particles @ polyaniline) composite particles, it is characterized in that noble metal nano particles is gold and silver or Pd nano particle.
3. the preparation method of polystyrene/(noble metal nano particles polyaniline) composite particles is characterized in that preparation process is as follows:
A. polystyrene particle (microballoon) is selected in the preparation of particle for use, and water is mixed with the polystyrene emulsion that solid content is 4 ~ 20 wt%;
Select monodispersed noble metal nano particles for use, water is mixed with the noble metal nano particles colloidal sol that solid content is 0.1 ~ 1.0 wt%; Noble metal nano particles is gold and silver or Pd nano particle;
B. the preparation of composite particles joins weight in its pure water of 100 ~ 1000 times with aniline, be cooled to 0 ° of C, stirring down, ultra-sonic dispersion added polystyrene emulsion after 10 ~ 20 minutes, ultrasonic and stirred 10 ~ 20 minutes, 0 ° of C continues down to stir 1 ~ 3 hour subsequently; In above-mentioned system, add noble metal nano particles colloidal sol, under 0 ° of C, stirred 0.5 ~ 1 hour; The aqueous solution that in above-mentioned system, adds ammonium persulphate, dripping hydrochloric acid then, after dripping off, 0 ° of C reacted 4 hours down, rise to room temperature and continue reaction 20 hours, with dilute hydrochloric acid solution centrifuge washing repeatedly, till upper solution becomes colorless, through centrifugation, vacuum-drying, obtain Powdered composite particles again.
4. according to the preparation method of the described polystyrene of claim 3/(noble metal nano particles @ polyaniline) composite particles, the weight ratio that it is characterized in that aniline and polystyrene particle is 1: 2 ~ 1: 20.
5. according to the preparation method of the described polystyrene of claim 3/(noble metal nano particles @ polyaniline) composite particles, it is characterized in that the mol ratio of ammonium persulphate and aniline is about 1:1.
6. according to the preparation method of the described polystyrene of claim 3/(noble metal nano particles @ polyaniline) composite particles, the mol ratio that it is characterized in that HCl and aniline is 1:1 ~ 1:2, and the concentration of hydrochloric acid scope is 0.25 ~ 1.00 mol/L.
7. according to the preparation method of the described polystyrene of claim 3/(noble metal nano particles @ polyaniline) composite particles, it is characterized in that the particle diameter ratio of polystyrene particle particle diameter and noble metal nano particles is not less than 10; The number average bead diameter of polystyrene particle is not less than 100 nanometers; The weight ratio of noble metal nano particles and polystyrene particle is no more than 3.40.
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| CN104974519A (en) * | 2015-08-03 | 2015-10-14 | 安徽理工大学 | Preparation method of fibrous Pd/PANI (polyaniline) nano composite material |
| CN105061759A (en) * | 2015-08-03 | 2015-11-18 | 安徽理工大学 | Preparation method for Pd / PANI nano composite material |
| CN105315565A (en) * | 2015-11-27 | 2016-02-10 | 湖北大学 | Sulfonated polystyrene/polyaniline/nano silver compound microsphere and preparation method thereof |
| CN106409381A (en) * | 2016-11-02 | 2017-02-15 | 宁波鸿源电子科技有限公司 | Polyaniline enhanced conductive aluminum sheet |
| CN109921048A (en) * | 2019-03-18 | 2019-06-21 | 岭南师范学院 | A kind of Pd/Ag/PANI nanocomposite and its low temperature preparation method and application |
| CN110459342A (en) * | 2019-08-16 | 2019-11-15 | 戴洪卫 | It is a kind of with the composite high-molecular conductive material and preparation method thereof for stablizing conductivity |
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| CN102702636A (en) * | 2012-06-14 | 2012-10-03 | 南京大学 | Polystyrene/polyaniline/magnetic nanoparticle composite particle and preparation method thereof |
| CN105061759B (en) * | 2015-08-03 | 2017-10-24 | 安徽理工大学 | A kind of preparation method of Pd/PANI nano composite materials |
| CN104974519A (en) * | 2015-08-03 | 2015-10-14 | 安徽理工大学 | Preparation method of fibrous Pd/PANI (polyaniline) nano composite material |
| CN105061759A (en) * | 2015-08-03 | 2015-11-18 | 安徽理工大学 | Preparation method for Pd / PANI nano composite material |
| CN104974519B (en) * | 2015-08-03 | 2017-10-24 | 安徽理工大学 | A kind of preparation method of fibrous Pd/PANI nano composite materials |
| CN105315565A (en) * | 2015-11-27 | 2016-02-10 | 湖北大学 | Sulfonated polystyrene/polyaniline/nano silver compound microsphere and preparation method thereof |
| CN105315565B (en) * | 2015-11-27 | 2018-08-03 | 湖北大学 | A kind of sulfonated polystyrene/polyaniline/nano silver complex microsphere and preparation method thereof |
| CN106409381A (en) * | 2016-11-02 | 2017-02-15 | 宁波鸿源电子科技有限公司 | Polyaniline enhanced conductive aluminum sheet |
| CN106409381B (en) * | 2016-11-02 | 2018-02-16 | 宁波鸿源电子科技有限公司 | A kind of polyaniline strengthens conductive aluminium flake |
| CN109921048A (en) * | 2019-03-18 | 2019-06-21 | 岭南师范学院 | A kind of Pd/Ag/PANI nanocomposite and its low temperature preparation method and application |
| CN109921048B (en) * | 2019-03-18 | 2020-12-15 | 岭南师范学院 | Pd/Ag/PANI nano composite material and low-temperature preparation method and application thereof |
| CN110459342A (en) * | 2019-08-16 | 2019-11-15 | 戴洪卫 | It is a kind of with the composite high-molecular conductive material and preparation method thereof for stablizing conductivity |
| CN110791090A (en) * | 2019-10-11 | 2020-02-14 | 杭州师范大学 | Macroscopic large-area two-dimensional dual-response high-plasma-sensitivity switch polyaniline @ gold nanoparticle core-shell-structure single-layer film |
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