CN101781520A - Water-based conducting polymer/metal composite nano-coating for porous wall board and preparation method thereof - Google Patents
Water-based conducting polymer/metal composite nano-coating for porous wall board and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of functional materials, in particular to a water-based conducting polymer/metal composite nano-coating for a porous wall board and a preparation method thereof. In the invention, the water-based conducting polymer/metal composite nano-coating for the porous wall board is a water-based disperse system of a conducting polymer/metal nano-core-shell structure, and the size of the conducting polymer/metal nano-core-shell structure is 20-300 nanometers, wherein the sizes of metal nano-particles of the core layer are 10-100 nanometers, the sizes of conducting polymers of the shell layer are 10-200 nanometers, and the molar ratio of the metal nano-particles to the conducting polymer monomers is 1:1-1:10. The water-based composite coating of the invention has no pollution and good stability and can be directly sprayed into holes of the porous wall board.
Description
Technical field
The present invention relates to field of functional materials, particularly, the present invention relates to a kind of water-based conducting polymer/metal composite nano-coating that is used for porous wall board and preparation method thereof.
Background technology
Along with fast development of information technology, computer network, information processing device, electronic communication equipment and various electrical equipment as the carrier of information technology in the industry-by-industry widespread use.For the electromagnetic radiation of attenuation apparatus and interference each other, eliminate space-pollution, prevent information-leakage, ensure person health, need carry out shielding processing to hertzian wave, the electromagnetic shielding problem has become very urgent problem in the modern protection works.
In recent years, many shield technologies have been developed, as metal meltallizing (cathode) sputtering, subsides tinsel, electroless plating etc., wherein electromagnetic screen coating have that cost is low, technology is easy (can spraying, blade coating, brushing etc.), practical, easily realize automatization and the advantages such as shell shape that can adapt to more complicated becoming present widely used electromagnetic shielding material.Common electromagnetic screen coating is made up of film forming matter, conductive filler material, auxiliary agent, solvent etc., it is coated on substrate surface forms one deck cured film, thereby produce the conductive shield effect.Conductive filler material commonly used is non-metal powders such as metal-powders such as silver, copper, nickel, carbon black, graphite and oxide compound.Wherein, the electroconductibility of silver powder is good, but costs an arm and a leg, and is difficult to popularize utilize.Copper is that the electroconductibility and the effectiveness of coating is good, but oxidation-resistance is poor.The nickel powder coating price is moderate, and resistance of oxidation is stronger than copper powder, is coating at the shield effectiveness of low frequency range not as copper but nickel is coating.Carbon black, graphite is as electrically conducting coating, its poorly conductive, and effectiveness is bad.The electroconductibility of other oxide-based conductive filler materials is difficult to reach requirement.Problems such as in addition, at present the electromagnetic screen coating of development is difficult to regulate effectiveness of shielding, and area density height, sticking power are low have limited applying of shielding coating.In addition, used solvent mainly is an organic solvent, easily causes the pollution of environment.
Along with the appearance and the fast development of conducting polymer, the characteristics that they have, and chemical stability is good, easy to use, light weight, easily machine-shaping, specific conductivity are easy to regulate have potential advantages in the shielding electromagnetic wave field.Can not only pass through the reflection loss hertzian wave, and absorption loss has more advantage, can remedy the defective of metallic substance.
Summary of the invention
The present inventor proposes and has finished the present invention in order to address the above problem.
The purpose of this invention is to provide a kind of water-based conducting polymer/metal composite nano-coating that is used for porous wall board.
A further object of the present invention provides the above-mentioned method that is used for the water-based conducting polymer/metal composite nano-coating of porous wall board of preparation.
According to the water-based conducting polymer/metal composite nano-coating that is used for porous wall board of the present invention, wherein, described composite nano-coating is the dispersion system of conducting polymer/metal nano core-shell structure, described conducting polymer/metal nano core-shell structure is of a size of the 20-300 nanometer, wherein the metal nanoparticle of stratum nucleare is of a size of 10～100 nanometers, the conducting polymer of shell is of a size of 10～200 nanometers, described metal nanoparticle is for being selected from nanometer silver, nanometer nickel, nano hydroxy ferrite, in the nanometer copper one or more, the monomer of described conducting polymer is for being selected from aniline, the pyrroles, thiophene, the alkylated substituted thiazoline fen, in the diethoxy thiophene one or more, the mol ratio of described metal nanoparticle and described conductive high polymer monomer are 1: 1～1: 10.
According to the water-based conducting polymer/metal composite nano-coating that is used for porous wall board of the present invention, its principle based on: metal nanoparticle is modified, be easy to form the nucleocapsid structure of conducting polymer/metal nano particle, this structure can prevent the oxidation of metal nano material.Therefore the organic acid that the doping agent of conductive polymers uses, has increased the dispersiveness of conducting polymer/metal nano composite material in water, has improved the stability of coating.In addition, the electroconductibility that the characteristic and the high-conductivity polymer of the high conduction of metal-powder is controlled combines, in the range of frequency of adjusting its shielding electromagnetic wave.
Method according to the above-mentioned water-based conducting polymer/metal composite nano-coating of preparation of the present invention may further comprise the steps:
1) be that 0.01～0.5% tensio-active agent is added to the water by weight percentage, add the ultrasonic mixing of metal nanoparticle again, filtering separation, washing, drying, obtain the metal nanoparticle of modification, wherein the metal nanoparticle add-on is a 100g/L water, and described metal nanoparticle is to be selected from nanometer silver, nanometer nickel, nanometer zinc, nanometer iron, nanometer iron carbonyl, the nanometer copper one or more;
2) modified metal nanoparticles that step 1) is obtained adds in the entry, and ultra-sonic dispersion is to even, and the add-on of modified metal nanoparticle is every premium on currency 10～100 mmoles;
3) high polymer monomer and organic acid are added step 2) in the modified metal nanoparticles solution that obtains, ultrasonic mixing, form mixed emulsion, monomeric add-on is every liter of mixed solution 100～1000 mmoles, organic acid add-on and monomeric molar ratio are 1: 1, described high polymer monomer is to be selected from aniline, pyrroles, thiophene, alkylated substituted thiazoline fen, the diethoxy thiophene one or more
Described organic acid is Witco 1298 Soft Acid, oleic acid, dodecyl sodium sulfonate, helianthic acid, camphorsulfonic acid, p-methyl benzenesulfonic acid, citric acid, oxysuccinic acid, oxalic acid or tartrate;
4) preparation aqueous oxidizing agent solution, its concentration is 100～8000 mmoles/L;
5) oxidizing agent solution with step 4) joins in the mixed emulsion of step 3), and oxygenant and monomeric mol ratio are 1: 1～1: 8, and stirring reaction 10～24 hours filters, and cleans, and obtains the nano particle of conducting polymer/metal nucleocapsid structure;
6) compound concentration is the water-soluble polymer aqueous solution of 50～150 gram/L;
7) in the polymer aqueous solution that the nano combined nanoparticulate dispersed of the conducting polymer/metal that step 5) is obtained obtains to step 6), ultrasonic mixing forms the water-based conducting polymer/metal nano composite dope, and the add-on of the nano combined nano particle of conducting polymer/metal is every rising molecular water solution 10～500 grams.
The method according to this invention, wherein, in step 1), described tensio-active agent comprises: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, oleic acid, stearic acid.
The method according to this invention, wherein, in step 4), described oxygenant comprises: persulphate, dichromate, potassium permanganate, potassium periodate, hyperbromic acid potassium, potassium perchlorate, hydrogen peroxide, iron trichloride, ferric sulfate, cerous sulfate, cerous nitrate, cupric chloride or benzoyl peroxide.
The method according to this invention, wherein, in step 6), described water-soluble polymer comprises: polyvinyl alcohol, polyoxyethylene glycol, polyacrylamide, polyvinylpyrrolidone, carboxymethyl cellulose, methylcellulose gum, ethyl cellulose or Natvosol.
Can be sprayed in the porous wall board according to conducting polymer/metal composite nano-coating of the present invention, have the effect of electromagnetic shielding action, antistatic, heat insulating.
Compared with prior art, the invention has the advantages that:
1) the invention provides conducting polymer/metal composite nano-coating,, pollution-free with water as solvent;
2) because the conducting polymer/metal composite nano material that forms has nucleocapsid structure, and the conducting polymer that metal is had chemical stability coats, and therefore, metal is difficult for oxidized, the stability of coating improves;
3) this water-based composite nano-coating matrix material that is metal and conducting polymer, therefore, the range of frequency of shielding enlarges, and not only shows shield effectiveness preferably at low frequency range, and the shield effectiveness that also shows at high frequency region;
4) high matrix material is according to the kind and the quantity of composition and the amount and the conductive polymers of nano metal powder, and its shielding efficiency in 1MHz～101GHz scope is 20～90dB;
5) content of the metal in this water-based conducting polymer/metal composite nano material reduces than the content of conventional metal-powder, and the area density of coating reduces, cost descends;
6) this water-borne coatings is applied in the porous wall board, not only can protect irradiation of electromagnetic waves, and has the effect of heat insulating, has energy-conservation effect;
7) this water-borne coatings is easy to use, and can directly be sprayed in the hole of porous wall board.
Description of drawings
Fig. 1 is the sem photograph of nanometer nickel particles among the embodiment 1.
Fig. 2 is the sem photograph of polyaniline among the embodiment 1/nickel composite nanoparticle.
Embodiment
Embodiment 1 preparation is used for the water-based conducting polymer/metal composite nano-coating of porous wall board
1) be that 0.3% Sodium dodecylbenzene sulfonate tensio-active agent is added to the water by weight percentage, add the ultrasonic mixing of nanometer nickel particles 2 hours again, filtering separation, washing, drying obtain the nanometer nickel particles of modification; Wherein the nano nickle granules add-on is a 100g/L water;
2) the modified Nano nickel particle that step 1) is obtained adds in the entry, and ultra-sonic dispersion is to even, and modified Nano nickel particulate add-on is every premium on currency 10 mmoles.
3) add high polymer monomer aniline and organic acid Witco 1298 Soft Acid, ultrasonic mixing forms mixed emulsion, and monomeric add-on is every liter of mixed solution 100 mmoles; Organic acid add-on and monomeric molar ratio are 1: 1;
4) the oxygenant ammonium persulphate is dissolved in the water formation solution, the add-on of oxygenant is every premium on currency 100 mmoles, the add-on of oxygenant for monomeric mol ratio be 1: 1;
5) oxidizing agent solution with step 4) joins in the mixed emulsion of step 3), and stirring reaction 10～24 hours filters, and cleans, and obtains the nano particle of electrically conductive polyaniline/nickel core-shell structure.
6) the water-soluble polymer polyvinyl alcohol is dissolved in heating for dissolving in the water, high molecular add-on is every premium on currency 50 grams;
7) in the polymer aqueous solution that the nano combined nanoparticulate dispersed of electrically conductive polyaniline/nickel that step 5) is obtained obtains to step 6), ultrasonic mixing forms waterborne conductive polyaniline/nickel nano composite dope, and the add-on of the nano combined nano particle of electrically conductive polyaniline/nickel is every rising molecular water solution 100 grams.
The water-based conducting polymer/metal composite nano-coating of the porous wall board that makes, described electrically conductive polyaniline/nickel core-shell structure is of a size of 80 nanometers, wherein the metal nickel nano particle of stratum nucleare is of a size of 20 nanometers, the electrically conductive polyaniline of shell is of a size of 60 nanometers, and the molar ratio of described nano nickle granules and described aniline monomer is 1: 10.
8) coating of the nano combined nano particle of this electrically conductive polyaniline/nickel is 61～69dB at the effectiveness of shielding of 50～1000MHz scope; Effectiveness of shielding under 101GHz is 40～58dB.
Embodiment 2 preparations are used for the water-based conducting polymer/metal composite nano-coating of porous wall board
1) be that 0.5% sodium laurylsulfonate tensio-active agent is added to the water by weight percentage, add the ultrasonic mixing of argent nanoparticle 2 hours again, filtering separation, washing, drying obtain the metal nanoparticle of modification; Wherein the metal nanoparticle add-on is a 100g/L water;
2) modified metal nanoparticles that step 1) is obtained adds in the entry, and ultra-sonic dispersion is to even, and the add-on of modified metal nanoparticle is every premium on currency 100 mmoles.
3) add high polymer monomer pyrroles and oleic acid, ultrasonic mixing forms mixed emulsion, and monomeric add-on is every liter of mixed solution 500 mmoles; Organic acid add-on and monomeric molar ratio are 1: 1;
4) will the oxygenant iron trichloride form solution in dissolving and the water, the add-on of oxygenant is every premium on currency 1000 mmoles, the add-on of oxygenant for monomeric mol ratio be 1: 2;
5) oxidizing agent solution with step 4) joins in the mixed emulsion of step 3), and stirring reaction 10～24 hours filters, and cleans, and obtains the nano particle of conducting polymer/metal nucleocapsid structure.
6) the water-soluble polymer polyoxyethylene glycol is dissolved in heating for dissolving in the water, high molecular add-on is every premium on currency 100 grams;
7) conductive polymers that step 5) is obtained/metal nano composite nanometer particle is distributed in the polymer aqueous solution that step 6) obtains, and ultrasonic mixing forms the water-based conducting polymer/metal nano composite dope.The add-on of the nano combined nano particle of conducting polymer/metal is every rising molecular water solution 100 grams.
The water-based conducting polymer/metal composite nano-coating that makes, described conducting polymer/metal nano core-shell structure is of a size of 150 nanometers, wherein the metal nanoparticle of stratum nucleare is of a size of 100 nanometers, the conducting polymer of shell is of a size of 50 nanometers, and the molar ratio of described metal nanoparticle and described conductive high polymer monomer is 1: 5.
8) effectiveness of shielding of this conducting polymer/metal composite nano particulate coating 9KHz～1000MHz scope is 48～68dB; Effectiveness of shielding under 101GHz is 36～45dB.
Embodiment 3 preparations are used for the water-based conducting polymer/metal composite nano-coating of porous wall board
1) be that 0.2% tensio-active agent sodium lauryl sulphate is added to the water by weight percentage, add the ultrasonic mixing of metal nano copper particle 2 hours again, filtering separation, washing, drying obtain the metal nano copper particle of modification; Wherein the metal nanoparticle add-on is a 100g/L water;
2) modified metal nanoparticles that step 1) is obtained adds in the entry, and ultra-sonic dispersion is to even, and the add-on of modified metal nanoparticle is every premium on currency 50 mmoles;
3) add high polymer monomer thiophene and organic acid helianthic acid, ultrasonic mixing forms mixed emulsion, and monomeric add-on is every liter of mixed solution 500 mmoles, and organic acid add-on and monomeric molar ratio are 1: 1;
4) will oxygenant hyperbromic acid potassium form solution in dissolving and the water, the add-on of oxygenant is every premium on currency 4000 mmoles, the add-on of oxygenant for monomeric mol ratio be 1: 4;
5) oxidizing agent solution with step 4) joins in the mixed emulsion of step 3), and stirring reaction 10～24 hours filters, and cleans, and obtains the nano particle of conducting polymer/metal nucleocapsid structure;
6) the water-soluble polymer polyacrylamide is dissolved in heating for dissolving in the water, high molecular add-on is every premium on currency 100 grams;
7) conductive polymers that step 5) is obtained/metal nano composite nanometer particle is distributed in the polymer aqueous solution that step 6) obtains, and ultrasonic mixing forms the water-based conducting polymer/metal nano composite dope.The add-on of the nano combined nano particle of conducting polymer/metal is every rising molecular water solution 200 grams.
The water-based conducting polymer/metal composite nano-coating that makes, described conducting polymer/metal nano core-shell structure is of a size of 130 nanometers, wherein the metal nanoparticle of stratum nucleare is of a size of 30 nanometers, the conducting polymer of shell is of a size of 100 nanometers, and the molar ratio of described metal nanoparticle and described conductive high polymer monomer is 1: 10.
8) effectiveness of shielding of this conducting polymer/metal composite nano particulate coating in 30MHz～1.5GHz scope reaches 67～82dB.
Comparative example's 1 preparation is used for the water-based conducting polymer/metal composite nano-coating of porous wall board
1) be that 0.5% Sodium dodecylbenzene sulfonate tensio-active agent is added to the water by weight percentage, add the ultrasonic mixing of nanometer nickel particles 2 hours again, filtering separation, washing, drying obtain the nanometer nickel particles of modification; Wherein the nano nickle granules add-on is a 100g/L water;
2) the modified Nano nickel particle that step 1) is obtained adds in the entry, and ultra-sonic dispersion is to even, and modified Nano nickel particulate add-on is every premium on currency 5 mmoles.
3) add high polymer monomer aniline and organic acid Witco 1298 Soft Acid, ultrasonic mixing forms mixed emulsion, and monomeric add-on is every liter of mixed solution 500 mmoles; Organic acid add-on and monomeric molar ratio are 1: 1;
4) the oxygenant ammonium persulphate is dissolved in the water formation solution, the add-on of oxygenant is every premium on currency 100 mmoles, the add-on of oxygenant for monomeric mol ratio be 1: 1;
5) oxidizing agent solution with step 4) joins in the mixed emulsion of step 3), and stirring reaction 10～24 hours filters, and cleans, and obtains the nano particle of electrically conductive polyaniline/nickel core-shell structure.
6) the water-soluble polymer polyvinyl alcohol is dissolved in heating for dissolving in the water, high molecular add-on is every premium on currency 50 grams;
7) in the polymer aqueous solution that the nano combined nanoparticulate dispersed of electrically conductive polyaniline/nickel that step 5) is obtained obtains to step 6), ultrasonic mixing forms waterborne conductive polyaniline/nickel nano composite dope, and the add-on of the nano combined nano particle of electrically conductive polyaniline/nickel is every rising molecular water solution 100 grams.
The water-based conducting polymer/metal composite nano-coating of the porous wall board that makes, described electrically conductive polyaniline/nickel nano composite material mainly is a nano particle, the particulate diameter is about 160 nanometers, and the molar ratio of described nano nickle granules and described aniline monomer is 1: 100.
8) effectiveness of shielding of this conducting polymer/metal composite nano particulate coating 9KHz～1000MHz scope is 12～19dB; Effectiveness of shielding under 101GHz is 47～53dB.Because it is metal nano content is lower in the composite coating, therefore lower at the effectiveness of shielding of low frequency range and intermediate frequency zone.
Comparative example's 2 preparations are used for the water-based conducting polymer/metal composite nano-coating of porous wall board
1) be that 0.2% sodium laurylsulfonate tensio-active agent is added to the water by weight percentage, add the ultrasonic mixing of argent nanoparticle 2 hours again, filtering separation, washing, drying obtain the metal nanoparticle of modification; Wherein the metal nanoparticle add-on is a 100g/L water;
2) modified metal nanoparticles that step 1) is obtained adds in the entry, and ultra-sonic dispersion is to even, and the add-on of modified metal nanoparticle is every premium on currency 500 mmoles.
3) add high polymer monomer pyrroles and oleic acid, ultrasonic mixing forms mixed emulsion, and monomeric add-on is every liter of mixed solution 100 mmoles; Organic acid add-on and monomeric molar ratio are 1: 1;
4) will the oxygenant iron trichloride form solution in dissolving and the water, the add-on of oxygenant is every premium on currency 1000 mmoles, the add-on of oxygenant for monomeric mol ratio be 1: 2;
5) oxidizing agent solution with step 4) joins in the mixed emulsion of step 3), and stirring reaction 10～24 hours filters, and cleans, and obtains the nano particle of conducting polymer/metal nucleocapsid structure.
6) the water-soluble polymer polyoxyethylene glycol is dissolved in heating for dissolving in the water, high molecular add-on is every premium on currency 100 grams;
7) conductive polymers that step 5) is obtained/metal nano composite nanometer particle is distributed in the polymer aqueous solution that step 6) obtains, and ultrasonic mixing forms the water-based conducting polymer/metal nano composite dope.The add-on of the nano combined nano particle of conducting polymer/metal is every rising molecular water solution 100 grams.
The water-based conducting polymer/metal composite nano-coating that makes, described conducting polymer/metal nano core-shell structure is of a size of 110 nanometers, wherein the metal nanoparticle of stratum nucleare is of a size of 100 nanometers, the conducting polymer of shell is of a size of 10 nanometers, and the molar ratio of described metal nanoparticle and described conductive high polymer monomer is 1: 5.
8) this conducting polymer/metal composite nano particulate coating is 59dB at the effectiveness of shielding of 50～1000MHz scope, and the effectiveness of shielding under 101GHz only is 9dB.In addition, because the content of metal nanoparticle is higher, the composite coating quality is heavier, after the spraying, can increase the weight of porous wall board, and the porous wall board that is used for buildings of the present invention is a kind of novel light body wall brick.
Claims (5)
1. water-based conducting polymer/metal composite nano-coating that is used for porous wall board, it is characterized in that, described composite nano-coating is the dispersion system of conducting polymer/metal nano core-shell structure, described conducting polymer/metal nano core-shell structure is of a size of the 20-300 nanometer, wherein the metal nanoparticle of stratum nucleare is of a size of 10～100 nanometers, the conducting polymer of shell is of a size of 10～200 nanometers, described metal nanoparticle is for being selected from nanometer silver, nanometer nickel, nanometer zinc, nanometer iron, nano hydroxy ferrite, in the nanometer copper one or more, the monomer of described conducting polymer is for being selected from aniline, the pyrroles, thiophene, the alkylated substituted thiazoline fen, in the diethoxy thiophene one or more, the mol ratio of described metal nanoparticle and described conductive high polymer monomer are 1: 1～1: 10.
2. a method for preparing the described water-based conducting polymer/metal composite nano-coating of claim 1 is characterized in that, said method comprising the steps of:
1) tensio-active agent is added to the water, add the ultrasonic mixing of metal nanoparticle again, filtering separation, washing, drying, obtain the metal nanoparticle of modification, wherein the metal nanoparticle add-on is a 100g/L water, and described metal nanoparticle is to be selected from nanometer silver, nanometer nickel, nanometer zinc, nanometer iron, nanometer iron carbonyl, the nanometer copper one or more;
2) modified metal nanoparticles that step 1) is obtained adds in the entry, and ultra-sonic dispersion is to even, and the add-on of modified metal nanoparticle is every premium on currency 10～100 mmoles;
3) high polymer monomer and organic acid are added step 2) in the modified metal nanoparticles solution that obtains, ultrasonic mixing, form mixed emulsion, monomeric add-on is every liter of mixed solution 100～1000 mmoles, organic acid add-on and monomeric molar ratio are 1: 1, described high polymer monomer is to be selected from aniline, pyrroles, thiophene, anils, pyrrole derivative, alkylated substituted thiazoline fen, the diethoxy thiophene one or more
Described organic acid is Witco 1298 Soft Acid, oleic acid, dodecyl sodium sulfonate, helianthic acid, camphorsulfonic acid, p-methyl benzenesulfonic acid, citric acid, oxysuccinic acid, oxalic acid or tartrate;
4) preparation aqueous oxidizing agent solution, its concentration is 100～8000 mmoles/L;
5) oxidizing agent solution with step 4) joins in the mixed emulsion of step 3), and oxygenant and monomeric mol ratio are 1: 1～1: 8, and stirring reaction 10～24 hours filters, and cleans, and obtains the nano particle of conducting polymer/metal nucleocapsid structure;
6) compound concentration is the water-soluble polymer aqueous solution of 50～150 gram/L;
7) conductive polymers that step 5) is obtained/metal nano composite nanometer particle is distributed in the polymer aqueous solution that step 6) obtains, ultrasonic mixing forms the water-based conducting polymer/metal nano composite dope, and the add-on of the nano combined nano particle of conducting polymer/metal is every rising molecular water solution 10～500 grams.
3. method according to claim 2 is characterized in that, in step 1), described tensio-active agent comprises: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, oleic acid, stearic acid.
4. method according to claim 2, it is characterized in that, in step 4), described oxygenant comprises: persulphate, dichromate, potassium permanganate, potassium periodate, hyperbromic acid potassium, potassium perchlorate, hydrogen peroxide, iron trichloride, ferric sulfate, cerous sulfate, cerous nitrate, cupric chloride or benzoyl peroxide.
5. method according to claim 2, it is characterized in that, in step 6), described water-soluble polymer comprises: polyvinyl alcohol, polyoxyethylene glycol, polyacrylamide, polyvinylpyrrolidone, carboxymethyl cellulose, methylcellulose gum, ethyl cellulose, Natvosol.
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| CN105330826A (en) * | 2015-12-04 | 2016-02-17 | 扬州大学 | Method for synthesizing polypyrrole microcapsules |
| CN105753115A (en) * | 2016-04-19 | 2016-07-13 | 陈守刚 | Triple sterilizing composite and preparation method thereof |
| CN105753115B (en) * | 2016-04-19 | 2018-07-06 | 陈守刚 | A kind of triple sterilization composite materials and preparation method thereof |
| CN105801854A (en) * | 2016-04-20 | 2016-07-27 | 桂林理工大学 | Method for preparing conducting polypyrrole by using malic acid as template and doping agent |
| CN108948976A (en) * | 2018-06-07 | 2018-12-07 | 太仓萃励新能源科技有限公司 | A kind of synthetic method of N-type conductive coating |
| CN109180974A (en) * | 2018-07-23 | 2019-01-11 | 赵阳 | A kind of quaternary phosphonium film of poly pyrrole and preparation method thereof |
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