CN100590139C - Method of synthesizing poly-pyrrole nano partical by diphenylamine sulfonic acid copolymerization method - Google Patents
Method of synthesizing poly-pyrrole nano partical by diphenylamine sulfonic acid copolymerization method Download PDFInfo
- Publication number
- CN100590139C CN100590139C CN200710039111A CN200710039111A CN100590139C CN 100590139 C CN100590139 C CN 100590139C CN 200710039111 A CN200710039111 A CN 200710039111A CN 200710039111 A CN200710039111 A CN 200710039111A CN 100590139 C CN100590139 C CN 100590139C
- Authority
- CN
- China
- Prior art keywords
- solution
- sulfonic acid
- oxygenant
- diphenylamine sulfonic
- pyrroles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses a method for synthesizing polypyrrole nano-particles with diphenylamine sulfoacid, its characters are as follow: it prepares the monomer solution with the pyrrole and diphenylamine sodium in the acidic solution in accordance with a molar ratio of 10:90 ~ 90:10, and then it adds the oxidant solution to the monomer solution for reaction. In which, the molar ratio of the pyrrole and diphenylamine sodium with the oxidizer are 1: 0.1 ~ 1.
Description
Technical field
The invention belongs in the synthetic method that does not have in-situ preparing polypyrrole nanoparticle under the outer doping condition.
Background technology
The polypyrrole nanoparticle has the specific conductivity height, electric conductivity is reversible, environmental stability good, biocompatibility is good, catalytic activity advantages of higher (Wang L X, Li X G, Yang Y L.Preparation, properties andapplications of polypyrroles[J] .Reactive ﹠amp; Functional Polymers, 2001,47:125-139.), and raw material is cheap, synthesis technique is simple, in fields such as secondary cell, transmitter, antistatic material, electromagnetic shielding, rhetoric electrode, bioengineered tissues wide actual application prospect is arranged.The synthetic method that adopts usually of pyrroles's homopolymer nanoparticle has microemulsion polymerization method (Mo Z L, Zuo D D, Chen H, etc.Synthesis of graphite nanosheets/AgCl/polypyrrole composites via two-stepinverse microemulsion method[J] .European Polymer Journal, 2007,43:300-306.Liu Y, Zhu Y, Yang L K.Adjusting the inner-structure of polypyrrolenanoparticles through microemulsion polymerization[J] .Materials Chemistryand Physics, 2006,98 (2-3): 304-308.) and dispersion copolymerization method (Pich A, Lu Y, P.Adler HJ, etc.Dispersion polymerization of pyrrole in the presence of poly (vinylmethyl ether) microgels[J] .Polymer, 2002,43:5723-5729.Mandal T K, Mandal B M.Ethylhydroxyethylcellulose stabilized polypyrrole dispersions[J] .Polymer, 1995,36 (9): 1911-1913.).Micro-emulsion polymerization generally is earlier with monomer, medium, emulsifying agent and help emulsion etc. to be mixed with the microemulsion of certain type, adopts the appropriate means initiated polymerization then, finally forms even, transparent or semitransparent, particle diameter in 5～10nm, stable polymer emulsion.Prepared polypyrrole specific conductivity is 10
-5～10
-1S/cm depends primarily on doping content.This method is because needs add a large amount of emulsifying agents (greater than 10%), and monomer content lower (less than 10%) causes emulsion so content is lower, has greatly limited the actual application value of microemulsion method.And the dispersion polymerization rule mainly is made up of monomer, oxygenant, spatial dispersion stablizer, polymerization reaction medium etc.The structure of prepared polymer nano-particle size of dispersion copolymerization method and stablizer, molecular weight and concentration have much relations, generally greater than 10nm.It is reaction medium with the water or the alcoholic acid aqueous solution generally that this method prepares the polypyrrole nanoparticle, with (NH
4)
2S
2O
8Or FeCl
3For oxygenant (initiator), be stablizer with polyvinyl alcohol, Type 3U etc., have the advantage that product cut size is controlled and size distribution is narrower.But dispersion copolymerization method prepares the defective of polypyrrole nanoparticle is that also needs add a large amount of additives.The report that utilizes poly ion liquid to prepare the polypyrrole nanoparticle for stablizer is also arranged in recent years, but ion liquid consumption is quite big, otherwise be difficult to obtain stable dispersion polymerization system (Marcilla R, Gonzalo C P, Rodriguez J, etc.Use of polymeric ionic liquidsas stabilizers in the synthesis of polypyrrole organic dispersions[J] .Synthetic Metals, 2006,156:1133-1138.).After making polypyrrole film by dispersion polymerization gained polypyrrole dispersion liquid, because the existence of the dispersion agent of insulativity, film forming specific conductivity often is lower than 1S/cm, if be applied to water soluble paint, behind the moisture evaporate to dryness, the specific conductivity of film is lower, is generally less than 1 * 10
-5S/cm (Pomposo JA, Ochoteco E, Pozo C, etc.Conductivity enhancement in raw polypyrrole andpolypyrrole nanoparticle dispersions[J] .Polymers for Advanced technologies, 2006,17 (1): 26-29.).
In a word, at present, the nanometer of polypyrrole all is to realize by the method that adds emulsifying agent or stablizer usually.Though can well solve the agglomeration traits of nanoparticle, yet its defective also comes from these emulsifying agents or stablizer just, promptly be that its reaction preceding preparation or reacted removal process are all very loaded down with trivial details, and tend to directly have influence on degree of purity of production and then damaged its physical and mechanical properties because be difficult to eliminate.Therefore, be badly in need of seeking a kind of simple and novel method of energy-conserving and environment-protective of preparation polypyrrole nanoparticle of not containing outer doping with the industrialized process of promotion polypyrrole.
Summary of the invention
Purpose of the present invention is exactly in order to overcome and to solve the prior art problem, provides a kind of efficient height, technology is simple, products therefrom is pure, environmentally friendly polypyrrole nanometer particle process method.
For realizing above purpose, the present invention is achieved through the following technical solutions:
A kind of method with the synthetic polypyrrole nanoparticle of diphenylamine sulfonic acid copolymerization method, it is characterized in that, with mol ratio is that 10: 90～90: 10 pyrroles and sodium diphenylaminesulfonate is mixed and made into monomer solution in acidic solution, the drips of solution that will contain oxygenant is added in the monomer solution and reacts completely, and the mol ratio of pyrroles and sodium diphenylaminesulfonate consumption sum and oxygenant is 1: (0.1～1).
Preferably, the mol ratio of described pyrroles and sodium diphenylaminesulfonate is 10: 90～50: 50.
Wherein, when pyrroles and sodium diphenylaminesulfonate are mixed, keep solution constant temperature in acidic solution.
Preferably, with after sodium diphenylaminesulfonate mixes in acidic solution, keep solution 0～25 ℃ of constant temperature half an hour～1 hour the pyrroles.
Wherein, described oxygenant is selected from Potassium Persulphate, ammonium persulphate, Sodium Persulfate, FeCl
3, K
2Cr
2O
7In at least a, perhaps with H
2O
2And FeCl
2Use as oxygenant jointly.
Wherein, the mol ratio of pyrroles and sodium diphenylaminesulfonate consumption sum and oxygenant is 1: 0.4～0.75.
Wherein, when the drips of solution that will contain oxygenant is added to monomer solution and dripping in back 25 hours, the temperature that keeps monomer solution is in 0～25 ℃ of scope and keep monomer solution constant temperature.
Wherein, preferably, the described solution of oxygenant that contains is for acid.
Wherein, when the acidic solution that will contain oxygenant is added drop-wise to monomer solution, keep temperature constant temperature in 10～25 ℃ of monomer solution.
The copolyreaction general molecular formula is as follows:
Beneficial effect of the present invention: the median size by the sulfonation polypyrrole nanoparticle of the present invention preparation is 10～50nm through transmissioning electric mirror test, is 78nm～360nm through the laser particle size analyzer test.The product conductivity range is 10
-5～10
-1S/cm, productive rate scope 7.9～20%.Preparation method among the present invention is simple, need not to add additives such as emulsifying agent or dispersion agent, simplified synthesis technique, the nanoparticle that what is more important obtained is pure, need not washing and remove additive, the synthetic new way that provides of polypyrrole nanoparticle is provided, has overcome the forming process problem of indissoluble polypyrrole to a certain extent, for its industrial application lays the first stone.The nanoparticle of gained can directly apply to the preparation aspect of antistatic film.
Description of drawings
Fig. 1 is the TEM shape appearance figure of embodiment 1 prepared polymer nano-particle, and black point-like thing is prepared polypyrrole nanoparticle among the figure.
Fig. 2 is the TEM shape appearance figure of embodiment 3 prepared polymer nano-particles, and black point-like thing is prepared polypyrrole nanoparticle among the figure.
Fig. 3 is the TEM shape appearance figure of embodiment 4 prepared polymer nano-particles, and black point-like thing is prepared polypyrrole nanoparticle among the figure.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment 1
Taking by weighing the 2.1702g sodium diphenylaminesulfonate joins in the 250mL vial, add the hydrochloric acid soln that 75mL concentration is 1.0mol/L again, become diphenylamine sulfonic acid solution after stirring reaction is complete, the pyrrole monomer of then measuring 0.145mL joins in the diphenylamine sulfonic acid solution, stir, with vial seal put into 10 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.With 0.8111g iron(ic) chloride (FeCl
3) put into the 80mL vial, add the hydrochloric acid soln that 25mL concentration is 1.0mol/L again, stir and make it abundant dissolving; With iron(ic) chloride (FeCl
3) solution moves in the separating funnel, splashes in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the blackish green polymers soln of nano-scale particle.Pipette the 2mL reaction solution and be diluted to 200mL, stir, leave standstill, precipitation, repetitive scrubbing, in washings, do not have SO with deionized water
4 2-, can use BaCl
2Have or not SO in the test solution
4 2-, do the laser particle size test with this sample, average particle size is 288nm, and the particle of transmissioning electric mirror test is 20～80nm, and particle morphology is as shown in Figure 1.Reacting liquid filtering, thorough washing with remainder obtain blackish green polymkeric substance, 50 ℃ of following dry weeks, get product 0.2737g, and productive rate is 12.2%, and its specific conductivity is 1.52 * 10
-2S/cm.
Embodiment 2
Taking by weighing the 1.3563g sodium diphenylaminesulfonate joins in the 250mL vial, add the hydrochloric acid soln that 75mL concentration is 0.1mol/L again, become diphenylamine sulfonic acid solution after stirring reaction is complete, the pyrrole monomer of then measuring 0.3617mL joins in the diphenylamine sulfonic acid solution, stir, with vial seal put into 10 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.With 0.8111g iron trichloride (FeCl
3) put into the 80mL vial, add the hydrochloric acid soln that 25mL concentration is 0.1mol/L again, stir and make it abundant dissolving, ferric chloride Solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After ferric chloride Solution dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the blackish green polymers soln of nano level copolymer pellet.Pipette the 2mL reaction solution and be diluted to 200mL, stir, leave standstill, precipitation, repetitive scrubbing, in washings, do not have SO with deionized water
4 2-, available BaCl
2Check SO
4 2-, do the laser particle size test with this sample, recording average particle size is 314nm.Reacting liquid filtering, thorough washing with remainder obtain blackish green polymkeric substance, 50 ℃ of following dry weeks, get product 0.2824g, and productive rate is 17.6%, and its specific conductivity is 3.68 * 10
-2S/cm.
Embodiment 3
Taking by weighing the 2.1702g sodium diphenylaminesulfonate joins in the 250mL vial, add the hydrochloric acid soln that 75mL concentration is 0.1mol/L again, become diphenylamine sulfonic acid solution after stirring reaction is complete, the pyrrole monomer of then measuring 0.145mL joins in the diphenylamine sulfonic acid solution, stir, with vial seal put into 10 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.The 1.1410g ammonium persulphate is added in the 80mL vial, add the hydrochloric acid soln that 25mL concentration is 0.1mol/L again, stir and make it abundant dissolving, ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After ammonium persulfate solution dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the blackish green polymers soln of nano level copolymer pellet.Pipette the 2mL reaction solution and be diluted to 200mL, stir, leave standstill, precipitation, repetitive scrubbing, in washings, do not have SO with deionized water
4 2-, available BaCl
2Check SO
4 2-, do the laser particle size test with this sample, recording average particle size is 78nm, and the particle of transmissioning electric mirror test is 10～50nm, and particle morphology is as shown in Figure 2.Reacting liquid filtering, thorough washing with remainder obtain blackish green polymkeric substance, 50 ℃ of following dry weeks, get product 0.2602g, and productive rate is 11.6%, and its specific conductivity is 1.73 * 10
-3S/cm.
Embodiment 4
Taking by weighing the 2.3058g sodium diphenylaminesulfonate joins in the 250mL vial, add the hydrochloric acid soln that 75mL concentration is 1.0mol/L again, become diphenylamine sulfonic acid solution after stirring reaction is complete, the pyrrole monomer of then measuring 0.91mL joins in the diphenylamine sulfonic acid solution, stir, with vial seal put into 10 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.The 1.1410g ammonium persulphate is added in the 80mL vial, add the hydrochloric acid soln that 25mL concentration is 1.0mol/L again, stir and make it abundant dissolving, ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the blackish green polymers soln of nano level copolymer pellet.Pipette the 2mL reaction solution and be diluted to 200mL, stir, leave standstill, precipitation, repetitive scrubbing, in washings, do not have SO with deionized water
4 2-, available BaCl
2Check SO
4 2-, do the laser particle size test with this sample, recording average particle size is 210nm, and the particle of transmissioning electric mirror test is 20～90nm, and particle morphology is as shown in Figure 3.Reacting liquid filtering, thorough washing with remainder obtain blackish green polymkeric substance, 50 ℃ of following dry weeks, get product 0.1848g, and productive rate is 7.9%, and its specific conductivity is 9.20 * 10
-5S/cm.
Embodiment 5
Taking by weighing the 2.1702g sodium diphenylaminesulfonate joins in the 250mL vial, add the hydrochloric acid soln that 75mL concentration is 1mol/L more respectively, become diphenylamine sulfonic acid solution after stirring reaction is complete, the pyrrole monomer of then measuring 0.145mL joins in the diphenylamine sulfonic acid solution, with vial seal put into 10 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.1.9882g four water iron protochlorides are added in the 80mL vial, add the hydrochloric acid soln that 25mL concentration is 1mol/L again, after stirring makes it fully dissolving, hydrogen peroxide with 0.515mL adds in the solution of ferrous chloride again, stir, the hydrogen peroxide solution that will contain ferrous ion moves in the separating funnel, splashes in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the blackish green polymers soln of nano level copolymer pellet.Pipette the 2mL reaction solution and be diluted to 200mL, stir, leave standstill, precipitation, repetitive scrubbing, in washings, do not have SO with deionized water
4 2-, available BaCl
2Check SO
4 2-, do the laser particle size test with this sample, recording average particle size is 320nm, the particle of transmissioning electric mirror test is 40～110nm.Reacting liquid filtering, thorough washing with remainder obtain blackish green polymkeric substance, 50 ℃ of following dry weeks, get product 0.3370g, and productive rate is 15.1%, and its specific conductivity is 2.34 * 10
-3S/cm.
Embodiment 6
Taking by weighing the 2.1702g sodium diphenylaminesulfonate joins in the 250mL vial, add the hydrochloric acid soln that 75mL concentration is 1.0mol/L more respectively, become diphenylamine sulfonic acid solution after stirring reaction is complete, the pyrrole monomer of then measuring 0.145mL joins in the diphenylamine sulfonic acid solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation. The 1.1410g ammonium persulphate is added in the 80mL vial, add the hydrochloric acid soln that 25mL concentration is 1.0mol/L again, stir and make it abundant dissolving, ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the blackish green polymers soln of nano level copolymer pellet.Pipette the 2mL reaction solution and be diluted to 200mL, stir, leave standstill, precipitation, repetitive scrubbing, in washings, do not have SO4 with deionized water
2-, available BaCl
2Check SO
4 2-, do the laser particle size test with this sample, recording average particle size is 320nm.Reacting liquid filtering, thorough washing with remainder obtain blackish green polymkeric substance, 50 ℃ of following dry weeks, get product 0.3080g, and productive rate is 13.8%, and its specific conductivity is 1.21 * 10
-4S/cm.
Embodiment 7
Taking by weighing the 2.1702g sodium diphenylaminesulfonate joins in the 250mL vial, add the hydrochloric acid soln that 75mL concentration is 1.0mol/L again, become diphenylamine sulfonic acid solution after stirring reaction is complete, the pyrrole monomer of then measuring 0.145mL joins in the diphenylamine sulfonic acid solution, stir, with vial seal put into 10 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.The 2.2820g ammonium persulphate is added in the 80mL vial, add the hydrochloric acid soln that 25mL concentration is 1.0mol/L again, stir and make it abundant dissolving, ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After ammonium persulfate solution dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the blackish green polymers soln of nano level copolymer pellet.Pipette the 2mL reaction solution and be diluted to 200mL, stir, leave standstill, precipitation, repetitive scrubbing, in washings, do not have SO with deionized water
4 2-, available BaCl
2Check SO
4 2-, do the laser particle size test with this sample, recording average particle size is 150nm.Reacting liquid filtering, thorough washing with remainder obtain blackish green polymkeric substance, 50 ℃ of following dry weeks, get product 0.2143g, and productive rate is 9.6%, and its specific conductivity is 1.33 * 10
-4S/cm.
The foregoing description only is used for that the present invention will be described, does not constitute the restriction to the claim scope, and other alternative means that it may occur to persons skilled in the art that are all in claim scope of the present invention.
Claims (4)
1. method with the synthetic polypyrrole nanoparticle of diphenylamine sulfonic acid copolymerization method, it is characterized in that, with mol ratio is that 10: 90～90: 10 pyrroles and sodium diphenylaminesulfonate is mixed and made into monomer solution in acidic solution, when pyrroles and sodium diphenylaminesulfonate mix in acidic solution, keep solution 0～25 ℃ of constant temperature half an hour～1 hour; The acidic solution that will contain oxygenant is added drop-wise in the monomer solution and reacts completely, the mol ratio of pyrroles and sodium diphenylaminesulfonate consumption sum and oxygenant is 1: 0.1～1, when the acidic solution that will contain oxygenant is added drop-wise to monomer solution and drip in back 25 hours, the temperature that keeps monomer solution is in 10～25 ℃ and keep monomer solution constant temperature.
2. the method with the synthetic polypyrrole nanoparticle of diphenylamine sulfonic acid copolymerization method according to claim 1 is characterized in that the mol ratio of described pyrroles and sodium diphenylaminesulfonate is 10: 90～50: 50.
3. the method with the synthetic polypyrrole nanoparticle of diphenylamine sulfonic acid copolymerization method according to claim 1 is characterized in that described oxygenant is selected from Potassium Persulphate, ammonium persulphate, Sodium Persulfate, FeCl
3, K
2Cr
2O
7In at least a, perhaps use H
2O
2And FeCl
2
4. the method with the synthetic polypyrrole nanoparticle of diphenylamine sulfonic acid copolymerization method according to claim 1 is characterized in that the mol ratio of pyrroles and sodium diphenylaminesulfonate consumption sum and oxygenant is 1: 0.4～0.75.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710039111A CN100590139C (en) | 2007-04-04 | 2007-04-04 | Method of synthesizing poly-pyrrole nano partical by diphenylamine sulfonic acid copolymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710039111A CN100590139C (en) | 2007-04-04 | 2007-04-04 | Method of synthesizing poly-pyrrole nano partical by diphenylamine sulfonic acid copolymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101033294A CN101033294A (en) | 2007-09-12 |
| CN100590139C true CN100590139C (en) | 2010-02-17 |
Family
ID=38730052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710039111A Expired - Fee Related CN100590139C (en) | 2007-04-04 | 2007-04-04 | Method of synthesizing poly-pyrrole nano partical by diphenylamine sulfonic acid copolymerization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100590139C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120135690A (en) * | 2011-06-07 | 2012-12-17 | 주식회사 한국엔티켐 | Preparation method of nano particles having conductivity and water dispersibility |
| CN102863617B (en) * | 2011-07-04 | 2015-02-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of polypyrrole nanometer microspheres |
| CN104624068A (en) * | 2015-01-22 | 2015-05-20 | 天津大学 | Method for polypyrrole nano material modified polymer ultrafiltration membrane |
| CN104530427B (en) * | 2015-01-27 | 2016-10-26 | 齐鲁工业大学 | A kind of preparation method of solid acanthosphere shape conductive copolymer |
| CN109320443B (en) | 2017-08-01 | 2021-02-26 | 财团法人工业技术研究院 | Method for preparing compound and method for preparing polymer containing compound |
| TWI652254B (en) | 2017-08-01 | 2019-03-01 | 財團法人工業技術研究院 | Method for preparing compound and method for preparing polymer employing the same |
| CN108424515B (en) * | 2018-03-28 | 2020-11-10 | 西安科技大学 | Method for preparing aniline-pyrrole copolymer with assistance of microwave |
| CN113214677A (en) * | 2021-04-19 | 2021-08-06 | 武汉纺织大学 | Modified sodium lignosulfonate disperse dye dispersant as well as preparation method and application thereof |
-
2007
- 2007-04-04 CN CN200710039111A patent/CN100590139C/en not_active Expired - Fee Related
Non-Patent Citations (7)
| Title |
|---|
| Facile synthesis and Characterization of the Copolymers andTheir Pure Nanoparticles from Aniline with 4-SulfonicDiphenylamine. XIN-GUI LI, et al.Journal of Polymer Science A: Polymer Chemistry,Vol.42 No.2004. 2004 |
| Facile synthesis and Characterization of the Copolymers andTheir Pure Nanoparticles from Aniline with 4-SulfonicDiphenylamine. XIN-GUI LI,et al.Journal of Polymer Science A: Polymer Chemistry,Vol.42 No.2004. 2004 * |
| Facile Synthesis and Optimization of Conductive CopolymerNanoparticles and Nanocomposite Films from Aniline withSulfodiphenylamine. Xin-Gui Li, et al.Chem. Eur. J.,Vol.2006 No.12. 2005 |
| Facile Synthesis and Optimization of Conductive CopolymerNanoparticles and Nanocomposite Films from Aniline withSulfodiphenylamine. Xin-Gui Li,et al.Chem.Eur.J,Vol.2006 No.12. 2005 * |
| Synthesis and nitrosation of processible copolymers frompyrrole and ethylaniline. Xin-Gui Li, et al.Polymer,Vol.45 No.2004. 2004 |
| Synthesis and nitrosation of processible copolymers frompyrrole and ethylaniline. Xin-Gui Li,et al.Polymer,Vol.45 No.2004. 2004 * |
| 聚吡咯纳米粒子的制备与应用. 谢允斌等.胶体与聚合物，第23卷第2期. 2005 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101033294A (en) | 2007-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100590139C (en) | Method of synthesizing poly-pyrrole nano partical by diphenylamine sulfonic acid copolymerization method | |
| Sapurina et al. | Polypyrrole nanotubes: the tuning of morphology and conductivity | |
| Zhang et al. | Fibrillar growth in polyaniline | |
| CN101250313B (en) | Nano-particle compound and preparation method thereof | |
| CN101407575B (en) | High dispersibility nano-scale poly (3,4-ehtylene dioxythiophene), preparation and use thereof | |
| CN108963227B (en) | Conductive polymer coated silicon composite carbon nanotube negative electrode material and preparation method and application thereof | |
| Sasso et al. | Polypyrrole and polypyrrole/wood-derived materials conducting composites: a review. | |
| CN106810675B (en) | A kind of graphene composite conductive material and preparation method | |
| CN101353477B (en) | Preparation of polyaniline / argentum nano composite material | |
| CN102321254A (en) | Preparation method for high-concentration graphene-polyaniline nanofiber composite dispersion liquid and high-concentration graphene-polyaniline nanofiber composite film | |
| CN109251326B (en) | Preparation method of conductive high-molecular polymer nanoparticles with good water phase dispersibility | |
| Zhang et al. | Electrochemical polymerization of 3, 4-ethylenedioxythiophene in aqueous solution containing N-dodecyl-β-d-maltoside | |
| CN101703915A (en) | Preparation method of conducting polyaniline-lignosulfonic acid composite hollow sphere | |
| CN102432875B (en) | Aqueous polyaniline and preparation method thereof | |
| CN101186745A (en) | Method for preparing polythiophene-metal oxide nano composite material | |
| CN102532539B (en) | Preparation method of one-dimensional conductive polypyrrole/ concave-convex rod nanameter composite material | |
| CN109473666A (en) | A kind of SbVO of graphene support4Nano particle composite material and preparation method thereof | |
| CN101838391A (en) | Polyaniline/silver conductive nanocomposite material and preparation method thereof | |
| CN102558553B (en) | Preparation method of one-dimensional conductive polyanion/attapulgite nano composite material | |
| CN103421188B (en) | A kind of preparation method of sheet polypyrrole with high conductivity | |
| CN102993413A (en) | Preparation method of dimeric surfactant doped PEDOT (poly(3,4-ethylenedioxythiophene)) conductive nano particle | |
| CN102875978A (en) | Preparation method of gold nanoparticle/poly(3,4-dioxyethyl)thiophene (PEDOT) composite material | |
| CN101070374A (en) | Chemical-oxidation direct preparing method for polyamino anthaquinone nano particles | |
| CN113292723B (en) | Preparation method of morphology-controllable polypyrrole conductive nano material | |
| CN106252642A (en) | The preparation method and applications of sulfur nanoparticulate dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100217 Termination date: 20130404 |