CN100480302C - Controllable synthesis method for polyaniline nano structure and use thereof - Google Patents
Controllable synthesis method for polyaniline nano structure and use thereof Download PDFInfo
- Publication number
- CN100480302C CN100480302C CNB2005100385363A CN200510038536A CN100480302C CN 100480302 C CN100480302 C CN 100480302C CN B2005100385363 A CNB2005100385363 A CN B2005100385363A CN 200510038536 A CN200510038536 A CN 200510038536A CN 100480302 C CN100480302 C CN 100480302C
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- acid
- concentration
- polyaniline nano
- synthesis method
- 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
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
This invention relates to a controllable synthesized method of new style polyaniline self-assembly nanostructure. The method is that poly reaction is happened at 100~2500C in autoclave, dopant is protonic acid of oxidative polymerization reaction, then polyaniline flake structure is got and order tactic polyaniline nanometer bar (fiber) array on its surface. The structure has great photism. The array can be used to electromagnetic wave shield materials, antistatic materials, big content capacitor material, triode, sensor material, gas separation material and high efficiency photism.
Description
One, technical field:
The present invention relates to a kind of controllable synthesis method and and purposes of novel polyphenyl amine self-assembled nano structures.
Two, background technology:
Polyaniline is a kind of important conducting polymer (plastics), it has stable chemical property, electric conductivity advantages of higher [1] A.G.MacDiarmid, Synthetic metals:A Novel role for organicpolymers, Angew.Chem.Int.Ed.2001,40,2581-2590.By different doping level control, the electric conductivity of polyaniline can realize the transformation by isolator-semi-conductor-metallic conductor.In recent years, the polyaniline of polyaniline and nanostructure is at solar cell, electromagnetic shielding material [2] Wan Meixiang, Li Junchao, Li Suzhen, a kind of conductive high-polymer microwave absorbent and method for making thereof, Chinese patent publication number 1110786, notification number 1040043, antistatic material [3] E Rodri osmanthus is JW Lin Desai now, antistatic fibers and preparation method thereof, Chinese patent, notification number 1145720, electrode materials [4] Wang Wanxi, solid polymer high-energy battery, Chinese patent, publication number 1156911, high capacity capacitor material [5] beam road, superhigh-capacitance capacitor with composite carbon nanotube and manufacture method thereof, Chinese patent, publication number 1388540, thermoelectric material [6] Zhang Zuxun, Zhang Shengtang, Hao Jixiang, heat energy in the environment directly can be changed into the polyaniline composition of electric energy and use its metal sandwich spare, Chinese patent, [publication number] 1254728, triode [7] N.J.Pinto, A.T.Johnson, A.G.MacDiarmid, C.H.Mueller, et.al., Electrospunpolyaniline/polyethylene oxide nanofiber field-effect transistor, Appl.Phys.Lett., 2003,83,4244-4246, aspect such as sensor material and gas separation material has obtained to use widely.The polyaniline of nanostructure has big specific surface area, can improve the speed of response and the sensitivity of chemical sensor greatly.People attempt preparing monodimension nanometer materials such as polyaniline nano pipe and nano wire, the hard template of use such as porous alumina [8] H.J.Qiu, J.Zhai with soft template and hard template method, S.H.Li, L.Jiang, M.X.Wan, Oriented growth of self-assembled polyanilinenanowire arrays using a novel method, Adv.Funct.Mater., 2003,13,925-928, polymer template [9] M.Kanungo of particle beam etching, A.Kumar and A.Q.Contractor, Anal.Chem., 2003,75,5673-5679 etc., soft template such as tensio-active agent [10] J.C.Michaelsonand A.J.McEvoy, Chem.Commun., 1994,1,79-80 and liquid crystal molecule [11] L.M.Huang, Z.B.Wang, H.T.Wang, X.L.Cheng, A.Mitra and Y.X.Yan, J.Mater.Chem., 2002,12,388-391 etc. can synthesize polyaniline nano fiber.Yet the polyaniline nanofiber array of proper alignment but is difficult to prepare with method except that hard template, and hard template cost such as porous alumina is higher, and productive rate is low.Therefore necessary development can prepare the pure chemistry method of polyaniline nanofiber array and the method that can reach effective control product pattern by simple component control.
Relate to polyaniline synthetic method and also can disclose 1415645 referring to Chinese patent, the preparation method of soluble conductive polyaniline, disclose a kind of preparation method of soluble conductive polyaniline, its key step is that polyaniline in eigenstate and protonic acid are carried out hot doping in water and solubility promoter composition mixed solvent.It is oxygenant chemical oxidization method compositing conducting polyaniline that Chinese patent discloses 1446839 usefulness Manganse Dioxide, the sour water suspension that aniline monomer is added and contain Manganse Dioxide carries out oxidizing reaction, its invention compositing conducting polyaniline is simple, the residual quantity of Manganse Dioxide is very low in the product, does not relate to the synthetic of monodimension nanometer materials such as polyaniline nano pipe and nano wire.
Three, summary of the invention:
The objective of the invention is: controllable synthesis method and purposes that a kind of novel polyphenyl amine self-assembled nano structures is provided.And be the low and simple controllable synthesis method of technology controlling and process of cost.
The invention provides oxidized form initiator such as iron trichloride, the ammonium persulphate etc. of a kind of method of utilizing the direct synthesized polyaniline aaerosol solution of aniline monomer: 0.01M-1M), mineral acids such as concentration 0.1M-5M protonic acid doping agent example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphoric acid, perchloric acid or organic acid doped dose are as oxalic acid etc.), aniline monomer concentration 0.01M-1M.After solution mixes, in corrosion-proof lining such as teflon-lined autoclave, control reaction temperature 100-250 ℃, time 1-30 hour.
Be nanofiber, nanometer lamella, nanometer lamella pleated structure arranged on spherical with the method for the invention synthetic polyaniline product, product structure is controlled, and simple synthetic method, the polyaniline nano structure product is at opto-electronic device, information, transmitter, molecular wire and molecular device, and has a wide range of applications on electromagnetic shielding and the stealthy technique.
With polyreaction in autoclave with 100-250 ℃ temperature, adopt protonic acid to carry out oxidative polymerization as doping agent, the concentration by the control protonic acid can obtain following product respectively: 1. polyaniline nano fiber; 2. the lamellar structure of polyaniline, slice surfaces has polyaniline nano-rod (fiber) array of proper alignment simultaneously; 3. spherical polyaniline particle, surface have large amount of thin sheets shape nanostructure.This polyaniline nano array self-assembled structures is expected to be used for electromagnetic shielding material, antistatic material, electrode materials, high capacity capacitor material, triode, sensor material and gas separation material.
The polyaniline sheet structure that this controllable method for preparing of the present invention synthesizes will have been widely used aspect luminescent device.Sign to the photoluminescence performance of the polyaniline that synthesizes is found, product has very strong photoluminescence in blue region, and there be very strong contacting directly in the triphenylamine functional group in luminous intensity and the sheet structure, HCl concentration used in synthetic is high more, triphenylamine functional group is many more, sheet structure is many more, and luminous intensity is high more.
Characteristics of the present invention have provided the controllable synthesis method of monodimension nanometer materials such as polyaniline nano pipe and nano wire.
Four, description of drawings
Fig. 1. gained polyaniline nano fiber transmission electron microscope photo of the present invention
Fig. 2. the SEM of gained polyaniline nano-lamellar structure of the present invention observes 1
Fig. 3. there is the SEM of nanometer lamella pleated structure to observe on gained polyaniline of the present invention is spherical
Fig. 4. gained fiber transmission electron microscope photo of the present invention
Fig. 5. the SEM of gained polyaniline nano-lamellar structure of the present invention observes
Fig. 6. the SEM of gained polyaniline nano-lamellar structure of the present invention observes 2 (including the shape structure that partly interweaves)
Fig. 7. products therefrom of the present invention all is that the SEM of polyaniline nano-lamellar structure observes
Fig. 8. the tem observation of gained polyaniline nano-lamellar structure of the present invention (polyaniline nano-rod of proper alignment (fiber) array)
Fig. 9. the tem observation of the gained polyaniline nano-lamellar structure of the present invention (nanometer rod that interweaves fibrous texture
Figure 10. gained polyaniline photoluminescence spectrum of the present invention
Five, embodiment
The iron trichloride of the preparation of reaction soln: 0.01M-1M (or oxidized form initiators such as ammonium persulphate, hydrochloro-auric acid), hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid all can, concentration 0.1M-5M, aniline monomer concentration 0.01M-1M.After solution mixes, reaction soln is transferred in the teflon-lined autoclave, put into 100-250 ℃ of baking oven control reaction temperature, also can come control reaction temperature with high temperature heat conductive oil or direct electrically heated.Time 1-30 hour.Temperature of reaction is at a plurality of temperature control points (100,150,180,200,250 ℃) of 100-250 ℃, a plurality of points (1,4,5,8,10,30 hour) between reaction times 1-30 hour are controlled, the result does not have marked difference, comprise different reaction soln systems, its difference mainly is on the productive rate of product.
Reaction soln system of the present invention is simpler, and its preparation easily.
After reaction is finished, obtain cyan suspension, filter the washing back and under transmission electron microscope (TEM) or scanning electron microscope, observe.When the concentration of acid was lower than 1M (especially 0.5-0.8M), product mainly was the nanofiber of diameter 40-80nm.When the concentration of acid is about 1M when (especially 0.9-1.0M), product mainly is the nano flake of nanofiber and size 2-4 micron, and the surface of nanometer sheet has the polyaniline nano-rod of proper alignment (fiber) array.The concentration of acid is 1M when above, and with the concentration raising of acid, product becomes gradually based on nanometer sheet, and the surface has polyaniline nano-rod (fiber) array of proper alignment, and the pattern of product as shown above.Acid concentration be that (especially 0.15-0.3M) the polyaniline spherical particle occurs constantly about 0.2M in the product, on nanometer lamella pleated structure is arranged.The analytical results of infrared spectra, UV spectrum, ultimate analysis, solid-state nuclear magnetic resonance shows that product is the polyaniline of doping attitude.The electric conductivity of working sample is roughly 0.001S.cm
-1About.
Especially temperature of reaction is controlled at 100-200 ℃, time 1-10 hour.
Claims (5)
1, the controllable synthesis method of polyaniline nano structure, utilize the direct synthesized polyaniline aaerosol solution of aniline monomer, it is characterized in that oxidized form initiator with 0.01M-1M, the agent of concentration 0.1M-5M protonic acid doping, after the solution of aniline monomer concentration 0.01M-1M mixes, in anticorrosion autoclave, control reaction temperature 100-250 ℃, synthesized in time 1-30 hour; The oxidized form initiator is iron trichloride, ammonium persulphate or hydrochloro-auric acid, and protonic acid is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid or perchloric acid.
2,, it is characterized in that adopting protonic acid as doping agent, and become polyaniline nano fiber by the concentration control nanostructure product of protonic acid by the controllable synthesis method of the described polyaniline nano structure of claim 1; The micron lamellar structure, slice surfaces has the polyaniline nano-rod array of proper alignment simultaneously; The spherical polyaniline particle of micron, there is large amount of thin sheets shape nanostructure on the surface.
3, by the controllable synthesis method of the described polyaniline nano structure of claim 1, when it is characterized in that the concentration 0.5-0.8M of protonic acid, product mainly is the nanofiber of diameter 40-80nm; When the concentration of acid was 0.9-1.0M, product mainly was the nano flake of nanofiber and size 2-4 micron, and the surface of nanometer sheet has the polyaniline nano-rod fiber array of proper alignment; The concentration of acid is 1M when above, and with the concentration raising of acid, product becomes gradually based on nanometer sheet, and the surface has the polyaniline nano-rod fiber array of proper alignment; The concentration of acid the polyaniline spherical particle occurs when being 0.15-0.3M in the product, on nanometer lamella pleated structure is arranged.
4,, it is characterized in that control reaction temperature 150-200 ℃ by the controllable synthesis method of the described polyaniline nano structure of claim 1
5, the application of polyaniline nano is characterized in that the polyaniline flake nano structure that adopts the described controllable synthesis method of claim 3 to synthesize, is used in the photo luminescent devices preparation of blue region and produces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100385363A CN100480302C (en) | 2005-03-23 | 2005-03-23 | Controllable synthesis method for polyaniline nano structure and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100385363A CN100480302C (en) | 2005-03-23 | 2005-03-23 | Controllable synthesis method for polyaniline nano structure and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1667021A CN1667021A (en) | 2005-09-14 |
| CN100480302C true CN100480302C (en) | 2009-04-22 |
Family
ID=35038318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100385363A Expired - Fee Related CN100480302C (en) | 2005-03-23 | 2005-03-23 | Controllable synthesis method for polyaniline nano structure and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100480302C (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323199C (en) * | 2005-12-05 | 2007-06-27 | 西安交通大学 | Preparation method of conductive polymer polyanilinc nano fiber |
| CN1332997C (en) * | 2006-03-02 | 2007-08-22 | 扬州大学 | Chemical synthesization of poly-o-toluidine |
| CN100402583C (en) * | 2006-03-03 | 2008-07-16 | 扬州大学 | Method for synthesizing polyaniline nano particles |
| CN101270186B (en) * | 2008-05-19 | 2012-06-20 | 攀钢集团攀枝花钢铁研究院有限公司 | Polyaniline watersoluble dispersion and preparation method thereof |
| CN102070783B (en) * | 2010-11-23 | 2013-04-17 | 陕西师范大学 | Controllable self-assembly low temperature hydrothermal preparation method of micron-nano polyaniline |
| CN102206342B (en) * | 2011-03-31 | 2012-10-17 | 南京大学 | Electric conduction polymer and synthesis method thereof and electroactive electrode with surface covered with electric conduction polymer |
| CN102585497B (en) * | 2012-01-09 | 2014-01-15 | 南昌航空大学 | Perchloric-acid-doped polyaniline/carbonyl iron powder composite wave-absorbing material |
| CN103145982B (en) * | 2013-03-25 | 2015-04-08 | 北京科技大学 | Controllable synthesis method of level structure of polyaniline |
| CN104119527A (en) * | 2013-04-25 | 2014-10-29 | 天津大学 | Au-polyaniline nano-composite particle and preparation method thereof |
| CN104122244A (en) * | 2013-04-25 | 2014-10-29 | 天津大学 | Application of Au-polyaniline nano-composite particle in surface enhanced Raman spectrum |
| CN103834265B (en) * | 2014-03-24 | 2015-12-09 | 中国科学院长春应用化学研究所 | A kind of polyaniline anti-corrosive paint |
| CN110041701B (en) * | 2019-04-25 | 2021-11-19 | 中科广化（重庆）新材料研究院有限公司 | Spherical polyaniline/graphene composite membrane material and preparation method and application thereof |
| CN110862564B (en) * | 2019-08-22 | 2020-12-18 | 东华大学 | Polyaniline film with oriented rod-like structure and preparation method thereof |
| CN115148957B (en) * | 2022-09-05 | 2022-12-20 | 楚能新能源股份有限公司 | Polyaniline electrode with double-sided self-supporting structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672377A (en) * | 1992-12-17 | 1997-09-30 | Nec Corporation | Method of forming a solid electrolytic capacitor |
| US6277952B1 (en) * | 1999-11-15 | 2001-08-21 | General Electric Company | Direct method for preparing doped polyaniline, product prepared thereby and resinous articles containing said product |
| JP2001288264A (en) * | 2000-03-31 | 2001-10-16 | Kanpoly Technology Co Ltd | Method for producing polyaniline-containing solution |
-
2005
- 2005-03-23 CN CNB2005100385363A patent/CN100480302C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672377A (en) * | 1992-12-17 | 1997-09-30 | Nec Corporation | Method of forming a solid electrolytic capacitor |
| US6277952B1 (en) * | 1999-11-15 | 2001-08-21 | General Electric Company | Direct method for preparing doped polyaniline, product prepared thereby and resinous articles containing said product |
| JP2001288264A (en) * | 2000-03-31 | 2001-10-16 | Kanpoly Technology Co Ltd | Method for producing polyaniline-containing solution |
Non-Patent Citations (6)
| Title |
|---|
| 导电聚苯胺的合成及其性能研究. 任斌.光实验室，第22卷第1期. 2005 |
| 导电聚苯胺的合成及其性能研究. 任斌.光实验室，第22卷第1期. 2005 * |
| 纳米管结构聚苯胺的电阻率和磁化率. 龙云泽.物理学报，第52卷第1期. 2003 |
| 纳米管结构聚苯胺的电阻率和磁化率. 龙云泽.物理学报，第52卷第1期. 2003 * |
| 聚苯胺的化学合成 结构及导电性能. 周震涛等.华南理工大学学报，第24卷第7期. 1999 |
| 聚苯胺的化学合成 结构及导电性能. 周震涛等.华南理工大学学报，第24卷第7期. 1999 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1667021A (en) | 2005-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100480302C (en) | Controllable synthesis method for polyaniline nano structure and use thereof | |
| Ponnamma et al. | Synthesis, optimization and applications of ZnO/polymer nanocomposites | |
| CN100586987C (en) | Preparation process of one-dimensional nanometer polyaniline material | |
| Geng et al. | One-dimensional BiPO4 nanorods and two-dimensional BiOCl lamellae: fast low-temperature sonochemical synthesis, characterization, and growth mechanism | |
| Wang | Preparation and application of polyaniline nanofibers: an overview | |
| CN1301901C (en) | Carbon nano particles, preparation method and transparent conductive polymer composite material containing said carbon nano particles | |
| CN103466702B (en) | Method for preparing porous bismuth oxide nano-material without template | |
| Rahy et al. | Polyaniline nanofiber synthesis by co-use of ammonium peroxydisulfate and sodium hypochlorite | |
| CN101492569B (en) | Oxidized graphite flake layer/polyaniline composite material and method for preparing the same | |
| CN101633779A (en) | Conductive polyaniline composite electrode material and preparation method thereof | |
| CN104003448B (en) | A kind of alpha-phase ferricoxide porous core-shell particles and controlledly synthesis preparation method thereof | |
| Li et al. | Polyaniline nanorings and flat hollow capsules synthesized by in situ sacrificial oxidative templates | |
| Kowsari et al. | Ultrasound and ionic-liquid-assisted synthesis and characterization of polyaniline/Y2O3 nanocomposite with controlled conductivity | |
| CN104211960A (en) | One-step chemical preparation method for graphene and polyaniline composite materials | |
| Xu et al. | Electrospinning preparation and photoluminescence properties of lanthanum phosphate nanowires and nanotubes | |
| CN104861971B (en) | Tungsten oxide quanta point material and preparation method thereof | |
| Munusamy et al. | Synthesis and characterization of GaN/PEDOT–PPY nanocomposites and its photocatalytic activity and electrochemical detection of mebendazole | |
| CN102532894B (en) | Preparation method of graphite oxide/polypyrrole composite material | |
| CN102558586A (en) | Preparation method of polyethylene-vinyl acetate composite film | |
| CN1974667A (en) | Prepn process of multiple wall carbon nanotube/polyaniline composite material | |
| CN100412110C (en) | Polyaniline nano fiber and its preparing process | |
| CN104072782B (en) | A kind of preparation method of magnetic poly phosphazene nano wire | |
| CN101690880B (en) | Method for preparing nano-structure aniline-co-pyrrole copolymer microsphere | |
| CN102993646B (en) | Polythiophene nanometer conductive composite material and preparation method thereof | |
| CN111559742A (en) | Method for improving stability of carbon nano tube |
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: 20090422 Termination date: 20100323 |