CN100335685C - Poly(p-phenylene vinylene) nano silk and method for preparing same - Google Patents
Poly(p-phenylene vinylene) nano silk and method for preparing same Download PDFInfo
- Publication number
- CN100335685C CN100335685C CNB2005100165698A CN200510016569A CN100335685C CN 100335685 C CN100335685 C CN 100335685C CN B2005100165698 A CNB2005100165698 A CN B2005100165698A CN 200510016569 A CN200510016569 A CN 200510016569A CN 100335685 C CN100335685 C CN 100335685C
- Authority
- CN
- China
- Prior art keywords
- ppv
- prepolymer
- silk
- electrospinning
- solution
- 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
Landscapes
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The present invention relates to photoelectric multifunctional polymer nanometer technology, particularly to photoelectric multifunctional polymer-poly-phenylene vinylene (PPV) nanometer technology. The present invention provides a poly-phenylene vinylene (PPV) nanometer thread, the diameter of the thread is dozens to several thousands of nanometers, and the thread has the advantages of uniform texture, no easy pollution, smooth surface, large length magnitude level more than centimeters, and good mechanical performance. The present invention simultaneously provides a technology method for preparing the nanometer thread by the prepolymer of the poly-phenylene vinylene in an electric spinning mode, which comprises that the prepolymer water solution of the PPV is modulated into electric spinning solution by alcohol to implement electric spinning; the PPV electric spinning thread is obtained by sintering. The present invention solves the problems of difficult dissolution of the PPV itself and indirect electric spinning. The technology method is very beneficial to preparing optoelectronic devices with the PPV nanometer thread as the functional material.
Description
Technical field
The present invention relates to the organic polymer nanometer technology, particularly multichannel photomultiplier functional polymer nanometer technology.
Background technology
The eighties discovery in last century p-phenylene vinylene [poly (phenylene vinylene)-PPV, (and C6H4-CH=CH-) n] with after the doping of p type adulterants such as arsenic pentafluoride, electrical conductivity can become electronic conductor by nearly insulator; The nineties finds that again PPV not only has good luminescence generated by light and electroluminescence characters, and has good photovoltaic transfer characteristic; Research finds that also PPV has good optical nonlinearity, is a kind of electronic polymer material with multichannel photomultiplier functional characteristic.PPV is stable in the air, compares with other electronic polymer with multichannel photomultiplier functional characteristic, is the highest material of finding at present of visible-light absorptivity.It is simple, with low cost and easily purify and advantages such as prepolymer is easily molten, easy processing that PPV has preparation technology, can adopt casting film to prepolymer solution, further the method for sintering prepares PPV optoelectronic thin-film device again.Therefore since the last century the nineties, PPV is subjected to the attention of scientific and technological circle always as the excellent material that has the multichannel photomultiplier functional characteristic in the electronic polymer.
Electrostatic spinning (electrospinning) is the method for preparing high molecular superfine fiber that last century, the '30s was found.With the electrospinning silk that method of electrostatic spinning is prepared, have quality evenly, be difficult for pollution, smooth surface and centimetre more than advantages such as length, nanoscale radius.Opto-electronic device to microminiaturized, under high density is integrated and the development of high-space resolutionization drives, people focus on the development with nano-sized materials to sight and use.Therefore the research of electricity consumption spinning method preparation with electronic polymer nano silk that light, electric work can characteristic obtains the great attention of scientific and technological circle.
2002, U.S. professor A.G.MacDiarmid reported at first and has adopted method of electrostatic spinning to prepare the electrospinning silk (Synth.Met., 2002,125,11) of soluble conductive polymer poly aniline; 2003, the domestic Wang Ce of Jilin University taught the preparation (Synth.Met., 2003,137,973) that seminar has also reported polyaniline electrospinning silk.Research for the PPV nanometer materials, the Jung-Li Jin professor seminar of Korea S in 2003 has reported that they adopt chemical vapour deposition technique (CVD) directly to prepare the nano wire of PPV and the method (Macromol.Symp. of nanotube, 2003,201,119), but the profile of material is limited by pore size of template, and template will remove easy pollution with chemistry or physical method, makes this process be difficult to directly be used for preparing the PPV opto-electronic device.
Because PPV decomposes when having indissoluble and fusing, directly the electricity consumption spinning method prepares the PPV nano silk at present.This outstanding multichannel photomultiplier function electronic polymer material is restricted in nano photoelectronic devices exploitation, Development Application.
Summary of the invention
The objective of the invention is to adopt method of electrostatic spinning, by PPV prepolymer solution is carried out spinning, further sintering then, PPV electrospinning silk, solve the indissoluble of PPV own, the direct difficult problem of electrospinning.
Final purpose of the present invention is PPV nano silk and the preparation technology thereof who obtains to help the opto-electronic device preparation.
The invention provides a kind of PPV electrospinning silk, diameter is tens to several thousand nanometers, this quality evenly, be difficult for pollution, smooth surface, centimetre more than order of magnitude length and good mechanical performance.Photoluminescence spectrum with fluorescence spectrum spectroscope measurement PPV electrospinning silk keeps the bimodal characteristics of luminescence at 515nm and 550nm place, and is consistent with the photoluminescence spectrum of PPV film.
Nano silk preparation method provided by the invention: according to the synthetic route (J.Polym.Sci.:Polym.Symp. of R.A.Weslling, 1985,72,55) and the optimization synthesis condition (Synth.Met. that provides of people such as P.L.Halliday, 1993,55-57,902), prepare number-average molecular weight at 6-9 ten thousand PPV prepolymers
The aqueous solution.
Last liquid is placed on evaporates to such an extent that PPV prepolymer content is the concentrated solution of 1.0-3.0wt% under the air at room temperature, being modulated into PPV prepolymer weak solution with lower alcohol again is electrospinning silk solution for later use.At ambient temperature, PPV prepolymer electrospinning silk solution put into syringe and connect the electrode of DC high-voltage power supply, collector (wire netting or film) connects electrode, at voltage is 6-20kV, the spout electrospinning of carrying out to collector 5-30cm distance, collect a period of time, get the nano silk of PPV prepolymer.Under 200-250 ℃, vacuum or inert gas shieldings such as nitrogen, argon gas,, obtain PPV nanometer electrospinning silk with prepolymer nano silk heating about 20-60 minute.
Take the PPV electrospinning silk photo that the present invention obtains and measure with scanning electronic microscope (ESM), learn that the electrospinning filament diameter is along with the change of drawing condition changes in tens to several thousand nanometer range.
The scaling method of prepolymer solution PPV content is: get a certain amount of prepolymer solution with its quality of the accurate weighing of electronic balance and sintering after the solid masses of PPV, calculate the content of PPV in the prepolymer solution.
Consider that PPV has good luminescence generated by light, electroluminescent and functional characteristics such as photovoltaic conversion and optical nonlinearity, if with the substrate of device attached on the collector of electric spinning equipment or with substrate as collector, patent of the present invention will very help directly luminescent device, photovoltaic device and the fiber waveguide device of the relevant PPV nano silk of preparation.Patent of the present invention has like this overcome existing employing chemical vapour deposition technique (CVD) will prepare PPV nano wire and nanotube in the foraminous die plate of appointment, also to remove template, have inhomogeneous, the easy pollution of product, profile and be subjected to the restriction etc. of pore size of template to be unfavorable for the shortcoming of PPV nano photoelectronic devices preparation with chemistry or physical method.
The specific embodiment
Will be further understood that the present invention from following illustrative embodiment.
[embodiment 1]
According to the optimization synthesis condition that people such as the synthetic route of R.A.Weslling and P.L.Halliday provide, prepare number-average molecular weight in 60,000 PPV prepolymer solution for later use.
Last liquid is placed on to be evaporated to PPV prepolymer content under the air at room temperature be the concentrated solution of 3.0wt%, transfers to the PPV prepolymer electrospinning silk solution that PPV prepolymer content is 0.8wt% with 1: 1 methyl alcohol and alcohol mixeding liquid.
At ambient temperature, PPV prepolymer electrospinning silk solution put into syringe and connect the electrode of DC high-voltage power supply, collector connects electrode, is 20kV, the spout electrospinning of carrying out to collector 5cm distance at voltage, collect a period of time, get the nanofiber of PPV prepolymer.Under 250 ℃, nitrogen protection with prepolymer fiber heating 30 minutes, the PPV nano silk.
[embodiment 2]
According to the optimization synthesis condition that people such as the synthetic route of R.A.Weslling and P.L.Halliday provide, prepare number-average molecular weight in 90,000 PPV prepolymer solution for later use.
PPV prepolymer solution is placed on to be evaporated to PPV prepolymer content under the air at room temperature be the concentrated solution of 1.0wt%, transfers to the PPV prepolymer electrospinning silk solution that PPV prepolymer content is 0.2wt% with ethanol.
At ambient temperature, PPV prepolymer electrospinning silk solution put into syringe and connect the electrode of DC high-voltage power supply, collector connects electrode, is 6kV, the spout electrospinning of carrying out to collector 30cm distance at voltage, collect a period of time, get the nano silk of PPV prepolymer.Under 220 ℃, vacuum condition with prepolymer nano silk heating 20 minutes, the PPV nano silk.
[embodiment 3]
According to the optimization synthesis condition that people such as the synthetic route of R.A.Weslling and P.L.Halliday provide, prepare number-average molecular weight in 80,000 PPV prepolymer solution for later use.
PPV prepolymer solution is placed on to be evaporated to PPV prepolymer content under the air at room temperature be the concentrated solution of 2.0wt%, transfers to the PPV prepolymer electrospinning silk solution that PPV prepolymer content is 0.6wt% with 1: 1.5 methyl alcohol and alcohol mixeding liquid.
At ambient temperature, PPV prepolymer electrospinning silk solution put into syringe and connect the electrode of DC high-voltage power supply, collector connects electrode, is 10kV, the spout electrospinning of carrying out to collector 17cm distance at voltage, collect a period of time, get the nano silk of PPV predecessor.Under 200 ℃, argon gas condition, the predecessor nano silk was heated about 60 minutes, the PPV nano silk.
Be understandable that therefore this do not run counter to this patent scope of invention and spirit if all condition details such as solvent, concentration and the electrospinning of the molecular weight of change PPV prepolymer, spinning solution and sintering must PPV electrospinning silk be possible.
Claims (7)
1. p-phenylene vinylene's nano silk, it is characterized by its diameter and be tens to the hundreds of nanometer, order of magnitude length more than centimetre is measured the photoluminescence spectrum of PPV electrospinning silk with the fluorescence spectrum spectroscope, keep the bimodal characteristics of luminescence at 515nm and 550nm place, consistent with the photoluminescence spectrum of PPV film.
2. p-phenylene vinylene's nano silk preparation method of claim 1, this method is carried out according to the following steps:
A. according to synthetic route (J.Polym.Sci.:Polym.Symp., 1985,72 of R.A.Weslling, 55) and people (Synth.Met., 1993,55-57 such as P.L.Halliday, 902) the optimization synthesis condition that provides is prepared the PPV prepolymer aqueous solution of number-average molecular weight at 6-9 about ten thousand;
B. above-mentioned solution be placed on evaporate under the air at room temperature PPV prepolymer concentrate, be modulated into the electrospinning silk solution for later use of PPV prepolymer again with lower alcohol;
C. at ambient temperature, PPV prepolymer electrospinning silk solution put into syringe and connect the electrode of DC high-voltage power supply, collector connects electrode, is 6-20kV, the spout electrospinning of carrying out to collector 5-30cm distance at voltage, collect a period of time, get the nano silk of PPV prepolymer;
D. under inert gas shieldings such as 200-250 ℃, vacuum or nitrogen with prepolymer nano silk heating about 20-60 minute, obtain the PPV nano silk.
3. in accordance with the method for claim 2, wherein PPV prepolymer concentrate to be characterized as PPV prepolymer content be 3.0-1.0wt%.
4. in accordance with the method for claim 2, wherein PPV prepolymer electrospinning solution to be characterized as PPV prepolymer content be 0.8-0.2wt%.
5. in accordance with the method for claim 2, wherein lower alcohol is ethanol or 1: 1-1: 1.5 methanol/ethanol mixtures.
6. wherein under the inert gas shielding such as vacuum or nitrogen the prepolymer nano silk was heated about 30 minutes in accordance with the method for claim 2.
7. in accordance with the method for claim 2, wherein collect very wire netting or metallic film, or have the wire netting or the metallic film of device substrate, or device substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100165698A CN100335685C (en) | 2005-02-01 | 2005-02-01 | Poly(p-phenylene vinylene) nano silk and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100165698A CN100335685C (en) | 2005-02-01 | 2005-02-01 | Poly(p-phenylene vinylene) nano silk and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1664181A CN1664181A (en) | 2005-09-07 |
| CN100335685C true CN100335685C (en) | 2007-09-05 |
Family
ID=35035481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100165698A Expired - Fee Related CN100335685C (en) | 2005-02-01 | 2005-02-01 | Poly(p-phenylene vinylene) nano silk and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100335685C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101378290B1 (en) * | 2006-10-31 | 2014-03-25 | 마젤란 시스템즈 인터내셔날, 엘엘시 | Process and apparatus for the production of yarn |
| CN101760806B (en) * | 2008-12-26 | 2012-02-22 | 黑龙江大学 | Polymer/carbon nano tube nano fiber material and preparation method and application thereof |
| CN102443858B (en) * | 2011-09-07 | 2013-11-06 | 南昌大学 | Preparation method of poly-p-phenylene ethylene derivative micro-nano fiber |
| CN102504284B (en) * | 2011-11-02 | 2013-10-16 | 黑龙江大学 | Method for preparing polyphenyl acetylene microballoon spheres |
| CN103981700A (en) * | 2014-05-07 | 2014-08-13 | 苏州大学 | Polyvinyl alcohol fluorescence fiber film, and making method and application thereof |
| CN105088391B (en) * | 2015-07-17 | 2017-05-10 | 黑龙江大学 | Poly(p-phenylene vinylene)/graphene composite nanofiber material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5645890A (en) * | 1995-02-14 | 1997-07-08 | The Trustess Of The University Of Pennsylvania | Prevention of corrosion with polyaniline |
| US5773568A (en) * | 1993-08-12 | 1998-06-30 | The Trustees Of The University Of Pennsylvania | Methods for preparing conductive polyanilines |
| CN1213672A (en) * | 1997-10-06 | 1999-04-14 | 中国人民解放军国防科工委后勤部军事医学研究所 | Synthetizing of poly-p-phenylacetylene |
| CN1389606A (en) * | 2002-07-12 | 2003-01-08 | 浙江大学 | Prepn. process of fishbone-shaped nano carbon fiber |
| CN1451671A (en) * | 2002-04-16 | 2003-10-29 | 中国科学院化学研究所 | Blue light-emitting superbranched conjugated polymer and preparing process thereof |
| CN1558702A (en) * | 2004-01-14 | 2004-12-29 | 北京交通大学 | An unorganic/organic composite structure white light emitting display |
-
2005
- 2005-02-01 CN CNB2005100165698A patent/CN100335685C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773568A (en) * | 1993-08-12 | 1998-06-30 | The Trustees Of The University Of Pennsylvania | Methods for preparing conductive polyanilines |
| US5645890A (en) * | 1995-02-14 | 1997-07-08 | The Trustess Of The University Of Pennsylvania | Prevention of corrosion with polyaniline |
| CN1213672A (en) * | 1997-10-06 | 1999-04-14 | 中国人民解放军国防科工委后勤部军事医学研究所 | Synthetizing of poly-p-phenylacetylene |
| CN1451671A (en) * | 2002-04-16 | 2003-10-29 | 中国科学院化学研究所 | Blue light-emitting superbranched conjugated polymer and preparing process thereof |
| CN1389606A (en) * | 2002-07-12 | 2003-01-08 | 浙江大学 | Prepn. process of fishbone-shaped nano carbon fiber |
| CN1558702A (en) * | 2004-01-14 | 2004-12-29 | 北京交通大学 | An unorganic/organic composite structure white light emitting display |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1664181A (en) | 2005-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100335685C (en) | Poly(p-phenylene vinylene) nano silk and method for preparing same | |
| Dante et al. | Nanoscale charge transport and internal structure of bulk heterojunction conjugated polymer/fullerene solar cells by scanning probe microscopy | |
| CN106782769B (en) | Flexible and transparent conductive laminated film of low roughness low square resistance and preparation method thereof | |
| US10350795B2 (en) | Flexible and electrically conductive polymer films and methods of making same | |
| Jiang et al. | Facile preparation of Cu/Ag core/shell electrospun nanofibers as highly stable and flexible transparent conductive electrodes for optoelectronic devices | |
| Gao et al. | Aligned coaxial nanowires of carbon nanotubes sheathed with conducting polymers | |
| Kymakis et al. | Carbon nanotube/PEDOT: PSS electrodes for organic photovoltaics | |
| US8940194B2 (en) | Electrodes with electrospun fibers | |
| US20050287366A1 (en) | Method for producing conducting polymer fibers with vinyl and conducting polymer fibers with vinyl produced thereby | |
| Prajongtat et al. | Moisture-resistant electrospun polymer membranes for efficient and stable fully printable perovskite solar cells prepared in humid air | |
| Chapi | Optical, electrical and electrochemical properties of PCL5/ITO transparent conductive films deposited by spin-coating‒Materials for single-layer devices | |
| Kim et al. | Optimal design of PEDOT: PSS polymer-based silver nanowire electrodes for realization of flexible polymer solar cells | |
| Rhee et al. | Stretchable hole extraction layer for improved stability in perovskite solar cells | |
| Huang et al. | A facile way for scalable fabrication of silver nanowire network electrodes for high-performance and foldable smart windows | |
| Jayathilaka et al. | Facile and scalable electrospun nanofiber-based alternative current electroluminescence (ACEL) device | |
| Li et al. | Facile fabrication of large-scale silver nanowire transparent conductive films by screen printing | |
| Hernández-Martínez et al. | Electrospinning of P3HT-PEO-CdS fibers by solution method and their properties | |
| Zhu et al. | Boron nitride quantum dots-decorated ferroelectric nanofibers for high performance wearable photodetectors | |
| CN1955213B (en) | Polymer nanofibre film mixed with fullerene and its preparation method | |
| Lin et al. | Novel poly (3-methylthiophene)-TiO2 hybrid materials for photovoltaic cells | |
| Xia et al. | Humidity response property of Ba0. 8Sr0. 2TiO3 ordered nanofiber arrays synthetized via electrospinning | |
| CN113284960B (en) | Flexible nanofiber membrane light-transmitting electrode with light conversion function and preparation method and application thereof | |
| WO2013103332A2 (en) | Liquid silane-based compositions and methods of fabrication | |
| Shim et al. | Fabrication and optical properties of conjugated polymer composited multi-arrays of TiO2 nanowires via sequential electrospinning | |
| KR20090085788A (en) | Poly (3,4-ethylenedioxythiophene)(pedot) nanowires for organic photoelectric device, method for cotrolling the properties of photoluminescence |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |