CN103343394A - Preparation method of polypyrrole nano fibers - Google Patents
Preparation method of polypyrrole nano fibers Download PDFInfo
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- CN103343394A CN103343394A CN2013103226698A CN201310322669A CN103343394A CN 103343394 A CN103343394 A CN 103343394A CN 2013103226698 A CN2013103226698 A CN 2013103226698A CN 201310322669 A CN201310322669 A CN 201310322669A CN 103343394 A CN103343394 A CN 103343394A
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Abstract
The invention belongs to the technical field of preparation of high polymer nano materials, and relates to a preparation method of polypyrrole nano fibers. The preparation method comprises the following steps of: adopting a diazosulfide fluorescer namely 3,3-bis(4-(4,4-diphenylamine)cinnamenyl)-{1,2,5-}diazosulfide base)-2,2'-dimethoxy-1,1'-binaphthyl (TBB for short) as a doping agent, and doping the diazosulfide fluorescer TBB to a high polymer main chain; and performing self assembly in an aqueous solution to prepare the polypyrrole nano fibers with fluorescence properties and electrical conductivity. The preparation method is simple, scientific and reliable in principle, environment-friendly and suitable for large-scale production; and the prepared polypyrrole nano fibers are good in flexibility, strong in enwinding property and good in stability, have excellent fluorescence properties while keeping good self electrical conductivity, and have wide application prospects in the fields of multifunctional antistatic coatings, display materials, micro and nano material marks, micro and nano light-emitting devices and solar batteries.
Description
Technical field:
The invention belongs to the high molecule nano material preparing technical field, relate to a kind of in conducting polymer doping novel fluorescence material preparation have the technology, particularly a kind of preparation method of polypyrrole nanofiber of the nanofiber of fluorescence and electric conductivity.
Background technology:
Conducting polymer is the novel photoelectric functional material that 20 th century later occur, electricity with a series of uniquenesses, electrochemistry, optics and mechanical property, conducting polymer is as the polymeric material of a new generation, the electrology characteristic that had both had metalloid, the light weight and the machinability that keep simultaneously polymer again, at display material, anti-static coating, sensor, fields such as all kinds of electronic devices and solar cell are widely used, common conducting polymer comprises polyacetylene, polythiophene, polypyrrole, polyaniline, polyhenylene, polyphenylene ethylene and poly-two alkynes, in these conducting polymers, the structure variation of polypyrrole, the mechanism of doping effect uniqueness, good stability, be widely used, it is one of conducting polymer at present of greatest concern, for example, Chinese patent CN201110235564.X discloses a kind of method for preparing the polypyrrole/graphene composite film material, adopt electrochemical method electropolymerization on conductive electrode to obtain the polypyrrole/graphene composite film material, this composite film material can be used as anticorrosive, can also be applied in capacitor, lithium ion battery, field such as sensor and fuel cell; Chinese patent CN201210003652.1 discloses a kind of preparation method of graphite oxide/Pt/Polypyrrole composite material, utilize ultrasonic dispersion technology that graphite oxide and polypyrrole are evenly mixed, solve electric conductivity and the thermal stability problems of composite, can be used on fields such as electrode material for super capacitor, electrochmical power source, sensor, environment and life science; Chinese patent CN200810112278.2 discloses a kind of poly-pyrrole minisize super capacitor based on the MEMS technology and manufacture method thereof, utilize the MEMS(MEMS) technology prepares the poly-pyrrole minisize super capacitor that is suitable for producing in batches, it is little to have volume, characteristics such as energy storage height and stable performance, in Micro-Robot electronic intelligence system, fields such as chemical sensor and battlefield friend or foe indicator have extensive use, these technology realize the multifunction application of polypyrrole by multiple material complex technique, in addition, change polypyrrole self microstructure by different preparation methods and also can realize its diversified application, as Chinese patent " high-molecular polyazoles " (CN200610156793.1), " polypyrrole nano line and its production and use " (CN201110066952.X), " polypyrrole nano-pillar embedding nanometer pore array material and preparation method thereof and stored energy application " (CN201110362797.6), " three-dimensional structure polypyrrole microelectrode and manufacture method thereof " (CN201010260851.1), " preparation method of electric polypyrrole nano hollow sphere " (CN200610032410.X) etc., utilize diverse ways to prepare high molecular, hollow ball-shape, the polypyrrole conductive material of one dimension wire and three-dimensional structure has potential application foreground in different field.Though conducting polymer such as polypyrrole and polyaniline has better electrical properties, but the optical property of polypyrrole and polyaniline is not outstanding, at present, the thinking that improves polypyrrole and polyaniline optical property mainly contains two kinds: a kind of is the thinking of composite, and other material of excellent optical performance is added in electric polypyrrole or the polyaniline; Another kind is the thinking of optimizing adulterant; Bronsted acid commonly used in polypyrrole or the polyaniline polymerization process is replaced with the compound that other has better optical property; Zhi Bei polypyrrole or polyaniline still are pure substances like this; have light simultaneously concurrently; electrical property; for example; azobenzene and derivative thereof are the photochromic compounds of a quasi-representative; ten thousand Mei Xiang seminars of chemistry institute of the Chinese Academy of Sciences replace the protonic acid doping used always to the polyaniline molecule chain with helianthic acid; prepare the polyaniline nano pipe that has the photoisomerization performance under the ultraviolet lighting; nano wire (Chem.Mater.14 (2002) 3486) and film (Appl.Phys.Lett.84 (2004) 1898); exploration has been made in the photoelectric functional application that realizes conducting polymer; but; these preparation method's complexity; the nanofiber light of preparation; poor electrical performance is not suitable for large-scale production.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that prior art exists, seek to design the preparation method that a kind of polypyrrole nanofiber is provided, adopt diazosulfide class fluorescer as adulterant, the polypyrrole nanofiber that has fluorescence and electric conductivity concurrently is prepared in self assembly in the aqueous solution, improves the optical property of electric polypyrrole and polyaniline.
To achieve these goals, the present invention adopts diazosulfide class fluorescer 3,3-two (4-(4,4-diphenyl amido) styryl)-{ 1,2,5-} diazosulfide base)-2,2 '-dimethoxy-1,1 '-dinaphthalene, abbreviate TBB as adulterant, TBB is doped on the high polymer main chain with diazosulfide class fluorescer, and the polypyrrole nanofiber that has fluorescence and electric conductivity concurrently is prepared in self assembly in the aqueous solution, and its specific embodiment is:
(1), fluorescer disperses: TBB is scattered in the deionized water with diazosulfide class fluorescer, and the weight ratio of diazosulfide class fluorescer TBB and deionized water is 1:10-20, and ultrasonic concussion obtained homogeneous phase solution after 1 hour, i.e. the fluorescer TBB aqueous solution;
(2), the pyrrole monomer distillation is purified: pyrrole monomer is put into conventional vacuum distillation apparatus, be heated to 60 ℃ and distill, obtain pure pyrrole monomer;
(3), fluorescer mixes with pyrrole monomer: under protection of nitrogen gas, be that the ratio of 1:20-50 mixes and obtains the pure pyrrole monomer aqueous solution with pure pyrrole monomer and deionized water according to volume ratio earlier, then under protection of nitrogen gas, with the pure pyrrole monomer aqueous solution and the fluorescer TBB aqueous solution according to volume ratio be the ratio of 1:2 mix the ultrasonic concussion reaction in back 12 hours mixed solution;
(4), oxidant adds: under protection of nitrogen gas, be the iron chloride (FeCl of 20-30wt% with weight percent concentration
3) solution joins in the mixed solution that step (3) obtains;
(5), the pyrrole monomer polymerization: under protection of nitrogen gas, oxidant (FeCl
3) cause pyrrole monomer polymerization generation polypyrrole, be doped on the macromolecular chain after diazosulfide class fluorescer TBB and the polypyrrole reaction, form polaron or bipolaron (being carrier), improve the electric conductivity of polypyrrole; The doping polypyrrole nano structure that reaction generates is water insoluble, exists with the form that precipitates;
(6), filtration washing: the doping polypyrrole nano structure filtration back that step (5) is obtained is washed till neutrality with deionized water, with ethanol filtrate filtered is washed till colourless back with ether washing 2-3 time again, obtains polypyrrole nanofiber sample;
(7), vacuumize: polypyrrole nanofiber sample is put into conventional vacuum drying chamber inner drying obtain black powder after 24 hours, be the polypyrrole nanofiber that has fluorescence and electric conductivity concurrently, its average diameter is 100 nanometers.
" J.Org.Chem.63 (1998) 7536 according to document for the diazosulfide class fluorescer TBB that the present invention relates to; Thin Solid Films 516 (2008) 5935; Adv.Funct.Mater.18 (2008) 3299 " disclosed synthetic method divide three the step prepare, the luminescence generated by light effect of diazosulfide class fluorescer TBB is strong, can see very strong red emission under UV-irradiation; Diazosulfide class fluorescer TBB is suitable for polyaniline equally and other conducting polymer mixes to improve its fluorescence property; Diazosulfide class fluorescer all can be as the adulterant of polypyrrole and polyaniline conductive polymer.
The present invention compared with prior art; its preparation method is simple; the principle science is reliable; environmental friendliness is fit to large-scale production, and the polypyrrole nanofiber flexibility of preparation is good; prehensile is strong; good stability has good fluorescence property in maintenance self satisfactory electrical conductivity, have wide practical use in multi-functional anti-static coating, display material, micro Nano material mark, micro-nano luminescent device and area of solar cell.
Description of drawings:
Fig. 1 is preparation flow and the molecular structure principle schematic of the diazosulfide class fluorescer TBB that the present invention relates to.
Fig. 2 is the scanning electron microscope sem photo of the polypyrrole nanofiber of the present invention's preparation.
(a) among Fig. 3 launches ruddiness for the fluorescence emission spectrum of the polypyrrole nanofiber of the present invention's preparation under the irradiation of ultraviolet light; (b) be the fluorescent quenching material for the polypyrrole of doping fluorescent agent TBB not or the polypyrrole of common protonic acid doping, do not have fluorescence signal.
The specific embodiment:
Also the present invention will be further described by reference to the accompanying drawings below by embodiment.
Embodiment:
Present embodiment adopts diazosulfide class fluorescer 3,3-two (4-(4,4-diphenyl amido) styryl)-1,2,5-} diazosulfide base)-2,2 '-dimethoxy-1,1 '-dinaphthalene abbreviates TBB as adulterant, and TBB is doped on the high polymer main chain with diazosulfide class fluorescer, the polypyrrole nanofiber that has fluorescence and electric conductivity concurrently is prepared in self assembly in the aqueous solution, and its specific embodiment is:
(1), fluorescer disperses: 1-2 is restrained diazosulfide class fluorescer TBB be scattered in 20 ml deionized water, ultrasonic concussion 1 hour obtains homogeneous phase solution, i.e. the fluorescer TBB aqueous solution;
(2), the pyrrole monomer distillation is purified: pyrrole monomer is put into conventional vacuum distillation apparatus, be heated to 60 ℃ and distill, obtain pure pyrrole monomer;
(3), fluorescer mixes with pyrrole monomer: under protection of nitrogen gas, earlier will pure pyrrole monomer and deionized water be that the ratio of 1:20-50 mixes and obtains the pure pyrrole monomer aqueous solution according to volume ratio, then with 10 milliliters of pure pyrrole monomer aqueous solution (volume ratio of pyrrole monomer and deionized water is 1:50 to 1:20) and 20 milliliters of fluorescer TBB aqueous solution evenly after ultrasonic concussions react and obtained mixed solution in 12 hours;
(4), oxidant adds: under protection of nitrogen gas, with 3 gram FeCl
36H
2The O solid joins in the mixed solution that step (3) obtains;
(5), the pyrrole monomer polymerization: under protection of nitrogen gas, oxidant (FeCl
3) cause pyrrole monomer polymerization generation polypyrrole, be doped on the macromolecular chain after diazosulfide class fluorescer TBB and the polypyrrole reaction, form polaron or bipolaron (being carrier), improve the electric conductivity of polypyrrole; The doping polypyrrole nano structure that reaction generates is water insoluble, exists with the form that precipitates;
(6), filtration washing: the doping polypyrrole nano structure filtration back that step (5) is obtained is washed till neutrality with deionized water, with ethanol filtrate filtered is washed till colourless back with ether washing 2-3 time again, obtains polypyrrole nanofiber sample;
(7), vacuumize: polypyrrole nanofiber sample is put into conventional vacuum drying chamber inner drying obtain black powder after 24 hours, be the polypyrrole nanofiber that has fluorescence and electric conductivity concurrently, its average diameter is 100 nanometers.
The black polypyrrole powder morphology that present embodiment adopts sem observation to collect, as shown in Figure 2, the scanning electron microscope sem photo shows, the fluorescer TBB doping polypyrrole of preparation is made up of nanofiber, and a lot of holes are arranged, the porosity height, specific area is big; To measure behind the polypyrrole pressed powder, its room-temperature conductivity is 0.4S/cm, and under UV-irradiation, fluorescer TBB doping polypyrrole nanofiber is launched very strong ruddiness, and its fluorescence spectrum as shown in Figure 3; Experimental result shows that the polypyrrole nanofiber of present embodiment preparation has outstanding conduction and optical property concurrently, at numerous areas such as photoelectric material and devices potential application foreground is arranged.
Claims (2)
1. the preparation method of a polypyrrole nanofiber, it is characterized in that adopting diazosulfide class fluorescer 3,3-two (4-(4,4-diphenyl amido) styryl)-{ 1,2,5-} diazosulfide base)-2,2 '-dimethoxy-1,1 '-dinaphthalene or be called TBB as adulterant, TBB is doped on the high polymer main chain with diazosulfide class fluorescer, the polypyrrole nanofiber that has fluorescence and electric conductivity concurrently is prepared in self assembly in the aqueous solution, and its specific embodiment is:
(1), fluorescer disperses: TBB is scattered in the deionized water with diazosulfide class fluorescer, and the weight ratio of diazosulfide class fluorescer TBB and deionized water is 1:10-20, and ultrasonic concussion obtained homogeneous phase solution after 1 hour, i.e. the fluorescer TBB aqueous solution;
(2), the pyrrole monomer distillation is purified: pyrrole monomer is put into conventional vacuum distillation apparatus, be heated to 60 ℃ and distill, obtain pure pyrrole monomer;
(3), fluorescer mixes with pyrrole monomer: under protection of nitrogen gas, be that the ratio of 1:20-50 mixes and obtains the pure pyrrole monomer aqueous solution with pure pyrrole monomer and deionized water according to volume ratio earlier, then under protection of nitrogen gas, with the pure pyrrole monomer aqueous solution and the fluorescer TBB aqueous solution according to volume ratio be the ratio of 1:2 mix the ultrasonic concussion reaction in back 12 hours mixed solution;
(4), oxidant adds: under protection of nitrogen gas, be that the ferric chloride solution of 20-30wt% joins in the mixed solution that step (3) obtains with weight percent concentration;
(5), pyrrole monomer polymerization: under protection of nitrogen gas, oxidant causes the pyrrole monomer polymerization and generates polypyrrole, be doped on the macromolecular chain after diazosulfide class fluorescer TBB and the polypyrrole reaction, form polaron or bipolaron, improve the electric conductivity of polypyrrole; The doping polypyrrole nano structure that reaction generates is water insoluble, exists with the form that precipitates;
(6), filtration washing: the doping polypyrrole nano structure filtration back that step (5) is obtained is washed till neutrality with deionized water, with ethanol filtrate filtered is washed till colourless back with ether washing 2-3 time again, obtains polypyrrole nanofiber sample;
(7), vacuumize: polypyrrole nanofiber sample is put into conventional vacuum drying chamber inner drying obtain black powder after 24 hours, be the polypyrrole nanofiber that has fluorescence and electric conductivity concurrently, its average diameter is 100 nanometers.
2. the preparation method of polypyrrole nanofiber according to claim 1, " J.Org.Chem.63 (1998) 7536 according to document to it is characterized in that the diazosulfide class fluorescer TBB that relates to; Thin Solid Films 516 (2008) 5935; Adv.Funct.Mater.18 (2008) 3299 " disclosed synthetic method divide three the step prepare, the luminescence generated by light effect of diazosulfide class fluorescer TBB can be seen red emission under UV-irradiation; Diazosulfide class fluorescer TBB is suitable for p-poly-phenyl amine and mixes to improve its fluorescence property; Diazosulfide class fluorescer can be as the adulterant of polypyrrole and polyaniline conductive polymer.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109402768A (en) * | 2018-11-08 | 2019-03-01 | 上海萃励电子科技有限公司 | A kind of synthetic method of poly- 3,4- ethyl dioxypyrrole nano wire |
| CN110746885A (en) * | 2019-11-27 | 2020-02-04 | 湖南辰砾新材料有限公司 | Sound-insulation weather-resistant waterproof coating and preparation method thereof |
| CN111219652A (en) * | 2020-01-17 | 2020-06-02 | 江苏大学 | Optical fiber lighting device |
| CN111747747A (en) * | 2020-07-17 | 2020-10-09 | 重庆大学 | Preparation method, product and application of carbon-based material with bionic fractal structure based on shaddock peel |
| CN112940310A (en) * | 2021-02-01 | 2021-06-11 | 江西科技师范大学 | Method for assembling ultrathin ordered conductive polymer film on liquid/gas interface |
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| CN102675877A (en) * | 2011-03-18 | 2012-09-19 | 中国科学院合肥物质科学研究院 | Polypyrrole nanowire, and preparation method and usage thereof |
| CN102924718A (en) * | 2012-11-16 | 2013-02-13 | 清华大学深圳研究生院 | Preparation method of nanostructured polypyrrole |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102675877A (en) * | 2011-03-18 | 2012-09-19 | 中国科学院合肥物质科学研究院 | Polypyrrole nanowire, and preparation method and usage thereof |
| CN102924718A (en) * | 2012-11-16 | 2013-02-13 | 清华大学深圳研究生院 | Preparation method of nanostructured polypyrrole |
Non-Patent Citations (1)
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| QINGGUO HE ETAL: "Amorphous molecular material containing bisthiophenyl-benzothiadiazole and triphenylamine with bipolar and low-bandgap characteristics for solar cells", 《THIN SOLID FILMS》, vol. 516, 17 October 2007 (2007-10-17), pages 5935 - 5940 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109402768A (en) * | 2018-11-08 | 2019-03-01 | 上海萃励电子科技有限公司 | A kind of synthetic method of poly- 3,4- ethyl dioxypyrrole nano wire |
| CN110746885A (en) * | 2019-11-27 | 2020-02-04 | 湖南辰砾新材料有限公司 | Sound-insulation weather-resistant waterproof coating and preparation method thereof |
| CN111219652A (en) * | 2020-01-17 | 2020-06-02 | 江苏大学 | Optical fiber lighting device |
| CN111747747A (en) * | 2020-07-17 | 2020-10-09 | 重庆大学 | Preparation method, product and application of carbon-based material with bionic fractal structure based on shaddock peel |
| CN112940310A (en) * | 2021-02-01 | 2021-06-11 | 江西科技师范大学 | Method for assembling ultrathin ordered conductive polymer film on liquid/gas interface |
| CN112940310B (en) * | 2021-02-01 | 2022-05-10 | 江西科技师范大学 | Method for assembling ultrathin ordered conductive polymer film on liquid/gas interface |
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