CN103343394B - Preparation method of polypyrrole nano fibers - Google Patents
Preparation method of polypyrrole nano fibers Download PDFInfo
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- CN103343394B CN103343394B CN201310322669.8A CN201310322669A CN103343394B CN 103343394 B CN103343394 B CN 103343394B CN 201310322669 A CN201310322669 A CN 201310322669A CN 103343394 B CN103343394 B CN 103343394B
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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 high molecule nano material preparing technical field, relate to technique, particularly a kind of preparation method of polypyrrole nanofibers that a kind of novel fluorescence material preparation of adulterating in conducting polymer has the nanofiber of fluorescence and electric conductivity.
Background technology:
Conducting polymer is the novel photoelectric functional material that 20 th century later occur, has the electricity of a series of uniqueness, electrochemistry, optics and mechanical property, conducting polymer, as the polymeric material of a new generation, had both had the electrology characteristic of metalloid, kept again light weight and the machinability of polymer, at display material simultaneously, anti-static coating, sensor, the fields such as all kinds of electronic device and solar cell are widely used, and common conducting polymer comprises polyacetylene, polythiophene, polypyrrole, polyaniline, polyhenylene, polyphenylene ethylene and poly-two alkynes, in these conducting polymers, the structure diversification of polypyrrole, mechanism of doping effect is unique, good stability, be widely used, it is one of conducting polymer of greatest concern at present, such as, Chinese patent CN201110235564.X discloses a kind of method preparing polypyrrole/graphene composite film material, adopt electrochemical method electropolymerization on conductive electrode to obtain polypyrrole/graphene composite film material, this composite film material as anticorrosive, can also be applied in capacitor, lithium ion battery, the field such as sensor and fuel cell, Chinese patent CN201210003652.1 discloses a kind of preparation method of graphite oxide/polypyrrole composite material, utilize ultrasonic disperse technology that graphite oxide and polypyrrole are carried out Uniform Doped, solve electric conductivity and the thermal stability problems of composite, can be used on the 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 MEMS technology and manufacture method thereof, utilize MEMS(MEMS) technology prepare be suitable for produce in batches poly-pyrrole minisize super capacitor, there is volume little, the features such as energy storage height and stable performance, at Micro-Robot electronic intelligence system, the 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), " embedding nanometer pore array material of polypyrrole nano-pillar 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., diverse ways is utilized to prepare high molecular, hollow ball-shape, the Polypyrrole Conducting Materials of one dimension wire and three-dimensional structure, potential application foreground is had in different field.Although the conducting polymer such as polypyrrole and polyaniline has more excellent electrical properties, but the optical property of polypyrrole and polyaniline is not given prominence to, at present, the thinking improving polypyrrole and polyaniline optical property mainly contains two kinds: a kind of is the thinking of composite, adds in electric polypyrrole or polyaniline by other material of excellent optical performance, another kind is the thinking optimizing adulterant, Bronsted acid conventional in polypyrrole or the polyaniline polymerization process compound that other has better optical property is replaced, the polypyrrole of such preparation or polyaniline are still pure substances, have light concurrently simultaneously, electrical property, such as, azobenzene and its derivatives is the photochromic compound of a quasi-representative, helianthic acid is replaced conventional protonic acid doping on polyaniline molecule chain by chemistry Suo Wanmeixiang seminar of the Chinese Academy of Sciences, there is under preparing ultraviolet lighting the polyaniline nanotube of photoisomerization performance, nano wire (Chem.Mater.14 (2002) 3486) and film (Appl.Phys.Lett.84 (2004) 1898), exploration has been made to the photoelectric functionalization application realizing conducting polymer, but, these preparation methods are complicated, the nanofiber light of preparation, poor electrical performance, be not suitable for large-scale production.
Summary of the invention:
The object of the invention is to the shortcoming overcoming prior art existence, seek to design the preparation method that a kind of polypyrrole nanofibers is provided, adopt diazosulfide class fluorescer as adulterant, the polypyrrole nanofibers having fluorescence and electric conductivity concurrently is prepared in self assembly in aqueous, improves the optical property of electric polypyrrole and polyaniline.
To achieve these goals, the present invention adopts diazosulfide class fluorescer 3,3-bis-(4-(4,4-diphenyl amido) styryl)-{ 1,2,5-} diazosulfide base)-2,2 '-dimethoxy-1,1 '-dinaphthalene, referred to as TBB as adulterant, be doped on high polymer main chain by diazosulfide class fluorescer TBB, the polypyrrole nanofibers having fluorescence and electric conductivity concurrently is prepared in self assembly in aqueous, and its specific embodiment is:
(1), fluorescer dispersion: be scattered in deionized water by diazosulfide class fluorescer TBB, the weight ratio of diazosulfide class fluorescer TBB and deionized water is 1:10-20, and ultrasonic vibration obtained homogeneous phase solution after 1 hour, i.e. the fluorescer TBB aqueous solution;
(2), pyrrole monomer distilation: pyrrole monomer is put into conventional vacuum distillation apparatus, be heated to 60 DEG C and distill, obtain pure pyrrole monomer;
(3), fluorescer mixes with pyrrole monomer: under the protection of nitrogen, first pure pyrrole monomer and deionized water are mixed according to the ratio that volume ratio is 1:20-50 and obtain the pure pyrrole monomer aqueous solution, then, under the protection of nitrogen, after being mixed according to the ratio that volume ratio is 1:2 with the fluorescer TBB aqueous solution by the pure pyrrole monomer aqueous solution, ultrasonic vibration reacts 12 hours to obtain mixed solution;
(4), oxidant adds: under the protection of nitrogen, be the iron chloride (FeCl of 20-30wt% by weight percent concentration
3) solution joins in the mixed solution that step (3) obtains;
(5), pyrrole monomer polymerization: under the protection of nitrogen, oxidant (FeCl
3) cause pyrrole monomer polymerization generation polypyrrole, be doped on macromolecular chain after diazosulfide class fluorescer TBB and polypyrrole react, form polaron or bipolaron (i.e. carrier), improve the electric conductivity of polypyrrole; The Doped polypyrrole nanostructured that reaction generates is water insoluble, exists with the form precipitated;
(6), filtration washing: Doped polypyrrole nanostructured step (5) obtained is washed till neutrality with deionized water after filtering, then with ethanol, the filtrate after filtration is washed till colourless rear washed with diethylether 2-3 time, obtains polypyrrole nanofibers sample;
(7), vacuumize: polypyrrole nanofibers sample is put into conventional vacuum drying chamber inner drying and obtain black powder after 24 hours, be the polypyrrole nanofibers having fluorescence and electric conductivity concurrently, its average diameter is 100 nanometers.
The diazosulfide class fluorescer TBB that the present invention relates to is according to document " J.Org.Chem.63 (1998) 7536; Thin Solid Films 516 (2008) 5935; Adv.Funct.Mater.18 (2008) 3299 " disclosed synthetic method divides three steps to be prepared, and 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 carries out adulterating to improve its fluorescence property; Diazosulfide class fluorescer all can as the adulterant of polypyrrole and polyaniline conductive polymer.
The present invention compared with prior art; its preparation method is simple; scientific in principle is reliable; environmental friendliness, be applicable to large-scale production, the polypyrrole nanofibers of preparation is flexible; prehensile is strong; good stability, has excellent fluorescence property while self satisfactory electrical conductivity of maintenance, has wide practical use in Multifunctional antistatic coating, display material, micro Nano material mark, micro-nano luminescent device and area of solar cell.
Accompanying drawing illustrates:
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 polypyrrole nanofibers prepared by the present invention.
The fluorescence emission spectrum of the polypyrrole nanofibers that (a) in Fig. 3 is prepared for the present invention, launches ruddiness under the irradiation of ultraviolet light; B () is fluorescent quenching material for the non-polypyrrole of doping fluorescent agent TBB or the polypyrrole of common protonic acid doping, do not have fluorescence signal.
Detailed description of the invention:
Below by embodiment, also the present invention will be further described by reference to the accompanying drawings.
Embodiment:
The present embodiment adopts diazosulfide class fluorescer 3,3-bis-(4-(4,4-diphenyl amido) styryl)-1,2,5-} diazosulfide base)-2,2 '-dimethoxy-1,1 '-dinaphthalene, referred to as TBB as adulterant, is doped on high polymer main chain by diazosulfide class fluorescer TBB, the polypyrrole nanofibers having fluorescence and electric conductivity concurrently is prepared in self assembly in aqueous, and its specific embodiment is:
(1), fluorescer dispersion: be scattered in 20 ml deionized water by 1-2 gram of diazosulfide class fluorescer TBB, ultrasonic vibration 1 hour, obtains homogeneous phase solution, i.e. the fluorescer TBB aqueous solution;
(2), pyrrole monomer distilation: pyrrole monomer is put into conventional vacuum distillation apparatus, be heated to 60 DEG C and distill, obtain pure pyrrole monomer;
(3), fluorescer mixes with pyrrole monomer: under the protection of nitrogen, first pure pyrrole monomer and deionized water are mixed according to the ratio that volume ratio is 1:20-50 and obtain the pure pyrrole monomer aqueous solution, then by 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 vibration react and obtain mixed solution in 12 hours;
(4), oxidant adds: under the protection of nitrogen, by 3 grams of FeCl
36H
2o solid joins in the mixed solution that step (3) obtains;
(5), pyrrole monomer polymerization: under the protection of nitrogen, oxidant (FeCl
3) cause pyrrole monomer polymerization generation polypyrrole, be doped on macromolecular chain after diazosulfide class fluorescer TBB and polypyrrole react, form polaron or bipolaron (i.e. carrier), improve the electric conductivity of polypyrrole; The Doped polypyrrole nanostructured that reaction generates is water insoluble, exists with the form precipitated;
(6), filtration washing: Doped polypyrrole nanostructured step (5) obtained is washed till neutrality with deionized water after filtering, then with ethanol, the filtrate after filtration is washed till colourless rear washed with diethylether 2-3 time, obtains polypyrrole nanofibers sample;
(7), vacuumize: polypyrrole nanofibers sample is put into conventional vacuum drying chamber inner drying and obtain black powder after 24 hours, be the polypyrrole nanofibers having fluorescence and electric conductivity concurrently, its average diameter is 100 nanometers.
The black polypyrrole powder morphology that the present embodiment adopts sem observation to collect, as shown in Figure 2, scanning electron microscope sem photo shows, the fluorescer TBB Doped polypyrrole prepared is made up of nanofiber, and have a lot of hole, porosity is high, and specific area is large; Measure after polypyrrole pressed powder, its room-temperature conductivity is 0.4S/cm, and under UV-irradiation, fluorescer TBB Doped polypyrrole nanofiber launches very strong ruddiness, and its fluorescence spectrum as shown in Figure 3; Experimental result shows, polypyrrole nanofibers prepared by the present embodiment has outstanding conduction and optical property concurrently, has potential application foreground at the numerous areas such as photoelectric material and device.
Claims (2)
1. the preparation method of a polypyrrole nanofibers, it is characterized in that adopting diazosulfide class fluorescer 3,3-bis-(4-(4,4-diphenyl amido) styryl)-{ 1,2,5-} diazosulfide base)-2,2 '-dimethoxy-1,1 '-dinaphthalene or be called that TBB is as adulterant, diazosulfide class fluorescer TBB is doped on high polymer main chain, the polypyrrole nanofibers having fluorescence and electric conductivity concurrently is prepared in self assembly in aqueous, and its specific embodiment is:
(1), fluorescer dispersion: be scattered in deionized water by diazosulfide class fluorescer TBB, the weight ratio of diazosulfide class fluorescer TBB and deionized water is 1:10-20, and ultrasonic vibration obtained homogeneous phase solution after 1 hour, i.e. the fluorescer TBB aqueous solution;
(2), pyrrole monomer distilation: pyrrole monomer is put into conventional vacuum distillation apparatus, be heated to 60 DEG C and distill, obtain pure pyrrole monomer;
(3), fluorescer mixes with pyrrole monomer: under the protection of nitrogen, first pure pyrrole monomer and deionized water are mixed according to the ratio that volume ratio is 1:20-50 and obtain the pure pyrrole monomer aqueous solution, then, under the protection of nitrogen, after being mixed according to the ratio that volume ratio is 1:2 with the fluorescer TBB aqueous solution by the pure pyrrole monomer aqueous solution, ultrasonic vibration reacts 12 hours to obtain mixed solution;
(4), oxidant adds: under the protection of nitrogen, is that the ferric chloride solution of 20-30wt% joins in the mixed solution that step (3) obtains by weight percent concentration;
(5), pyrrole monomer polymerization: under the protection of nitrogen, oxidant causes pyrrole monomer polymerization and generates polypyrrole, be doped on macromolecular chain after diazosulfide class fluorescer TBB and polypyrrole react, form polaron or bipolaron, improve the electric conductivity of polypyrrole; The Doped polypyrrole nanostructured that reaction generates is water insoluble, exists with the form precipitated;
(6), filtration washing: Doped polypyrrole nanostructured step (5) obtained is washed till neutrality with deionized water after filtering, with ethanol, the filtrate after filtration is washed till colourless rear washed with diethylether 2-3 time again, obtains polypyrrole nanofibers sample;
(7), vacuumize: polypyrrole nanofibers sample is put into conventional vacuum drying chamber inner drying and obtain black powder after 24 hours, be the polypyrrole nanofibers having fluorescence and electric conductivity concurrently, its average diameter is 100 nanometers.
2. the preparation method of polypyrrole nanofibers according to claim 1, is characterized in that the luminescence generated by light effect of the diazosulfide class fluorescer TBB related to can see red emission under UV-irradiation; Diazosulfide class fluorescer TBB is suitable for p-poly-phenyl amine to carry out adulterating to improve its fluorescence property.
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