CN101962818B - Preparation method of doping type fluorescent micron-nano fibers - Google Patents
Preparation method of doping type fluorescent micron-nano fibers Download PDFInfo
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Abstract
The invention relates to a preparation method of doping type fluorescent micron-nano fibers, relating to a preparation method of fluorescent fibers and solving the problems of complex method realizing fluorescent light with different colors through the traditional organic fluorescent fibers of a monogenic dye, poor spectrum stability and short service life of physically blended organic fluorescent fibers and large diameters of the traditional organic fluorescent fibers. The preparation method of the doping type fluorescent micron-nano fibers comprises the following steps of: dissolving dialdehyde triphenylamine and poly [2-methoxyl-5(2'-ethylhexoxy) para-phenylacetylene] into a polymer solution according to different mass ratios; and then carrying out electrostatic spinning to obtain the doping type fluorescent micron-nano fibers. The doping type fluorescent micron-nano fibers have good fluorescence spectrum stability, long service life reaching two years and diameters of 10 nanometers-3 micrometers, and can be used in the life and highly technical fields of textile clothing, aviation, navigation, national defense industry, building decoration, transportation, night operation, daily life, amusement, leisure, optical-fiber communication, laser waveguide, and the like.
Description
Technical field
The present invention relates to the preparation method of fluorescent fiber.
Background technology
Fluorescent material is meant can fluorescigenic material under the effect of all kinds energy excitation.Fluorescent material is widely used in numerous high-tech areas such as waveguide laser emission and communication, bill anti-counterfeit, screen display, textile clothing, information record, optical computer, explosives sensor, probe biomolecule.The fluorescent characteristic of fluorescent fiber is a very important index, fluorescent characteristic comprises excitation wavelength, emission wavelength, characteristic peak, fluorescence intensity, fluorescence fastness and the fluorescent stability of fluorescent material, for satisfying application purpose, then mainly pay attention to fluorescence intensity, fluorescence fastness and three indexs of fluorescent stability.The organic fluorescence fiber is that organic fluorescence molecule and organic polymer with conjugated system is compound, utilize the organic matter fluorescence molecule characteristic that energy falls after rise after producing transition of electronic energy under the exciting of electricity and light etc., obtain the light of different wave length, thereby make the organic fluorescence fiber demonstrate fluorescence color.
The existing organic fluorescence fiber that is prepared by a certain dyestuff can only obtain the fluorescence of a certain color, emission band narrow (being generally less than 100nm), can not cover the broad band emission of whole visible spectrum, the organic fluorescence fiber of different colours is realized the method complexity by dosing different dyestuffs; Adopt the organic fluorescence fiber of the multispectral launching technique preparation of physical blending, be doping content and the transfer of the energy between each component by reasonable control dyestuff, make blue light and orange light two primary colors synthetic, or red-green-blue is synthetic, realize white light emission and polychrome emission, but the diameter of organic fluorescence fiber is several millimeters, and its diameter range is big, has limited the application of organic fluorescence fiber.
Summary of the invention
The present invention realizes the method complexity of different colours fluorescence in order to solve existing homogencous dyes organic fluorescence fiber, the big problem of organic fluorescence fibre diameter of physical blending, and the preparation method of doping type fluorescence micro/nano fibers is provided.
The preparation method of doping type fluorescence micro/nano fibers of the present invention carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be 1: 0.24～0.26 to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains white light doping type fluorescence micro/nano fibers.
The preparation method of doping type fluorescence micro/nano fibers of the present invention can also carry out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be 1: 0～0.1 to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains blue light doping type fluorescence micro/nano fibers.
The preparation method of doping type fluorescence micro/nano fibers of the present invention can also carry out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be 1: 0.15～0.2 to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains green glow doping type fluorescence micro/nano fibers.
The preparation method of doping type fluorescence micro/nano fibers of the present invention can also carry out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be 1: 0.27～0.3 to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains gold-tinted doping type fluorescence micro/nano fibers.
The preparation method of doping type fluorescence micro/nano fibers of the present invention can also carry out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) to phenylacetylene] at 0～0.1: 1 by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains orange photodoping type fluorescence micro/nano fibers.
The method of the doping type fluorescence micro/nano fibers of the present invention's preparation utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.The diameter of fluorescence micro/nano fibers is 10nm～3 μ m, is bundle fiber or felted film.Polymer solution concentration is high more, and viscosity is big more, and surface tension is big more, and the drop splitting ability weakens with the surface tension increase after leaving nozzle.Usually when other condition is constant, along with the diameter of the increase fiber of polymer solution concentration also increases.The increase of spinning voltage can cause charged fiber to produce bigger acceleration in electric field, and helps the fiber elongation, increases draw ratio.Nanofiber diameter can reduce along with the increase of receiving range, the fluorescence micro/nano fibers that the present invention obtains have diameter evenly, smooth surface, draw ratio is big and the outstanding advantages such as length of Centimeter Level.Micro nanometer fiber is as accurate one-dimensional material, have the property different with film or bulk material, emission color as fluorescence can change along with the diameter dimension of fiber, the diameter that the present invention obtains is poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to the phenylacetylene] of the dialdehyde-based triphenylamine of emission blue-fluorescence of the fiber of 10nm～3 μ m and different proportion and emission fluorescent orange, shift by the energy between controlled doping concentration and each component, not only can realize the white light emission, obtain the white light fluorescence micro/nano fibers, and utilize photochromic composition principle that it is made up, thereby it is abundant to form color and luster, bright and colourful effect, obtain blue light, green glow, gold-tinted, orange light fluorescence micro/nano fibers, and the fluorescence spectrum good stability that obtains, working life reaches 2 years.The fluorescence micro/nano fibers that the present invention obtains is long-pending big with respect to the ratio table of film, with the gas that is detected or other materials great contact area is arranged, can effectively react, stronger sensitivity is arranged, can be applicable to sensor, in addition can be widely used in textile garment, aviation and navigation, national defense industry, architectural decoration, communications and transportation, night work, daily life, amusement and leisure and optical-fibre communications, life and high-tech sectors such as laser waveguide.
Description of drawings
Fig. 1 is the stereoscan photograph of the white light fluorescence micro/nano fibers of the specific embodiment 11 preparations; Fig. 2 is the white light fluorescence micro/nano fibers UV absorption spectrogram of the specific embodiment 11 preparations; Fig. 3 is the white light fluorescence micro/nano fibers fluorescence spectrum figure of the specific embodiment 11 preparation, and wherein solid line-expression is the fluorescence spectrum of fiber, dotted line-----expression be the fluorescence spectrum of the film that constitutes by fiber; Fig. 4 is that the white light fluorescence micro/nano fibers of the specific embodiment 11 preparation is after the preparation and place the fluorescence spectrum figure that detects after half a year, wherein solid line-expression is the fluorescence spectrum of white light fluorescence micro/nano fibers after preparation, dotted line-----expression be fluorescence spectrum after the white light fluorescence micro/nano fibers is placed half a year; Fig. 5 is the stereoscan photograph of the blue light fluorescence micro/nano fibers of the specific embodiment 22 preparations; Fig. 6 is the blue light fluorescence micro/nano fibers UV absorption spectrogram of the specific embodiment 22 preparations; Fig. 7 is the blue light fluorescence micro/nano fibers fluorescence spectrum figure of the specific embodiment 22 preparations, wherein solid line-expression is fluorescence spectrum after the blue light fluorescence micro/nano fibers preparation, dotted line-----expression be fluorescence spectrum after blue light fluorescence micro/nano fibers placement half a year; Fig. 8 is the stereoscan photograph of the green glow fluorescence micro/nano fibers of the specific embodiment 33 preparations; Fig. 9 is the fluorescence spectrum figure of the green glow fluorescence micro/nano fibers of the specific embodiment 33 preparations, wherein solid line-expression is fluorescence spectrum after the green glow fluorescence micro/nano fibers preparation, dotted line-----expression be fluorescence spectrum after green glow fluorescence micro/nano fibers placement half a year; Figure 10 is the stereoscan photograph of the gold-tinted fluorescence micro/nano fibers of the specific embodiment 44 preparations; Figure 11 be the specific embodiment 44 preparation the gold-tinted fluorescence micro/nano fibers fluorescence spectrum figure, solid line-expression be fluorescence spectrum after the gold-tinted fluorescence micro/nano fibers preparation, dotted line-----expression be fluorescence spectrum after gold-tinted fluorescence micro/nano fibers placement half a year; Figure 12 is the stereoscan photograph of the orange light fluorescence micro/nano fibers of the specific embodiment 55 preparations; Figure 13 is the fluorescence spectrum figure of the orange light fluorescence micro/nano fibers of the specific embodiment 55 preparations, wherein solid line-expression is fluorescence spectrum after the preparation of orange light fluorescence micro/nano fibers, dotted line-----expression be fluorescence spectrum after orange light fluorescence micro/nano fibers placement half a year.
The specific embodiment
The specific embodiment one: the preparation method of the doping type fluorescence micro/nano fibers of present embodiment carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be 1: 0.24～0.26 to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains white light doping type fluorescence micro/nano fibers.
When the polymer of present embodiment was composition, polymer was wherein pressed arbitrarily than combination.
When the organic solvent of present embodiment was composition, organic solvent was wherein pressed arbitrarily than combination.
Present embodiment prepares the method for fluorescence micro/nano fibers and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.The fluorescent nano-fiber that present embodiment obtains, its diameter are 10nm～3 μ m, are bundle fiber or felted film.Polymer solution concentration is high more, and viscosity is big more, and surface tension is big more, and the drop splitting ability weakens with the surface tension increase after leaving nozzle.Usually when other condition is constant, along with the diameter of the increase fiber of polymer solution concentration also increases.The increase of spinning voltage can cause charged fiber to produce bigger acceleration in electric field, and helps the fiber elongation, increases draw ratio.Nanofiber diameter can reduce along with the increase of receiving range.Present embodiment in macromolecule main body material, mix poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to the phenylacetylene] of the dialdehyde-based triphenylamine of emission blue-fluorescence and emission fluorescent orange, shift by the energy between controlled doping concentration and each component, can realize the white light emission, obtain the white light fluorescence micro/nano fibers, fluorescence spectrum good stability, working life reach 2 years.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: the 1g polymer adds 11mL～14mL organic solvent in the step 1.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different with the specific embodiment one or two is: the 1g polymer adds the 13mL organic solvent in the step 1.Other is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different with one of specific embodiment one to three is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 1: 0.245～0.255 in the step 2.Other is identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different with one of specific embodiment one to four is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 1: 0.25 in the step 2.Other is identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different with one of specific embodiment one to five is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 7h～11h.Other is identical with one of specific embodiment one to five.
The specific embodiment seven: what present embodiment was different with one of specific embodiment one to six is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 9h.Other is identical with one of specific embodiment one to six.
The specific embodiment eight: what present embodiment was different with one of specific embodiment one to seven is: the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 61mL～64mL in the step 2.Other is identical with one of specific embodiment one to seven.
The specific embodiment nine: what present embodiment was different with one of specific embodiment one to eight is: the voltage of electrostatic spinning is that 12kV～28kV, shower nozzle are 8cm～28cm to the collector distance in the step 3.Other is identical with one of specific embodiment one to eight.
The specific embodiment ten: what present embodiment was different with one of specific embodiment one to nine is: the voltage of electrostatic spinning is that 20kV, shower nozzle are 18cm to the collector distance in the step 3.Other is identical with one of specific embodiment one to nine.
The specific embodiment 11: the preparation method of the doping type fluorescence micro/nano fibers of present embodiment carries out according to the following steps: the ratio that, adds the 12.5mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polymethyl methacrylate, and organic solvent is a chloroform; Two, be to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] at 1: 0.25 by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 63mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, be collector with the iron net, is that 15kV, shower nozzle are to carry out electrostatic spinning under the condition of 15cm to the collector distance at voltage, obtains white light doping type fluorescence micro/nano fibers.
The stereoscan photograph of the doping type fluorescence micro/nano fibers that present embodiment obtains as shown in Figure 1, as can be seen from Figure 1, the diameter of doping type fluorescence micro/nano fibers is 400nm～1.2 μ m, smooth surface, the diameter distribution uniform is greenish orange look felted film on macroscopic view.
The UV absorption spectrogram of the doping type fluorescence micro/nano fibers that present embodiment obtains as shown in Figure 2.As can be seen from Figure 2, in 400nm～700nm nanometer visible region, fiber has the absorption of broad, covered whole from blueness to orange red zone, and absorb stronger in blue region.
The fluorescence spectrum figure of the white light fluorescence micro/nano fibers that present embodiment obtains is shown in 3, solid line-expression be the test result of fiber, dotted line-----expression be the test result of the film that constitutes by fiber, as can be seen from Figure 3, fiber has two strong absworption peaks and an acromion at 435n, 550nm and 585nm place, representing blueness, yellow green and orange emission respectively, and the intensity at preceding two peaks is very consistent.And under the same proportioning situation, the emission peak of film but mainly presents two of 450nm and 575nm, and blue peak intensity has exceeded the instrument detecting scope.The white light fluorescence micro/nano fibers that present embodiment obtains in the result of fluorescence intensity after the preparation and after placing half a year as shown in Figure 4, solid line-expression be the fluorescence intensity of white light fluorescence micro/nano fibers after preparation, dotted line-----expression be fluorescence intensity after the white light fluorescence micro/nano fibers is placed half a year, as can be seen from Figure 4, after the white light fluorescence micro/nano fibers of the manner preparation is placed half a year, its fluorescence intensity does not reduce, have stronger fluorescent stability, the working life of the white light fluorescence micro/nano fibers of the manner preparation reaches 2 years.
Present embodiment prepares the method for fluorescent nano-fiber and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.
The specific embodiment 12: the preparation method of the doping type fluorescence micro/nano fibers of present embodiment carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be 1: 0～0.1 to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains blue light doping type fluorescence micro/nano fibers.
When the polymer of present embodiment was composition, polymer was wherein pressed arbitrarily than combination.
When the organic solvent of present embodiment was composition, organic solvent was wherein pressed arbitrarily than combination.
Present embodiment prepares the method for fluorescent nano-fiber and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.The fluorescent nano-fiber that present embodiment obtains, its diameter are 10nm～3 μ m, are bundle fiber or felted film.Polymer solution concentration is high more, and viscosity is big more, and surface tension is big more, and the drop splitting ability weakens with the surface tension increase after leaving nozzle.Usually when other condition is constant, along with the diameter of the increase fiber of polymer solution concentration also increases.The increase of spinning voltage can cause charged fiber to produce bigger acceleration in electric field, and helps the fiber elongation, increases draw ratio.Nanofiber diameter can reduce along with the increase of receiving range.Present embodiment in macromolecule main body material, mix poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to the phenylacetylene] of the dialdehyde-based triphenylamine of emission blue-fluorescence and emission fluorescent orange, shift by the energy between controlled doping concentration and each component, can realize blue emission, obtain the blue light fluorescence micro/nano fibers, shift by the energy between controlled doping concentration and each component, can realize blue emission, obtain the blue light fluorescence micro/nano fibers, fluorescence spectrum good stability, working life reach 2 years.
The specific embodiment 13: what present embodiment and the specific embodiment 12 were different is: the 1g polymer adds 11mL～14mL organic solvent in the step 1.Other is identical with the specific embodiment 12.
The specific embodiment 14: what present embodiment was different with the specific embodiment 12 or 13 is: the 1g polymer adds the 13mL organic solvent in the step 1.Other is identical with the specific embodiment 12 or 13.
The specific embodiment 15: what present embodiment was different with one of specific embodiment 12 to 14 is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 1: 0.01～0.08 in the step 2.Other is identical with one of specific embodiment 12 to 14.
The specific embodiment 16: what present embodiment was different with one of specific embodiment 12 to 15 is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 1: 0.05 in the step 2.Other is identical with one of specific embodiment 12 to 15.
The specific embodiment 17: what present embodiment was different with one of specific embodiment 12 to 16 is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 7h～11h.Other is identical with one of specific embodiment 12 to 16.
The specific embodiment 18: what present embodiment was different with one of specific embodiment 12 to 17 is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 9h.Other is identical with one of specific embodiment 12 to 17.
The specific embodiment 19: what present embodiment was different with one of specific embodiment 12 to 18 is: the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 61mL～64mL in the step 2.Other is identical with one of specific embodiment 12 to 18.
The specific embodiment 20: what present embodiment was different with one of specific embodiment 12 to 19 is: the voltage of electrostatic spinning is that 12kV～28kV, shower nozzle are 8cm～28cm to the collector distance in the step 3.Other is identical with one of specific embodiment 12 to 19.
The specific embodiment 21: what present embodiment was different with one of specific embodiment 12 to 20 is: the voltage of electrostatic spinning is that 20kV, shower nozzle are 18cm to the collector distance in the step 3.Other is identical with one of specific embodiment 12 to 20.
The specific embodiment 22: the preparation method of the fluorescence micro/nano fibers of present embodiment carries out according to the following steps: the ratio that, adds the 15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a Merlon, organic solvent is N, dinethylformamide; Two, be to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] at 1: 0.05 by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 10h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, be collector with the aluminium foil, is that 25kV, shower nozzle are to carry out electrostatic spinning under the condition of 15cm to the collector distance at voltage, obtains the little fluorescence micro/nano fibers of blue light.
The stereoscan photograph of the blue light fluorescence micro/nano fibers that present embodiment obtains as shown in Figure 5, as can be seen from Figure 5, the diameter of blue light fluorescence micro/nano fibers is 1.4 μ m～3 μ m, smooth surface, diameter is more even, is near-white felted film on macroscopic view.
The UV absorption spectrogram of the blue light fluorescence micro/nano fibers that present embodiment obtains as shown in Figure 6.As can be seen from Figure 6, fiber has strong absorption at 375nm, 450～700nm place, corresponding green with red absorption band.
The fluorescence spectrum figure of the blue light fluorescence micro/nano fibers that present embodiment obtains is shown in 7, wherein solid line-expression is fluorescence spectrum after the blue light fluorescence micro/nano fibers preparation, dotted line-----expression be fluorescence spectrum after the blue light fluorescence micro/nano fibers is placed half a year, as can be seen from Figure 7, the strong emission peak of blue light is arranged at the 450nm place, mainly be rendered as the emission peak of dialdehyde-based triphenylamine.Through the electrostatic spinning process, fiber has been realized blue emission; After the blue light fluorescence micro/nano fibers was placed half a year, its fluorescence intensity did not reduce, and has stronger fluorescent stability, and the working life of the blue light fluorescence micro/nano fibers of the manner preparation reaches 2 years.
Present embodiment prepares the method for fluorescent nano-fiber and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.
The specific embodiment 23: the preparation method of the doping type fluorescence micro/nano fibers of present embodiment carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, a kind of or wherein several combination in polymethyl methacrylate and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be 1: 0.15～0.2 to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains green glow doping type fluorescence micro/nano fibers.
When the polymer of present embodiment was composition, polymer was wherein pressed arbitrarily than combination.
When the organic solvent of present embodiment was composition, organic solvent was wherein pressed arbitrarily than combination.
Present embodiment prepares the method for fluorescence micro/nano fibers and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.The fluorescent nano-fiber that present embodiment obtains, its diameter are 10nm～3 μ m, are bundle fiber or felted film.Polymer solution concentration is high more, and viscosity is big more, and surface tension is big more, and the drop splitting ability weakens with the surface tension increase after leaving nozzle.Usually when other condition is constant, along with the diameter of the increase fiber of polymer solution concentration also increases.The increase of spinning voltage can cause charged fiber to produce bigger acceleration in electric field, and helps the fiber elongation, increases draw ratio.Nanofiber diameter can reduce along with the increase of receiving range.Present embodiment in macromolecule main body material, mix poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to the phenylacetylene] of the dialdehyde-based triphenylamine of emission blue-fluorescence and emission fluorescent orange, shift by the energy between controlled doping concentration and each component, can realize green emission, obtain the green glow fluorescence micro/nano fibers, fluorescence spectrum good stability, working life reach 2 years.
The specific embodiment 24: what present embodiment and the specific embodiment 23 were different is: the 1g polymer adds 11mL～14mL organic solvent in the step 1.Other is identical with the specific embodiment 23.
The specific embodiment 25: what present embodiment was different with the specific embodiment 23 or 24 is: the 1g polymer adds the 13mL organic solvent in the step 1.Other is identical with the specific embodiment 23 or 24.
The specific embodiment 26: what present embodiment was different with one of specific embodiment 23 to 25 is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 1: 0.16～0.19 in the step 2.Other is identical with one of specific embodiment 23 to 25.
The specific embodiment 27: what present embodiment was different with one of specific embodiment 23 to 26 is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 1: 0.18 in the step 2.Other is identical with one of specific embodiment 23 to 26.
The specific embodiment 28: what present embodiment was different with one of specific embodiment 23 to 27 is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 7h～11h.Other is identical with one of specific embodiment 23 to 27.
The specific embodiment 29: what present embodiment was different with one of specific embodiment 23 to 28 is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 9h.Other is identical with one of specific embodiment 23 to 28.
The specific embodiment 30: what present embodiment was different with one of specific embodiment 23 to 29 is: the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 61mL～64mL in the step 2.Other is identical with one of specific embodiment 23 to 29.
The specific embodiment 31: what present embodiment was different with one of specific embodiment 23 to 30 is: the voltage of electrostatic spinning is that 12kV～28kV, shower nozzle are 8cm～28cm to the collector distance in the step 3.Other is identical with one of specific embodiment 23 to 30.
The specific embodiment 32: what present embodiment was different with one of specific embodiment 23 to 31 is: the voltage of electrostatic spinning is that 20kV, shower nozzle are 18cm to the collector distance in the step 3.Other is identical with one of specific embodiment 23 to 31.
The specific embodiment 33: the preparation method of the doping type fluorescence micro/nano fibers of present embodiment carries out according to the following steps: the ratio that, adds the 15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, and organic solvent is a chloroform; Two, be to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] at 1: 0.2 by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, be collector with the iron net, is that 20kV, shower nozzle are to carry out electrostatic spinning under the condition of 10cm to the collector distance at voltage, obtains green glow doping type fluorescence micro/nano fibers.
The stereoscan photograph of the green glow fluorescence micro/nano fibers that present embodiment obtains as shown in Figure 8, as can be seen from Figure 8, the diameter of green glow fluorescence micro/nano fibers is 800nm～2 μ m, smooth surface, diameter is comparatively even, is the felted film on macroscopic view.
The fluorescence spectrum figure of the green glow fluorescent nano-fiber that present embodiment obtains is shown in 9, solid line-expression be fluorescence spectrum after the green glow fluorescence micro/nano fibers preparation, dotted line-----expression be fluorescence spectrum after the green glow fluorescence micro/nano fibers is placed half a year, as can be seen from Figure 9, at 450nm, there are three main emission peaks at 500～600nm place, and it is rendered as green light after mixing.Through electrostatic spinning process, dialdehyde-based triphenylamine, the energy transfer has taken place between poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], fiber has been realized green emission.After placement half a year of the green glow fluorescence micro/nano fibers that present embodiment obtains, its fluorescence intensity does not reduce, and has stronger fluorescent stability, and the working life of the green glow fluorescence micro/nano fibers of the manner preparation is 2 years.
Present embodiment prepares the method for fluorescent nano-fiber and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.
The specific embodiment 34: the preparation method of the doping type fluorescence micro/nano fibers of present embodiment carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be 1: 0.27～0.3 to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains gold-tinted doping type fluorescence micro/nano fibers.
When the polymer of present embodiment was composition, polymer was wherein pressed arbitrarily than combination.
When the organic solvent of present embodiment was composition, organic solvent was wherein pressed arbitrarily than combination.
Present embodiment prepares the method for fluorescence micro/nano fibers and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.The fluorescent nano-fiber that present embodiment obtains, its diameter are 10nm～3 μ m, are bundle fiber or felted film.Polymer solution concentration is high more, and viscosity is big more, and surface tension is big more, and the drop splitting ability weakens with the surface tension increase after leaving nozzle.Usually when other condition is constant, along with the diameter of the increase fiber of polymer solution concentration also increases.The increase of spinning voltage can cause charged fiber to produce bigger acceleration in electric field, and helps the fiber elongation, increases draw ratio.Nanofiber diameter can reduce along with the increase of receiving range.Present embodiment in macromolecule main body material, mix poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to the phenylacetylene] of the dialdehyde-based triphenylamine of emission blue-fluorescence and emission fluorescent orange, shift by the energy between controlled doping concentration and each component, can realize yellow emission, obtain the gold-tinted fluorescence micro/nano fibers, fluorescence spectrum good stability, working life reach 2 years.
The specific embodiment 35: what present embodiment and the specific embodiment 34 were different is: the 1g polymer adds 11mL～14mL organic solvent in the step 1.Other is identical with the specific embodiment 34.
The specific embodiment 36: what present embodiment was different with the specific embodiment 34 or 35 is: the 1g polymer adds the 13mL organic solvent in the step 1.Other is identical with the specific embodiment 34 or 35.
The specific embodiment 37: what present embodiment was different with one of specific embodiment 34 to 36 is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 1: 0.275～0.295 in the step 2.Other is identical with one of specific embodiment 34 to 36.
The specific embodiment 38: what present embodiment was different with one of specific embodiment 34 to 37 is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 1: 0.28 in the step 2.Other is identical with one of specific embodiment 34 to 37.
The specific embodiment 39: what present embodiment was different with one of specific embodiment 34 to 38 is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 7h～11h.Other is identical with one of specific embodiment 34 to 38.
The specific embodiment 40: what present embodiment was different with one of specific embodiment 34 to 39 is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 9h.Other is identical with one of specific embodiment 34 to 39.
The specific embodiment 41: what present embodiment was different with one of specific embodiment 34 to 40 is: the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 61mL～64mL in the step 2.Other is identical with one of specific embodiment 34 to 40.
The specific embodiment 42: what present embodiment was different with one of specific embodiment 34 to 41 is: the voltage of electrostatic spinning is that 12kV～28kV, shower nozzle are 8cm～28cm to the collector distance in the step 3.Other is identical with one of specific embodiment 34 to 42.
The specific embodiment 43: what present embodiment was different with one of specific embodiment 34 to nine is: the voltage of electrostatic spinning is that 20kV, shower nozzle are 18cm to the collector distance in the step 3.Other is identical with one of specific embodiment 34 to nine.
The specific embodiment 44: the preparation method of the doping type fluorescence micro/nano fibers of present embodiment carries out according to the following steps: the ratio that, adds the 10mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polyacrylonitrile, and organic solvent is a chloroform; Two, be to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] at 1: 0.28 by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 8h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, be collector with the aluminium net, is that 15kV, shower nozzle are to carry out electrostatic spinning under the condition of 10cm to the collector distance at voltage, obtains gold-tinted doping type fluorescence micro/nano fibers.
The stereoscan photograph of the gold-tinted fluorescence micro/nano fibers that present embodiment obtains as shown in figure 10, as can be seen from Figure 10, the diameter of gold-tinted fluorescence micro/nano fibers is 700nm～2.5 μ m, smooth surface, diameter is comparatively even, is the felted film on macroscopic view.
The fluorescence spectrum figure of the gold-tinted fluorescence micro/nano fibers that present embodiment obtains is shown in 11, solid line-expression be test result after the gold-tinted fluorescence micro/nano fibers preparation, dotted line-----expression be test result after the gold-tinted fluorescence micro/nano fibers is placed half a year, as can be seen from Figure 11, at 400nm～500nm, two main emission bands are arranged between 500nm～600nm, mainly be rendered as the emission peak of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene].Through electrostatic spinning process, dialdehyde-based triphenylamine, the energy transfer has taken place between poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], fiber has been realized yellow emission.After placement half a year of the gold-tinted fluorescence micro/nano fibers that present embodiment obtains, its fluorescence intensity does not reduce, and has stronger fluorescent stability, and the working life of the gold-tinted fluorescence micro/nano fibers of the manner preparation is 2 years.
Present embodiment prepares the method for fluorescent nano-fiber and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.
The specific embodiment 45: the preparation method of the doping type fluorescence micro/nano fibers of present embodiment carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) to phenylacetylene] at 0～0.1: 1 by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, conductor, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains orange photodoping type fluorescence micro/nano fibers.
When the polymer of present embodiment was composition, polymer was wherein pressed arbitrarily than combination.
When the organic solvent of present embodiment was composition, organic solvent was wherein pressed arbitrarily than combination.
Present embodiment prepares the method for fluorescence micro/nano fibers and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.The fluorescence micro/nano fibers that present embodiment obtains, its diameter are 10nm～3 μ m, are bundle fiber or felted film.Polymer solution concentration is high more, and viscosity is big more, and surface tension is big more, and the drop splitting ability weakens with the surface tension increase after leaving nozzle.Usually when other condition is constant, along with the diameter of the increase fiber of polymer solution concentration also increases.The increase of spinning voltage can cause charged fiber to produce bigger acceleration in electric field, and helps the fiber elongation, increases draw ratio, and fibre diameter can reduce along with the increase of receiving range.Present embodiment in macromolecule main body material, mix poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to the phenylacetylene] of the dialdehyde-based triphenylamine of emission blue-fluorescence and emission fluorescent orange, shift by the energy between controlled doping concentration and each component, can realize orange light emission, obtain orange light fluorescence micro/nano fibers, fluorescence spectrum good stability, working life reach 2 years.
The specific embodiment 46: what present embodiment and the specific embodiment 45 were different is: the 1g polymer adds 11mL～14mL organic solvent in the step 1.Other is identical with the specific embodiment 45.
The specific embodiment 47: what present embodiment was different with the specific embodiment 45 or 46 is: the 1g polymer adds the 13mL organic solvent in the step 1.Other is identical with the specific embodiment 45 or 46.
The specific embodiment 48: what present embodiment was different with one of specific embodiment 45 to 47 is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 0.01～0.09: 1 in the step 2.Other is identical with one of specific embodiment 45 to 47.
The specific embodiment 49: what present embodiment was different with one of specific embodiment 45 to 48 is: the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] is 0.05: 1 in the step 2.Other is identical with one of specific embodiment 45 to 48.
The specific embodiment 50: what present embodiment was different with one of specific embodiment 45 to 49 is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 7h～11h.Other is identical with one of specific embodiment 45 to 49.
The specific embodiment 51: what present embodiment was different with one of specific embodiment 45 to 50 is: after dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] joined in the polymer solution of step 1 preparation in the step 2, mixing time was 9h.Other is identical with one of specific embodiment 45 to 50.
The specific embodiment 52: what present embodiment was different with one of specific embodiment 45 to 51 is: the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 61mL～64mL in the step 2.Other is identical with one of specific embodiment 45 to 51.
The specific embodiment 53: what present embodiment was different with one of specific embodiment 45 to 52 is: the voltage of electrostatic spinning is that 12kV～28kV, shower nozzle are 8cm～28cm to the collector distance in the step 3.Other is identical with one of specific embodiment 45 to 52.
The specific embodiment 54: what present embodiment was different with one of specific embodiment 45 to 53 is: the voltage of electrostatic spinning is that 20kV, shower nozzle are 18cm to the collector distance in the step 3.Other is identical with one of specific embodiment 45 to 53.
The specific embodiment 55: the preparation method of the doping type fluorescence micro/nano fibers of present embodiment carries out according to the following steps: the ratio that, adds the 10mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polymethyl methacrylate, and organic solvent is a chloroform; Two, be to take by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene] at 0.06: 1 by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 8h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g: 62mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, be collector with the iron net, is that 25kV, shower nozzle are to carry out electrostatic spinning under the condition of 18cm to the collector distance at voltage, obtains orange photodoping type fluorescence micro/nano fibers.
The stereoscan photograph of the orange light fluorescence micro/nano fibers that present embodiment obtains as shown in figure 12, as can be seen from Figure 12, the diameter of orange light fluorescent nano-fiber is 600nm～3 μ m, smooth surface, diameter is comparatively even, and having the part tow to assemble becomes band structure together, is the felted film on macroscopic view.
The fluorescence spectrum figure of the orange light fluorescent nano-fiber that present embodiment obtains is shown in 13, solid line-expression be test result after the preparation of orange light fluorescence micro/nano fibers, dotted line-----expression be test result after orange light fluorescence micro/nano fibers is placed half a year, as can be seen from Figure 13, orange light fluorescent nano-fiber has orange light intensity emission peak at 500～600nm place, mainly be rendered as the emission peak of poly-[2-methoxyl group-5 (2 '-ethyl hexyl oxy) is to phenylacetylene].Through the electrostatic spinning process,, fiber has been realized orange light emission.After placement half a year of the orange light fluorescence micro/nano fibers that present embodiment obtains, its fluorescence intensity does not reduce, and has stronger fluorescent stability, and the working life of the orange light fluorescence micro/nano fibers of the manner preparation is 2 years.
Present embodiment prepares the method for fluorescent nano-fiber and utilizes electrostatic spinning technique to finish at ambient temperature, and preparation time is short, and easy to operate, technology is simple, and energy consumption is low, and the amount of preparation is bigger, is convenient to practicality.
Claims (10)
1. the preparation method of doping type fluorescence micro/nano fibers, the preparation method who it is characterized in that the doping type fluorescence micro/nano fibers carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be that 1:0.24～0.26 takes by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g:60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains white light doping type fluorescence micro/nano fibers.
2. the preparation method of doping type fluorescence micro/nano fibers according to claim 1 is characterized in that the mass ratio of dialdehyde-based triphenylamine in the step 2 and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene] is 1:0.245～0.255.
3. the preparation method of doping type fluorescence micro/nano fibers, the preparation method who it is characterized in that the doping type fluorescence micro/nano fibers carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be that 1:0～0.1 takes by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g:60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains blue light doping type fluorescence micro/nano fibers.
4. the preparation method of doping type fluorescence micro/nano fibers according to claim 3 is characterized in that the mass ratio of dialdehyde-based triphenylamine in the step 2 and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene] is 1:0.01～0.08.
5. the preparation method of doping type fluorescence micro/nano fibers, the preparation method who it is characterized in that the doping type fluorescence micro/nano fibers carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be that 1:0.15～0.2 takes by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g:60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains green glow doping type fluorescence micro/nano fibers.
6. the preparation method of doping type fluorescence micro/nano fibers according to claim 5 is characterized in that the mass ratio of dialdehyde-based triphenylamine in the step 2 and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene] is 1:0.16～0.19.
7. the preparation method of doping type fluorescence micro/nano fibers, the preparation method who it is characterized in that the doping type fluorescence micro/nano fibers carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be that 1:0.27～0.3 takes by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g:60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains gold-tinted doping type fluorescence micro/nano fibers.
8. the preparation method of doping type fluorescence micro/nano fibers according to claim 7 is characterized in that the mass ratio of dialdehyde-based triphenylamine in the step 2 and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene] is 1:0.28.
9. the preparation method of doping type fluorescence micro/nano fibers, the preparation method who it is characterized in that the doping type fluorescence micro/nano fibers carries out according to the following steps: one, the ratio that adds 10mL～15mL organic solvent in the 1g polymer, take by weighing polymer and organic solvent, and polymer joined in the organic solvent, obtain polymer solution after the dissolving, polymer wherein is a polystyrene, polymethyl methacrylate, a kind of or wherein several combination in Merlon and the polyacrylonitrile, organic solvent is a chloroform, N, dinethylformamide, N,N-dimethylacetamide, benzene, toluene, chlorobenzene, a kind of or wherein several combination in dichloroethanes and the oxolane; Two, be that 0.01～0.09:1 takes by weighing dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene] by the mass ratio of dialdehyde-based triphenylamine and poly-[2-methoxyl group-5(2'-ethyl hexyl oxy) to phenylacetylene], and join in the polymer solution of step 1 preparation, stir 6h～12h, obtain spinning solution, wherein the mass volume ratio of dialdehyde-based triphenylamine and polymer solution is 1g:60mL～65mL; Three, will join through the spinning solution that step 2 obtains in the storage device of electrostatic spinning machine, with wire netting, semiconductive thin film or conducting solution is collector, at voltage is that 10kV～30kV, shower nozzle are to carry out electrostatic spinning under the condition of 5cm～30cm to the collector distance, obtains orange photodoping type fluorescence micro/nano fibers.
10. the preparation method of doping type fluorescence micro/nano fibers according to claim 9, the voltage that it is characterized in that electrostatic spinning in rapid three is that 12kV～28kV, shower nozzle are 8cm～28cm to the collector distance.
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| CN103644845B (en) * | 2013-12-20 | 2016-06-08 | 北京科技大学 | Nanofiber optical pickocff that a kind of nucleic acid is modified and preparation method thereof |
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| CN104131361A (en) * | 2014-08-13 | 2014-11-05 | 浙江华峰氨纶股份有限公司 | Preparation method for fluorescent spandex |
| CN105133188B (en) * | 2015-07-31 | 2018-06-29 | 南京邮电大学 | Adulterate the polymer nanofiber film and preparation method and application of carbazole derivates |
| CN108265400B (en) * | 2018-03-28 | 2020-12-11 | 北京化工大学 | Preparation method of flexible white fluorescent nanofiber membrane |
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