CN115322291A - Organic ultralong room temperature phosphorescent nanofiber material and preparation method thereof - Google Patents
Organic ultralong room temperature phosphorescent nanofiber material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic ultralong room temperature phosphorescent nano-fiber material, which relates to the field of organic luminescent materials.
Description
Technical Field
The invention relates to the field of organic luminescent materials, in particular to an organic ultralong room temperature phosphorescent nanofiber material and a preparation method thereof.
Background
One-dimensional or quasi-one-dimensional nanostructures and their use in the field of optoelectronics have been intensively studied. Such materials include various anisotropic shaped organic and inorganic nano-objects such as nanowires, nanorods, nanofibers, which share common characteristics, length much greater than their radius and very high specific surface area. Compared with a two-dimensional structure such as a thin film, the anisotropic structure can effectively enhance charge transfer and energy transmission, so that the one-dimensional nano structure can be effectively used for generating and detecting optical phenomena when being applied to photoelectric materials.
Generally, in a one-dimensional nanostructure made of inorganic semiconductor material, due to its unique photoelectric characteristics, it is possible to finely tune the electronic band gap and related optical characteristics. While the case of organic semiconductors is quite different. Although electronic band gaps can be controlled and adjusted by chemical synthesis methods to provide a variety of pi-conjugated small molecules, oligomers, and a variety of polymers that can be applied in Organic Light Emitting Diodes (OLEDs), organic Field Effect Transistors (OFETs), photodetectors, lasers, and photovoltaic devices, in general, supramolecular assembly and material property control at the nanoscale are inadequate and device performance tends to be limited. When the size of the material is reduced to the nanometer scale, a plurality of novel physical effects such as surface effect, small-size effect, macroscopic quantum tunneling effect and surface plasmon effect can be generated. By utilizing the effects, the nanoscale material can be applied to luminescence, but the development of the nano luminescent fiber is difficult to promote due to the problems of uncontrollable micro-nano scale, low luminous efficiency, poor stability and the like.
The organic room temperature phosphorescent material is a radiative transition overcoming spin forbidden resistance from triplet excited state exciton to ground state, has a service life of millisecond or even second, and can still continuously emit light after an excitation light source is closed. The phosphorescent material can eliminate fluorescent background interference, is used in the fields of advanced anti-counterfeiting and encryption, and can also be used for preparing high-efficiency phosphorescent OLED devices.
The organic long afterglow material is combined with the nano fiber, the advantages of easy modification, flexibility, low cost and the like of the organic material are fully exerted, and the application range of the organic long afterglow material is expected to be extended by combining the unique surface property of the nano material. The method has wide application space in the fields of optics and organic electronics such as illumination display, anti-counterfeiting encryption, biosensing and the like.
Disclosure of Invention
The invention aims to provide an organic ultralong room temperature phosphorescence nanofiber material which has a nanofiber structure and an ultralong room temperature phosphorescence phenomenon; the invention also aims to provide a preparation method of the mechanical ultralong room temperature phosphorescent nanofiber material, which is simple and convenient to prepare and low in cost.
In order to solve the above problems, the present invention provides the following technical solutions:
a precursor polymer material has a structure as shown in any one of formulas I-VI:
wherein m/n = 25/1 to 300/1,mol/mol.
A preparation method of the precursor polymer material comprises the following specific synthetic steps:
weighing 50-600 mg of vinyl carbazole, 1-15 g of compound and 100-200 mg of initiator under an inert atmosphere, adding 40-80 mL of over-dried tetrahydrofuran, stirring and refluxing at 50-60 ℃ for 10-20 h, and cooling to room temperature after the reaction is finished; dropwise adding the mixture into methanol of 200 to 600 mL for precipitation, and drying after suction filtration; sequentially extracting with acetone/petroleum ether/dichloromethane, and dialyzing in deionized water; finally, drying the product to obtain a white solid, namely the precursor polymer material;
the compound I is one of acrylamide, acrylonitrile, acrylic acid, N-vinyl pyrrolidone, methyl acrylate and vinyl acetate, and the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, tert-butyl hydroperoxide, cyclohexanone peroxide and dibenzoyl peroxide.
A preparation method of an organic ultralong room temperature phosphorescent nanofiber material comprises the following steps: dissolving the precursor polymer material synthesized in the method of claim 2 in a solvent at normal temperature and pressure to prepare a precursor solution, and obtaining the nanofiber by an electrostatic spinning method.
Preferably, the specific preparation steps of the nanofiber are as follows:
weighing a proper amount of precursor polymer material, adding a proper amount of solvent, and dissolving to prepare a precursor solution with the concentration of 0.01-1.0 g/mL; placing the prepared precursor solution in a material pushing device, wherein the distance from a spinning needle head to a receiving plate is 5-50 cm, applying 5-50 kV voltage at the material pushing speed of 0.0005-0.05 mm/s, and preparing the nano-fibers by a high-voltage electrostatic spinning method;
the solvent comprises one or more of water, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, a proper amount of fluorescent dye is added into the prepared precursor solution to obtain the nanofiber for changing the room-temperature phosphorescence color, wherein the fluorescent dye is a compound VII and/or VIII, and the structural formulas of the compound VII and VIII are as follows:
an organic super-long room temperature phosphorescent nanofiber material is prepared by the preparation method, and the diameter of the nanofiber is 10-1000 nm; the phosphorescence life of the nano-fiber at room temperature is 100 to 4000 ms, and the nano-fiber can continuously emit light after an excitation light source is removed under a dark condition. In the room temperature phosphorescence direction, the phosphorescence lifetime is usually more than 100 ms, and the light emission can be continued after the excitation, and the duration is generally ten times of the phosphorescence lifetime.
The invention has the advantages that:
(1) The invention synthesizes the precursor polymer material with abundant hydrogen bond function and rigid matrix characteristic, utilizes the electrostatic spinning technology to form the nano-fiber, and has excellent organic room temperature phosphorescence phenomenon.
(2) The organic ultralong room temperature phosphorescent nanofiber material and the preparation method thereof have the advantages of low raw material cost, simple synthesis, green, environment-friendly and nonhazardous solvent, and are expected to realize industrial production.
(3) The organic ultralong room temperature phosphorescent nanofiber material has the advantages of adjustable color and adjustable light emitting performance.
(4) The organic super-long room temperature phosphorescent nano-fiber of the invention is prepared by co-emitting light by vinylcarbazole and non-conjugated molecules. The non-conjugated molecular monomer occupying the main body in the polymer plays a role in inhibiting non-radiative transition of the luminescent unit, and the inter-system transition is effectively promoted by utilizing the action of abundant hydrogen bonds, so that the ultra-long room-temperature phosphorescence of the nanofiber is realized under the micro-nano scale. The phosphorescence has long service life, and can continuously emit light after the excitation light source is removed in dark condition. On one hand, the research that only the luminescence of the nanofiber is fluorescence (the nanofiber cannot continuously emit light after an excitation light source is removed under a dark condition) is expanded, on the other hand, the ultra-long room-temperature phosphorescent nanofiber is potentially applied to a flexible micro-nano device by utilizing the ultra-long luminescence life of the ultra-long room-temperature phosphorescent nanofiber, and the problem that the existing micro-nano luminescent material is short in luminescence life is solved.
Drawings
FIG. 1 is SEM image of organic super-long room temperature phosphorescent nano fiber material (I').
FIG. 2 shows fluorescence and phosphorescence emission spectra of organic ultralong room temperature phosphorescence nanofiber material (I').
FIG. 3 is a graph showing the decay curve of the phosphorescence lifetime of the organic ultralong room temperature phosphorescence nanofiber material (I').
FIG. 4 shows fluorescence and phosphorescence emission spectra of organic ultralong room temperature phosphorescence nanofiber material (II').
FIG. 5 is a phosphorescence lifetime decay curve of the organic ultralong room temperature phosphorescence nano fiber material (II').
FIG. 6 is a scanning electron microscope SEM image of an organic ultralong room temperature phosphorescent nanofiber material (VII').
FIG. 7 shows fluorescence and phosphorescence emission spectra of organic ultralong room temperature phosphorescent nanofiber material (VII').
FIG. 8 is a phosphorescence lifetime decay curve of the organic ultralong room temperature phosphorescent nanofiber material (VII').
Fig. 9 is a scanning electron microscope SEM image of the organic ultralong room temperature phosphorescent nanofiber material (viii').
FIG. 10 shows fluorescence and phosphorescence emission spectra of organic ultralong room temperature phosphorescent nanofiber material (VIII').
FIG. 11 is a phosphorescent lifetime decay curve of the organic ultralong room temperature phosphorescent nanofiber material (VIII').
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
The starting materials and reagents in the following examples were all commercially available.
Example 1:
this example prepares an organic ultralong room temperature phosphorescent nanofiber material (i').
Weighing vinylcarbazole 193 mg, acrylamide 7.1 g and initiator azobisisobutyronitrile 166 mg under inert atmosphere, adding 60 mL ultra-dry tetrahydrofuran, stirring and refluxing at 55 ℃ for 16 h, and cooling to room temperature after reaction. Adding the mixture into 500 mL methanol dropwise for precipitation, and drying after suction filtration. It was extracted sequentially with acetone/petroleum ether/dichloromethane, followed by dialysis in deionized water. And finally, drying the product to obtain a white solid which is a precursor polymer material I.
The structure is as follows (wherein m/n = 100/1,mol/mol):
weighing a proper amount of precursor polymer material I, adding water as a solvent, and dissolving by heating, stirring, ultrasonic waves and other modes to prepare a precursor solution with the concentration of 0.01 g/mL; the prepared solution is placed in a material pushing device, the distance from a spinning needle head to a receiving plate is 10 cm, 25 kV voltage is applied at the material pushing speed of 0.001 mm/s, and the nano fiber I' is prepared by a high-voltage electrostatic spinning method.
FIG. 1 is a SEM image of the organic ultralong room temperature phosphorescent nanofibers I' obtained in example 1, and shows that the diameters of the nanofibers are 10 to 1000 nm.
FIG. 2 shows fluorescence and phosphorescence emission spectra of the organic ultralong room temperature phosphorescence nanofiber I' obtained in the above example 1, and it can be seen that the nanofiber is a phosphorescence material, and the band is concentrated in the emission of 380-600 nm, which is blue phosphorescence emission.
FIG. 3 is a graph showing the phosphorescence lifetime decay of the organic ultralong room temperature phosphorescent nanofiber I' obtained in example 1, and it can be seen that the phosphorescence lifetime of the nanofiber is 1945 ms.
Example 2:
this example prepares an organic ultralong room temperature phosphorescent nanofiber material (ii').
Weighing vinylcarbazole 193 mg, acrylonitrile 5.3 g and initiator azobisisobutyronitrile 166 mg under inert atmosphere, adding 60 mL ultra-dry tetrahydrofuran, stirring and refluxing at 55 ℃ for 16 h, and cooling to room temperature after reaction. Dropwise adding the mixture into 500 mL methanol for precipitation, and drying after suction filtration. It was extracted sequentially with acetone/petroleum ether/dichloromethane. And finally, drying the product to obtain a white solid which is a precursor polymer material II.
The structure is as follows (wherein m/n = 100/1,mol/mol):
weighing a proper amount of precursor polymer material II, adding N, N-dimethylformamide as a solvent, and dissolving by heating, stirring, ultrasonic waves and the like to prepare a precursor solution with the concentration of 0.01 g/mL; the prepared solution is placed in a material pushing device, the distance from a spinning needle head to a receiving plate is 10 cm, 25 kV voltage is applied at the material pushing speed of 0.001 mm/s, and the nano fiber II' is prepared by a high-voltage electrostatic spinning method.
FIG. 4 shows fluorescence and phosphorescence emission spectra of the organic ultralong room temperature phosphorescence nanofiber II' obtained in the above example 2, and it can be seen that the nanofiber is a phosphorescence material, and the band is concentrated on the emission of 400-750 nm, which is green phosphorescence emission.
FIG. 5 is a graph showing the phosphorescence lifetime decay of the organic ultralong room temperature phosphorescent nanofiber II' obtained in example 2, and it can be seen that the phosphorescence lifetime of the nanofiber is 108 ms.
Example 3:
this example prepared an organic ultralong room temperature phosphorescent nanofiber material (iii').
Under inert atmosphere, weighing 48.2 mg vinyl carbazole, 7.2 g acrylic acid and 100 mg initiator dibenzoyl peroxide, adding 60 mL ultra-dry tetrahydrofuran, stirring and refluxing 20 h at 50 ℃, and cooling to room temperature after reaction. Dropwise adding the mixture into 600 mL methanol for precipitation, performing suction filtration and drying. It was extracted sequentially with acetone/petroleum ether/dichloromethane, followed by dialysis in deionized water. And finally, drying the product to obtain a white solid which is a precursor polymer material III.
The structure is as follows (where m/n = 25/1,mol/mol):
weighing a proper amount of precursor polymer material III, adding water as a solvent, and dissolving by heating, stirring, ultrasonic waves and other modes to prepare a precursor solution with the concentration of 1.0 g/mL; the prepared solution is placed in a material pushing device, the distance from a spinning needle head to a receiving plate is 50cm, 50 kV voltage is applied at the material pushing speed of 0.05mm/s, and the nano fiber III' is prepared by a high-voltage electrostatic spinning method.
Example 4:
this example prepares an organic ultralong room temperature phosphorescent nanofiber material (iv').
Weighing 579 mg of vinyl carbazole, 11.1 g of N-vinyl pyrrolidone and 200 mg of initiator cyclohexanone peroxide, adding 80 mL ultra-dry tetrahydrofuran, stirring and refluxing at 55 ℃ for 16 h, and cooling to room temperature after the reaction is finished. Dropwise adding 200 mL methanol to precipitate, filtering, and drying. It was extracted sequentially with acetone/petroleum ether/dichloromethane, followed by dialysis in deionized water. And finally, drying the product to obtain a white solid which is a precursor polymer material IV.
The structure is as follows (wherein m/n = 300/1,mol/mol):
weighing a proper amount of precursor polymer material IV, adding N, N-dimethylacetamide as a solvent, and dissolving by heating, stirring, ultrasonic waves and the like to prepare a precursor solution with the concentration of 0.01 g/mL; the prepared solution is placed in a material pushing device, the distance between a spinning needle head and a receiving plate is 10 cm, 25 kV voltage is applied at the material pushing speed of 0.001 mm/s, and the nano-fiber IV' is prepared through a high-voltage electrostatic spinning method.
Example 5:
this example prepares an organic ultralong room temperature phosphorescent nanofiber material (v').
Weighing 386 mg of vinyl carbazole, 8.6 g of methyl acrylate and 166 mg of initiator tert-butyl hydroperoxide, adding 60 mL ultra-dry tetrahydrofuran, stirring and refluxing 10 h at 60 ℃, and cooling to room temperature after the reaction is finished. Adding the mixture into 500 mL methanol dropwise for precipitation, and drying after suction filtration. It was extracted sequentially with acetone/petroleum ether/dichloromethane. And finally, drying the product to obtain a white solid which is the precursor polymer material V.
The structure is as follows (wherein m/n = 200/1,mol/mol):
weighing a proper amount of precursor polymer material V, adding water, and dissolving by heating, stirring, ultrasonic waves and the like to prepare a precursor solution with the concentration of 0.01 g/mL; the prepared solution is placed in a material pushing device, the distance from a spinning needle head to a receiving plate is 25 cm, 25 kV voltage is applied at the material pushing speed of 0.0005 mm/s, and the nano-fiber V' is prepared by a high-voltage electrostatic spinning method.
Example 6:
this example prepared an organic ultralong room temperature phosphorescent nanofiber material (vi').
Weighing vinylcarbazole 193 mg, vinyl acetate 8.6 g and initiator azodiisoheptanonitrile 166 mg under inert atmosphere, adding 60 mL ultra-dry tetrahydrofuran, stirring and refluxing at 55 ℃ for 16 h, and cooling to room temperature after the reaction is finished. Adding the mixture into 500 mL methanol dropwise for precipitation, and drying after suction filtration. It was extracted sequentially with acetone/petroleum ether/dichloromethane. And finally, drying the product to obtain a white solid which is a precursor polymer material VI.
The structure is as follows (wherein m/n = 100/1,mol/mol):
weighing a proper amount of precursor polymer material VI, adding N-methyl pyrrolidone serving as a solvent, and dissolving by heating, stirring, ultrasonic waves and the like to prepare a precursor solution with the concentration of 0.01 g/mL; the prepared solution is placed in a material pushing device, the distance between a spinning needle head and a receiving plate is 10 cm, 25 kV voltage is applied at the material pushing speed of 0.001 mm/s, and the nano fiber VI' is prepared by a high-voltage electrostatic spinning method.
Example 7:
this example prepares an organic ultralong room temperature phosphorescent nanofiber material (vii').
Weighing a proper amount of precursor polymer material I and a proper amount of fluorescent dye VII, adding water, dissolving by heating, stirring, ultrasonic waves and the like to prepare a precursor solution with the concentration of 0.01 g/mL; the prepared solution is placed in a material pushing device, the distance from a spinning needle head to a receiving plate is 10 cm, 25 kV voltage is applied at the material pushing speed of 0.001 mm/s, and the nanofiber VII' is prepared by a high-voltage electrostatic spinning method. The structural formula of the fluorescent dye VII is as follows:
FIG. 6 is a SEM image of the organic super-long room temperature phosphorescent nanofiber VII' obtained in example 7, and the diameter of the nanofiber is 10 to 300 nm.
FIG. 7 is the fluorescence and phosphorescence emission spectra of the organic super-long room temperature phosphorescence nanofiber VII' obtained in the above example 7, and it can be seen that the nanofiber is a phosphorescence material, and the band is concentrated on the emission of 550-650 nm, which is green phosphorescence emission.
Fig. 8 is a phosphorescence lifetime decay image of the organic ultralong room temperature phosphorescent nanofiber vii 'obtained in example 7, and it can be seen that the phosphorescence lifetime of the nanofiber vii' is 268 ms.
Example 8:
this example prepares an organic ultralong room temperature phosphorescent nanofiber material (viii').
Weighing a proper amount of precursor polymer material I and a proper amount of fluorescent dye VIII, adding water, dissolving by heating, stirring, ultrasonic waves and the like to prepare a precursor solution with the concentration of 0.01 g/mL; the prepared solution is placed in a material pushing device, the distance from a spinning needle head to a receiving plate is 5 cm, 5 kV voltage is applied at the material pushing speed of 0.001 mm/s, and the nanofiber VIII' is prepared by a high-voltage electrostatic spinning method.
The structural formula of the fluorescent dye VIII is as follows:
FIG. 9 is a scanning electron microscope SEM image of the organic super-long room temperature phosphorescent nanofibers VIII' obtained in example 8, and the diameters of the nanofibers can be seen to be 10-300 nm.
FIG. 10 shows fluorescence and phosphorescence emission spectra of the organic ultralong room temperature phosphorescent nanofiber VIII' obtained in example 8, and it can be seen that the nanofiber is a phosphorescent material, and the band is concentrated on emission of 550-750 nm, which is red phosphorescent emission.
Fig. 11 is a phosphorescence lifetime decay image of the organic ultralong room temperature phosphorescent nanofiber viii 'obtained in example 8, and it can be seen that the phosphorescence lifetime of the nanofiber viii' is 605 ms.
The phosphorescence lifetime is one of experimental characterization means that the nanofibers can continuously emit light after the excitation light source is removed in the dark, and the phosphorescence lifetime shown in fig. 3, 5, 8, and 11 can prove that the nanofibers can continuously emit light after the excitation light source is removed. In the room temperature phosphorescence direction, the phosphorescence lifetime is usually more than 100 ms, and the light emission can be continued after the excitation, and the duration is generally ten times of the phosphorescence lifetime.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or are equivalent to the scope of the invention are intended to be embraced therein.
Claims (6)
1. A precursor polymer material is characterized in that the structure is as shown in any one of formulas I-VI:
wherein m/n = 25/1 to 300/1,mol/mol.
2. A method for preparing a precursor polymer material according to claim 1, comprising the following steps:
weighing 50-600 mg of vinyl carbazole, 1-15 g of compound and 100-200 mg of initiator under an inert atmosphere, adding 40-80 mL of over-dried tetrahydrofuran, stirring and refluxing at 50-60 ℃ for 10-20 h, and cooling to room temperature after the reaction is finished; dropwise adding the mixture into methanol of 200 to 600 mL for precipitation, and drying after suction filtration; sequentially extracting with acetone/petroleum ether/dichloromethane, and dialyzing in deionized water; finally, drying the product to obtain a white solid, namely the precursor polymer material;
the compound I is one of acrylamide, acrylonitrile, acrylic acid, N-vinyl pyrrolidone, methyl acrylate and vinyl acetate, and the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, tert-butyl hydroperoxide, cyclohexanone peroxide and dibenzoyl peroxide.
3. A method for preparing organic ultralong room temperature phosphorescent nanofiber material, which is characterized in that a precursor polymer material synthesized in claim 2 is dissolved in a solvent to prepare a precursor solution at normal temperature and normal pressure, and the nanofiber is obtained by an electrostatic spinning method.
4. The preparation method of the organic ultralong room temperature phosphorescent nanofiber material as claimed in claim 3, wherein the specific preparation steps of the nanofiber are as follows:
weighing a proper amount of precursor polymer material, adding a proper amount of solvent, and dissolving to prepare a precursor solution with the concentration of 0.01-1.0 g/mL; placing the prepared precursor solution in a material pushing device, wherein the distance from a spinning needle head to a receiving plate is 5-50 cm, applying 5-50 kV voltage at the material pushing speed of 0.0005-0.05 mm/s, and preparing the nano fibers by a high-voltage electrostatic spinning method;
the solvent comprises one or more of water, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
5. The preparation method of the organic ultralong room-temperature phosphorescent nanofiber material as claimed in claim 4, wherein a proper amount of fluorescent dye is added into the prepared precursor solution to obtain the nanofiber for changing the room-temperature phosphorescent color, wherein the fluorescent dye is a compound VII and/or VIII, and the structural formulas of the compound VII and VIII are as follows:
6. an organic super-long room temperature phosphorescent nanofiber material, which is prepared by the preparation method of any one of 3~5, and the diameter of the nanofiber is 10-1000 nm; the room-temperature phosphorescence service life of the nanofiber is 100 to 4000 ms, and the nanofiber can continuously emit light after an excitation light source is removed under a dark condition.
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