CN104674458A - Flexible thin film material with fluorescent color change response characteristic under ultraviolet stimulation and preparation method thereof - Google Patents
Flexible thin film material with fluorescent color change response characteristic under ultraviolet stimulation and preparation method thereof Download PDFInfo
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- CN104674458A CN104674458A CN201510077091.3A CN201510077091A CN104674458A CN 104674458 A CN104674458 A CN 104674458A CN 201510077091 A CN201510077091 A CN 201510077091A CN 104674458 A CN104674458 A CN 104674458A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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Abstract
The invention discloses a flexible thin film material with a fluorescent color change response characteristic under ultraviolet stimulation in the field of intelligent fluorescent materials and a preparation method thereof. A novel fluorescent thin film material is prepared by using a cyano-substituted diphenylethylene compound and polyvinyl alcohol through hydrogen-bond interaction based on an electrostatic spinning method. Pure cyano-substituted diphenylethylene powder or solution does not have a characteristic of ultraviolet-induced fluorescent color change; on the basis of the cyano-substituted diphenylethylene compound, a polymer with a dispersing effect is introduced and the spatial arrangement manner of organic molecules of cyano-substituted diphenylethylene is changed, so that the fluorescent performance of the cyano-substituted diphenylethylene can be quickly regulated through ultraviolent irradiation. The composite material fully utilizes the characteristic that high-dispersion amorphous thin films are prepared through the electrostatic spinning method, thus obtaining the novel fluorescent thin film material with the response characteristic under ultraviolet stimulation. A new means is provided for the preparation of intelligent materials, fluorescent sensing materials and optical anti-counterfeiting devices with excellent optical characteristics.
Description
Technical field
The invention belongs to Intelligent fluorescent field of material technology, in particular, provide and a kind ofly there is ultraviolet stimulate flexible thin-film material of fluorescence variable color response and preparation method thereof.For novel stimuli responsive fluorescence membrane material preparation provides new mentality of designing and feasible scheme.
Background technology
The fluorescent material with stimulation-response function due to its signal sensitive, the features such as speed is fast obtain the extensive concern of industrial quarters and academia gradually, and this kind of material has extremely strong using value in the field such as sensor, optical anti-counterfeiting.In recent years, become design gradually by pattern of rows and columns of external condition (as light, electricity, heat, magnetic etc.) regulatory molecule and prepare the main policies of such stimulation-response function material.But solution and powder body material have significant limitation in actual applications, in order to meet the realization of fluorescent device and sensing function, preparing orderly stimulation-response function fluorescence membrane material and remaining a challenge.
Along with the progressively development of nanometer technology, electrostatic spinning becomes a kind of new way of simple and effective production nanofiber.This novel process technology in multiple fields extensive application, such as: the fields such as ultra-clean nanofiltration, water treatment, cosmetics and the energy.The device of high-voltage electrostatic spinning technology is mainly by high-voltage DC power supply, form with the shuttle (being generally copper syringe needle) of spinneret and collecting board three part.Electrostatic spinning mainly utilizes the gradient electric field between shower nozzle and dash receiver, the droplet of shower nozzle is out of shape gradually thus is formed " Taylor circular cone ", progressively increase voltage, the tension force that electric field force overcomes liquid surface is spouting from spinning nozzle with the form of fibre bundle by charged liquid thread.The film obtained by electrostatic spinning technique is unordered on a microscopic scale, and is homogeneous in macroscopically its physical property.Change to a certain extent will be there is in the optical property of the fluorescence membrane therefore obtained by this specific process of electrostatic spinning compared to film prepared by commonsense method.Prepare simplicity and the designability of film based on electrostatic spinning, be expected to the novel optical material obtaining having special optical performance by this kind of method.
Oligomerization Stilbene-based compound is the important fluorescent material of a class, enjoys the concern of scholars because it has excellent photoelectric characteristic.But, due to the complexity of its space structure during molecule formation solid, make the solid-state glow color of Stilbene-based compound often there is unpredictability.Therefore, the how Interactions Mode of reasonable design organic molecule and arrangement mode, and then its optical property of modulation is one of major issue of this type of luminous organic material field face.
The present invention close in conjunction with current Intelligent fluorescent material immobilized with become membranization Problems existing, using cyano group substituted diphenylamine ethylene type compound as the molecule primitive preparing intelligent response fluorescence membrane, introduce polyvinyl alcohol as the medium molecule forming thin-film material, prepare the Intelligent fluorescent film of ultraviolet light response through method of electrostatic spinning.By kind and the concentration of modulation Stilbene-based compound, realize the regulation and control to fluorescence color and intensity, obtain luminosity and the controlled monochromatic light-emitting film material of intensity.Thus be conducive to the chemical stability and the fluorescent stability that improve compound, and extend the life-span of luminescent material.Compared to the simple diphenyl ethene compounds responded without ultraviolet, series film material achieves material stimulates fluorescence response characteristic to ultraviolet, for Development of Novel optical pickocff and fluorescence falsification preventing material provide theoretical premise and criteria in application.
Summary of the invention
The object of the present invention is to provide and a kind ofly there is flexible thin-film material of Ultraluminescence variable color response and preparation method thereof, for the design and synthesis of organic Intelligent fluorescent film of Development of Novel provides new thinking and Feasibility Solution.
The present invention is by having prepared a class novel fluorescence thin-film material by hydrogen bond action between molecule based on method of electrostatic spinning by cyano group substituted diphenylamine vinyl compound and polyvinyl alcohol.The talan powder that cyano group replaces or solution all do not have the characteristic of photoluminescence variable color; On cyano group substituted diphenylamine ethene basis, introduce the polymer with peptizaiton, change the space arrangement mode of cyano group substituted diphenylamine ethene organic molecule, make it possible to the optical property that can be regulated and controled rapidly the talan that cyano group replaces by ultraviolet lighting.This composite takes full advantage of the feature that electrostatic spinning prepares high dispersive and randomness film, obtain the novel fluorescence thin-film material with ultraviolet stimuli responsive characteristic, for the preparation with the intellectual material of high-quality optical characteristics, sensing material and optical anti-counterfeiting device provides new thinking and approach.
Preparation process is as follows:
1) preparation of electrostatic spinning solution:
A. weighing amount of substance is 4 × 10
-5~ 9 × 10
-3the cyano group diphenyl ethene compounds Isosorbide-5-Nitrae of mol '-bis-[2-(adjacent benzonitrile base) vinyl] benzene (be called for short ER1) or Isosorbide-5-Nitrae-bis--p-(cyano styrene base)-benzene (being called for short ER3).
B. weigh polyvinyl alcohol (PVA), its amount of substance is 0.001 ~ 0.003mol;
C. ER1 (or ER3) and PVA are dissolved in jointly the hexafluoroisopropanol of 10 ~ 50ml.
D. ER1 (or ER3) being stirred 2 ~ 24h with the solution of PVA makes it dissolve completely.
2) preparation of fluorescence membrane:
A. the preparation of electrostatic spinning instrument: be 10 ~ 25cm by syringe needle and the distance adjustment of collecting between screen; Instrument humidity Wei≤30%; Temperature Wei≤50 DEG C; The syringe needle shape selecting spinning nozzle is round;
B. ER1 (or ER3) and the hexafluoroisopropanol solution of PVA are added in spray nozzle device;
C. apply the high voltage of 20 ~ 30KV, solution changes electrified jet under high-tension effect, and described injection stream is deposited on the surface of base material;
E. the polymer cure in described injection stream thus form nanofiber, final forms the film be about for white under 30cm × 40cm natural daylight.
By above-mentioned prepared material:
1. carry out ultraviolet lighting 1-2 minute, the fluorescence that can be observed film becomes blueness from green.
2. carry out fluorescence spectrum sign display film ultraviolet and there occurs blue shift according to before rear glow peak position and illumination.
The invention has the advantages that: based on electrostatic spinning process, cyano group substituted diphenylamine vinyl compound and polyvinyl alcohol have been prepared a class novel ultraviolet light stimuli responsive thin-film material by the hydrogen bond action between molecule.And single cyano group substituted diphenylamine vinyl compound itself there is no this characteristic.Electrostatic spinning process can realize cyano group substituted diphenylamine ethene high degree of dispersion in the polymer matrix, thus changes the space arrangement mode of cyano group substituted diphenylamine ethylene molecule, makes the optical property that can be regulated and controled rapidly cyano group substituted diphenylamine ethene by ultraviolet lighting.This composite takes full advantage of the feature that electrostatic spinning prepares flexible self-supporting film, obtain the novel fluorescence thin-film material with ultraviolet stimuli responsive, achieve optimization and the change of the optical function of former cyano group talan, widen application space and the preparation scope of single compound film.For the preparation of the novel intelligent film and optical anti-counterfeiting material with high-quality optical characteristics provides new thinking and approach.
Accompanying drawing explanation
Fig. 1: ER1 and PVA laminated film ultraviolet response fluorogram;
Fig. 2: ER3 and PVA laminated film ultraviolet response fluorogram.
Detailed description of the invention
[embodiment 1]
1. take 0.18g main body cyano group diphenyl ethene compounds ER1 and 0.9g PVAC polyvinylalcohol;
2. both are mixed, put into 30ml hexafluoroisopropanol solution, at 100ml there-necked flask, to stir two hours under 2000r/min condition;
3. the preparation of fluorescence membrane:
A. the preparation of electrostatic spinning instrument: be 17cm by syringe needle and the distance adjustment of collecting between screen; Instrument humidity is 25%; Temperature is 50 DEG C; The syringe needle shape selecting spinning nozzle is round;
B. the hexafluoroisopropanol solution containing cyano group diphenyl ethene compounds ER1 and PVAC polyvinylalcohol is added in spray nozzle device;
C. apply the high voltage of 22KV, solution changes electrified jet under high-tension effect, and described injection stream is deposited on the surface of base material;
D. the polymer cure and in described injection stream thus form nanofiber, final form natural daylight under be white film.
Product is characterized: fluorometric investigation is carried out to the film before and after illumination, can find out that obvious blue shift occurs film fluorescence after ultraviolet lighting by figure mono-.
[embodiment 2]
1. take 0.18g main body cyano group diphenyl ethene compounds ER3 and 0.9g PVAC polyvinylalcohol;
2. both are mixed, put into 30ml hexafluoroisopropanol solution, in 100ml there-necked flask, to stir two hours under 2000r/min condition;
3. the preparation of fluorescence membrane:
A. the preparation of electrostatic spinning instrument: be 17cm by syringe needle and the distance adjustment of collecting between screen; Instrument humidity is 25%; Temperature is 50 DEG C; The syringe needle shape selecting spinning nozzle is round;
B. the hexafluoroisopropanol solution containing cyano group diphenyl ethene compounds ER3 and PVAC polyvinylalcohol is added in spray nozzle device;
C. apply the high voltage of 25KV, solution changes electrified jet under high-tension effect, and described injection stream is deposited on the surface of base material;
D. the polymer cure and in described injection stream thus form nanofiber, final form natural daylight under be white film.
Product is characterized: fluorometric investigation is carried out to the film before and after illumination, can find out that obvious blue shift occurs film fluorescence after ultraviolet lighting by figure bis-.
Claims (2)
1. one kind has flexible thin-film material of ultraviolet stimulation fluorescence variable color response and preparation method thereof, it is characterized in that, based on method of electrostatic spinning, described material (cyano group substituted diphenylamine ethene and polyvinyl alcohol) prepares fluorescence membrane material by hydrogen bond action between object and host molecule.Change the space arrangement mode of cyano group substituted diphenylamine ethene organic molecule, make the optical property that can be regulated and controled rapidly composite film material by ultraviolet lighting.
2. one kind has flexible thin-film material of Ultraluminescence variable color response and preparation method thereof, and it is characterized in that, its concrete operation step is as follows:
1) preparation of electrostatic spinning solution:
A. weighing amount of substance is 4 × 10
-5~ 9 × 10
-3the cyano group diphenyl ethene compounds Isosorbide-5-Nitrae of mol '-bis-[2-(adjacent benzonitrile base) vinyl] benzene (be called for short ER1) or Isosorbide-5-Nitrae-bis--p-(cyano styrene base)-benzene (being called for short ER3).
B. weigh polyvinyl alcohol (PVA), its amount of substance is 0.001 ~ 0.003mol;
C. ER1 (or ER3) and PVA are dissolved in jointly the hexafluoroisopropanol of 10 ~ 50ml.
D. ER1 (or ER3) being stirred 2 ~ 24h with the solution of PVA makes it dissolve completely.
2) preparation of fluorescence membrane:
A. the preparation of electrostatic spinning instrument: be 10 ~ 25cm by syringe needle and the distance adjustment of collecting between screen; Instrument humidity Wei≤30%; Temperature Wei≤50 DEG C; The syringe needle shape selecting spinning nozzle is round;
B. ER1 (or ER3) and the hexafluoroisopropanol solution of PVA are added in spray nozzle device;
C. apply the high voltage of 20 ~ 30KV, solution changes electrified jet under high-tension effect, and described injection stream is deposited on the surface of base material;
E. the polymer cure in described injection stream thus form nanofiber, final forms the film be about for white under 30cm × 40cm natural daylight.
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| CN201510077091.3A CN104674458A (en) | 2015-02-12 | 2015-02-12 | Flexible thin film material with fluorescent color change response characteristic under ultraviolet stimulation and preparation method thereof |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02293825A (en) * | 1989-05-09 | 1990-12-05 | Nec Corp | Nonlinear organic optical material |
| JPH08184866A (en) * | 1994-12-28 | 1996-07-16 | Toyo Ink Mfg Co Ltd | Stilbene derivative for organic nonlinear optical material and its use |
| JPH08184865A (en) * | 1994-12-28 | 1996-07-16 | Toyo Ink Mfg Co Ltd | Stilbene derivative for organic nonlinear optical material and its use |
| JP2000226571A (en) * | 1999-02-03 | 2000-08-15 | Kyocera Corp | Photochromic material and photofunctional device using the same |
| US20020188043A1 (en) * | 2001-03-06 | 2002-12-12 | Kim Eun K. | Photochromic diarylethene substituted with isoxazole group |
| US20030174560A1 (en) * | 2002-02-26 | 2003-09-18 | Klaus-Hermann Dahmen | Photochromic compounds for molecular switches and optical memory |
| CN101735801A (en) * | 2009-12-03 | 2010-06-16 | 苏州大学 | Method for preparing fluorescent fiber membrane |
| CN103642484A (en) * | 2013-12-12 | 2014-03-19 | 北京化工大学 | Diphenylethylene type co-crystallization materials with multi-stimulus fluorescence response property and preparation method thereof |
| CN103981700A (en) * | 2014-05-07 | 2014-08-13 | 苏州大学 | Polyvinyl alcohol fluorescence fiber film, and making method and application thereof |
-
2015
- 2015-02-12 CN CN201510077091.3A patent/CN104674458A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02293825A (en) * | 1989-05-09 | 1990-12-05 | Nec Corp | Nonlinear organic optical material |
| JPH08184866A (en) * | 1994-12-28 | 1996-07-16 | Toyo Ink Mfg Co Ltd | Stilbene derivative for organic nonlinear optical material and its use |
| JPH08184865A (en) * | 1994-12-28 | 1996-07-16 | Toyo Ink Mfg Co Ltd | Stilbene derivative for organic nonlinear optical material and its use |
| JP2000226571A (en) * | 1999-02-03 | 2000-08-15 | Kyocera Corp | Photochromic material and photofunctional device using the same |
| US20020188043A1 (en) * | 2001-03-06 | 2002-12-12 | Kim Eun K. | Photochromic diarylethene substituted with isoxazole group |
| US20030174560A1 (en) * | 2002-02-26 | 2003-09-18 | Klaus-Hermann Dahmen | Photochromic compounds for molecular switches and optical memory |
| CN101735801A (en) * | 2009-12-03 | 2010-06-16 | 苏州大学 | Method for preparing fluorescent fiber membrane |
| CN103642484A (en) * | 2013-12-12 | 2014-03-19 | 北京化工大学 | Diphenylethylene type co-crystallization materials with multi-stimulus fluorescence response property and preparation method thereof |
| CN103981700A (en) * | 2014-05-07 | 2014-08-13 | 苏州大学 | Polyvinyl alcohol fluorescence fiber film, and making method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 徐海兵等: "光致变色金属(Ru,Pt,Ln)-二芳基乙烯分子开关", 《科学通报》 * |
| 罗千福等: "二芳基乙烯类光致变色材料的合成概述", 《有机化学》 * |
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Application publication date: 20150603 |