CN102643444A - Preparation method of pyrazolone/polymer composite photochromic film - Google Patents
Preparation method of pyrazolone/polymer composite photochromic film Download PDFInfo
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- CN102643444A CN102643444A CN2012100741546A CN201210074154A CN102643444A CN 102643444 A CN102643444 A CN 102643444A CN 2012100741546 A CN2012100741546 A CN 2012100741546A CN 201210074154 A CN201210074154 A CN 201210074154A CN 102643444 A CN102643444 A CN 102643444A
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Abstract
The invention relates to a preparation method of a pyrazolone/polymer composite photochromic film. A high-performance water-insoluble pyrazolone photochromic material, i.e. 1, 3-diphenyl-4-(3'-bromobenzylidene)-5-pyrazolone-shrinking phenyl semicarbazide (DP3BrBP-PSC) is used as a photochromic unit, water-soluble high polymers, i.e. hydroxypropyl methyl cellulose (HPMC) and polyvinyl alcohol (PVA) are used at the same time, distilled water is used as solvent, a physical doping dispersion method is used and continuous agitation is conducted to obtain composite material suspension; and after the suspension is statically placed in a dark place and is defoamed and a pouring method is used for preparing the pyrazolone/polymer composite photochromic film which has the advantages of high photochromic property, even texture and good transparency, flexibility and mechanical property. The preparation method has the advantages of simplicity in operation and lower cost.
Description
Technical field
The present invention relates to the preparation method of a kind of pyrazolone/polymkeric substance composite photochromic film.
Background technology
The research of photochromic material started from the beginning of last century; Be meant compound on two or at least one direction, to absorb the external electromagnetic ripple and the reversible configuration conversion between the two states takes place; Compound receives certain wavelengths of electromagnetic (h ν) to excite the back to be converted into configuration B by configuration A, and compd B is planted at other under hertzian wave (h ν ') radiation or the heat effect of a wavelength and turned back to original original state.Under the electromagenetic wave radiation effect; Thermodynamically stable configuration A is converted into more unsettled configuration B and with the noticeable change of absorption spectrum or emmission spectrum colour-change has taken place promptly, also comprises the change of other physicochemical property such as specific refractory power, solubleness, viscosity, humidity, specific inductivity.At present, photochromic material mainly is divided into inorganic photochromic material and organic photochromic material two big systems.Wherein organic photochromic material enjoys people's extensive concern because of it in the potential application of high-tech area.The many organic photochromic systems of research mainly concentrate on diarylethene, fulgide, spiro-pyrans 、 Luo oxazine, nitrogen benzide and relative heterogeneous ring compound at present; Yet in the compound of these systems, exhausted most photochromic compound can only variable color in solution.From the angle analysis of practicability, organic photochromic material must have photochromic properties under film, fiber, sheet etc. are solid-state could satisfy the application in high density information storage and holographic false proof field better.Therefore, solid-state variable color down is to realize the material key in application.
Pyrazoline ketone photochromic compound is one type of novel organic photochromic material; Being one type of novel photochromic material that under the powder crystal state, has the ability of reverse photochromism performance, is the performance function material that fields such as information storage, molecular switch, nonlinear optics, holographic security technology have application potential most.But such system is an organic molecule, is not easy to manufacture device.In order to quicken the application of this type off-color material; The present invention adopts physical doping that pyrazoline ketone photochromic material is distributed to pyrazolone/polymkeric substance composite photochromic film that processability in the polymer matrix is good, have the ability of reverse photochromism responsiveness; Realize the variable color behavior of pyrazoline ketone photochromic compound in polymeric matrix; To satisfy the technical requirements of practicability, develop the stronger photochromic polymer material of practicality and have more Research Significance material.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of simple pyrazolone/polymkeric substance composite photochromic film.
The preparation method of pyrazolone provided by the invention/polymkeric substance composite photochromic film; Adopt the good water-fast pyrazoline ketone photochromic material of discoloration as color-changing unit; Selecting high molecular weight water soluble polymer simultaneously for use is matrix, is that solvent constantly stirs and utilizes the doping dispersion method with zero(ppm) water, obtains the blend suspension liquid; Lucifuge leaves standstill and adopts behind the froth breaking casting to prepare photochromic laminated film, and is simple to operate and cost is lower.
The pyrazoline ketone photochromic material that the present invention adopts is: 1, and 3-phenylbenzene-4-(3
'-bromobenzene methylene radical)-5-pyrazolone-shrinking Carbaphen (DP3BrBP-PSC).The high molecular weight water soluble polymer of selecting for use comprises: Vltra tears (HPMC), Z 150PH (PVA).The concrete steps that the present invention includes:
1) under the situation of magnetic agitation, high molecular weight water soluble polymer is joined in the zero(ppm) water; 2) under room temperature lucifuge condition of stirring, in the solution of above-mentioned step 1), slowly add pyrazoline ketone photochromic material, stir, obtain the blend suspension liquid.3) above-mentioned suspension liquid lucifuge is left standstill froth breaking after, adopt casting, suspension liquid slowly is poured in the clean glass guide channel, after the room temperature lucifuge drying, obtain composite discolored thin film.
The invention has the advantages that and adopt a kind of simple physics doping dispersion method that prepare photochromic laminated film, method is simple and cost is low.This film quality is even, has the good transparency, snappiness and mechanical property, and demonstrates superior ultraviolet light induced discoloration and good fatigue resistence.
Description of drawings
Fig. 1 is the uv absorption spectrum behind the embodiment one DP3BrBP-PSC/HPMC polymer composite film process different time UV-irradiation.
Fig. 2 be after embodiment one variable color the DP3BrBP-PSC/HPMC polymer composite film 110 ℃ the heating different times uv absorption spectrums.
Fig. 3 is the uv absorption spectrum behind the embodiment two DP3BrBP-PSC/PVA polymer composite films process different time UV-irradiation.
Fig. 4 is the variable color reversible cycle figure of embodiment two DP3BrBP-PSC/PVA polymer composite films.
Fig. 5 is for implementing row two DP3BrBP-PSC/PVA polymer composite films colour-change figure and information storage figure before and after the 365nm UV-irradiation.
Embodiment
Below in conjunction with embodiment the present invention is described further, but the present invention is not limited to following examples.
Embodiment one
Room temperature under the condition of magnetic agitation, joins 0.25 gram HPMC white powder in 20 ml distilled waters lentamente, constantly stirs HPMC is fully dissolved, and forms settled solution.Then, under the condition of lucifuge, slowly join 0.05 gram DP3BrBP-PSC white powder in the settled solution; Continue to stir 3 hours, DP3BrBP-PSC is distributed in the settled solution well, obtain the blend suspension liquid; After lucifuge leaves standstill froth breaking; The blend suspension liquid slowly is poured in the clean glass guide channel, and room temperature lucifuge dried overnight obtains pyrazolone/polymkeric substance composite photochromic film.Laminated film has good photochromic properties, behind the 365nm UV-irradiation, by white yellowing.
Above-mentioned composite package has good photochromic properties; Through the 365nm UV-irradiation; This laminated film uv absorption spectrum is as shown in Figure 1; A new absorption peak appears in discovery in the scope of 340-500nm, and the absorption intensity at this peak strengthens with the increase of UV-irradiation time, and the color of laminated film is by white yellowing simultaneously.Yellow laminated film after variable color is 110 ℃ of heating down; Gradually fade again to white; Its UV spectrum that fades is as shown in Figure 2; Its photon absorbing intensity of peak in 340-500nm reduces along with the prolongation of heat-up time gradually, and curve last and that variable color is preceding almost coincide, and shows that this laminated film has photochromic reversibility.
Embodiment two
60 ℃, under the condition of magnetic agitation, 3 gram PVA white particles are joined in 20 ml distilled waters lentamente, stirred 1 hour, PVA is fully dissolved, form settled solution.Then, under room temperature lucifuge condition, slowly join 0.06 gram DP3BrBP-PSC white powder in the settled solution; Continue to stir 5 hours, DP3BrBP-PSC is distributed in the settled solution well, obtain the blend suspension liquid; After lucifuge leaves standstill froth breaking; The blend suspension liquid slowly is poured in the clean glass guide channel, and room temperature lucifuge dried overnight obtains pyrazolone/polymkeric substance composite photochromic film.Laminated film has good photochromic properties, behind the 365nm UV-irradiation, by white yellowing.
Through the 365nm UV-irradiation; This laminated film uv absorption spectrum is as shown in Figure 3; A new absorption peak appears in discovery in the scope of 340-525nm; And the absorption intensity at this peak strengthens with the increase of UV-irradiation time, and the color of laminated film shows that by white yellowing this pyrazolone/polymkeric substance composite photochromic film has good photochromic properties equally simultaneously.
Fig. 4 is the variable color reversible cycle figure of above-mentioned laminated film; Carry out repeatedly finding after 10 times that the absorption intensity decay of this laminated film is little; Explain that this laminated film has higher fatigue resistence, has the potential using value in fields such as information storage and light-operated molecular switches.
Fig. 5 is above-mentioned laminated film colour-change figure and information storage figure before and after the 365nm UV-irradiation.
Claims (3)
1. the preparation method of simple pyrazolone/polymkeric substance composite photochromic film adopts excellent property and water-fast pyrazoline ketone photochromic material 1,3-phenylbenzene-4-(3
'-bromobenzene methylene radical)-5-pyrazolone-shrinking Carbaphen (DP3BrBP-PSC) is as color-changing unit; Select high molecular weight water soluble polymer simultaneously for use: Vltra tears (HPMC), Z 150PH (PVA); Disperse blending method with zero(ppm) water for solvent utilization doping; Constantly stir and obtain the matrix material suspension liquid, after lucifuge leaves standstill froth breaking, adopt casting to prepare pyrazolone/polymkeric substance composite photochromic film.
2. according to claim 1 is the pyrazolone/polymkeric substance composite photochromic film of matrix with high molecular weight water soluble polymer HPMC; It is characterized in that, be solvent with zero(ppm) water, room temperature; Under the magnetic agitation condition, preparation quality is than being the settled solution of 1%-3%; Under room temperature lucifuge condition of stirring, in solution, slowly add an amount of DP3BrBP-PSC simultaneously, stir; Obtain mixing suspension liquid; After lucifuge leaves standstill froth breaking, adopt casting, slowly this suspension liquid is poured in the clean glass guide channel of certain size size; After the room temperature lucifuge drying, can make the photochromic laminated film of different size, different thickness and different off-color material dopings.
3. described according to claim 1 is the pyrazolone/polymkeric substance composite photochromic film of matrix with high molecular weight water soluble polymer PVA; It is characterized in that, be solvent with zero(ppm) water, 40 ℃-90 ℃; Under the magnetic agitation condition, preparation quality is than being the settled solution of 8%-15%; Under the room temperature lucifuge condition of stirring, in solution, slowly add an amount of DP3BrBP-PSC simultaneously, stir; Obtain mixing suspension liquid; After lucifuge leaves standstill froth breaking, adopt casting, slowly this suspension liquid is poured in the clean glass guide channel of certain size size; After the room temperature lucifuge drying, make the photochromic laminated film of different size, different thickness and different off-color material dopings.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102785441A (en) * | 2012-08-23 | 2012-11-21 | 东北林业大学 | Preparing method of photochromic composite films |
| CN102875822A (en) * | 2012-10-30 | 2013-01-16 | 天津科技大学 | Preparation method of photochromic latex emulsion |
| CN103102693A (en) * | 2013-03-01 | 2013-05-15 | 新疆大学 | Preparation method of pyrazolone/gelatin-xanthan gum composite photochromic film |
| CN107828268A (en) * | 2017-11-10 | 2018-03-23 | 江苏视客新材料股份有限公司 | Spiro-pyrans class photochromic coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709054A (en) * | 2009-09-16 | 2010-05-19 | 新疆大学 | Preparation and application of pyrazolone methyl thiosemicarbazone photochromic compound |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709054A (en) * | 2009-09-16 | 2010-05-19 | 新疆大学 | Preparation and application of pyrazolone methyl thiosemicarbazone photochromic compound |
Non-Patent Citations (2)
| Title |
|---|
| 《PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES》 20111231 Yuan Hui et al. "Photochromism of a pyrazolone derivative in crystalline state and in HPMC composite film" 第1562-1567页 1－3 第10卷, 第10期 * |
| YUAN HUI ET AL.: ""Photochromism of a pyrazolone derivative in crystalline state and in HPMC composite film"", 《PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES》, vol. 10, no. 10, 31 December 2011 (2011-12-31), pages 1562 - 1567 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102785441A (en) * | 2012-08-23 | 2012-11-21 | 东北林业大学 | Preparing method of photochromic composite films |
| CN102785441B (en) * | 2012-08-23 | 2014-12-17 | 东北林业大学 | Preparing method of photochromic composite films |
| CN102875822A (en) * | 2012-10-30 | 2013-01-16 | 天津科技大学 | Preparation method of photochromic latex emulsion |
| CN103102693A (en) * | 2013-03-01 | 2013-05-15 | 新疆大学 | Preparation method of pyrazolone/gelatin-xanthan gum composite photochromic film |
| CN107828268A (en) * | 2017-11-10 | 2018-03-23 | 江苏视客新材料股份有限公司 | Spiro-pyrans class photochromic coating and preparation method thereof |
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Application publication date: 20120822 |