CN116284544A - Polymer with negative photochromic effect and application thereof - Google Patents
Polymer with negative photochromic effect and application thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 230000000694 effects Effects 0.000 title claims abstract description 38
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003287 optical effect Effects 0.000 claims abstract description 20
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 150000003254 radicals Chemical class 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229920006254 polymer film Polymers 0.000 claims description 37
- -1 undec-9-en-9-yl-10-yl radical Chemical class 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000007142 ring opening reaction Methods 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 239000007850 fluorescent dye Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 230000002441 reversible effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000007699 photoisomerization reaction Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
The invention discloses a polymer with negative photochromic effect and application, the polymer is prepared by taking prepared 6- [ (1E) -2- (9-methyl-9-aza-tricyclo [3.3.2.13,7] undec-9-ene-9-positive ion-10-radical free radical) vinyl ] -4-nitro-2- { [ (1-oxypropylene-2-alkenyl) oxy ] methyl } benzene-1-alkoxide ion (NSPMA), methyl acrylate and azodiisobutyronitrile as raw materials and adopting a one-step free radical copolymerization method. The negative photochromic polymer obtained by the invention has the characteristics of simple synthetic route, excellent performance, convenient regulation and control, good optical switch cycle performance and the like; the fluorescent dye can perform ring-closing reaction under green light irradiation to form a colorless non-fluorescent closed ring, spontaneous ring-opening reaction can occur due to molecular thermal motion to form a red and orange-red fluorescent open ring, the regulation and control are simple and convenient, the optical switch has excellent circulation performance, can be applied to optical erasable at room temperature, and has a huge application prospect in the aspects of optical erasable and anti-counterfeiting encryption of information.
Description
Technical Field
The invention belongs to the technical field of chemical material preparation and display materials, and particularly relates to a polymer with a negative photochromic effect and application thereof.
Background
Photochromic molecules undergo a reversible change in structure upon external stimuli (e.g., light, heat, etc.), and in most cases, the change in structure is often accompanied by changes in terms of color, fluorescence, etc. In recent years, optical switch fluorescent materials based on photochromic molecules have been widely studied, and have great application prospects in the aspects of optical information storage, encryption, optical anti-counterfeiting and the like. The spiropyran is taken as the photochromic molecule which is most widely researched at the earliest time, C-O in the molecule is broken after being irradiated by ultraviolet light, the molecule is changed from a closed-loop state to an open-loop state, and the molecule returns to the closed-loop state again after being stimulated by visible light or heat. This reversible change in structure allows the color and fluorescence of the spiropyran to be reversibly switched between the presence and absence, and therefore spiropyran is often used to construct optical switching fluorescent materials.
However, since ultraviolet light is required in the opening and closing process of the spiropyran, this certainly forms a big tripolite for practical application of the spiropyran, on the one hand, the structure of the spiropyran is destroyed by continuous irradiation of ultraviolet light, and serious photobleaching is caused by such irreversible influence, so that the recyclability of the optical switch fluorescent material is deteriorated. On the other hand, compared with visible light, ultraviolet light has poorer transmittance and is limited in part of application scenes. The negative photochromic spiropyran can well overcome the defects of the traditional spiropyran, because the thermodynamic stable form of the negative photochromic spiropyran is mainly a colored and fluorescent open-loop state, after being irradiated by visible light, molecules are closed, the colors and the fluorescence disappear, the closed-loop state is a thermodynamic unstable state, and after the visible light is removed, the molecules spontaneously return to the open-loop state. The whole open-close loop process can realize the change of color and fluorescence without the intervention of ultraviolet light.
Most of the negative photochromic spiropyrans have only reversible switching in color, and the negative photochromic spiropyrans with color and fluorescence changes are less, and most of the negative photochromic systems are small-molecule-based systems and the macromolecular systems in polymer form are less. Therefore, developing a negative photochromic polymer system with both color and fluorescence changes has great practical significance and application prospect.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a polymer with a negative photochromic effect and application thereof, wherein the polymer is prepared by taking prepared 6- [ (1E) -2- (9-methyl-9-azatricyclo [3.3.2.13,7] undec-9-ene-9-positive ion-10-radical) free radical) vinyl ] -4-nitro-2- { [ (1-oxyprop-2-enyl) oxy ] methyl } benzene-1-alkoxide ion (NSPMA), methyl acrylate and azodiisobutyronitrile as raw materials and adopting a one-step free radical copolymerization method. We have further found that the photoisomerization of the polymer with negative photochromic effect is simple, and under the irradiation of green light (525 nm), it is easy to undergo photoisomerization, and after the green light is removed, the photoisomerization returns to the original state spontaneously. The unique property of the photochromic polymer is fully utilized, and further application research shows that the polymer can be well applied in the field of optical erasable and writeable.
In order to solve the technical problems, the invention adopts the basic conception of the technical scheme that:
a polymer with negative photochromic effect, called poly (NSPMA-co-MA), is prepared from NSPMA, methyl acrylate and Azodiisobutyronitrile (AIBN) through proportional mixing and free radical polymerization.
The structural formula of the target molecule NSPMA is as follows:
wherein R is 1 Is C 1 -C 18 One of n-alkyl, hydroxymethyl and hydroxyethyl, R 2 Is one of H, CN, nitro and methoxy, R 3 Is one of methacryloxy and acryloxy. Preferably R 1 Is methyl, R 2 Is nitro, R 3 The following description will take as an example the acryloyloxy group.
The structural formula of the polymer poly (NSPMA-co-MA) with negative photochromic effect is as follows:
NSPMA is an abbreviation for 6- [ (1E) -2- (9-methyl-9-azatricyclo [3.3.2.13,7] undec-9-en-9-yl-10-yl radical) vinyl ] -4-nitro-2- { [ (1-oxyprop-2-enyl) oxy ] methyl } benzene-1-ol ion, prepared by:
dissolving a certain amount of 4, 5-dimethyl-4-aza-adamantane iodide salt and 3-acryloyloxymethyl-5-nitro salicylaldehyde prepared according to the prior art into absolute ethyl alcohol, adding a certain amount of piperidine, placing the mixture in a dark condition for reaction for 12 hours, removing 85-95% of solvent by rotary evaporation after the reaction is finished, separating and purifying the product by a column, and drying the product in vacuum to obtain a target molecule NSPMA.
The specific reaction process of the target molecule NSPMA prepared by the preparation method is as follows:
the molar ratio of the 4, 5-dimethyl-4-aza-adamantane iodide salt to the 3-acryloxymethyl-5-nitro salicylaldehyde is 1:1-2, preferably 1:1.2-1.5,4,5-dimethyl-4-aza-adamantane iodide salt to the piperidine is 1:1.1-1.3, preferably 1:1.15-1.25.
Preparation of a polymer poly (NSPMA-co-MA) with negative photochromic effect, comprising the steps of:
(1.1) mixing NSPMA, azodiisobutyronitrile and methyl acrylate in proportion and dissolving in a proper amount of dry toluene solution;
(1.2) stirring the solution prepared in the step (1.1) under ice bath conditions, vacuumizing and filling nitrogen, and circulating the process for three times, wherein the final mixed solution is in a nitrogen protection state;
(1.3) heating the mixed solution obtained in the step (1.2) to 70 ℃ and stirring for reaction for 12 hours;
(1.4) after the reaction in the step (1.3), the reaction solution was rapidly cooled and then precipitated in methanol, and the precipitate was dried under vacuum at 50℃to obtain a polymer poly (NSPMA-co-MA) having a negative photochromic effect.
The polymer poly (NSPMA-co-MA) with negative photochromic effect prepared by the preparation method has the following specific reaction process:
in step 1.1, the molar ratio of NSPMA to azodiisobutyronitrile is 1:0.5-10, preferably 1:0.75-6, and the molar ratio of NSPMA to methyl acrylate is 1:50-2000, preferably 1:75-600.
The prepared polymer poly (NSPMA-co-MA) with the negative photochromic effect is dissolved in a certain amount of chloroform to form a solution, and then the solution is uniformly coated on a glass sheet to obtain a polymer film with the negative photochromic effect, namely the polymer film can be used for optical erasable. Wherein the concentration of the polymer poly (NSPMA-co-MA) in chloroform is 20-60 mg/mL.
The polymer poly (NSPMA-co-MA) with the negative photochromic effect is red in an initial state and has orange-red fluorescence, and after green light stimulation, the negative photochromic groups in the polymer react from ring opening to ring closing, and the color and the fluorescence fade gradually. After the polymer is placed in the dark after the visible light is removed, the negative photochromic groups in the polymer spontaneously undergo ring-opening reaction, and the color and fluorescence are recovered. The polymer can be used for optical erasable by the change of color and fluorescence after being stimulated.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects.
(1) The invention adopts a simple free radical copolymerization method to successfully prepare the polymer with negative photochromic effect, and has excellent self-film-forming performance.
(2) The photochromic polymer prepared by the invention can undergo a ring-closing reaction under green light irradiation to form a colorless non-fluorescent closed ring, and can undergo spontaneous ring-opening reaction due to molecular thermal motion to form red and orange-red fluorescent open rings, so that the photochromic polymer is simple and convenient to regulate and control, has excellent optical switch cycle performance, and can be applied to optical erasable at room temperature.
(3) The preparation of the target molecule and the polymer is simple and quick. Has great advantages in scale-up synthesis and practical production application.
The negative photochromic polymer obtained by the invention has the characteristics of simple synthetic route, excellent performance, convenient regulation, good optical switch cycle performance and the like, and has great application prospect in the aspects of optical erasable and information anti-counterfeiting encryption.
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention and together with the description serve to explain the invention, without limitation to the invention. It is evident that the drawings in the following description are only examples, from which other drawings can be obtained by a person skilled in the art without the inventive effort. In the drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the prepared target molecule NSPMA in DMSO-d 6.
FIG. 2 is a gel permeation chromatogram of the prepared polymer.
FIG. 3 is a graph of UV-visible absorption spectra of the polymer film produced under various stimuli.
FIG. 4 is a graph showing fluorescence emission spectra of the prepared polymer film under different stimuli.
FIG. 5 is a graph of light-responsive fluorescence emission patterns of the prepared polymer films under different stimuli.
FIG. 6 is a graph of the reversible response cycle of a prepared polymer film stored under visible light irradiation and in the dark.
FIG. 7 shows the use of the prepared polymer film in optical writing and erasing.
It should be noted that these drawings and the written description are not intended to limit the scope of the inventive concept in any way, but to illustrate the inventive concept to those skilled in the art by referring to the specific embodiments.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention, and the following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
Example 1: preparation of NSPMA:
4, 5-dimethyl-4-azaadamantane iodide (1.056 mmol) and 5-nitrosalicylaldehyde (1.3204 mmol) prepared according to the prior art are dissolved in 20mL of anhydrous dichloromethane, piperidine (1.2566 mmol) is added, the mixture is stirred for 12h under a dark condition, 85-95% of solvent is removed by rotary evaporation after the reaction is finished, the product is purified by column separation, and the target molecule NSPMA is obtained by vacuum drying.
Example 2: FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of NSPMA in example 1, and it can be seen from FIG. 1 that the target compound has been successfully prepared.
Example 3: the preparation of the polymer with the negative photochromic effect comprises the following specific steps:
methyl acrylate 371mg, NSPMA11.8mg and AIBN7.1mg were dissolved in 1mL of dry toluene, and the reaction was carried out under vacuum-nitrogen atmosphere three times and under nitrogen atmosphere at 70℃with stirring for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, precipitated in methanol, and dried under vacuum at 30℃overnight to give a polymer poly (NSPMA-co-MA) having a negative photochromic effect.
Example 4: a polymer film having a negative photochromic effect is prepared. The method comprises the following specific steps:
taking the solid of the polymer obtained in the example 3, dissolving 40mg of the polymer solid in 1mL of chloroform to form a solution, finally coating the solution on a square glass sheet, and obtaining the polymer film with negative photochromic effect after the chloroform is volatilized in a light-proof ventilation state.
Example 5: the prepared polymer poly (NSPMA-co-MA) was tested for gel permeation chromatograms.
FIG. 2 is a gel permeation chromatogram of the polymer poly (NSPMA-co-MA) prepared in example 3. As can be seen from FIG. 2, the polymer poly (NSPMA-co-MA) has a number average molecular weight of about 47200 and a polymerization distribution index of 1.85.
Example 6: the polymer film with negative photochromic effect prepared in example 4 was tested for uv-visible absorption spectrum under visible-dark state.
Fig. 3 is an ultraviolet-visible absorption spectrum of the polymer film with negative photochromic effect prepared in example 4 in the interval of 300 nm to 700 nm. As can be seen from fig. 4, in the initial state, the polymer film has a very significant absorption peak near 510 nm, which is an open-loop absorption peak of NSPMA molecules in the polymer film, and the absorption peak is significantly reduced when the polymer film is irradiated with green light, because the NSPMA molecules in the polymer film are converted from the open-loop state to the closed-loop state, and then the closed-loop polymer film is placed in the dark state, the characteristic absorption peak of NSPMA gradually recovers with time, and the NSPMA molecules are converted back to the open-loop state.
Example 7: the polymer film with negative photochromic effect prepared in example 4 was tested for fluorescence emission spectrum under visible-dark state.
Fig. 4 is a fluorescence emission spectrum of the polymer film with negative photochromic effect prepared in example 4 in the interval of 580 nm to 700 nm. In the initial state, the polymer had an orange-red fluorescence, which appeared at 615 nm, which is the fluorescence emission peak of NSPMA in the polymer film. Then after green light irradiation, NSPMA is gradually changed from an open loop state to a closed loop state, and a fluorescence emission peak at 615 nanometers is gradually disappeared. Finally, the polymer film was placed in the dark state, NSPMA spontaneously returned from the closed-loop state to the open-loop state, and the fluorescence emission peak at 615 nm was gradually restored to the original state.
Example 8: the polymer film with a negative photochromic effect prepared in example 4 was tested for a photo-response spectrum under green-dark conditions.
Fig. 5 is a photo-response spectrum of the polymer film with negative photochromic effect prepared in example 4. The polymer film was first irradiated with green light for various durations (0 second, 1 second, 3 seconds, 6 seconds, 10 seconds, 13 seconds, 16 seconds, 20 seconds, 24 seconds, 28 seconds), and it was found that the peak fluorescence emission at 615 nm of the polymer film gradually decreased and was minimized at about 20 seconds. The polymer film was then left in the dark state for various durations (1 minute, 2 minutes, 4 minutes, 8 minutes, 12 minutes, 16 minutes, 20 minutes, 24 minutes, 28 minutes, 32 minutes, 36 minutes, 40 minutes, 44 minutes, 48 minutes, 52 minutes, 56 minutes), and the peak fluorescence emission at 615 nm was gradually returned to the initial state, and returned to the initial fluorescence value at about 44 minutes.
Example 9: reversible cycle experiments of polymer films with negative photochromic effects after alternating green and dark states.
The polymer film with negative photochromic effect prepared in example 4 is taken, and after green light and dark state are alternately treated, the fluorescence intensity at 615 nanometers is respectively tested, and the result is shown in fig. 6, which shows that the NSPMA part in the polymer still has better reversible fluorescence switch performance after 25 times of optical switch cycle test.
Example 10: optically erasable test
120mg of the polymer solid having a negative photochromic effect obtained in example 3 was dissolved in 3mL of chloroform to form a solution, and finally the solution was coated on a circular glass plate having a diameter of 6cm, and after the chloroform was volatilized in a state of being ventilated away from light, a polymer film was obtained. As shown in fig. 7, in the initial state, the polymer film is red and has orange-red fluorescence. And then, printing the designed pattern on a film through a laser printer to obtain a recoverable pattern mask, a three-character mask and a two-dimensional code mask. Then, the printed mask is covered on the polymer film and irradiated with green light, and during the irradiation, the transparent part of the mask can pass through the green light, while the black pattern part is not allowed, so that the color and fluorescence of the areas of the polymer film irradiated by the green visible light disappear, while the areas not irradiated still keep the red color and orange red fluorescence of the polymer film, and the color and fluorescence difference of the two areas enables the designed pattern to be clearly displayed on the polymer film. Finally, after the polymer is placed in the dark for a period of time, the pattern gradually disappears, and the polymer film is changed back to the initial state again, so that the next use is convenient. By the above procedure we have successfully performed light erasable applications on polymer films. And through designing different patterns, can clear messenger's pattern display on the polymer membrane, for example circulate and retrieve the pattern, three-dimensional through characters and two-dimensional code (can use the cell-phone to sweep one and sweep the function and successfully discern). This shows that the polymer film has very powerful application foreground in optical erasable.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (10)
1. A polymer with negative photochromic effect is characterized by being prepared from 6- [ (1E) -2- (9-methyl-9-azatricyclo [3.3.2.13,7] undec-9-ene-9-positive ion-10-radical free radical) vinyl ] -4-nitro-2- { [ (1-oxypropylene-2-alkenyl) oxy ] methyl } benzene-1-alkoxide ion, azodiisobutyronitrile and methyl acrylate serving as raw materials, wherein the structural formula is as follows:
2. the polymer with negative photochromic effect according to claim 1, wherein the 6- [ (1E) -2- (9-methyl-9-azatricyclo [3.3.2.13,7] undec-9-en-9-yl-10-yl radical) vinyl ] -4-nitro-2- { [ (1-oxypropylene-2-enyl) oxy ] methyl } benzene-1-ol radical ion, abbreviated as NSPMA, is prepared by reacting 4, 5-dimethyl-4-azaadamantine iodide salt with 3-acryloyloxymethyl-5-nitrosalicylaldehyde, and has the structural formula:
wherein R is 1 Is C 1 -C 18 One of n-alkyl, hydroxymethyl and hydroxyethyl, R 2 Is one of H, CN, nitro and methoxy, R 3 Is one of methacryloxy and acryloxy.
3. The polymer with negative photochromic effect of claim 2, wherein the polymer poly (NSPMA-co-MA) with negative photochromic effect is obtained by a one-step radical copolymerization method after mixing methyl acrylate, NSPMA and azobisisobutyronitrile according to a radical polymerization method.
4. A polymer with negative photochromic effect according to claim 2, characterized in that R 1 Is methyl, R 2 Is nitro, R 3 Is an acryloyloxy group.
5. A polymer with negative photochromic effect according to claim 2, characterized by the synthetic step of NSPMA:
dissolving a certain amount of 4, 5-dimethyl-4-aza-adamantane iodide salt and 3-acryloyloxymethyl-5-nitro salicylaldehyde prepared according to the prior art into anhydrous DCM, adding a certain amount of piperidine, placing the mixture under a dark condition, removing 85-95% of solvent by rotary evaporation after the reaction is finished, separating and purifying the product by a column, and drying in vacuum to obtain NSPMA.
6. A polymer with negative photochromic effect according to claim 5, characterized in that the molar ratio of 4, 5-dimethyl-4-azaadamantane iodide salt to 3-acryloxymethyl-5-nitrosalicylaldehyde is 1:0.1-100, preferably 1:1.2-1.5,4,5-dimethyl-4-azaadamantane iodide salt to piperidine is 1:0.1-100, preferably 1:1.15-1.25.
7. A process for the preparation of a polymer having a negative photochromic effect according to any one of claims 1 to 6, comprising in particular the following steps:
step 1.1, mixing NSPMA, azodiisobutyronitrile and methyl acrylate in proportion and dissolving in refined toluene;
step 1.2, nitrogen and oxygen are discharged for three times, three minutes each time, and then the reaction is carried out for 12 hours at 70 ℃;
step 1.3, placing the reaction bottle in an ice bath for rapid cooling, and then precipitating the reaction liquid in methanol;
step 1.4, placing the obtained precipitate in a vacuum drying oven at 50 ℃ overnight to obtain the polymer poly (NSPMA-co-MA) with negative photochromic effect.
8. The preparation method according to claim 7, wherein in step 1.1, the molar ratio of NSPMA to azobisisobutyronitrile is 1:0.5-10, preferably 1: the molar ratio of NSPMA to methyl acrylate is 1:50-2000, preferably 1:75-600, and is 0.75-6.
9. Use of a polymer having a negative photochromic effect according to any one of claims 1 to 6 for photopatternable applications, characterized in that:
the polymer is dissolved in a certain amount of chloroform to form a solution, and then the solution is coated on a round glass sheet, and after the solvent volatilizes, the polymer film applied to optical erasable can be obtained.
10. Use according to claim 9, characterized in that the concentration of the polymer poly (NSPMA-co-MA) in chloroform is 20-60 mg/mL.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110163282A1 (en) * | 2010-01-06 | 2011-07-07 | Korea University Research And Business Foundation | Photochromic material |
| CN113234189A (en) * | 2021-06-01 | 2021-08-10 | 湖南科技大学 | Method for applying photoswitch polymorphic fluorescent polymer to data encryption |
| CN115160478A (en) * | 2022-07-11 | 2022-10-11 | 湖南科技大学 | Method for applying photochromic polymer to dynamic encryption of time-resolved information |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110163282A1 (en) * | 2010-01-06 | 2011-07-07 | Korea University Research And Business Foundation | Photochromic material |
| CN113234189A (en) * | 2021-06-01 | 2021-08-10 | 湖南科技大学 | Method for applying photoswitch polymorphic fluorescent polymer to data encryption |
| CN115160478A (en) * | 2022-07-11 | 2022-10-11 | 湖南科技大学 | Method for applying photochromic polymer to dynamic encryption of time-resolved information |
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