CN112210364B - Photochromic material and preparation method and application thereof - Google Patents

Photochromic material and preparation method and application thereof Download PDF

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CN112210364B
CN112210364B CN202011092491.9A CN202011092491A CN112210364B CN 112210364 B CN112210364 B CN 112210364B CN 202011092491 A CN202011092491 A CN 202011092491A CN 112210364 B CN112210364 B CN 112210364B
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photochromic material
ink
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CN112210364A (en
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雷云祥
黄小波
肖福明
吴华悦
刘妙昌
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Wenzhou University
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Abstract

The invention relates to the technical field of photochromic materials, in particular to a photochromic material and a preparation method and application thereof. The photochromic material comprises a compound A and a compound B. The compound A is taken as a guest compound, the compound B is taken as a main compound, and the compound A is doped into the compound B, so that the photochromic anti-counterfeiting ink has an obvious photochromic effect and can be used in the fields of anti-counterfeiting printing, writing ink and the like.

Description

Photochromic material and preparation method and application thereof
Technical Field
The invention relates to the technical field of photochromic materials, in particular to a photochromic material and a preparation method and application thereof.
Background
Along with the development of society, counterfeit and shoddy products bring great economy, environment and even health problems to human society. Under the stimulation of certain ultraviolet excitation light, the color of the color-changing material can be rapidly changed obviously, such as from white to yellow or red, and can be rapidly returned to the initial color under the irradiation of an LED white light lamp. Therefore, the method is widely applied to the fields of biological imaging, devices, encryption and anti-counterfeiting and the like.
However, the conventional photochromic material has the disadvantages that the contrast of the color change of the material is weak, the illumination time required for the color change is long, and certain fatigue is shown after several times of recovery. Most importantly, the cost is too high due to the complex synthesis of materials, so that the large-scale industrial production is difficult to realize. There is a need to develop simple, efficient and economical photochromic materials.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a photochromic material, so as to solve the technical problems of weak contrast of color change of the photochromic material, etc. existing in the prior art.
The second purpose of the invention is to provide a preparation method of the photochromic material, and the synthesis process of the photochromic material is simple and the conditions are mild.
The third purpose of the invention is to provide the application of the photochromic material, such as the fields of anti-counterfeiting printing, writing ink and the like.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
photochromic materials comprising compound a and compound B;
the structural formula of the compound A is as follows:
Figure BDA0002722606420000021
R1selected from H, halogen, substituted or unsubstituted aryl-containing structures; the aryl-containing structure comprises
Figure BDA0002722606420000022
Figure BDA0002722606420000023
Any one of (a);
R2selected from said substituted or unsubstituted aryl-containing structures;
the structural formula of the compound B is as follows:
Figure BDA0002722606420000024
R3and R4Each independently selected from H, F, Cl, Br, I, -OH and-OCH3and-CH3Any one of the above.
The photochromic material of the invention adopts the compound A as a guest compound and the compound B as a host compound, and the compound A is doped into the compound B, so that the photochromic material has obvious photochromic effect.
The photochromic material can rapidly change the appearance color from white to deep red under the action of ultraviolet, can maintain the deep red state for more than 12 hours under the dark condition, and can maintain the deep red for 5-10 min under the conventional indoor light. And after the photochromic material is changed into deep red, the photochromic material is changed into white from the deep red by irradiating for about 10s by adopting an LED, a white light lamp, a mobile phone light source and the like; and the material can still keep excellent color-changing performance after the material is reciprocated for more than 10 times.
In addition, the compound A is simple to synthesize, the compound B is wide in source and low in cost, and the method is suitable for industrial production.
In addition, the doped material is very insensitive to humidity, oxygen and the like, and still has very excellent photochromic effect in a humid environment.
Reference to the invention denotes the position of attachment of the group to the remainder of the compound.
In the substituted aryl group-containing structure according to the embodiment of the present invention, the substituent may be any of an alkyl group, an alkoxy group, a halogen group, and an ester group. Such as may be C1～3Alkyl groups including methyl, ethyl, n-propyl, isopropyl, and the like.
In a particular embodiment of the invention, the structural formula of compound a is selected from any one of the following:
Figure BDA0002722606420000031
In a particular embodiment of the invention, the halogen comprises any of F, Cl, Br and I, preferably Br.
In a particular embodiment of the invention, the aryl-containing structure is selected from
Figure BDA0002722606420000041
Figure BDA0002722606420000042
Any one of the above.
In a particular embodiment of the invention, the compound B is benzophenone or 4-methylbenzophenone.
In a particular embodiment of the invention, the process for the preparation of compound a comprises any one of route a) and route b):
Figure BDA0002722606420000043
wherein R is R1Or R2。
The specific method of route a) comprises:
at room temperature, carrying out bromination reaction on 2, 6-dimethyl pyrone and a brominating agent such as N-bromosuccinimide (NBS) to obtain a compound I;
carrying out Suzuki coupling reaction on the compound I and the compound C to obtain a compound Ax。
Wherein the Suzuki coupling reaction conditions comprise: and reacting the compound I and the compound C for 10-15 h at 75-85 ℃ in a nitrogen atmosphere by taking a mixture of tetrahydrofuran and water as a solvent under the action of tetratriphenylphosphine palladium and potassium carbonate.
The specific method of route b) comprises:
carrying out bromination reaction on the 2, 6-dimethyl pyrone and a brominating agent such as N-bromosuccinimide (NBS) at room temperature to obtain a compound II;
carrying out Suzuki coupling reaction on the compound II and the compound C to obtain a compound A y1Or Ay2。
Wherein the Suzuki coupling reaction conditions comprise: and reacting the compound II with the compound C for 10-15 h at 75-85 ℃ in a nitrogen atmosphere by taking a mixture of tetrahydrofuran and water as a solvent under the action of tetratriphenylphosphine palladium and potassium carbonate.
The volume ratio of tetrahydrofuran to water as the solvent is (5-15): 1, for example, 10: 1.
In practical operation, in the bromination reaction of 2, 6-dimethylpyranone NBS, a compound I with a mono-substituted bromine group and a compound II with a di-substituted bromine group are obtained simultaneously, and the compound I and the compound II are obtained by separation modes such as conventional column chromatography and the like.
In a particular embodiment of the invention, the molar ratio of compound I to compound C is 1: 1.5, for example 1: 1.2.
In a particular embodiment of the invention, the molar ratio of compound II to compound C is 1: 1.5, for example 1: 1.2.
In a specific embodiment of the invention, the amount of the tetrakistriphenylphosphine palladium added is 2-10% of the mass of the compound I, and is preferably 5%; the addition amount of the potassium carbonate is 5-15% of the mass of the compound I, and is preferably 10%.
In a specific embodiment of the invention, the addition amount of the tetrakistriphenylphosphine palladium is 2-10% of the mass of the compound II, and is preferably 5%; the adding amount of the potassium carbonate is 5-15% of the mass of the compound II, and the preferable amount is 10%.
In a specific embodiment of the present invention, the ratio of the amount of the compound i to the solvent is 1 mmol/2 to 3 mL, for example, 1 mmol/2.2 mL.
In a specific embodiment of the present invention, the ratio of the amount of the compound ii to the solvent is 1 mmol/2.2 mL, for example, 1 mmol/2.3 mL.
In practical operation, after the Suzuki coupling reaction is finished, the corresponding compound A is obtained by a conventional column chromatography separation and purification modex、Ay1、Ay2。
In a specific embodiment of the present invention, the molar ratio of compound a to compound B is 1: 50 to 20000. More preferably, the molar ratio of compound a to compound B is 1: 2000, more preferably 1: 200 to 1000, and still more preferably 1: 1000.
In various embodiments, the molar ratios of compound a to compound B can be 1: 50, 1: 100, 1: 200, 1: 300, 1: 400, 1: 500, 1: 600, 1: 700, 1: 800, 1: 900, 1: 1000, 1: 1200, 1: 1400, 1: 1600, 1: 1800, 1: 2000, 1: 3000, 1: 4000, 1: 5000, 1: 10000, 1: 15000, 1: 20000, and the like.
The invention also provides a preparation method of the photochromic material, which comprises the following steps:
and the compound B is uniformly mixed with the compound A in a molten state.
The compound B adopted by the invention has better meltability, and can dissolve the compound A in a molten state, so that the compound A is uniformly dispersed in the compound B.
In an embodiment of the present invention, the compound B is melted to a molten state under heating at 50 to 60 ℃.
In a specific embodiment of the present invention, the method further comprises: and after uniformly mixing, naturally cooling to room temperature. Naturally cooling to room temperature to slowly crystallize the compound B in a molten state containing the guest molecule, namely the compound A, so as to obtain the solid photochromic material. The preparation method is simple to operate and suitable for large-scale production.
The invention also provides application of any one of the photochromic materials in preparation of ink and/or ink.
Further, the ink and/or ink is anti-counterfeiting printing ink and/or ink, or writing and drawing ink and/or ink.
In practical practice, the photochromic material prepared as described above may be heated to a molten state and used as an ink to perform calligraphy and painting on the surface of a substrate. Wherein the base material includes any one of printing paper and filter paper. The characters or patterns obtained by the writing and drawing obtained by the method are white under a white light lamp, and after the white characters or patterns are irradiated by ultraviolet light, the white characters or patterns are quickly changed into deep red, so that the writing and drawing anti-counterfeiting ink has high anti-counterfeiting property and high encryption property.
In a specific embodiment of the invention, after the printing or writing and drawing, the color development is carried out under the irradiation of ultraviolet light with the wavelength of 300-450 nm, and the color recovery is carried out under the irradiation of 500-600 nm or white light.
Compared with the prior art, the invention has the following beneficial effects:
(1) the photochromic material can rapidly change the appearance color from white to deep red under the action of ultraviolet, can maintain the deep red state for more than 12 hours under the dark condition, and can maintain the deep red for 5-10 min under the conventional indoor light. And after the photochromic material is changed into deep red, the photochromic material is changed into white from the deep red by irradiating for about 10s by adopting an LED, a white light lamp, a mobile phone light source and the like; and the material can still keep excellent color-changing performance after the material is reciprocated for more than 10 times.
(2) The photochromic material has wide raw material sources and simple synthesis, and is suitable for large-scale production.
(3) The photochromic material can be used for anti-counterfeiting printing and writing ink and has higher anti-counterfeiting property and encryption property.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic diagram illustrating an appearance color change of a photochromic material before and after different light irradiations according to an embodiment 1 of the present invention;
fig. 2 shows the repeatability of the ultraviolet absorption of the photochromic material in the alternate irradiation treatment of ultraviolet light and LED white light provided in embodiment 1 of the present invention;
fig. 3 is a schematic diagram illustrating changes in appearance color of a photochromic material provided in example 1 of the present invention before and after different light irradiation at different temperatures or in water;
FIG. 4 is a diagram of the UV absorption spectra of the photochromic material provided in example 1 of the present invention before and after different light irradiation;
FIG. 5 is a graph of the color change of a pattern written using the photochromic material provided in example 1 of the present invention before and after different light;
fig. 6 is a schematic diagram of the change of the appearance color of the photochromic material before and after different lights are emitted in example 2 of the present invention;
FIG. 7 is a diagram of the UV absorption spectra of the photochromic material provided in example 2 of the present invention before and after different light irradiation;
FIG. 8 is a graph of the color change of a pattern written using the photochromic material provided in example 2 of the present invention before and after different light;
FIG. 9 is a schematic diagram showing the color change of the photochromic material before and after different lights are applied;
FIG. 10 is a graph of the UV absorption spectra of a photochromic material according to example 4 of the present invention before and after different light irradiation;
FIG. 11 is a graph of the color change before and after different light levels of a pattern written using the photochromic material provided in example 1 of the present invention and Compound B1, respectively; wherein "CHEMIS" was written using molten compound B1 and "TRY" was written using the molten photochromic material of example 1;
FIG. 12 shows Compound A of the present invention2Nuclear magnetic hydrogen spectrum of (a);
FIG. 13 shows Compound A of the present invention5Nuclear magnetic hydrogen spectrum of (a);
FIG. 14 shows Compound A of the present invention8Nuclear magnetic hydrogen spectrum diagram of (1).
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In a particular embodiment of the invention, compound B of compound a is used having the following structural formula:
a compound A:
Figure BDA0002722606420000091
compound B:
Figure BDA0002722606420000101
the synthetic route of compound a adopted in each example of the present invention is as follows:
including either of route a) and route b):
Figure BDA0002722606420000102
wherein R is R1Or R2。
The specific method of route a) comprises:
at room temperature, carrying out bromination reaction on 2, 6-dimethyl pyrone and a brominating agent such as N-bromosuccinimide (NBS) to obtain a compound I;
carrying out Suzuki coupling reaction on the compound I and the compound C to obtain a compound Ax。
Wherein the Suzuki coupling reaction conditions comprise: and reacting the compound I and the compound C for 10-15 h at 75-85 ℃ in a nitrogen atmosphere by taking a mixture of tetrahydrofuran and water as a solvent under the action of tetratriphenylphosphine palladium and potassium carbonate.
The specific method of route b) comprises:
carrying out bromination reaction on the 2, 6-dimethyl pyrone and a brominating agent such as N-bromosuccinimide (NBS) at room temperature to obtain a compound II;
carrying out Suzuki coupling reaction on the compound II and the compound C to obtain a compound Ay1Or Ay2。
Wherein the Suzuki coupling reaction conditions comprise: and reacting the compound II with the compound C for 10-15 h at 75-85 ℃ in a nitrogen atmosphere by taking a mixture of tetrahydrofuran and water as a solvent under the action of tetratriphenylphosphine palladium and potassium carbonate.
The volume ratio of tetrahydrofuran to water as the solvent is (5-15): 1, for example, 10: 1.
In practical operation, in the bromination reaction of 2, 6-dimethylpyranone NBS, a compound I with a mono-substituted bromine group and a compound II with a di-substituted bromine group are obtained simultaneously, and the compound I and the compound II are obtained by separation modes such as conventional column chromatography and the like.
Taking compound a1 as an example, the synthetic route and method are detailed below:
Figure BDA0002722606420000111
carrying out bromination reaction on 2, 6-dimethyl pyrone and N-bromosuccinimide (NBS) at room temperature to obtain a compound I;
then taking 10mmol of compound I and 12mmol of compound C1The method comprises the following steps of mixing tetratriphenylphosphine palladium accounting for 5% of the mass of a compound I, potassium carbonate accounting for 10% of the mass of the compound I, 20mL of tetrahydrofuran and 2mL of water, and reacting for 12 hours at 75-85 ℃ under the nitrogen protection atmosphere. After the reaction is finished, the target compound A is obtained by column chromatography separation and purification1。
Compound A2Reaction according to the first of scheme b), compound II with compound C1Suzuki reaction was performed at a molar ratio of 1: 2.4.
Compound A3Reaction according to the second of scheme b), compound II with compound C1Suzuki reaction was performed at a molar ratio of 1: 1.2.
Compound A4By carrying out the reaction according to scheme a), compounds I and C2Performing Suzuki reaction at a molar ratio of 1: 1.2; compound C2Has the structural formula
Figure BDA0002722606420000121
Compound A5According to the first of route b)Reaction is carried out, compound II and compound C2Suzuki reaction was performed at a molar ratio of 1: 2.4.
Compound A6Reaction according to the second of scheme b), compound II with compound C2Suzuki reaction was performed at a molar ratio of 1: 1.2.
Compound A7By carrying out the reaction according to scheme a), compounds I and C3Performing Suzuki reaction at a molar ratio of 1: 1.2; compound C3Has the structural formula
Figure BDA0002722606420000122
Compound A8Reaction according to the first of scheme b), compound II with compound C3Suzuki reaction was performed at a molar ratio of 1: 2.4.
Compound A9Reaction according to the second of scheme b), compound II with compound C3Suzuki reaction was performed at a molar ratio of 1: 1.2.
Compound A10By carrying out the reaction according to scheme a), compounds I and C4Performing Suzuki reaction at a molar ratio of 1: 1.2; compound C4Has the structural formula
Figure BDA0002722606420000123
Compound A11Reaction according to the first of scheme b), compound II with compound C4Suzuki reaction was performed at a molar ratio of 1: 2.4.
Compound A12Reaction according to the second of scheme b), compound II with compound C 4Suzuki reaction was carried out at a molar ratio of 1: 1.2.
Compound A13By carrying out the reaction according to scheme a), the compounds I and C5Performing Suzuki reaction at a molar ratio of 1: 1.2; compound C5Has the structural formula
Figure BDA0002722606420000131
Compound A14According to the routeb) The first of (1) reacting compound II with compound C5Suzuki reaction was performed at a molar ratio of 1: 2.4.
Compound A15Reaction according to the second of scheme b), compound II with compound C5Suzuki reaction was performed at a molar ratio of 1: 1.2.
The structure of each compound is characterized by nuclear magnetic hydrogen spectrum and mass spectrum, and the compound with the corresponding structure is proved to be prepared. With a compound A2、A5And A8For example, the nuclear magnetic hydrogen spectra are shown in fig. 12 to 14.
Example 1
The embodiment provides a preparation method of a photochromic material, which comprises the following steps:
0.01mmol of Compound A was weighed2And 10mmol of a compound B1Heating benzophenone to 50 deg.C in a container to melt benzophenone and adding compound A2Dissolving, mixing the two uniformly, and naturally cooling to room temperature to obtain the photochromic material.
Example 2
The embodiment provides a preparation method of a photochromic material, which comprises the following steps:
0.01mmol of Compound A was weighed5And 10mmol of a compound B1Heating benzophenone to 50 deg.C in a container to melt benzophenone and compound A5And dissolving, and naturally cooling to room temperature after uniformly mixing the two to obtain the photochromic material.
Example 3
The embodiment provides a preparation method of a photochromic material, which comprises the following steps:
0.01mmol of Compound A was weighed8And 10mmol of a compound B1Heating benzophenone to 50 deg.C in a container to melt benzophenone and adding compound A5Dissolving, mixing the two uniformly, and naturally cooling to room temperature to obtain the photochromic material.
Example 4
The embodiment provides a preparation method of a photochromic material, which comprises the following steps:
0.01mmol of Compound A was weighed2And 10mmol of a compound B24-methylbenzophenone, heating to 60 ℃ in a vessel to melt the 4-methylbenzophenone and reacting compound A2Dissolving, mixing the two uniformly, and naturally cooling to room temperature to obtain the photochromic material.
Example 5
The embodiment provides a preparation method of a photochromic material, which comprises the following steps:
0.01mmol of Compound A was weighed1And 10mmol of a compound B1Heating benzophenone to 50 deg.C in a container to melt benzophenone and adding compound A 1And dissolving, and naturally cooling to room temperature after uniformly mixing the two to obtain the photochromic material.
Example 6
The embodiment provides a preparation method of a photochromic material, which comprises the following steps:
0.01mmol of Compound A was weighed3And 10mmol of a compound B1Heating benzophenone to 50 deg.C in a container to melt benzophenone and adding compound A3Dissolving, mixing the two uniformly, and naturally cooling to room temperature to obtain the photochromic material.
Example 7
The embodiment provides a preparation method of a photochromic material, which comprises the following steps:
0.01mmol of Compound A was weighed4And 10mmol of a compound B1Heating benzophenone to 50 deg.C in a container to melt benzophenone and adding compound A4Dissolving, mixing the two uniformly, and naturally cooling to room temperature to obtain the photochromic material.
Example 8
The embodiment provides a preparation method of a photochromic material, which comprises the following steps:
0.01mmol of Compound A was weighed6And 10mmol of a compound B1Heating benzophenone to 50 deg.C in a container to melt benzophenoneAnd reacting the compound A6Dissolving, mixing the two uniformly, and naturally cooling to room temperature to obtain the photochromic material.
Experimental example 1
To illustrate the photochromic performance of the photochromic material of the present invention, the change of the appearance color of the photochromic material of example 1 before and after different lights is detected, as shown in fig. 1, which is a schematic diagram of the change of the appearance color of the photochromic material of example 1 of the present invention before and after different lights. FIG. 1(a) shows the melting of benzophenone and the addition of Compound A from example 12Photograph when dissolved (not cooled to room temperature) as a clear liquid; naturally cooling to room temperature after 30min, and forming white solid with appearance shown in figure 1 (b); after being irradiated for 30s by ultraviolet light at 360nm, the material turns into red solid, and the appearance is shown in figure 1 (c); after the LED white light lamp was irradiated for 10 seconds, the LED white light lamp was restored to the original white solid state, and the appearance thereof was as shown in fig. 1 (d).
In order to further verify the repeatability of the color change performance of the photochromic material, the photochromic material prepared in the embodiment 1 is taken, the initial ultraviolet absorption of the photochromic material is tested, the ultraviolet absorption of the photochromic material is tested after the photochromic material is irradiated by 360nm ultraviolet light for 30s, the ultraviolet absorption of the photochromic material is tested again after the photochromic material is irradiated by an LED white light for 10s, and the test is alternately repeated for multiple times. The repeatability of the ultraviolet absorption of the photochromic material provided in example 1 in the alternate irradiation process of ultraviolet light and LED white light is shown in fig. 2. As can be seen from fig. 2, the photochromic material of the present invention has good reproducibility.
Experimental example 2
To illustrate the dullness of the photochromic material of the present invention to humidity, etc., the photochromic material of example 1 was tested for its apparent color change before and after different light irradiation in water, as shown in fig. 3, which is a schematic diagram of the change of the apparent color of the photochromic material of example 1 of the present invention before and after different light irradiation in water.
By taking 25 ℃ as an example, after the photochromic material is irradiated by 360nm ultraviolet light for 30s at 25 ℃, the color of the solid is changed from white to red, then the photochromic material is placed in room for 5min under natural light, the color of the solid is kept red, and then the color of the solid is restored from red to white after the photochromic material is irradiated by an LED white light lamp for 10 s. This is because the weak intensity of natural light in a room allows the material to remain in the red state for a certain period of time.
And (3) soaking the photochromic material in water at 25 ℃ for five minutes, and filtering to obtain a sample with high humidity. After the powder in the water is irradiated by 360nm ultraviolet light for 30s, the color of the powder is changed from white to red, then the powder is placed under natural light for 5min, the color of the solid is kept red, and then the color of the solid is restored from red to white after the powder is irradiated by an LED white light for 10 s.
As can be seen from the above, the photochromic material of the present invention has a dull feeling to humidity.
Experimental example 3
Fig. 4 is a graph of the ultraviolet absorption spectrum of the photochromic material provided in example 1 of the present invention before and after different light irradiation. As can be seen from the graph, a new absorption peak was generated at about 530nm after the ultraviolet irradiation, compared to after the ultraviolet irradiation before the ultraviolet irradiation, and the new absorption peak at 530nm disappeared after the LED white light irradiation.
Fig. 5 shows the color change of the pattern written by the photochromic material provided in example 1 of the present invention before and after different light. FIG. 5(a) is a white pattern obtained by heating the photochromic material of example 1 to a molten state and then directly writing and painting the photochromic material on the surface of a substrate as an ink; after irradiation with UV light at 360nm, the appearance was red, as shown in FIG. 5 (b); and then, after the LED white light lamp is adopted for irradiation, the appearance is recovered to be white.
Experimental example 4
The change of the appearance color of the photochromic material of the embodiment 2 before and after different light irradiation is detected, as shown in fig. 6, which is a schematic diagram of the change of the appearance color of the photochromic material of the embodiment 2 of the present invention before and after different light irradiation. FIG. 6 (a) is the appearance of the initial photochromic material of example 2; after the film is irradiated for 30s by ultraviolet light of 360nm, the appearance is red, as shown in FIG. 6 (b); the photochromic material is kept red after being placed under dark condition for 24h, and the appearance is shown in figure 6 (c); then, the LED white lamp was irradiated for 10 seconds, and the LED white lamp was restored to the original white solid state, and the appearance was as shown in fig. 6 (d).
Fig. 7 is a graph of the ultraviolet absorption spectrum of the photochromic material provided in example 2 of the present invention before and after different light irradiations. As can be seen from the graph, a new absorption peak is generated at about 525nm after the ultraviolet irradiation, compared to that after the ultraviolet irradiation before the ultraviolet irradiation, and the new absorption peak at 525nm disappears after the LED white light irradiation.
Fig. 8 is a graph showing the color change of a pattern written by using the photochromic material provided in example 2 of the present invention before and after different light irradiations. FIG. 8(a) is a drawing in which the photochromic material of example 2 is heated to be melted and then directly written and drawn as ink on the surface of a base material, and the appearance is nearly white; after 365nm ultraviolet irradiation, the appearance is red, as shown in fig. 8 (b); and then, after the LED white light lamp is adopted for irradiation, the appearance is restored to be close to white.
Experimental example 5
The change of the appearance color of the photochromic material of the embodiment 3 before and after different light irradiation is detected, as shown in fig. 9, which is a schematic diagram of the change of the appearance color of the photochromic material of the embodiment 3 of the present invention before and after different light irradiation. In FIG. 9 (a) is the appearance of the initial photochromic material of example 3; after irradiating with 360nm ultraviolet light for 2min, the appearance is red, as shown in FIG. 9 (b); the photochromic material remained red after being placed under dark condition for 12h, and the appearance is shown in fig. 9 (c); then, the LED white lamp was irradiated for 10 seconds, and the LED white lamp was returned to the original white solid state, and the appearance was as shown in fig. 9 (d).
Fig. 10 is a graph of the ultraviolet absorption spectrum of the photochromic material provided in example 4 of the present invention before and after different light irradiation. As is clear from the figure, a new absorption peak is generated at about 525nm after the ultraviolet irradiation before the ultraviolet irradiation, compared with after the ultraviolet irradiation, and the new absorption peak at 525nm disappears after the LED white light irradiation.
Similarly, examples 5 to 8 provide photochromic materials having similar effects.
Experimental example 6
The photochromic material of example 1 of the present invention, Compound B, was used separately1Writing a design, examining the photochromic material and compound of example 1 under certain lighting conditionsThe color change of the pattern written by object B1 before and after illumination. Referring specifically to FIG. 11, "CHEMIS" in FIG. 11 is written in the molten state using Compound B1, and "TRY" is written in the molten state using the photochromic material of example 1. "CHEMIS" showed no change in appearance color after irradiation of 360nm UV light, while "TRY" showed a change in pattern color to red after irradiation of 360nm UV light. After the pattern irradiated by the ultraviolet light is irradiated by the LED white light lamp, the color of the 'CHEMIS' pattern is still unchanged, and the color of the 'TRY' pattern is returned to the original color from red.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (15)

1. Photochromic materials, characterized by comprising a compound a and a compound B;
the structural formula of the compound A is as follows:
Figure FDA0003548397240000011
R1selected from H, halogen, substituted or unsubstituted aryl-containing structures; the aryl-containing structure comprises
Figure FDA0003548397240000012
Figure FDA0003548397240000013
Any one of (a);
R2selected from said substituted or unsubstituted aryl-containing structures;
the structural formula of the compound B is as follows:
Figure FDA0003548397240000014
R3and R4Each independently selected from H, F, Cl, Br, I, -OH and-OCH3and-CH3Any one of the above.
2. The photochromic material of claim 1, wherein the structural formula of compound a is selected from any one of the following:
Figure FDA0003548397240000021
3. the photochromic material of claim 1, wherein the aryl-containing structure is selected from
Figure FDA0003548397240000022
Any one of the above.
4. The photochromic material of claim 1 wherein compound B is benzophenone or 4-methylbenzophenone.
5. The photochromic material according to any one of claims 1 to 4, wherein the molar ratio of the compound A to the compound B is 1: 50 to 20000.
6. The photochromic material of any one of claims 1 to 4 wherein the molar ratio of compound A to compound B is 1: 100 to 2000.
7. The photochromic material of any one of claims 1 to 4, wherein the molar ratio of compound A to compound B is 1: 200 to 1000.
8. A process for the preparation of a photochromic material according to any one of claims 1 to 7, characterized in that it comprises the following steps:
the compound B is uniformly mixed with the compound A in a molten state.
9. The method for preparing a photochromic material according to claim 8, wherein the compound B is melted to a molten state under the heating condition of 50 to 60 ℃.
10. The method for preparing a photochromic material according to claim 9, further comprising: and after uniformly mixing, naturally cooling to room temperature.
11. Use of a photochromic material according to any one of claims 1 to 7 in the preparation of an ink and/or ink.
12. Use according to claim 11, wherein the ink is a security printing ink or a writing and painting ink; the ink is anti-counterfeiting printing ink or writing and drawing ink.
13. The use according to claim 12, wherein the photochromic material is heated to a molten state to print or write and draw on the surface of the substrate.
14. Use according to claim 13, wherein the substrate comprises printing paper or filter paper.
15. The use according to claim 13, wherein the printed or written painting develops under the irradiation of ultraviolet light of 300 to 450nm and recovers the color under the irradiation of 500 to 600nm or white light.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
US5011944A (en) * 1988-05-27 1991-04-30 Ciba-Geigy Corporation Substituted α-pyrones
US5068062A (en) * 1988-04-07 1991-11-26 Teijin Limited Reversibly color-changeable materials
JP2006257165A (en) * 2005-03-15 2006-09-28 Bii Son Yun Photochromic ink composition, method for producing the same and method for printing raw fabric by utilizing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5068062A (en) * 1988-04-07 1991-11-26 Teijin Limited Reversibly color-changeable materials
US5011944A (en) * 1988-05-27 1991-04-30 Ciba-Geigy Corporation Substituted α-pyrones
JP2006257165A (en) * 2005-03-15 2006-09-28 Bii Son Yun Photochromic ink composition, method for producing the same and method for printing raw fabric by utilizing the same

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