CN111751336B - Application of D-A type organic doped crystal afterglow material in anti-counterfeiting - Google Patents

Application of D-A type organic doped crystal afterglow material in anti-counterfeiting Download PDF

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CN111751336B
CN111751336B CN201910237924.6A CN201910237924A CN111751336B CN 111751336 B CN111751336 B CN 111751336B CN 201910237924 A CN201910237924 A CN 201910237924A CN 111751336 B CN111751336 B CN 111751336B
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CN111751336A (en
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汪天洋
胡文平
冯文慧
韩江丽
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Tianjin University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6408—Fluorescence; Phosphorescence with measurement of decay time, time resolved fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N2021/6417—Spectrofluorimetric devices

Abstract

The invention discloses an application of a D-A type organic doped crystal afterglow material in anti-counterfeiting, wherein a substance to be determined which does not contain the D-A type organic doped crystal afterglow material is defined as false, a substance to be determined which contains the D-A type organic doped crystal afterglow material is defined as true, when the true or false is judged, the substance to be determined is irradiated by ultraviolet-visible excitation light, and when the substance to be determined emits long afterglow light, the substance to be determined is judged as true; and when the substance to be determined does not emit long afterglow light, determining that the substance to be determined is false. The D-A type organic doped crystal afterglow material can stably show afterglow performance in solid powder, can disappear after being calcined at high temperature, and does not influence the performance of the solid powder.

Description

Application of D-A type organic doped crystal afterglow material in anti-counterfeiting
Technical Field
The invention belongs to the technical field of organic long afterglow crystal materials, and particularly relates to an application of a D-A type organic doped crystal afterglow material in anti-counterfeiting.
Background
Anti-counterfeiting is widely applied in various industries, for example, the authenticity of oil in the petrochemical industry is directly related to the service life of a used instrument or a vehicle; the truth of raw materials in the production industry directly influences the quality of products; the truth of medicine or tobacco industry in life is directly related to the physical health of people; the truth and falseness of pesticide and fertilizer seeds in agricultural production directly relate to the problem of the civilian life, so that the anti-counterfeiting is of great importance. The anti-counterfeiting material is the basis of anti-counterfeiting technology, and the developed anti-counterfeiting material is the key for promoting the progress of the anti-counterfeiting technology.
Long Persistent Luminescence (LPL) material is commonly called noctilucent powder or Long afterglow powder. The anti-counterfeiting material has been developed gradually by applying the principle of irradiation and luminescence. At present, inorganic long afterglow anti-counterfeiting materials and organic long afterglow anti-counterfeiting materials are researched more. The LPL material based on the inorganic system not only needs expensive rare elements, but also has the manufacturing temperature of over 1000 ℃, and high energy consumption, which is not favorable for commercial application.
Compared with inorganic long-afterglow materials, the organic LPL material has attractive application prospects in various high and new technology fields such as biological imaging, optical recording, information storage, anti-counterfeiting systems and the like due to the advantages of low price, simplicity and convenience in synthesis, good biocompatibility, flexibility, easiness in modification of functional groups and the like. However, the pure organic LPL phenomenon can only be observed in severe environments such as ultra-low temperature, oxygen-free, strong ultraviolet illumination, etc., so that the related fields are still in the stage of basic research at present, and meanwhile, the afterglow time of the organic long afterglow material is short, and many materials can not be identified by naked eyes, so that the application of the organic long afterglow material in anti-counterfeiting is limited to a great extent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the application of the D-A type organic doped crystal afterglow material in anti-counterfeiting, the preparation method of the D-A type organic doped crystal afterglow material is simple, the raw materials are cheap and easily available, the conditions are mild, and harsh conditions such as high temperature and high pressure are not needed, the D-A type organic doped crystal afterglow material can emit long afterglow light after being excited by ultraviolet-visible light, the long afterglow light emitting time is long, the long afterglow light emitting time can be recognized by human eyes, and the D-A type organic doped crystal afterglow material is thoroughly decomposed at 530 ℃.
The purpose of the invention is realized by the following technical scheme.
An application of D-A type organic doped crystal afterglow material in anti-counterfeiting.
In the technical scheme, a substance to be determined which does not contain the D-A type organic doped crystal afterglow material is defined as false, a substance to be determined which contains the D-A type organic doped crystal afterglow material is defined as true, when the true or false is judged, the substance to be determined is irradiated by ultraviolet-visible excitation light, and when the substance to be determined emits long afterglow light, the substance to be determined is judged to be true; and when the substance to be determined does not emit long afterglow light, determining that the substance to be determined is false.
In the above technical solution, when the substance to be determined is true, the preparation method of the substance to be determined is: mixing the D-A type organic doped crystal afterglow material and solid powder.
In the technical scheme, the decomposition temperature of the solid powder is more than 550 ℃.
In the technical scheme, after the authenticity is judged, when the substance to be determined is true, the temperature of the substance to be determined is raised to decompose the D-A type organic doped crystal afterglow material in the substance to be determined, wherein the temperature of the substance to be determined is higher than or equal to 530 ℃ and lower than the decomposition temperature of the solid powder.
In the above technical scheme, the D-A type organic doped crystal afterglow material is: the receptor material A forms regular flaky crystals, the donor material D is freely dispersed in the crystals of the receptor material A,
the structural formula of the receptor material A is as follows:
Figure GDA0003156819790000021
the structural formula of the donor material D is as follows:
Figure GDA0003156819790000022
wherein, R is1And R2All have the structural formulas
Figure GDA0003156819790000023
Figure GDA0003156819790000031
In the above technical solution, R is1And R2The structural formula is the same.
In the technical scheme, the preparation method of the D-A type organic doped crystal afterglow material comprises the following steps:
uniformly mixing a donor material D and an acceptor material A to obtain solid powder, adding the solid powder into absolute ethyl alcohol to obtain a suspension, carrying out ultrasonic treatment on the suspension for 1-2 min, standing the suspension for 1-3 hours at room temperature of 20-25 ℃ in an atmospheric environment, wherein crystals generated at the bottom of the liquid are the D-A type organic doped crystal afterglow material, and the ratio of the donor material D to the acceptor material A is (0.5-10): 100 in terms of molar amount; the concentration of solid powder in the suspension was 10 mg/mL.
In the technical scheme, after standing at room temperature of 20-25 ℃ in an atmospheric environment, centrifuging a solution containing the crystal, washing the crystal with ethanol after centrifugation, and drying at room temperature of 20-25 ℃.
The D-A type organic long afterglow luminescent composite material provided by the invention can be excited by ultraviolet-visible light and has better afterglow luminescent performance, the D-A type organic long afterglow luminescent composite material can form a regular crystal morphology, the rest afterglow performance belongs to the best one in the crystal afterglow materials, the afterglow time of the current crystal afterglow material is mostly less than 2s, the afterglow time of the D-A type organic doped crystal afterglow luminescent material exceeds 3s, and the time improvement is very beneficial to the application of the organic crystalline LPL material.
The D-A type organic doped crystal afterglow material can stably show afterglow performance in solid powder, can disappear after being calcined at high temperature, and does not influence the performance of the solid powder.
Drawings
FIG. 1(a) is a photomicrograph of a D-A type organic doped crystalline after-glow material in example 1;
FIG. 1(a-1) is a photomicrograph of a single crystal of the D-A type organic doped crystalline afterglow material of example 1;
FIG. 1(b) is a polarizing microscope photograph of the D-A type organic doped crystal afterglow material of example 1;
FIG. 1(b-1) is a polarization microscope photograph of a single crystal of the D-A type organic doped crystalline afterglow material of example 1;
FIG. 1(c) is a SEM picture of a D-A type organic doped crystalline afterglow material of example 1;
FIGS. 1(c-1) to 1(c-5) are SEM-EDS pictures of D-A type organic doped crystal afterglow materials of example 1;
FIG. 2(a) is a microscope picture (in an excited state) of the D-A type organic doped crystal afterglow material of example 1;
FIG. 2(b) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 1;
FIG. 2(c) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 1;
FIG. 2(D) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 1;
FIG. 2(e) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 1;
FIG. 2(f) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 1;
FIG. 2(g) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 1;
FIG. 2(h) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 1;
FIG. 3 is an afterglow performance decay spectrum of D-A type organic doped crystal afterglow material of example 1;
FIG. 4(a) is a photograph (in an excited state) of a second substance in example 1;
FIG. 4(b) is a photograph (in an afterglow state) of a second substance in example 1;
FIG. 4(c) is a photograph (in an afterglow state) of a second substance in example 1;
FIG. 4(d) is a photograph (in an afterglow state) of a second substance in example 1;
FIG. 4(e) is a photograph (in an afterglow state) of a second substance in example 1;
FIG. 4(f) is a photograph (in an afterglow state) of a second substance in example 1;
FIG. 5(a) is a microscope picture of D-A type organic doped crystal afterglow material of example 2;
FIG. 5(b) is a microscope picture (in excited state) of the D-A type organic doped crystal afterglow material of example 2;
FIG. 5(c) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 2;
FIG. 5(D) is a microscope photograph of the D-A type organic doped crystal afterglow material of example 2 (in afterglow state);
FIG. 5(e) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 2;
FIG. 5(f) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 2;
FIG. 6(a) is a photograph (in an excited state) of a second substance in example 2;
FIG. 6(b) is a photograph (in an afterglow state) of a second substance in example 2;
FIG. 6(c) is a photograph (in an afterglow state) of a second substance in example 2;
FIG. 6(d) is a photograph (in an afterglow state) of a second substance in example 2;
FIG. 7(a) is a microscope photograph of the D-A type organic doped crystal afterglow material of example 3;
FIG. 7(b) is a microscope picture (in excited state) of the D-A type organic doped crystal afterglow material of example 3;
FIG. 7(c) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 3;
FIG. 7(D) is a microscope photograph of the D-A type organic doped crystal afterglow material of example 3 (in afterglow state);
FIG. 7(e) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 3;
FIG. 7(f) is a microscope photograph (in afterglow state) of the D-A type organic doped crystal afterglow material of example 3;
FIG. 8(a) is a photograph (in an excited state) of a second substance in example 3;
FIG. 8(b) is a photograph (in an afterglow state) of a second substance in example 3;
FIG. 8(c) is a photograph (in an afterglow state) of a second substance in example 3;
FIG. 8(d) is a photograph (in an afterglow state) of a second substance in example 3;
FIG. 9(a) is a thermogram of donor material D in example 1;
FIG. 9(b) is a thermogram of the acceptor material A in example 1;
FIG. 9(c) is a thermogram of a D-A type organic doped crystalline afterglow material of example 1;
FIG. 10 is TiO2And the second one in example 1XRD after the temperature of the substance is raised;
FIG. 11 is TiO2And XRD after temperature increase of the second material in example 2;
FIG. 12 is a thermogram of a D-A type organic doped crystalline afterglow material of example 2;
FIG. 13 is TiO2And XRD after temperature increase of the second material in example 3;
FIG. 14 is a thermogram of a D-A type organic doped crystalline afterglow material of example 3.
Detailed Description
Sources of drugs
The route references for the synthesis of donor materials D (W, 2M-W and 4M-W) are: near UVevis LED-explicit two-branched sensitizers for cationic, radial, and thiol-ene photopolymerization, Dyes and Pigments 126(2016) 54-61;
the supplier of the receptor material A (PPT) was: beijing YinuoKai Tech Co Ltd (purity: 97%)
The applicant has applied for invention patent to D-A type organic doped crystal afterglow material, the name of the invention is: the D-A type organic doped crystal afterglow material capable of being excited by ultraviolet-visible light and its preparation process have the application number: 2018110842748, filing date: year 2018, month 9, and day 17.
Titanium dioxide powder was purchased from: the commodity is purchased from enoki.
The instruments and models involved were tested in the following examples:
leica DM2700M functional optical microscope
Nikon Eclipse Ci-POL polarizing microscope
Hitachi super high resolution SU8010 field emission scanning electron microscope
Ocean optical multi-band spectrometer
The D-A type organic doped crystal afterglow material can be excited by ultraviolet-visible light.
In the following examples, after standing at room temperature in an atmospheric environment of 20 to 25 ℃, the solution containing the crystals was centrifuged, the crystals were washed with ethanol after centrifugation, and dried at room temperature of 20 to 25 ℃ for 3 hours, and the obtained crystals were used for the following tests.
In the following examples, parts by mass are in mg and parts by volume are in mL.
The technical scheme of the invention is further explained by combining specific examples.
Example 1:
the application of D-A type organic doped crystal afterglow material in anti-counterfeiting is characterized in that the D-A type organic doped crystal afterglow material in the embodiment is formed by that an acceptor material A forms regular flaky crystals, a donor material D is uniformly and freely dispersed in the flaky crystals of the acceptor material A, and the preparation method of the D-A type organic doped crystal afterglow material comprises the following steps:
uniformly mixing a donor material D (W) and an acceptor material A (PPT) to obtain solid powder, adding the solid powder into absolute ethyl alcohol to obtain suspension, carrying out ultrasonic treatment on the suspension for 1min, standing for 1 h at room temperature of 20-25 ℃ in an atmospheric environment, and obtaining D-A type organic doped crystal afterglow material (W/PPT) as crystals generated at the bottom of the liquid, wherein the ratio of the donor material D to the acceptor material A is 1:100 by mol ratio; the concentration of solid powder in the suspension was 10 mg/mL.
The structural formula of the receptor material A is as follows:
Figure GDA0003156819790000061
the structural formula of the donor material D is:
Figure GDA0003156819790000062
wherein R is1And R2All have the structural formulas
Figure GDA0003156819790000063
The reaction formula of the preparation method in example 1 is as follows:
Figure GDA0003156819790000064
regular cuboid crystals can be clearly seen through an optical microscope and a polarimetric microscope in FIGS. 1(a) and 1(b), and the sizes are relatively uniform, so that the D-A type organic doped crystal afterglow material obtained in example 1 is proved to be in a crystal structure. FIG. 1(a) is a microphotograph of D-A type organic doped crystal afterglow material, wherein the crystal is a square or rectangular plate crystal, and the side surface of the crystal demonstrates two-dimensional layered accumulation of the D-A type organic doped crystal afterglow material; FIG. 1(a-1) is a photomicrograph of a single crystal, approximately 100 μm or so in size; FIGS. 1(b) and 1(b-1) are polarized microscope photographs of a single D-A type organic doped crystal afterglow material crystal, demonstrating that the prepared D-A type organic doped crystal afterglow material is a single crystal; from the characterization of SEM-EDS, five elements of C (shown in FIG. 1C-1), O (shown in FIG. 1C-2), P (shown in FIG. 1C-3), S (shown in FIG. 1C-4), and N (shown in FIG. 1C-5) can be detected, which indicates that the donor material D has been uniformly doped into the acceptor material A and forms better doped crystals.
As can be seen from fig. 2a in the fluorescence microscope, when 365nm violet light irradiates the D-a type organic doped crystal afterglow material of the present invention, the fluorescence color emitted by the crystal is bluish blue (as in fig. 2a), the crystal material emits a green afterglow light (as in fig. 2b) after the light source is removed, the afterglow luminance of the D-a type organic doped crystal afterglow material is stronger in the first 3s (as in fig. 2c representing 1 st s, fig. 2D representing 2s, and fig. 2e representing 3s), the afterglow luminance gradually decreases after 4s (as in fig. 2 f), and is not obvious after 5s (as in fig. 2g) and 6s (as in fig. 2h), and the afterglow of the D-a type organic doped crystal afterglow material still has a visually recognizable afterglow light after 6s of the light source is removed.
FIG. 3 is an afterglow performance decay spectrum of the D-A type organic doped crystal afterglow material obtained in example 1, and it can be known from the graph that decay spectrum tests are performed under different powers, and the test results are similar (the power of the test in FIG. 3 is 100mW), which shows that the relationship between the afterglow time and the power of the D-A type organic doped crystal afterglow material is not large, the power only affects the afterglow luminance of the compound, and it can be seen from FIG. 3 that the afterglow decay time can reach about 3 s. Further illustrates that the D-A type organic doped crystal afterglow material has good afterglow performance.
The following two substances were prepared for comparison as substances to be determined:
a first substance: titanium dioxide powder;
second method for obtaining substance (preparation method): mixing the D-A type organic doped crystal afterglow material and titanium dioxide (solid powder), wherein the ratio of the D-A type organic doped crystal afterglow material to the titanium dioxide is 1:5 in parts by mass.
Defining a substance to be determined which does not contain the D-A type organic doped crystal afterglow material as false, defining the substance to be determined which contains the D-A type organic doped crystal afterglow material as true, irradiating the substance to be determined with 405nm purple excitation light when judging the true or false, and judging the substance to be determined as true when the substance to be determined emits long afterglow light; and when the substance to be determined does not emit long afterglow light, determining that the substance to be determined is false.
When the first substance was irradiated with 405nm violet excitation light (excitation intensity of 75mW), the first substance appeared yellowish brown, and it could be judged that the substance to be determined was false.
When the second substance is irradiated by 405nm purple excitation light (the excitation intensity is 75mW), the fluorescence emitted by the second substance is blue (as shown in FIG. 4 a); at 1 st s after the purple excitation light is removed, the second substance emits a strong green afterglow light (as shown in FIG. 4 b); at 2s after the purple excitation light is removed, the second substance emits a very bright afterglow light (as shown in FIG. 4 c); 3s after the purple excitation light is removed, the second substance emits a afterglow light with still strong brightness (as shown in FIG. 4 d); 5s after the purple excitation light is removed, the second substance emits a afterglow light with still strong brightness (as shown in FIG. 4 e); at 6s after the removal of the violet excitation light, the second substance glows with diminished afterglow light but still has a visually recognizable intensity (as shown in FIG. 4 f), and thus the substance to be determined can be determined to be authentic.
After the authenticity is judged, the temperature of the second substance is raised to 550 ℃ so as to decompose the D-A type organic doped crystal afterglow material in the second substance. XRD characterization of the heated second material (as shown in curve b in FIG. 10) from the results of XRD characterization, it can be seen that the second material was heatedCrystal form of and TiO2(Curve a in FIG. 10) does not change at all, indicating that this temperature does not affect the TiO2And the D-A type organic doped crystal afterglow material is completely decomposed.
FIG. 9(a) is the thermogram of the donor material D, FIG. 9(b) is the thermogram of the acceptor material A, FIG. 9(c) is the thermogram of the D-A type organic doped crystal after-glow material in example 1, and from the thermogravimetric test data, the decomposition temperature of the donor material D is 317 deg.C (as in FIG. 9a), the decomposition temperature of the acceptor material A is 437 deg.C (as in FIG. 9b), and the D-A type organic doped crystal after-glow material is completely decomposed at 530 deg.C (as in FIG. 9c), which is significantly reduced compared with the inorganic long after-glow material.
Example 2
The D-A type organic doped crystal afterglow material consists of acceptor material A forming regular flaky crystal and donor material D dispersed homogeneously and freely between the flaky crystal of the acceptor material A. The preparation method of the D-A type organic doped crystal afterglow material (2M-W/PPT) comprises the following steps:
uniformly mixing a donor material D (2M-W) and an acceptor material A (PPT) to obtain solid powder, adding the solid powder into absolute ethyl alcohol to obtain suspension, carrying out ultrasonic treatment on the suspension for 2min, standing for 3 hours at room temperature of 20-25 ℃ in an atmospheric environment, wherein crystals generated at the bottom of the liquid are D-A type organic doped crystal afterglow materials (2M-W/PPT), and the ratio of the donor material D to the acceptor material A is 1:100 in molar ratio; the concentration of solid powder in the suspension was 10 mg/mL.
The structural formula of the receptor material A is as follows:
Figure GDA0003156819790000081
the structural formula of the donor material D is:
Figure GDA0003156819790000082
wherein R is1And R2All have the structural formulas：
Figure GDA0003156819790000091
The reaction formula of the preparation method in example 2 is as follows:
Figure GDA0003156819790000092
from the optical microscope (as shown in FIG. 5 a), it can be seen that in example 2, the crystals of the D-A type organic doped crystal afterglow material are plate-shaped crystals, when the D-A type organic doped crystal afterglow material is irradiated by a 365nm violet excitation light source, the fluorescence emitted by the crystals of the D-A type organic doped crystal afterglow material is blue (as shown in FIG. 5 b), the crystals of the D-A type organic doped crystal afterglow material emit green afterglow light (as shown in FIG. 5 c) after the excitation light source is removed, when the 1 st s of the excitation light source is removed, the afterglow luminance of the D-A type organic doped crystal afterglow material is strong (as shown in FIG. 5D), when the 3 rd s of the excitation light source is removed (as shown in FIG. 5 e), and when the 4 th s of the excitation light source is removed (as shown in FIG. 5 f).
The following two substances were prepared for comparison as substances to be determined:
a first substance: titanium dioxide powder;
second method for obtaining substance (preparation method): mixing the D-A type organic doped crystal afterglow material and titanium dioxide (solid powder), wherein the ratio of the D-A type organic doped crystal afterglow material to the titanium dioxide is 1:5 in parts by mass.
Defining a substance to be determined which does not contain the D-A type organic doped crystal afterglow material as false, defining the substance to be determined which contains the D-A type organic doped crystal afterglow material as true, irradiating the substance to be determined with 405nm purple excitation light when judging the true or false, and judging the substance to be determined as true when the substance to be determined emits long afterglow light; and when the substance to be determined does not emit long afterglow light, determining that the substance to be determined is false.
When the first substance was irradiated with 405nm violet excitation light (excitation intensity of 75mW), the first substance appeared yellowish brown, and it could be judged that the substance to be determined was false.
When the second substance is irradiated with 405nm violet excitation light (excitation intensity is 75mW), the second substance emits blue fluorescence (as shown in FIG. 6 a), and the second substance emits a strong green afterglow light (as shown in FIG. 6 b) at 1 st s after the violet excitation light is removed; at 2s after the purple excitation light is removed, the second substance emits a very bright afterglow light (as shown in FIG. 6 c); at 4s after the purple excitation light is removed, the afterglow light emitted from the second substance disappears and still has a visually recognizable intensity (as shown in FIG. 6 d), and thus the substance to be determined can be determined to be true.
After the authenticity is judged, the temperature of the second substance is raised to 550 ℃ so as to decompose the D-A type organic doped crystal afterglow material in the second substance. XRD characterization is carried out on the second substance after temperature rise (as shown in a curve b in figure 11), and from the XRD characterization result, the crystal form and TiO of the second substance after heating can be seen2(Curve a in FIG. 11) does not change at all, indicating that this temperature does not affect the TiO2And the D-A type organic doped crystal afterglow material is completely decomposed.
FIG. 12 is a thermogravimetric graph of the D-A type organic doped crystal afterglow material, and from the thermogravimetric test data, the D-A type organic doped crystal afterglow material decomposes completely at 530 ℃, which is significantly reduced compared with the inorganic long afterglow material.
Example 3
The D-A type organic doped crystal afterglow material consists of acceptor material A forming regular flaky crystal and donor material D dispersed homogeneously and freely between the flaky crystal of the acceptor material A. The preparation method of the D-A type organic doped crystal afterglow material comprises the following steps:
uniformly mixing a donor material D (4M-W) and an acceptor material A (PPT) to obtain solid powder, adding the solid powder into absolute ethyl alcohol to obtain suspension, carrying out ultrasonic treatment on the suspension for 2min, standing for 3 hours at room temperature of 20-25 ℃ in an atmospheric environment, wherein crystals generated at the bottom of the liquid are D-A type organic doped crystal afterglow materials (4M-W/PPT), and the ratio of the donor material D to the acceptor material A is 1:100 in molar ratio; the concentration of solid powder in the suspension was 10 mg/mL.
The structural formula of the receptor material A is as follows:
Figure GDA0003156819790000101
the structural formula of the donor material D is:
Figure GDA0003156819790000102
wherein R is1And R2All have the structural formulas
Figure GDA0003156819790000103
The reaction formula of the preparation method of the D-A type organic doped crystal afterglow material in the embodiment 3 is as follows:
Figure GDA0003156819790000111
from the optical microscope (as shown in FIG. 7 a), it can be seen that in example 3, the crystals of the D-A type organic doped crystal afterglow material are plate-shaped crystals, when the D-A type organic doped crystal afterglow material is irradiated by a 365nm purple excitation light source, the fluorescence emitted by the crystals of the D-A type organic doped crystal afterglow material is blue (as shown in FIG. 7 b), the crystals of the D-A type organic doped crystal afterglow material emit green afterglow light (as shown in FIG. 7 c) after the excitation light source is removed, the afterglow luminance of the D-A type organic doped crystal afterglow material is stronger at 1s after the excitation light source is removed (as shown in FIG. 7D), the afterglow of the D-A type organic doped crystal afterglow material is darker at 3s after the excitation light source is removed (as shown in FIG. 7 e), and the afterglow of the D-A type organic doped crystal afterglow material gradually disappears at 4s after the excitation light source is removed (as shown in FIG. 7 b) but still can be seen with naked eyes f shown).
The following two substances were prepared for comparison as substances to be determined:
a first substance: titanium dioxide powder;
second method for obtaining substance (preparation method): mixing the D-A type organic doped crystal afterglow material and titanium dioxide (solid powder), wherein the ratio of the D-A type organic doped crystal afterglow material to the titanium dioxide is 1:5 in parts by mass.
Defining a substance to be determined which does not contain the D-A type organic doped crystal afterglow material as false, defining the substance to be determined which contains the D-A type organic doped crystal afterglow material as true, irradiating the substance to be determined with 405nm purple excitation light when judging the true or false, and judging the substance to be determined as true when the substance to be determined emits long afterglow light; and when the substance to be determined does not emit long afterglow light, determining that the substance to be determined is false.
When the first substance was irradiated with 405nm violet excitation light (excitation intensity of 75mW), the first substance appeared yellowish brown, and it could be judged that the substance to be determined was false.
When the second substance is irradiated with 405nm violet excitation light (excitation intensity is 75mW), the second substance emits blue fluorescence (as shown in FIG. 8 a), and the second substance emits a strong green afterglow light (as shown in FIG. 8 b) at 1 st s after the violet excitation light is removed; at 2s after the purple excitation light is removed, the second substance emits a very bright afterglow light (as shown in FIG. 8 c); at 4s after the purple excitation light is removed, the afterglow light emitted from the second substance disappears and still has a visually recognizable intensity (as shown in FIG. 8 d), and thus the substance to be determined can be determined to be true.
After the authenticity is judged, the temperature of the second substance is raised to 550 ℃ so as to decompose the D-A type organic doped crystal afterglow material in the second substance. XRD characterization of the heated second material (as shown in curve b in FIG. 13) from the results of XRD characterization, it can be seen that the crystal form of the heated second material is in contact with TiO2(Curve a in FIG. 13) does not change at all, indicating that this temperature does not affect the TiO2And the D-A type organic doped crystal afterglow material is completely decomposed.
FIG. 14 is a thermogravimetric graph of the D-A type organic doped crystal afterglow material, and from the thermogravimetric test data, the D-A type organic doped crystal afterglow material decomposes completely at 530 ℃, which is significantly reduced compared with the inorganic long afterglow material.
In the solution of the invention, the ratio of the amounts of the substances of the donor material D and the acceptor material A and R are adjusted1And R2The structural formula of (c) can achieve the same technical effects as the above embodiments.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (8)

1. The application of the D-A type organic doped crystal afterglow material in anti-counterfeiting is characterized in that a substance to be determined, which does not contain the D-A type organic doped crystal afterglow material, is defined as false, a substance to be determined, which contains the D-A type organic doped crystal afterglow material, is defined as true, when the true or false is judged, the substance to be determined is irradiated by ultraviolet-visible excitation light, and when the substance to be determined emits long afterglow light, the substance to be determined is judged to be true; when the substance to be determined does not emit long afterglow light, determining that the substance to be determined is false; the D-A type organic doped crystal afterglow material comprises the following components: the receptor material A forms regular flaky crystals, the donor material D is freely dispersed in the crystals of the receptor material A,
the structural formula of the receptor material A is as follows:
Figure FDA0003078486270000011
the structural formula of the donor material D is as follows:
Figure FDA0003078486270000012
wherein, R is1And R2All have the structural formulas
Figure FDA0003078486270000013
2. Use according to claim 1, characterized in that, when the substance to be determined is authentic, it is prepared by: mixing the D-A type organic doped crystal afterglow material and solid powder.
3. Use according to claim 2, wherein the solid powder has a decomposition temperature of greater than 550 ℃.
4. The use according to claim 3, wherein after the authenticity is judged, when the substance to be determined is true, the temperature of the substance to be determined is raised to decompose the D-A type organic doped crystal afterglow material in the substance to be determined, wherein the temperature of the raised substance to be determined is not less than 530 ℃ and less than the decomposition temperature of the solid powder.
5. The use according to claim 4, characterized in that the preparation method of the D-A type organic doped crystalline after-glowing material comprises the following steps:
and uniformly mixing the donor material D and the acceptor material A to obtain solid powder, adding the solid powder into absolute ethyl alcohol to obtain a suspension, carrying out ultrasonic treatment on the suspension for 1-2 min, standing for 1-3 hours at room temperature of 20-25 ℃ in an atmospheric environment, and obtaining the D-A type organic doped crystal afterglow material as crystals generated at the bottom of the liquid.
6. The use according to claim 5, wherein the ratio of donor material D to acceptor material A is (0.5-10): 100, on a molar basis.
7. Use according to claim 6, wherein the concentration of solid powder in the suspension is 10 mg/mL.
8. The use according to claim 7, wherein the solution containing the crystals is centrifuged after being left to stand at room temperature in an atmospheric environment of 20 to 25 ℃, and the crystals are washed with ethanol after being centrifuged and dried at room temperature of 20 to 25 ℃.
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