Organic phosphorescent compound and composite material and preparation method thereof
By doping organic phosphorescent compounds R–G–Bpin with π-conjugated aromatic or heteroaromatic skeletons into a polymer matrix, organic phosphorescent materials with long-lifetime room temperature phosphorescence properties were prepared, solving the problems of high cost and toxicity of traditional heavy metal phosphorescent materials. This enabled the preparation of efficient and tunable phosphorescent materials, which are suitable for anti-counterfeiting labels, information encryption and other fields.
Patent Information
- Application Number
- CN202511073723.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-01
- Publication Date
- 2025-11-11
AI Technical Summary
Traditional heavy metal complex phosphorescent materials are expensive, highly toxic, and have poor environmental adaptability. Furthermore, their phosphorescence emission efficiency and lifespan in air are limited, making it difficult to meet the needs of large-scale applications.
Organic room temperature phosphorescent composites are prepared by incorporating R–G–Bpin, an organic phosphorescent compound with a π-conjugated aromatic or heteroaromatic skeleton, into a polymer matrix and then preparing the composite material by solution casting or melt blending. In the material, R is a linking group, Bpin is a pinacol boryl ester group, and G is an aromatic skeleton such as carbazole or indole.
It achieves a room temperature phosphorescence lifetime of more than 2 seconds in air ranging from blue to cyan, has tunable structure, is environmentally friendly, easy to prepare, and is suitable for large-scale production.
Smart Images
Figure CN120923528A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic photofunctional materials technology, and particularly relates to a class of organic phosphorescent compounds and their composite materials and preparation methods. Background Technology
[0002] In recent years, organic room temperature phosphorescence (ORTP) materials have become an important research direction in organic light-emitting materials due to their broad potential in fields such as anti-counterfeiting, information encryption, bioimaging, and flexible optoelectronic devices. However, traditional phosphorescent materials mostly rely on heavy metal complexes (such as iridium and platinum), which are costly, highly toxic, and have poor environmental adaptability, limiting their large-scale application. Therefore, developing purely organic, processable, and structurally tunable room temperature phosphorescent materials has significant scientific and practical application value.
[0003] Aromatic molecules such as carbazole, indole, dibenzofuran, and dibenzothiophene are often used as parent nuclei in ORTP design due to their strong conjugation and high triplet energy levels. However, their phosphorescence emission efficiency and lifetime are limited at room temperature in air. In recent years, some studies have attempted to enhance phosphorescence efficiency by introducing hydrogen bonds, rigid groups, and polar groups to promote intersystem crossing (ISC) and triplet stability; however, the effects have remained limited. Therefore, significantly enhancing the room-temperature phosphorescence performance and extending the lifetime of materials remains a problem that needs to be solved. Summary of the Invention
[0004] The purpose of this invention is to develop a class of organic phosphorescent materials with room temperature phosphorescence properties and long-lifetime luminescence capability, as well as their preparation methods and applications.
[0005] To achieve the above objectives, the present invention provides the following technical solution: In a first aspect, the present invention provides an organic phosphorescent compound, the general structural formula of which is: R–G–Bpin; In the general structural formula, the G group is an aromatic or heteroaromatic skeleton with a π-conjugated structure, and the aromatic or heteroaromatic skeleton is one of carbazole, indole, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzimazole, benzothiazole, benzothiphene-pyrazole, benzoxazole, benzothiadiazole, carbazole-pyridine, phenanthrene, fluorene, benzene, biphenyl, and terphenyl. The R group is a linking group, which is a single bond, –CH2–, –NH–, –CO–, –CH=CH–, or –C. n H 2n+1 One of them; The Bpin group is pinacol boryl ester or other borate ester group, and the Bpin is attached to any or more sites on the aromatic ring or heteroaromatic ring of the G group.
[0006] Preferably, G is one of carbazole, indole, benzimidazole or benzothiazole; The G group contains 1 to 3 substituents, which are hydrogen, C1–C 16 One of alkyl, alkoxy, halogen, cyano, carboxyl, amino, amide, or sulfonyl groups.
[0007] Preferably, the organophosphorescent compound has one of the following structural formulas:
[0008] .
[0009] Secondly, the present invention provides an organic room temperature phosphorescent composite material with a long lifespan, the organic room temperature phosphorescent composite material comprising one or more combinations of organic phosphorescent compounds as described in any one of claims 1-3 and a polymer matrix; The organic phosphorescent compound is doped into the polymer matrix at a mass ratio of 1:10-10000; The polymer matrix is one of polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, polyurethane, polyamide, polycarbonate or copolymers thereof, as well as rubber and elastomer materials.
[0010] Preferably, the long lifetime refers to the lifetime of the organic room temperature phosphorescent composite material emitting blue to cyan room temperature phosphorescence in room temperature air after emitting fluorescence under 254-365 nm ultraviolet excitation and then turning off ultraviolet irradiation, which is greater than or equal to 0.6 seconds.
[0011] Preferably, the organic room temperature phosphorescent composite material includes organic room temperature phosphorescent composite material a prepared by solution casting film formation method and organic room temperature phosphorescent composite material b prepared by melt blending process; The preparation method of the organic room temperature phosphorescent composite material a obtained by the solution casting film formation method includes the following steps: (1) Dissolve one or more of the organophosphorescent compounds in an organic solvent to obtain a first solution; (2) Dissolve the polymer matrix in water to obtain a second solution; (3) Add the first solution dropwise to the second solution at a mass ratio of 1:10-10000, and stir until homogeneous to obtain a mixed solution; (4) The mixture is applied to the substrate by coating, casting, spin coating or spraying, and dried and cured to obtain organic room temperature phosphorescent composite material a; The preparation method of the organic room temperature phosphorescent composite material b obtained by the melt blending process includes the following steps: (a) Premixing one or more of the organophosphorescent compounds and the polymer matrix at a mass ratio of 1:10-10000 to obtain a premix; (b) The premix is placed in an extruder, internal mixer or twin-screw mixing equipment and melt-blended at a polymer softening or melting temperature to obtain a melt blend; (c) The melt blend is processed by extrusion, injection molding, calendering, blown film or hot pressing to obtain organic room temperature phosphorescent composite material b.
[0012] Thirdly, the present invention provides the application of the organic room temperature phosphorescent composite material in the preparation of anti-counterfeiting label materials, information encryption materials, ultraviolet-responsive display devices, visual label materials, data storage materials, bioimaging materials, 3D printing materials or flexible optoelectronic devices.
[0013] Fourthly, the present invention provides a method for preparing an organic room temperature phosphorescent composite material, the method comprising a solution casting film formation method and a melt blending processing method; The steps of the solution casting film formation method are as follows: (1) Dissolve one or more of the organophosphorescent compounds as described in any one of claims 1-3 in an organic solvent to obtain a first solution; (2) Dissolve the polymer matrix in water to obtain a second solution; (3) Add the first solution dropwise to the second solution at a mass ratio of 1:10-10000, and stir until homogeneous to obtain a mixed solution; (4) The mixture is applied to the substrate by coating, casting, spin coating or spraying, and dried and cured to obtain organic room temperature phosphorescent composite material a; The steps of the melt blending process are as follows: (a) Premixing one or more of the organophosphorescent compounds as described in any one of claims 1-3 with a polymer matrix at a mass ratio of 1:10-10000 to obtain a premix; (b) The premix is placed in an extruder, internal mixer or twin-screw mixing equipment and melt-blended at a polymer softening or melting temperature to obtain a melt blend; (c) The melt blend is processed by extrusion, injection molding, calendering, blown film or hot pressing to obtain organic room temperature phosphorescent composite material b.
[0014] Preferably, in the solution casting film-forming method and the melt blending processing method, the polymer matrix is one of polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, polyurethane, polyamide, polycarbonate or copolymers thereof, as well as rubber and elastomer materials.
[0015] The beneficial effects of this invention are as follows: (1) The organic phosphorescent compound disclosed in this invention, when doped into a polymer matrix, can exhibit blue to cyan-blue room temperature phosphorescence under air and room temperature conditions, and has a long phosphorescence lifetime, greater than 2 seconds, preferably 3 to 6 seconds. This breaks through the bottleneck of limited phosphorescence efficiency and lifetime of traditional organic phosphorescent materials in air, making it more feasible in practical applications.
[0016] (2) The compound of the present invention, with the general formula RG–Bpin, has a high degree of structural tunability. By changing the connection sites of the π-conjugated aromatic or heteroaromatic core (G), the linking group (R), and the pinacol boryl ester group (Bpin), the orbital polarity and excited state behavior of the molecule can be flexibly adjusted, thereby achieving precise control of phosphorescence wavelength, lifetime, and emission intensity to meet the needs of different applications.
[0017] (3) Compared with traditional phosphorescent materials that rely on heavy metal complexes, this invention uses a pure organic molecular system, which does not contain metals and is environmentally friendly. At the same time, its preparation method is simple, and it can be prepared by solution casting or melt blending. The process is simple and conducive to large-scale production and industrial application.
[0018] In summary, this invention addresses the problems of high cost, high toxicity, and poor environmental adaptability of existing room-temperature phosphorescent materials, while providing a high-performance, structurally tunable, easily prepared, and environmentally friendly organic phosphorescent material, thus opening up a new direction for the development of organic photofunctional materials. Attached Figure Description
[0019] Figure 1 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the 1-position Bpin carbazole-doped PVA material; Figure 2 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the 2-position Bpin carbazole-doped PVA material; Figure 3 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the 3-position Bpin carbazole-doped PVA material; Figure 4 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the 4-position Bpin carbazole-doped PVA material; Figure 5The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the 3-position Bpin dibenzofuran-doped PVA material; Figure 6 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the 3-position Bpin dibenzothiophene-doped PVA material; Figure 7 The fluorescence emission spectrum (left) and phosphorescence emission spectrum (right) of the 5-position Bpin indole-doped PVA material; Figure 8 The phosphorescence emission spectra of organic room-temperature phosphorescent materials prepared with different doping ratios are shown. Figure 9 Phosphorescence lifetime diagrams of organic room-temperature phosphorescent materials prepared with different doping ratios are shown. Figure 10 The figure shows the phosphorescence effect of the organic room temperature phosphorescent materials prepared in Examples 1-7. Figure 11 The figure shows the phosphorescence lifetime of the organic room temperature phosphorescent materials prepared in Examples 1-7. Figure 12 An example diagram illustrating the application of a programmable tag with room-temperature phosphorescence properties; Figure 13 This is a picture of an organic room temperature phosphorescent film anti-counterfeiting product. Detailed Implementation
[0020] The technical solution of the present invention will be described in detail below with reference to several specific embodiments. It should be emphasized that the scope of protection of the present invention is not limited to the specific details described in these embodiments. Any equivalent substitutions, improvements, or modifications made based on the basic principles of the present invention should be included within the scope of protection of the present invention. Furthermore, those skilled in the art can make appropriate adjustments and extensions to the technical solution according to actual needs without departing from the core idea of the present invention, and all such adjustments and extensions fall within the scope of the present invention.
[0021] Example 1 Preparation of blue phosphorescent film by 1-position Bpin carbazole doping of PVA The organophosphorescent compound is 1-position Bpin carbazole, and its structural formula is shown in Formula 1 below:
[0022] Formula 1 The polymer matrix is polyvinyl alcohol (PVA).
[0023] The preparation method of the blue phosphorescent film 1 is as follows: (1) Weigh 1 g of polyvinyl alcohol (PVA) and add it to 15 mL of deionized water. Stir at 90 °C until completely dissolved and cool to room temperature.
[0024] (2) Weigh 10 mg of 1-Bpin modified carbazole (CZ1B) and dissolve it in 1 mL of tetrahydrofuran (THF). Slowly add the solution to the above PVA solution and stir for 15 minutes to obtain a uniform dispersion.
[0025] (3) Pour the dispersion evenly onto a quartz plate, let it stand at room temperature for 10 h, and then let it dry naturally to obtain a blue phosphorescent film 1.
[0026] Fluorescence spectroscopy of 1-position Bpin carbazole-doped PVA films was performed at room temperature using 270 nm UV light as the excitation source. Simultaneously, phosphorescence emission spectra were measured at room temperature using 270 nm UV light as the excitation source with a delay of 1 ms. The results are as follows. Figure 1 As shown.
[0027] from Figure 1 The results show that the fluorescence spectrum of the thin film has a peak near 375 nm, and the phosphorescence emission peak is located near 460 nm, showing deep blue phosphorescence emission.
[0028] Example 2 Blue phosphorescent film prepared by 2-position Bpin carbazole doping of PVA The organophosphorescent compound is 2-position Bpin carbazole, and its structural formula is shown in Formula 2 below:
[0029] Formula 2 The polymer matrix is polyvinyl alcohol (PVA).
[0030] The preparation method of the blue phosphorescent film 2 is as follows: (1) Weigh 1 g of polyvinyl alcohol (PVA) and add it to 15 mL of deionized water. Stir at 90 °C until completely dissolved and cool to room temperature.
[0031] (2) Weigh 10 mg of 2-Bpin modified carbazole (CZ2B) and dissolve it in 1 mL of tetrahydrofuran (THF). Slowly add the solution to the above PVA solution and stir for 15 minutes to obtain a uniform dispersion.
[0032] (3) Pour the dispersion evenly onto a quartz plate, let it stand at room temperature for 10 h, and then let it dry naturally to obtain a blue phosphorescent film 2.
[0033] Fluorescence spectroscopy of 2-position Bpin-carbazole-doped PVA films was performed at room temperature using 270 nm UV light as the excitation source. Simultaneously, phosphorescence emission spectra were measured at room temperature using 270 nm UV light as the excitation source with a delay of 1 ms. The results are as follows. Figure 2 As shown.
[0034] from Figure 2 It can be seen that the phosphorescence emission peak is located near 455 nm, and the fluorescence spectrum of the thin film shows a peak near 375 nm, indicating deep blue phosphorescence emission.
[0035] Example 3 Blue phosphorescent film prepared by 3-position Bpin carbazole doping of PVA The organophosphorescent compound is 3-position Bpin carbazole, and its structural formula is shown in Formula 3 below:
[0036] Formula 3 The polymer matrix is polyvinyl alcohol (PVA).
[0037] The preparation method of the blue phosphorescent film 3 is as follows: (1) Weigh 1 g of polyvinyl alcohol (PVA) and add it to 15 mL of deionized water. Stir at 90 °C until completely dissolved and cool to room temperature.
[0038] (2) Weigh 10 mg of 3-Bpin modified carbazole (CZ3B) and dissolve it in 1 mL of tetrahydrofuran (THF). Slowly add the solution to the above PVA solution and stir for 15 minutes to obtain a uniform dispersion.
[0039] (3) Pour the dispersion evenly onto a quartz plate, let it stand at room temperature for 10 h, and then let it dry naturally to obtain a blue phosphorescent film 3.
[0040] Fluorescence spectroscopy of 3-position Bpin-carbazole-doped PVA films was performed at room temperature using 270 nm UV light as the excitation source. Simultaneously, phosphorescence emission spectra were measured at room temperature using 270 nm UV light as the excitation source with a delay of 1 ms. The results are as follows. Figure 3 As shown.
[0041] from Figure 3 The results show that the fluorescence spectrum of the thin film has a peak near 365 nm, and the phosphorescence emission peak is located near 440 nm, showing deep blue phosphorescence emission.
[0042] Example 4 Blue phosphorescent film prepared by 4-position Bpin carbazole doping of PVA The organophosphorescent compound is 4-position Bpin carbazole, and its structural formula is shown in Formula 4 below:
[0043] Formula 4 The polymer matrix is polyvinyl alcohol (PVA).
[0044] The preparation method of the blue phosphorescent film 4 is as follows: (1) Weigh 1 g of polyvinyl alcohol (PVA) and add it to 15 mL of deionized water. Stir at 90 °C until completely dissolved and cool to room temperature.
[0045] (2) Weigh 10 mg of 4-position Bpin modified carbazole (CZ4B) and dissolve it in 1 mL of tetrahydrofuran (THF). Slowly add the solution to the above PVA solution and stir for 15 minutes to obtain a uniform dispersion.
[0046] (3) Pour the dispersion evenly onto a quartz plate, let it stand at room temperature for 10 h, and then let it dry naturally to obtain a blue phosphorescent film 4.
[0047] Fluorescence spectroscopy of 4-position Bpin-carbazole-doped PVA films was performed at room temperature using 270 nm UV light as the excitation source. Simultaneously, phosphorescence emission spectra were measured at room temperature using 270 nm UV light as the excitation source with a delay of 1 ms. The results are as follows. Figure 4 As shown.
[0048] from Figure 4 It can be seen that the fluorescence spectrum of the thin film has a peak near 375 nm, and the phosphorescence emission peak is located near 455 nm, showing deep blue phosphorescence emission.
[0049] Example 5 Blue phosphorescent film prepared by 3-position Bpin dibenzofuran doping of PVA 5 The organophosphorescent compound is a 3-position Bpin dibenzofuran, and its structural formula is shown in Formula 5 below:
[0050] Formula 5 The polymer matrix is polyvinyl alcohol (PVA).
[0051] The preparation method of the blue phosphorescent film 5 is as follows: (1) Weigh 1 g of polyvinyl alcohol (PVA) and add it to 15 mL of deionized water. Stir at 90 °C until completely dissolved and cool to room temperature.
[0052] (2) Weigh 10 mg of 3-Bpin modified dibenzofuran (DBF3B) and dissolve it in 1 mL of tetrahydrofuran (THF). Slowly add it dropwise to the above PVA solution and stir for 15 minutes to obtain a uniform dispersion.
[0053] (3) Pour the dispersion evenly onto a quartz plate, let it stand at room temperature for 10 h, and then let it dry naturally to obtain a blue phosphorescent film 5.
[0054] Fluorescence spectroscopy of 3-Bpin dibenzofuran-doped PVA films was performed at room temperature using 270 nm UV light as the excitation source. Simultaneously, phosphorescence emission spectra were measured at room temperature using 270 nm UV light as the excitation source with a delay of 1 ms. The results are as follows. Figure 5 As shown.
[0055] from Figure 5 It can be seen that the fluorescence spectrum of the thin film has a peak near 325 nm, and the phosphorescence emission peak is located near 440 nm, showing deep blue phosphorescence emission.
[0056] Example 6 Blue phosphorescent film prepared by 3-position Bpin dibenzothiophene doping PVA 6 The organophosphorescent compound is 3-Bpin dibenzothiophene, and its structural formula is shown in Formula 6 below:
[0057] Formula 6 The polymer matrix is polyvinyl alcohol (PVA).
[0058] The preparation method of the blue phosphorescent film 6 is as follows: (1) Weigh 1 g of polyvinyl alcohol (PVA) and add it to 15 mL of deionized water. Stir at 90 °C until completely dissolved and cool to room temperature.
[0059] (2) Weigh 10 mg of 3-Bpin modified dibenzothiophene (DBT3B) and dissolve it in 1 mL of tetrahydrofuran (THF). Slowly add it dropwise to the above PVA solution and stir for 15 minutes to obtain a uniform dispersion.
[0060] (3) Pour the dispersion evenly onto a quartz plate, let it stand at room temperature for 10 h, and then let it dry naturally to obtain a blue phosphorescent film 6.
[0061] Fluorescence spectroscopy of 3-position Bpin dibenzothiophene-doped PVA films was performed at room temperature using 270 nm UV light as the excitation source. Simultaneously, phosphorescence emission spectra were measured at room temperature using 270 nm UV light as the excitation source with a delay of 1 ms. The results are as follows. Figure 6 As shown.
[0062] from Figure 6 It can be seen that the fluorescence spectrum of the thin film has a peak near 350 nm, and the phosphorescence emission peak is located near 450 nm, showing deep blue phosphorescence emission.
[0063] Example 7 Blue phosphorescent film prepared by 5-position Bpin indole-doped PVA 7 The organophosphorescent compound is 5-Bpin dibenzothiophene, and its structural formula is shown in Formula 7 below:
[0064] Formula 7 The polymer matrix is polyvinyl alcohol (PVA).
[0065] The preparation method of the blue phosphorescent film 7 is as follows: (1) Weigh 1 g of polyvinyl alcohol (PVA) and add it to 15 mL of deionized water. Stir at 90 °C until completely dissolved and cool to room temperature.
[0066] (2) Weigh 10 mg of 5-Bpin modified indole (ID5B) and dissolve it in 1 mL of tetrahydrofuran (THF). Slowly add it dropwise to the above PVA solution and stir for 15 minutes to obtain a uniform dispersion.
[0067] (3) Pour the dispersion evenly onto a quartz plate, let it stand at room temperature for 10 h, and then let it dry naturally to obtain a blue phosphorescent film 7.
[0068] Fluorescence spectroscopy of 5-position Bpin indole-doped PVA films was performed at room temperature using 270 nm UV light as the excitation source. Simultaneously, phosphorescence emission spectra were measured at room temperature using 270 nm UV light as the excitation source with a delay of 1 ms. The results are as follows. Figure 7 As shown.
[0069] from Figure 7 It can be seen that the fluorescence spectrum of the thin film has a peak near 345 nm, and the phosphorescence emission peak is located near 450 nm, showing deep blue phosphorescence emission.
[0070] Example 8 Thin films were prepared by doping with different concentrations, ranging from 1 / 10 to 100,000, according to the composition and preparation method of Example 3. Phosphorescence emission spectra were measured at room temperature using 270 nm ultraviolet light as the excitation source and with a delay of 1 ms. The results are as follows: Figure 8 As shown. The phosphorescence lifetime of the blue phosphorescent film prepared in this invention was measured under 270 nm ultraviolet light source excitation, and the results are as follows. Figure 9 As shown.
[0071] Example 9 The phosphorescence effect of the blue phosphorescent films 1-7 prepared in this invention was detected after excitation with a 254 nm UV lamp for 2 seconds at room temperature and then with the UV lamp turned off. The results are as follows. Figure 10 As shown; Meanwhile, the phosphorescence lifetime of the blue phosphorescent films 1-7 prepared in this invention under 270nm ultraviolet light source excitation was measured, and the results are as follows: Figure 11 As shown.
[0072] from Figure 10 and Figure 11 It can be seen that the phosphorescence lifetime of blue phosphorescent film 1 is 3.96 s, showing ultra-long room temperature phosphorescence; The blue phosphorescent film 2 has a phosphorescence lifetime of 5.20 s, exhibiting ultra-long room temperature phosphorescence; The phosphorescence lifetime of the blue phosphorescent film 3 is 4.64 s, exhibiting ultra-long room temperature phosphorescence. The phosphorescence lifetime of the blue phosphorescent film 4 is 4.27 s, exhibiting ultra-long room temperature phosphorescence; The blue phosphorescent film 5 has a phosphorescence lifetime of 2.87 s, exhibiting ultra-long room temperature phosphorescence. The blue phosphorescent film 6 has a phosphorescence lifetime of 0.69 s, exhibiting ultra-long room temperature phosphorescence. The blue phosphorescent film 7 has a phosphorescence lifetime of 1.81s, exhibiting ultra-long room temperature phosphorescence.
[0073] Example 10 Fabrication of a programmable tag with room temperature phosphorescence properties (1) The dispersion prepared in step (1) of Examples 1-7 is uniformly coated on a quartz plate. After the solvent has completely evaporated, a room temperature phosphorescent film is obtained. (2) Irradiate the room temperature phosphorescent film with an ultraviolet light mask to complete the writing process and obtain a programmable tag with room temperature phosphorescent properties; after writing, excite it with ultraviolet light, and after removing the ultraviolet light, the written information can be read, and it can be rewritten and reused.
[0074] Figure 12 This is an example diagram illustrating the application of the programmable tag with room-temperature phosphorescence properties prepared in this embodiment.
[0075] Example 11 The preparation of an organic room-temperature phosphorescent thin film anti-counterfeiting product includes the following steps: (1) Weigh an appropriate amount of sample at a mass ratio of 1:100 between the guest material (any one of the structural formulas 1-7) and polyvinyl alcohol. Heat the weighed guest material and polyvinyl alcohol at 250°C to melt them and mix them evenly to obtain a precursor melt. (2) The precursor melt is poured into molds of different shapes, and after it has cooled completely, it is shaped and modified to produce anti-counterfeiting products of various shapes of organic room temperature phosphorescent film.
[0076] Figure 13 This is a photograph of the organic room temperature phosphorescent film anti-counterfeiting product prepared in this embodiment.
Claims
1. An organophosphorescent compound, characterized in that, The general structural formula of the organophosphorescent compound is: R–G–Bpin; In the general structural formula, the G group is an aromatic or heteroaromatic skeleton with a π-conjugated structure, and the aromatic or heteroaromatic skeleton is one of carbazole, indole, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, benzimazole, benzothiazole, benzothiphene-pyrazole, benzoxazole, benzothiadiazole, carbazole-pyridine, phenanthrene, fluorene, benzene, biphenyl, and terphenyl. The R group is a linking group, which is a single bond, –CH2–, –NH–, –CO–, –CH=CH–, or –C. n H 2n+1 One of them; The Bpin group is pinacol boryl ester or other borate ester group, and the Bpin is attached to any or more sites on the aromatic ring or heteroaromatic ring of the G group.
2. The organophosphorescent compound according to claim 1, characterized in that, G is one of carbazole, indole, benzimidazole or benzothiazole; The G group contains 1 to 3 substituents, which are hydrogen, C1–C 16 One of alkyl, alkoxy, halogen, cyano, carboxyl, amino, amide, or sulfonyl groups.
3. The organophosphorescent compound according to claim 2, wherein the organophosphorescent compound is one of the following structural formulas: 。 4. A long-life organic room-temperature phosphorescent composite material, characterized in that, The organic room temperature phosphorescent composite material comprises one or more combinations of organic phosphorescent compounds as described in any one of claims 1-3 and a polymer matrix; The organic phosphorescent compound is doped into the polymer matrix at a mass ratio of 1:10-10000; The polymer matrix is one of polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, polyurethane, polyamide, polycarbonate or copolymers thereof, as well as rubber and elastomer materials.
5. The organic room-temperature phosphorescent composite material according to claim 4, characterized in that, The long lifetime refers to the fact that after the organic room temperature phosphorescent composite material emits fluorescence under 254-365 nm ultraviolet excitation, it emits blue to cyan room temperature phosphorescence in room temperature air after the ultraviolet irradiation is turned off, with a lifetime greater than or equal to 0.6 seconds.
6. The organic room-temperature phosphorescent composite material according to claim 5, characterized in that, The organic room temperature phosphorescent composite material includes organic room temperature phosphorescent composite material a prepared by solution casting film formation method and organic room temperature phosphorescent composite material b prepared by melt blending process; The preparation method of the organic room temperature phosphorescent composite material a obtained by the solution casting film formation method includes the following steps: (1) Dissolve one or more of the organophosphorescent compounds in an organic solvent to obtain a first solution; (2) Dissolve the polymer matrix in water to obtain a second solution; (3) Add the first solution dropwise to the second solution at a mass ratio of 1:10-10000, and stir until homogeneous to obtain a mixed solution; (4) The mixture is applied to the substrate by coating, casting, spin coating or spraying, and dried and cured to obtain organic room temperature phosphorescent composite material a; The preparation method of the organic room temperature phosphorescent composite material b obtained by the melt blending process includes the following steps: (a) Premixing one or more of the organophosphorescent compounds and the polymer matrix at a mass ratio of 1:10-10000 to obtain a premix; (b) The premix is placed in an extruder, internal mixer or twin-screw mixing equipment and melt-blended at a polymer softening or melting temperature to obtain a melt blend; (c) The melt blend is processed by extrusion, injection molding, calendering, blown film or hot pressing to obtain organic room temperature phosphorescent composite material b.
7. The application of the organic room temperature phosphorescent composite material as described in any one of claims 4-6 in the preparation of anti-counterfeiting label materials, information encryption materials, ultraviolet-responsive display devices, visual label materials, data storage materials, bioimaging materials, 3D printing materials, or flexible optoelectronic devices.
8. A method for preparing an organic room-temperature phosphorescent composite material, characterized in that, The preparation methods include solution casting film formation and melt blending processing. The steps of the solution casting film formation method are as follows: (1) Dissolve one or more of the organophosphorescent compounds as described in any one of claims 1-3 in an organic solvent to obtain a first solution; (2) Dissolve the polymer matrix in water to obtain a second solution; (3) Add the first solution dropwise to the second solution at a mass ratio of 1:10-10000, and stir until homogeneous to obtain a mixed solution; (4) The mixture is applied to the substrate by coating, casting, spin coating or spraying, and dried and cured to obtain organic room temperature phosphorescent composite material a; The steps of the melt blending process are as follows: (a) Premixing one or more of the organophosphorescent compounds as described in any one of claims 1-3 with a polymer matrix at a mass ratio of 1:10-10000 to obtain a premix; (b) The premix is placed in an extruder, internal mixer or twin-screw mixing equipment and melt-blended at a polymer softening or melting temperature to obtain a melt blend; (c) The melt blend is processed by extrusion, injection molding, calendering, blown film or hot pressing to obtain organic room temperature phosphorescent composite material b.
9. The preparation method according to claim 8, characterized in that, In the solution casting film formation method and the melt blending process, the polymer matrix is one of polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, polyurethane, polyamide, polycarbonate or copolymers thereof, as well as rubber and elastomer materials.