Polymer-doped yellow organic long afterglow crystal material as well as preparation method and application thereof
The yellow organic long afterglow crystal material prepared by polymer doping technology uses materials such as polymethyl methacrylate and triphenylphosphine to solve the problem that organic materials are difficult to achieve long afterglow at room temperature, and achieves yellow afterglow luminescence and Full spectrum afterglow characteristics, suitable for applications such as data encryption and anti-counterfeiting.
Patent Information
- Application Number
- CN202411268938.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-11
- Publication Date
- 2024-12-13
AI Technical Summary
Existing organic materials are difficult to achieve long afterglow emission in room temperature atmospheric environments, mainly due to spin-ban and non-radiative transitions, energy is consumed in the form of heat, and most of the materials emit green afterglow, and other colors have less afterglow. Lack of full spectrum afterglow characteristics.
By polymer doping technology, polymethyl methacrylate is used as a matrix, combining the electron-rich material triphenylphosphine and the guest material 5,9-dibromo-7H-dibenzo[c,g]carbazole, by evaporation Crystallization prepares yellow organic long afterglow crystal material, and regulates energy transfer to achieve yellow afterglow luminescence.
Yellow afterglow luminescence is achieved in room temperature atmospheric environment, with the afterglow time exceeding 4 seconds, and has good afterglow luminescence performance. It is suitable for applications such as data encryption and anti-counterfeiting, and realizes the full spectrum afterglow characteristics of organic long afterglow materials.
Smart Images
Figure CN119119667A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of organic afterglow materials, and in particular relates to a polymer-doped yellow organic long afterglow crystal material and a preparation method and application thereof. Background Art
[0002] Due to the unique advantages of long lifetime and large Stokes shift, organic room temperature phosphorescent (RTP) materials have attracted extensive attention in many research fields such as anti-counterfeiting, bio-imaging, sensors and electronic devices. Compared with inorganic materials, organic molecules have better biocompatibility, easier structure modification, and are free from the constraints of rare earth elements, which is of great research significance.
[0003] However, due to the inherent spin-forbidden ISC and non-radiative transitions of triplet excitons, efficient and long-lasting RTP emission from metal-free pure organic materials is difficult to achieve. This is mainly because the lowest excited triplet exciton (T1) of organic molecules returns to the ground state (S0) through radiative transition to produce phosphorescence, but the long afterglow luminescence of organic molecules can usually be observed at low temperatures (77K) or inert atmospheres, while at room temperature atmospheric conditions, the triplet excitons of organic molecules are easily quenched by oxygen molecules in the air. At the same time, at room temperature atmospheric conditions, the vibration of organic molecules is strong, resulting in a high non-radiative transition rate (Knr), and the energy is mainly consumed in the form of heat. Therefore, it is difficult to observe the long afterglow luminescence of pure organic molecules at room temperature atmospheric conditions.
[0004] How to obtain room temperature phosphorescence and realize the long afterglow phenomenon at room temperature can be achieved mainly through two means: 1) Promote the spin-orbit coupling (SOC) of molecules to promote the intersystem crossing (ISC) process from the excited singlet state to the excited triplet state of molecules; 2) Inhibit the non-radiative transition of molecules so that more energy is released in the form of light energy. This has led researchers to develop crystal engineering, heavy atom effects, H-aggregation, host-guest doping, introduction of polymer matrices and some other methods to prepare pure organic long afterglow materials with excellent luminescence properties in atmospheric environment. Among these methods for preparing pure organic long afterglow materials, polymer doping has a better preparation effect. Polymers can increase the rigidity of the molecular structure, effectively compress the non-radiative transition of molecules, and at the same time play a role in isolating oxygen, thereby obtaining pure organic long afterglow luminescent materials.
[0005] However, the real luminescence is still the luminescent molecules, but since most of the current organic long afterglow materials have large conjugated structures and aggregated luminescence, the afterglow emitted by most materials is green, and the afterglow of other colors is still rare. Therefore, it is very important to develop more types of new afterglow materials with more afterglow color changes, which is also the key to achieving the full spectrum afterglow characteristics of organic long afterglow materials. Summary of the invention
[0006] One of the purposes of the present invention is to provide a polymer-doped yellow organic long afterglow crystalline material, which has good afterglow luminescence performance under room temperature and atmospheric environment, and the afterglow color is yellow, which is conducive to realizing the full-spectrum afterglow characteristics of the organic long afterglow material.
[0007] The second object of the present invention is to provide a method for preparing a polymer-doped yellow organic long afterglow crystalline material, which has a simple process, mild conditions, and cheap and readily available materials, and is suitable for the preparation and application of yellow organic long afterglow crystalline materials.
[0008] The third object of the present invention is to provide an application of a polymer-doped yellow organic long afterglow crystalline material.
[0009] One of the purposes of the present invention adopts the technical solution:
[0010] A polymer-doped yellow organic long afterglow crystal material is prepared by evaporation and crystallization of a polymer, a main material and a guest material;
[0011] The polymer is polymethyl methacrylate;
[0012] The main material is The guest material is
[0013] As a further improvement, the mass ratio of the polymer, the host material and the guest material is (80-120):(20-40):1.
[0014] As a further improvement, the mass ratio of the polymer, the host material and the guest material is 100:30:1.
[0015] As a further improvement, the relative molecular mass of the polymethyl methacrylate is 10000 to 20000. More preferably, the relative molecular mass of the polymethyl methacrylate is 13000.
[0016] As a further improvement, the excitation wavelength of the polymer-doped yellow organic long afterglow crystal material is 360-380 nm, more preferably 365 nm.
[0017] The technical solution adopted in the second object of the present invention is:
[0018] A method for preparing a polymer-doped yellow organic long afterglow crystalline material comprises the following steps:
[0019] (1) mixing the polymer, the host material and the guest material uniformly according to a mass ratio to obtain a solid powder;
[0020] (2) The solid powder is stirred and dissolved in a solvent, and then evaporated and crystallized to obtain a polymer-doped yellow organic long afterglow crystalline material.
[0021] As a further improvement, in step (2), the solvent is dichloromethane and ethanol; the volume ratio of dichloromethane to ethanol is 1:(8-12).
[0022] As a further improvement, in step (2), the solid powder is stirred and dissolved in a solvent. The specific operation is: first, dichloromethane is added to the solid powder to dissolve it, and then ethanol is added to dissolve it.
[0023] As a further improvement, in step (2), for every 0.1 to 0.14 g of solid powder, the corresponding amount of solvent used is 5 to 6 mL.
[0024] As a further improvement, in step (2), the temperature of evaporation crystallization is 20-30°C.
[0025] The technical solution adopted in the third object of the present invention is:
[0026] The above polymer-doped yellow organic long afterglow crystalline material is used as a luminescent material in data encryption and / or afterglow anti-counterfeiting.
[0027] The beneficial effects of the present invention are mainly:
[0028] 1) The polymer-doped yellow organic long afterglow crystalline material provided by the present invention uses polymer polymethyl methacrylate (PMMA) as a matrix, selects triphenylphosphine, an electron-rich material that is easy to crystallize and cheap and readily available, as a main material, and introduces 5,9-dibromo-7H-dibenzo[c,g]carbazole as a guest material to construct a new bright yellow long afterglow luminescent material. The material can be excited by ultraviolet light, has stable performance, has an afterglow time of more than 4s in a room temperature atmospheric environment, has good afterglow luminescence performance, and has a yellow afterglow color, which is conducive to realizing the full spectrum afterglow characteristics of organic long afterglow materials, and can also provide a theoretical basis and material basis for practical applications such as data encryption and anti-counterfeiting.
[0029] 2) The preparation method of the polymer-doped yellow organic long afterglow crystalline material provided by the present invention uses a polymer with a simple structure as a matrix, uses the electron-rich material triphenylphosphine as a main material, and uses 5,9-dibromo-7H-dibenzo[c,g]carbazole as a guest material to prepare the yellow organic long afterglow crystalline material. The whole preparation method is simple, the materials are cheap and easy to obtain, the structure is simple, the conditions are mild, and harsh conditions such as high temperature and high pressure are not required; at the same time, the prepared material belongs to a polymer-doped yellow organic long afterglow material, has good yellow afterglow luminescence performance, and is suitable for industrial market applications.
[0030] 3) The present invention studies polymer-doped yellow organic long afterglow crystalline materials, constructs a rigid environment through the polymer matrix, and regulates the energy transfer between the host and the guest, thereby achieving an effective combination of polymer and phosphorescent materials, demonstrating its application potential in the fields of information encryption and anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 This is an optical image of the afterglow display of the polymer-doped yellow organic long afterglow crystal material prepared in Example 1 of the present invention after being irradiated with 365nm ultraviolet light (af);
[0032] Figure 2 This is an optical image of the afterglow display of the polymer-doped organic crystal material prepared in Comparative Example 1 after being illuminated by 365nm ultraviolet light (ad). DETAILED DESCRIPTION
[0033] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the accompanying drawings, embodiments and test examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the scope of protection of the present invention. The experimental methods used in the following embodiments are conventional methods unless otherwise specified; the raw materials used are commonly used in the art, available to the public or commercially available unless otherwise specified; the terms and abbreviations involved are all conventional meanings in the art. Among them, in the following examples, the relative molecular mass of polymethyl methacrylate is 13000.
[0034] Example 1
[0035] This embodiment provides a polymer-doped yellow organic long afterglow crystal material, which is prepared by evaporation and crystallization of a polymer, a host material and a guest material. The polymer is polymethyl methacrylate (PMMA); the host material is (triphenylphosphine); the guest material is (5,9-dibromo-7H-dibenzo[c,g]carbazole). The mass ratio of the polymer, the host material and the guest material is 100:30:1.
[0036] The polymer-doped yellow organic long afterglow crystalline material is prepared by a method comprising the following steps:
[0037] According to the mass ratio of polymer, host material and guest material of 100:30:1, accurately weigh 0.0010g of guest material (5,9-dibromo-7H-dibenzo[c,g]carbazole), 0.1000g of polymer (PMMA) and 0.030g of host material (triphenylphosphine) to obtain a solid powder; add 0.5mL of dichloromethane to dissolve the solid powder, and then add 5mL of ethanol to mix well, and then place it at room temperature (20-30°C) to volatilize and crystallize to obtain the polymer (PMMA) doped yellow organic long afterglow crystalline material of Example 1.
[0038] Comparative Example 1
[0039] This comparative example provides a polymer-doped organic crystalline material, and its preparation process is basically the same as that of Example 1, except that the guest material used is different, and the other conditions and parameters are the same as those of Example 1. The guest material used in this comparative example is 7-bromo-5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene, and its structural formula is
[0040] Test Example 1: Afterglow Performance Test of the Material in Example 1
[0041] In the room temperature atmosphere, the polymer-doped yellow organic long afterglow crystal material of Example 1 was excited by a 365nm ultraviolet lamp, and then the excitation light source was turned off, and the afterglow brightness change of the crystal material after the light source was removed was recorded. The results are as follows: Figure 1 shown.
[0042] Depend on Figure 1 It can be seen that the 365nm ultraviolet lamp excites the material of Example 1 ( Figure 1 a), and then turn off the excitation light source. After removing the light source, the crystal material emits a bright yellow afterglow ( Figure 1 b). Figure 1 b~1e represent the afterglow changes of 1s, 2s, 3s and 4s after the light source is removed. During this time, the afterglow brightness of the crystal material is strong, and then the afterglow gradually weakens. After the 5th second ( Figure 1 f) Afterglow is not obvious. It can be seen that the afterglow time of the yellow organic long afterglow crystal material of Example 1 is more than 4s, and the afterglow performance is excellent.
[0043] Test Example 2: Afterglow Performance Test of Comparative Example 1 Material
[0044] In an atmospheric environment at room temperature, a 365nm ultraviolet lamp was used to excite the polymer-doped organic crystal material of Comparative Example 1, and then the excitation light source was turned off, and the afterglow brightness change of the crystal material after the light source was removed was recorded. The results are as follows: Figure 2 shown.
[0045] Depend on Figure 2It can be seen that the 365nm ultraviolet lamp excites the material of Comparative Example 1 ( Figure 2 a), and then turn off the excitation light source. After removing the light source, the crystal material emits a green afterglow ( Figure 2 b). Figure 2 b~2c represent the afterglow changes of the crystal material at 0s and 0.5s after the light source is removed. During this time, the afterglow brightness of the crystal material is strong, and then the afterglow gradually weakens. After 1s ( Figure 2 d) Afterglow is not obvious. It can be seen that the afterglow time of the polymer-doped organic crystal material in Comparative Example 1 is 1 s, the afterglow performance is poor, and the afterglow color is green, and no yellow afterglow light can be obtained.
[0046] In summary, the polymer-doped yellow organic long afterglow crystalline material provided by the present invention uses polymer polymethyl methacrylate (PMMA) as a matrix, selects triphenylphosphine, an electron-rich material that is easy to crystallize and cheap and readily available, as a main material, and introduces 5,9-dibromo-7H-dibenzo[c,g]carbazole as a guest material to construct a bright yellow long afterglow luminescent new material. The material can be excited by ultraviolet light, and has stable performance. The afterglow time in room temperature atmospheric environment exceeds 4s, has good afterglow luminescence performance, and the afterglow color is yellow, which is conducive to realizing the full spectrum afterglow characteristics of organic long afterglow materials, and can also provide a theoretical basis and material basis for practical applications such as data encryption and anti-counterfeiting.
Claims
1. A polymer-doped yellow organic long afterglow crystalline material, characterized in that: It is prepared by evaporation and crystallization of polymer, host material and guest material; The polymer is polymethyl methacrylate; The main material is The guest material is 2. The polymer-doped yellow organic long afterglow crystalline material according to claim 1, characterized in that: The mass ratio of the polymer, the main material and the guest material is (80-120):(20-40):
1.
3. The polymer-doped yellow organic long afterglow crystalline material according to claim 2, characterized in that: The mass ratio of the polymer, the host material and the guest material is 100:30:
1.
4. The polymer-doped yellow organic long afterglow crystalline material according to claim 1, characterized in that: The relative molecular mass of the polymethyl methacrylate is 10000-20000.
5. A method for preparing the polymer-doped yellow organic long afterglow crystalline material according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) mixing the polymer, the host material and the guest material uniformly according to a mass ratio to obtain a solid powder; (2) The solid powder is stirred and dissolved in a solvent, and then evaporated and crystallized to obtain a polymer-doped yellow organic long afterglow crystalline material.
6. The method for preparing the polymer-doped yellow organic long afterglow crystalline material according to claim 5, characterized in that: In step (2), the solvent is dichloromethane and ethanol; the volume ratio of dichloromethane to ethanol is 1:(8-12).
7. The method for preparing the polymer-doped yellow organic long afterglow crystalline material according to claim 6, characterized in that: In step (2), the solid powder is stirred and dissolved in a solvent. The specific operation is: first, dichloromethane is added to the solid powder to dissolve it, and then ethanol is added to dissolve it.
8. The method for preparing the polymer-doped yellow organic long afterglow crystalline material according to claim 5, characterized in that: In step (2), for every 0.1 to 0.14 g of solid powder, the corresponding amount of solvent used is 5 to 6 mL.
9. The method for preparing the polymer-doped yellow organic long afterglow crystalline material according to claim 5, characterized in that: In step (2), the temperature of evaporation crystallization is 20-30°C.
10. An application of the polymer-doped yellow organic long afterglow crystalline material as claimed in any one of claims 1 to 4, characterized in that: Application as luminescent material in data encryption and / or afterglow anti-counterfeiting.