In-situ polymerized room temperature phosphorescent material, preparation method and application thereof
Aromatic carbonyl compounds were doped into polymethyl methacrylate via in-situ polymerization to prepare room-temperature phosphorescent materials with strong processability and long afterglow time. This solved the problem of weak luminescence of phosphorescent molecules in existing technologies, and achieved processability and long afterglow effect of the materials, making them suitable for decoration and anti-counterfeiting.
Patent Information
- Application Number
- CN202310788011.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-06-29
- Publication Date
- 2026-02-17
- Estimated Expiration
- 2043-06-29
AI Technical Summary
Existing technologies make it difficult to prepare efficient and processable room-temperature phosphorescent materials, and the phosphorescent molecules doped into the polymer matrix emit weak light, which is difficult to offset the non-radiative decay caused by oxygen or molecular motion.
An in-situ polymerization method is used to fix aromatic carbonyl compounds as room temperature phosphorescent molecules in the form of monomolecules by highly entangled polymer chains. Phosphorescence quantum yield is promoted through π-π* and n-π* transitions, while molecular motion and rotation are restricted and non-radiative decay is suppressed.
A room-temperature phosphorescent material with strong processability and long afterglow time was prepared, which is suitable for large-scale production and application, and can be used for decoration and anti-counterfeiting, with a long afterglow effect.
Smart Images
Figure CN117106437B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of light-emitting materials, and particularly relates to an in-situ polymerized room-temperature phosphorescent material and a preparation method and application thereof. BACKGROUND
[0002] Phosphorescent materials have the characteristics of long luminescence lifetime and high quantum yield, and have broad application prospects in the fields of organic light-emitting diodes, information encryption, sensors, biological imaging and the like. Therefore, the research on phosphorescent materials is increasingly valued.
[0003] However, it is not easy to obtain an organic room-temperature phosphorescent molecule with high-efficiency luminescence. The main reason is that pure organic compounds have low spin-orbit coupling (SOC) ability, which makes them usually show low-efficiency intersystem crossing (ISC). In addition, the triplet excitons are prone to rapid non-radiative decay due to thermal molecular motion and collision or the quenching effect of oxygen. At present, the crystal strategy is the most widely used method to obtain good room-temperature phosphorescent materials. However, the growth of crystals is very dependent on the growth environment, lacks sufficient reproducibility, and the poor processability of the crystals limits their practical application. Therefore, doping luminescent molecules into a polymer matrix is another potential design strategy for room-temperature phosphorescent materials, which is conducive to improving the processability of the materials and expanding the application range thereof.
[0004] Polymethyl methacrylate (PMMA) is the most commonly used polymer matrix at present due to its low price and solubility in many organic solvents. At present, the way to dope luminescent molecules into PMMA is mainly to prepare a corresponding PMMA doped film. Taking a drop-casting method as an example, PMMA is usually dissolved in an organic solvent, and then mixed with a solution of a luminescent dopant. After evaporation of the solvent, a dopant-PMMA film is constructed by drop-casting. This method is simple to prepare, but the rigidity of the prepared film is usually poor, which is difficult to offset the adverse effects of non-radiative transition caused by oxygen or molecular motion on phosphorescent emission. Therefore, the luminescence of the fluorescent powder existing in the form of a single molecule is usually weak, and it is difficult to observe its afterglow by naked eyes.
[0005] Therefore, it is very meaningful to find a room-temperature phosphorescent material preparation method which can limit the non-radiative relaxation of organic luminescent molecules and has strong processability. Based on this, it is a technical problem to be solved to provide a room-temperature phosphorescent material with a simple preparation method, low cost and being conducive to large-area popularization and application. SUMMARY
[0006] In view of the above defects of the prior art, in the first aspect of the present application, a room-temperature phosphorescent material with strong processability and long phosphorescent lifetime is provided. The room-temperature phosphorescent material comprises a matrix composed of polymethyl methacrylate and a room-temperature phosphorescent molecule doped in the matrix, and the room-temperature phosphorescent molecule is an aromatic carbonyl compound.
[0007] In the room temperature phosphorescent material, the room temperature phosphorescent molecules are fixed by the highly entangled polymer chains in the form of single molecules, so that the movement and rotation of the room temperature phosphorescent molecules are greatly limited, the non-radiative decay of the room temperature phosphorescent molecules is effectively inhibited, and the phosphorescent lifetime is improved. The room temperature phosphorescent molecules take the aromatic carbonyl compound as the doping component, the conjugated aromatic ring in the molecule is beneficial to the π-π * transition, so as to promote the improvement of the phosphorescent quantum yield. The carbonyl group is beneficial to the n-π* transition, can promote the spin-orbit coupling of the molecule, so as to promote the intersystem crossing process, and is also beneficial to the formation of the hydrogen bond interaction with the polymethyl methacrylate polymer chain.
[0008] Preferably, the room temperature phosphorescent molecule comprises at least one of the substances with the structural formula as follows:
[0009] PO: DMPOPO:
[0010] OPO: MOPO-PiCl:
[0011] NMP2O:
[0012] Preferably, in the room temperature phosphorescent material, the doping amount of the room temperature phosphorescent molecule accounts for 1.0% to 2.0% of the polymethyl methacrylate in terms of mass percentage.
[0013] In the second aspect of the present application, a preparation method of the room temperature phosphorescent material with simple preparation method, low cost and easy large-scale production is provided, and the preparation method comprises the following steps:
[0014] (1) dissolving an initiator and a room temperature phosphorescent molecule in methyl methacrylate to prepare a reaction solution, and performing a prepolymerization reaction on the reaction solution at a certain temperature to obtain a methyl methacrylate prepolymer;
[0015] (2) performing a polymerization reaction on the methyl methacrylate prepolymer at a certain temperature to obtain the room temperature phosphorescent material.
[0016] Preferably, in the step (1), the initiator is at least one of benzoyl peroxide and azobisisobutyronitrile.
[0017] Further preferably, when the initiator is benzoyl peroxide, the addition amount of benzoyl peroxide accounts for 0.2% to 0.5% of the methyl methacrylate in terms of mass percentage; when the initiator is azobisisobutyronitrile, the addition amount of azobisisobutyronitrile accounts for 0.6% to 0.8% of the methyl methacrylate in terms of mass percentage.
[0018] The proper addition amount can avoid too long pre-polymerization time and too fast reaction rate caused by explosive polymerization.
[0019] Preferably, in the step (1), the pre-polymerization temperature is 85-80℃, and the reaction time is 0.5-1.0h.
[0020] Preferably, in the step (2), the polymerization is carried out in two stages, first at 60-65℃ for 20-28h, and then at 80-110℃ for 2-4h.
[0021] The segmented heating polymerization is beneficial to further fix the room temperature phosphorescent molecules in the form of single molecules to the highly entangled polymer chains in the in-situ polymerization process, to prepare the room temperature phosphorescent material with long afterglow.
[0022] In the third aspect of the present application, the room temperature phosphorescent material of the first aspect of the present application or the room temperature phosphorescent material of the second aspect of the present application is used as a luminescent material in the preparation of an artware.
[0023] Compared with the prior art, the present application has the following advantages and beneficial effects:
[0024] The present application provides a room temperature phosphorescent material, which comprises polymethyl methacrylate and room temperature phosphorescent molecules uniformly doped therein. The room temperature phosphorescent material has strong processability and has the advantage of long afterglow time.
[0025] The present application provides a preparation method of a room temperature phosphorescent material, which fixes the room temperature phosphorescent molecules in the form of single molecules to the highly entangled polymer chains in the in-situ polymerization process, to prepare the room temperature phosphorescent material with long afterglow. The method has simple process, low cost and is easy to mass production.
[0026] The present application provides the application of the room temperature phosphorescent material as a luminescent material in the preparation of an artware. The artware has long afterglow time, is used for decoration and anti-counterfeiting, and has wide popularization and application prospect. BRIEF DESCRIPTION OF DRAWINGS
[0027] Figure 1 It is a flowchart of the preparation method of the room temperature phosphorescent material;
[0028] Figure 2 It is an afterglow photo of the room temperature phosphorescent material prepared in Examples 1-5. The top of the photo corresponds to the type of the room temperature phosphorescent molecule of the related example.
[0029] Figure 3 It is an afterglow photo of the room temperature phosphorescent artware with different 3D shapes prepared in Example 6. DETAILED DESCRIPTION
[0030] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.
[0031] Example 1
[0032] Preparation method of room temperature phosphorescent materials:
[0033] (1) As Figure 1 As shown, 6 mg of benzoyl peroxide and 18 mg of PO were dissolved in 1.8 g of methyl methacrylate to prepare a reaction solution. The reaction solution was subjected to a prepolymerization reaction at 80 °C for 0.5 h to obtain a methyl methacrylate prepolymer.
[0034] (2) The methyl methacrylate prepolymer was first polymerized at 60°C for 24 hours, and then the temperature was raised to 100°C and the reaction continued for 2 hours to obtain a room temperature phosphorescent material.
[0035] Example 2
[0036] Preparation method of room temperature phosphorescent materials:
[0037] (1) As Figure 1 As shown, 6 mg of benzoyl peroxide and 18 mg of DMOPO were dissolved in 1.8 g of methyl methacrylate to prepare a reaction solution. The reaction solution was subjected to a prepolymerization reaction at 80 °C for 0.5 h to obtain a methyl methacrylate prepolymer.
[0038] (2) The methyl methacrylate prepolymer was first polymerized at 60°C for 24 hours, and then the temperature was raised to 100°C and the reaction continued for 2 hours to obtain a room temperature phosphorescent material.
[0039] Example 3
[0040] Preparation method of room temperature phosphorescent materials:
[0041] (1) As Figure 1 As shown, 6 mg of benzoyl peroxide and 18 mg of OPO were dissolved in 1.8 g of methyl methacrylate to prepare a reaction solution. The reaction solution was subjected to a prepolymerization reaction at 80 °C for 0.5 h to obtain a methyl methacrylate prepolymer.
[0042] (2) The methyl methacrylate prepolymer was first polymerized at 60°C for 24 hours, and then the temperature was raised to 100°C and the reaction continued for 2 hours to obtain a room temperature phosphorescent material.
[0043] Example 4
[0044] Preparation method of room temperature phosphorescent materials:
[0045] (1) AsFigure 1 As shown, 6 mg of benzoyl peroxide and 18 mg of MOPO-PiCl were dissolved in 1.8 g of methyl methacrylate to prepare a reaction solution. The reaction solution was subjected to a prepolymerization reaction at 80 °C for 0.5 h to obtain a methyl methacrylate prepolymer.
[0046] (2) The methyl methacrylate prepolymer was first polymerized at 60°C for 24 hours, and then the temperature was raised to 100°C and the reaction continued for 2 hours to obtain a room temperature phosphorescent material.
[0047] Example 5
[0048] Preparation method of room temperature phosphorescent materials:
[0049] (1) As Figure 1 As shown, 6 mg of benzoyl peroxide and 18 mg of NMP2O were dissolved in 1.8 g of methyl methacrylate to prepare a reaction solution. The reaction solution was subjected to a prepolymerization reaction at 80 °C for 0.5 h to obtain a methyl methacrylate prepolymer.
[0050] (2) The methyl methacrylate prepolymer was first polymerized at 60°C for 24 hours, and then the temperature was raised to 100°C and the reaction continued for 2 hours to obtain a room temperature phosphorescent material.
[0051] Example 6
[0052] Method for preparing room temperature phosphorescent crafts:
[0053] (1) Dissolve 6 mg benzoyl peroxide and 36 mg NMP2O in 1.8 g methyl methacrylate to prepare a reaction solution. Add the reaction solution to containers of different 3D shapes respectively, and then carry out a prepolymerization reaction at 80 °C for 0.5 h to obtain methyl methacrylate prepolymer.
[0054] (2) The methyl methacrylate prepolymer was first polymerized at 60°C for 24 hours, then heated to 100°C and continued to react for 2 hours. The container was removed to obtain room temperature phosphorescent crafts with different 3D shapes.
[0055] Example 7
[0056] Preparation method of room temperature phosphorescent materials:
[0057] (1) As Figure 1 As shown, 12 mg of azobisisobutyronitrile and 18 mg of NMP2O were dissolved in 1.8 g of methyl methacrylate to prepare a reaction solution. The reaction solution was subjected to a prepolymerization reaction at 85 °C for 1.0 h to obtain a methyl methacrylate prepolymer.
[0058] (2) The methyl methacrylate prepolymer is first polymerized at 65°C for 20 h, then the temperature is raised to 110°C and the reaction is continued for 2 h to obtain the room-temperature phosphorescent material.
[0059] Example 8
[0060] Method for preparing room-temperature phosphorescent material:
[0061] (1) As shown in the following scheme, 12 mg of azobisisobutyronitrile and 18 mg of NMP2O are dissolved in 1.8 g of methyl methacrylate to obtain a reaction solution, and the reaction solution is subjected to prepolymerization at 80°C for 0.5 h to obtain a methyl methacrylate prepolymer; Figure 1 (2) The methyl methacrylate prepolymer is first polymerized at 60°C for 28 h, then the temperature is raised to 80°C and the reaction is continued for 4 h to obtain the room-temperature phosphorescent material.
[0062] Test Example 1
[0063] The afterglow time of the room-temperature phosphorescent materials or room-temperature phosphorescent artworks prepared in some examples is tested.
[0064] The room-temperature phosphorescent materials obtained in Examples 1-5 are irradiated with 365 nm band ultraviolet light, the ultraviolet light source is removed immediately after irradiation, and the disappearance process of the afterglow in the visible light range and the corresponding time are recorded by a camera. From
[0065] It can be seen that the light emission intensity of Examples 1-5 under ultraviolet light irradiation is visible to the naked eye, and has a long afterglow time. Among them, the room-temperature phosphorescent material prepared by doping NMP2O in Example 5 has the longest afterglow time, with a total duration of up to 6 s. Figure 2 Similarly, the room-temperature phosphorescent artworks of different 3D shapes prepared in Example 6 are irradiated with 365 nm band ultraviolet light, the ultraviolet light source is removed immediately after irradiation, and the disappearance process of the afterglow in the visible light range and the corresponding time are recorded by a camera. From
[0066] It can be seen that the room-temperature phosphorescent artworks of heart shape, flower shape and star shape prepared in Example 6 have light emission intensity under ultraviolet light irradiation, which is visible to the naked eye, the afterglow is not extinguished for 5 s, and have a long afterglow time. The light emission performance of room-temperature phosphorescent artworks of different 3D shapes does not change significantly with the shape change, and has good stability. Figure 3
[0067] In combination with the inventive idea of the present application, the reason for the above result can be that in the above examples, different room temperature phosphorescent molecules are fixed by highly entangled polymer chains in the form of single molecules, which greatly limits their movement and rotation, effectively inhibits the non-radiative decay of the phosphorescent molecules, and improves their phosphorescent lifetime. The room temperature phosphorescent molecules use aromatic carbonyl compounds as doping components, and the presence of conjugated aromatic rings in the molecules is conducive to π-π * transition, thereby promoting the improvement of phosphorescent quantum yield. The carbonyl group is conducive to n-π* transition, can promote the spin-orbit coupling of the molecule to promote the intersystem crossing process, and is also conducive to the formation of hydrogen bond interaction with the polymethyl methacrylate polymer chain. The present application uses different containers to make room temperature phosphorescent artware of different shapes, and therefore the method of the present application has the advantages of simple process, low cost, and easy mass production. The artware is used for decoration and anti-counterfeiting, and has a wide popularization and application prospect.
[0068] The preferred embodiments of the present application are described in detail above. It should be understood that those skilled in the art can make many modifications and changes without creative labor based on the concept of the present application. Therefore, any technical solution obtained by logical analysis, reasoning or limited experiment based on the prior art according to the concept of the present application shall be within the protection scope determined by the claims.
Claims
1. A method for preparing a room temperature phosphorescent material, characterized by, The method comprises the following steps: (1) dissolving an initiator and a room-temperature phosphorescent molecule in methyl methacrylate to prepare a reaction solution, and performing a prepolymerization of the reaction solution at a certain temperature to obtain a methyl methacrylate prepolymer; The room-temperature phosphorescent molecule comprises at least one of the following substances with the structural formula: OPO: , MOPO-PiCl: , NMP2O: ; The prepolymerization is performed at a temperature of 85-90℃ for 0.5-1.0 h; (2) performing a polymerization of the methyl methacrylate prepolymer at a certain temperature to obtain a room-temperature phosphorescent material, wherein the room-temperature phosphorescent material comprises a matrix composed of polymethyl methacrylate and a room-temperature phosphorescent molecule doped in the matrix; The polymerization is performed in two stages, i.e., first at 60-65℃ for 20-28 h and then at 90-110℃ for 2-4 h.
2. The method of claim 1, wherein the method comprises: In the room-temperature phosphorescent material, the doping amount of the room-temperature phosphorescent molecule accounts for 1.0%-2.0% of the polymethyl methacrylate in terms of mass percentage.
3. The method of claim 1, wherein the method is characterized by: In the step (1), the initiator is at least one of benzoyl peroxide and azobisisobutyronitrile.
4. The method of claim 3, wherein the method further comprises: When the initiator is benzoyl peroxide, the addition amount of benzoyl peroxide accounts for 0.2%-0.5% of the methyl methacrylate in terms of mass percentage; and when the initiator is azobisisobutyronitrile, the addition amount of azobisisobutyronitrile accounts for 0.6%-0.8% of the methyl methacrylate in terms of mass percentage.
5. A use of a room-temperature phosphorescent material prepared by the method of any one of claims 1-4 as a luminescent material in the preparation of an artware.