Long afterglow rtp material based on pva doping mechanism and preparation method thereof

Abstract

The application discloses a long-afterglow RTP material based on a PVA doping mechanism and a preparation method thereof, and belongs to the technical field of supramolecular materials, and comprises the following raw materials: PVA, isophthalic acid and chloroacetic acid, and deionized water is used as a solution; the long-afterglow RTP material is obtained by using a certain preparation method based on the above raw materials. The long-afterglow RTP material based on the PVA doping mechanism and the preparation method thereof have the advantages that all the medicines are commercially available, cheap and easy to obtain, the solvent used is deionized water, and the long-afterglow RTP material has the advantages of weak afterglow intensity, short delay time, poor stability, poor processability, long preparation period, high cost and the like, which are effectively improved; the preparation process is simple, the operation is simple, energy consumption is low, the yield is high, the cost is low, the preparation process is low-toxicity and environment-friendly, and the long-afterglow RTP material can be used for large-scale production.

Description

Technical Field

[0001] This invention relates to the field of supramolecular materials technology, and in particular to a long-afterglow RTP material based on PVA doping mechanism and its preparation method. Background Technology

[0002] RTP materials have potential applications in fields such as advanced information encryption. To prepare RTP materials simply and efficiently, non-covalent interaction forces are used to dope small molecules with polymers to obtain long afterglow materials.

[0003] Supramolecular RTP materials, due to their unique non-covalent interactions, possess various functionalities such as tunable color and stimulus-responsiveness, making them increasingly attractive in fields such as information encryption and anti-counterfeiting, bioimaging and sensing, and optoelectronic devices. However, achieving efficient and sustained RTP emission from metal-free organic phosphors is challenging due to their inherent spin-forbidden intersystem crossing (ISC) and the sensitivity of triplet excitons. Furthermore, the development of most RTP materials is hampered by factors such as weak afterglow intensity, short delay time, poor stability, poor processability, long preparation cycles, and high costs. Summary of the Invention

[0004] The purpose of this invention is to provide a long-afterglow RTP material based on PVA doping mechanism and its preparation method. All reagents used in this invention are commercially available, inexpensive and readily available. The solvent used is deionized water. This invention effectively improves the shortcomings of RTP materials, such as weak afterglow intensity, short delay time, poor stability, poor processability, long preparation cycle and high cost. The preparation process is simple, easy to operate, low in energy consumption, high in yield, low in cost and low in toxicity and environmentally friendly, and can be used for large-scale production.

[0005] To achieve the above objectives, this invention provides a long-afterglow RTP material based on a PVA doping mechanism and its preparation method, comprising the following raw materials:

[0006] PVA, isophthalic acid, and chloroacetic acid.

[0007] Preferably, the content of PVA is 400-700 mg, the content of isophthalic acid is 30-60 mg, and the content of chloroacetic acid is 3-12 mg.

[0008] A method for preparing long-afterglow RTP materials based on PVA doping mechanism includes the following steps:

[0009] S1. Weigh a certain amount of PVA, isophthalic acid and chloroacetic acid, and add them to a beaker;

[0010] S2. Add deionized water to a beaker and stir at a constant temperature until the sample is completely dissolved.

[0011] S3. After the solution reaches a clear state, pour it into a clean, open container and vacuum dry it to remove the aqueous solution, thus obtaining a thin film.

[0012] S4. After heating to 100-150℃, remove the film, cool it, and then grind it into powder using an agate mortar or grinder to obtain the long afterglow RTP material PA-IPA-CA.

[0013] Preferably, in step S2, the stirring temperature is 120–150°C and the stirring time is 20–60 min.

[0014] Preferably, in step S3, the vacuum drying temperature is 80–100°C.

[0015] Preferably, in S1, the mass ratio of PVA, isophthalic acid and chloroacetic acid is 600:50:7mg.

[0016] Preferably, in step S1, a fluorescent dye is added to the three-component system of PVA, isophthalic acid, and chloroacetic acid. The content of the fluorescent dye is 2-10 mg, and the fluorescent dye is Rhodamine B, Rhodamine 6G, or sodium fluorescein.

[0017] Therefore, the long-afterglow RTP material based on PVA doping mechanism and its preparation method of the present invention have the following beneficial effects:

[0018] (1) Introducing carbonyl groups, heteroatoms, and halogens to enhance spin-orbit coupling and fill triplet excitons makes the afterglow stronger and the lifetime longer.

[0019] (2) The organic phosphor isophthalic acid (IPA) is embedded in the polymer matrix PVA through a supramolecular self-assembly mechanism to effectively suppress non-radiative inactivation pathways.

[0020] (3) Introducing chloroacetic acid (CA) into the PVA-IPA system enhances spin-orbit coupling, promoting the ISC process from the excited singlet to the triplet state. This leads to a decrease in the probability of fluorescence and an increase in the probability of phosphorescence, thereby enhancing phosphorescence intensity. Secondly, the introduction of CA into the PVA-IPA system not only introduces Cl atoms, but the carboxyl group (-COOH) on CA also forms hydrogen bonds with the hydroxyl group (-OH) on the PVA backbone or with the (-COOH) group on IPA, further enhancing the rigidity of the supramolecular system. Furthermore, the rigid environment provided by this strong intermolecular hydrogen bonding shields the quencher, inhibiting the free movement of IPA molecules, thus stabilizing the triplet exciton and further suppressing nonradiative transitions.

[0021] (4) This invention obtains a polymer doping system with RTP phenomenon by non-covalent interaction force doping, and successfully prepares multicolor afterglow material by energy resonance transfer. The preparation process of this material is simple and efficient, low cost, short cycle and excellent performance.

[0022] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of various non-covalent bonds inside the PVA-IPA-CA material in Embodiment 1 of the present invention;

[0024] Figure 2 This is a schematic diagram of the afterglow of the three materials PVA-IPA-CA-RhB, PVA-IPA-CA-Rh6G, and PVA-IPA-CA-FLS in Embodiment 2 of the present invention. Detailed Implementation

[0025] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0026] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0027] Example 1

[0028] A method for preparing long-afterglow RTP materials based on PVA doping mechanism includes the following steps:

[0029] S1. Weigh out PVA, isophthalic acid and chloroacetic acid in a mass ratio of 600:50:7mg and add all three components to a beaker;

[0030] S2. Add 20 ml of deionized water to a beaker and stir at 150 °C for 30 min until the sample is completely dissolved.

[0031] S3. After the solution reaches a clear state, pour it into a clean glass petri dish and dry it under vacuum at 100°C to remove the aqueous solution, thus obtaining a thin film.

[0032] S4. After heating to 120°C, the film is removed, cooled, and then ground with a grinder to obtain a white powder, thus obtaining a long-afterglow RTP material PA-IPA-CA with green delayed phosphorescence.

[0033] Depend on Figure 1It can be seen that the long-afterglow RTP material PVA-IPA-CA has abundant non-covalent interactions. From the perspective of the material's optical properties, this strong intermolecular hydrogen bond interaction provides a rigid environment that shields against quenchers (such as oxygen), effectively increasing the ISC rate and making the afterglow stronger and longer. From the perspective of the material's preparation process, the abundant non-covalent bonds endow PA-IPA-CA material with excellent stability, processability, low cost, low energy consumption, high yield, low toxicity and environmental friendliness, making the preparation process simple, efficient and suitable for large-scale production.

[0034] Example 2

[0035] A method for preparing long-afterglow RTP materials based on PVA doping mechanism includes the following steps:

[0036] S1. Weigh out three groups of PVA, isophthalic acid and chloroacetic acid in a mass ratio of 600:50:7 mg and add them to three beakers respectively; then weigh out Rhodamine B (RhB), Rhodamine 6G (Rh6G) and fluorescein sodium (FLS) in a content of 4 mg each and add them to three beakers respectively.

[0037] S2. Add 20 ml of deionized water to each of the three beakers and stir at 150 °C for 30 min until the sample is completely dissolved.

[0038] S3. After the solution reaches a clear state, pour it into clean glass petri dishes and dry it under vacuum at 100°C to remove the aqueous solution, thus obtaining three kinds of films.

[0039] S4. After heating all three films to 120°C, remove them, cool them, and grind them into powder using a grinder to obtain four-component doped materials with red long-afterglow delayed fluorescence, PA-IPA-CA-RhB, yellow long-afterglow delayed fluorescence, PA-IPA-CA-Rh6G, and green long-afterglow delayed fluorescence, respectively.

[0040] Depend on Figure 2 The diagram shows the afterglow of the three materials. Using the long-afterglow RTP material PVA-IPA-CA as the energy donor and three commercially available fluorescent dyes RhB, Rh6G, and FLS as the energy acceptors, multicolor long-afterglow delayed fluorescent materials PVA-IPA-CA-RhB, PVA-IPA-CA-Rh6G, and PVA-IPA-CA-FLS can be obtained through an efficient PRET mechanism.

[0041] Therefore, this invention provides a long-afterglow RTP material based on PVA doping mechanism and its preparation method. All reagents used in this invention are commercially available, inexpensive, and readily available. The solvent used is deionized water. This invention effectively improves the shortcomings of RTP materials, such as weak afterglow intensity, short delay time, poor stability, poor processability, long preparation cycle, and high cost. The preparation process is simple, easy to operate, consumes little energy, has a high yield, is low in cost, and is low in toxicity and environmentally friendly, making it suitable for large-scale production.

[0042] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A long-afterglow RTP material based on PVA doping mechanism, characterized in that, Including the following raw materials: PVA, isophthalic acid and chloroacetic acid, in deionized water; The preparation method of long afterglow RTP material based on PVA doping mechanism includes the following steps: S1. Weigh a certain amount of PVA, isophthalic acid and chloroacetic acid and add them to a beaker; add a fluorescent dye to the three-component system of PVA, isophthalic acid and chloroacetic acid, the content of the fluorescent dye is 2~10mg; the fluorescent dye is Rhodamine B, Rhodamine 6G or sodium fluorescein. S2. Add deionized water to a beaker and stir at a constant temperature until the sample is completely dissolved. S3. After the solution reaches a clear state, pour it into a clean, open container and vacuum dry it to remove the aqueous solution, thus obtaining a thin film. S4. After heating to 100~150℃, remove the film, cool it, and then grind it into powder using an agate mortar or grinder to obtain long afterglow RTP material.

2. The long-persistent RTP material based on PVA doping mechanism according to claim 1, characterized in that: The content of PVA is 400~700mg, the content of isophthalic acid is 30~60mg, and the content of chloroacetic acid is 3~12mg.

3. The long-persistent RTP material based on PVA doping mechanism according to claim 1, characterized in that: In step S2, the stirring temperature is 120~150℃ and the stirring time is 20~60min.

4. The long-afterglow RTP material based on PVA doping mechanism according to claim 1, characterized in that: In step S3, the vacuum drying temperature is 80~100℃.

5. The long-persistent RTP material based on PVA doping mechanism according to claim 1, characterized in that: In S1, the mass ratio of PVA, isophthalic acid and chloroacetic acid is 600:50:7 mg.

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