Long-life room-temperature phosphorescent material as well as preparation method and application thereof

Abstract

The invention relates to a long-life room-temperature phosphorescent material and a preparation method and application thereof.According to the phosphorescent material, epoxy resin is doped with an epoxy prepolymer containing a fluorine-containing chain segment to serve as a host matrix, F-pi and pi-pi non-covalent synergistic interaction is formed between the host matrix and aromatic fluorescent guest molecules, the energy level difference of the excited state is adjusted, and the phosphorescent material is obtained. Intersystem crossing (ISC) and radiative transition rates are optimized, so that the phosphorescence lifetime and environmental adaptability are improved; a fluorine-containing chain segment introduced into a polymer system can be enriched on the surface of a material to form a needle-shaped structure, so that the surface energy of the material is remarkably reduced, the antifouling property is excellent, and additional functions of lyophobicity, transparency, chemical stability and the like are also realized while ultra-long room-temperature phosphorescence is realized; and cooperative enhancement and multifunctional integration of optical performance and surface performance are realized.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to the technical field of anti-counterfeiting materials, and particularly relates to a long-life room-temperature phosphorescent material and a preparation method and application thereof. BACKGROUND

[0002] Polymer-based room-temperature phosphorescent (RTP) materials have attracted extensive attention due to their good processability and morphological adaptability (such as thin films, coatings, microspheres, etc.), and provide a new solution for anti-counterfeiting technology. For example, patent ZL2022115938156 forms a rigid hydrogen bond network between the rich hydroxyl groups in polyvinyl alcohol (PVA) and amide compounds, effectively inhibits the non-radiative deactivation of triplet excitons, and finally obtains efficient and ultra-long-life phosphorescent emission. However, the hydrogen bond interaction is easily disturbed by water molecules, and phosphorescence quenching easily occurs in a humid environment, which limits its application in actual environment. Patent ZL2022114301297 describes an organic long-afterglow luminescent material and its application, which dopes biphenyl polymer mBPipQ into an epoxy resin matrix, has room-temperature phosphorescent properties of about 7s, and still has phosphorescent properties after soaking in strong acid (PH = 1) or strong base (PH = 14) solution for 10 days.

[0003] Although the existing research has improved the performance of RTP materials to some extent, there are still the following problems: the weak interaction such as hydrogen bond is easily destroyed by water molecules in a humid environment, leading to phosphorescence quenching or significant decrease in lifetime. Although traditional epoxy resins (such as aliphatic or bisphenol A type) can reduce this influence to some extent, the guest molecules doped in the polymer matrix have poor stability, and it is difficult to achieve ultra-long-life phosphorescence. The phosphorescent lifetime of most epoxy resin-based RTP materials still stays at the level of milliseconds to seconds, which is difficult to meet the requirements of high-security anti-counterfeiting, information encryption and other application scenarios that require long-life afterglow. Therefore, it is of great research value and application prospect to develop a new type of epoxy resin-based anti-counterfeiting material that can still maintain stable and ultra-long room-temperature phosphorescent emission in harsh environmental conditions. SUMMARY

[0004] Therefore, the present disclosure provides a long-life room-temperature phosphorescent material and a preparation method thereof, which solves the problems of short phosphorescent lifetime and insufficient environmental stability of existing epoxy-based RTP materials.

[0005] To achieve the above-mentioned purposes, in a first aspect, the long-life room-temperature phosphorescent material provided by the present disclosure comprises:

[0006] aromatic fluorescent guest molecules and a host matrix, and an epoxy prepolymer containing a fluorine-containing segment is doped in the epoxy resin as the host matrix;

[0007] The aromatic fluorescent guest molecules and the host matrix are cross-linked and cured to form the long-life room-temperature phosphorescent material.

[0008] Preferably, the aromatic fluorescent guest molecules are one or more of naphthalene, phenanthrene, perylene, anthracene, pyrene, triphenylene, benz[a]pyrene, fluoranthene, coronene and phenoxazine.

[0009] Preferably, the aromatic fluorescent guest molecules are 0.01-1wt% of the total mass of the host matrix.

[0010] Preferably, the crosslinking agent for crosslinking and curing comprises a thermosetting crosslinking agent and a photocuring crosslinking agent.

[0011] The thermosetting crosslinking agent comprises an acid anhydride curing agent and an amine curing agent, the acid anhydride curing agent is one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and phthalic anhydride; the amine curing agent is diethylenetriamine and / or ethylenediamine; the photocuring crosslinking agent is triaryl sulfonium phosphorus acid salt.

[0012] In a second aspect, the preparation method of the long-life room-temperature phosphorescent material according to any one of the first aspect comprises:

[0013] The epoxy acrylate monomer and the fluorine-containing acrylate are synthesized into an epoxy prepolymer containing a fluorine-containing segment through a copolymerization reaction;

[0014] The aromatic fluorescent guest molecules are prepared into a suspension liquid, which is added into a mixed solution containing the epoxy prepolymer, the epoxy resin and the crosslinking agent, so as to crosslink and cure the mixed system to obtain the long-life room-temperature phosphorescent material.

[0015] Preferably, the epoxy acrylate monomer is one or more of glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate and 3,4-epoxycyclohexylmethyl-methacrylate.

[0016] Preferably, the fluorine-containing acrylate is one or more of hexafluorobutyl acrylate, 1H,1H,2H,2H-nonfluorohexyl acrylate, tridecafluorooctyl acrylate and 1H,1H,2H,2H-heptadecafluorodecyl acrylate.

[0017] Preferably, the mass ratio of the epoxy prepolymer containing a fluorine-containing segment to the epoxy resin is 1:1-1:20.

[0018] Preferably, the epoxy resin is one or more of E-51, F-51, diphenyloxypropane diglycidyl ether and bisphenol A diglycidyl ether; and / or,

[0019] The initiator for the copolymerization reaction is one or more of azobisisobutyronitrile, azobisisoheptyl nitrile and dibenzoyl peroxide.

[0020] In a third aspect, the long-life room-temperature phosphorescent material according to any one of the first aspect has an application in the field of information encryption, anti-counterfeiting and anti-fouling.

[0021] Compared with the prior art, the present application has the following remarkable advantages and beneficial effects:

[0022] 1. By confining aromatic fluorescent guest small molecules in the three-dimensional cross-linked network of epoxy host resin, and utilizing the synergistic effect of F-π and π-π interaction, the phosphorescent lifetime is effectively improved. The structure forms a rigid constraint on the guest molecules, significantly reduces the molecular vibration, and thus inhibits the non-radiative transition path. At the same time, by optimizing the excited state energy level through molecular structure design, the efficiency of intersystem crossing (ISC) and radiative transition is further promoted. Finally, the multi-level confinement structure realizes the "three-level protection" of triplet excitons, so that the material exhibits an ultra-long phosphorescent lifetime of up to 30 seconds at room temperature, which is much higher than that of traditional polymer-based RTP materials.

[0023] 2. It has excellent moisture resistance and chemical stability. After being soaked in water for 6 weeks, it still maintains strong phosphorescent emission performance. Even after being soaked in strong acid (pH=1) and strong base (pH=14) for 6 weeks, it can still emit strong yellow afterglow, which widens the application of room-temperature phosphorescent materials under harsh conditions.

[0024] 3. By introducing fluorine-containing segments into the polymer system, the material surface can be enriched to form a needle-like structure, significantly reducing the surface energy and having excellent anti-fouling performance. While realizing ultra-long room-temperature phosphorescence, it also has additional functions such as lyophobicity, transparency and chemical stability, realizing the synergistic enhancement of optical performance and surface performance and multi-functional integration. BRIEF DESCRIPTION OF DRAWINGS

[0025] The accompanying drawings, which are incorporated into and form part of the specification, illustrate embodiments consistent with the present disclosure and, together with the specification, serve to explain the technical solutions of the present disclosure.

[0026] Figure 1 Afterglow images of different epoxy host phosphorescent materials prepared in Examples 2-4 after excitation by 365 nm ultraviolet light;

[0027] Figure 2 Phosphorescent time of thermally cured room-temperature phosphorescent materials of Examples 6-17 after excitation by 365 nm light, where a is Examples 6-8, b is Examples 9-11, c is Examples 12-14, and d is Examples 15-17;

[0028] Figure 3 Afterglow images of room-temperature phosphorescent materials of Examples 6, 9, 12 and 15 after excitation by 365 nm light;

[0029] Figure 4 Fluorescence and phosphorescence spectra of room temperature phosphorescent material for example 4 under 365 nm;

[0030] Figure 5 Applications of room temperature phosphorescent material for example 4 in the field of anti-counterfeiting and information encryption, where a is a schematic diagram of an anti-counterfeiting device and the anti-counterfeiting application of Cor@PTADGE / PFG coating, b is the afterglow image of the two-dimensional code prepared on the Cor@PTADGE / PFG coating and the college badge after removing ultraviolet light;

[0031] Figure 6 Applications of room temperature phosphorescent material for example 4 in the field of anti-fouling, where a is the sliding situation of sewage on the surface of the coating, b is the image of removing sewage by wiping, c is the image of removing ink by wiping, d is the image of removing hexadecane by wiping, e is the self-cleaning effect achieved by water, f is the image of removing dye by wiping;

[0032] Figure 7 Stability of room temperature phosphorescent material for example 4 under harsh conditions, where a is the photos of Cor@PTADGE / PFG coating dipping effect and anti-counterfeiting behavior of the coating in various aqueous solutions (including milk, coffee, water, pH=1, pH=13 and glycerol) under ambient conditions after turning off the 365 nm ultraviolet light source, b is the afterglow image of Cor@PTADGE / PFG coating in different solvents, c is the afterglow duration time of Cor@PTADGE / PFG coating before and after soaking in different solvents. DETAILED DESCRIPTION

[0033] Various exemplary embodiments, features, and aspects of the present disclosure will be described in detail below with reference to the accompanying drawings. Although various aspects of the embodiments are illustrated in the drawings, the drawings are not necessarily drawn to scale unless specifically indicated. The word "exemplary" used herein means "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.

[0034] To solve the problems in the background art, the long-life room temperature phosphorescent material described in the present disclosure is characterized by:

[0035] Doping an epoxy prepolymer containing fluorine-containing segments into the epoxy resin as the main matrix, realizing the formation of F-π and π-π non-covalent cooperative interaction between the aromatic fluorescent guest molecules, adjusting the excitation state energy level difference, optimizing the intersystem crossing (ISC) and radiation transition rate, thereby improving the phosphorescent lifetime and environmental adaptability.

[0036] Unlike traditional strategies that rely on highly dense cross-linked networks to stabilize guest molecules, this invention strengthens intermolecular non-covalent interactions as the primary stabilization mechanism. This design strategy allows fluorescent guest molecules to maintain a certain molecular orientation and aggregation state within the matrix, resulting in materials that maintain high phosphorescence lifetime while exhibiting better environmental adaptability. Furthermore, this invention introduces fluorinated segments into the polymer system. These segments accumulate on the material surface, forming needle-like structures that significantly reduce surface energy and endow the material with excellent hydrophobic and oleophobic properties. The fluorinated segments and epoxy groups work synergistically to construct a multi-level confinement structure, including a cross-linked network, hydrophobic segments, and weak non-covalent interactions, achieving "three-level protection" for triplet excitons. This "three-level protection" is as follows:

[0037] First, through F-π and π-π non-covalent interactions, intermolecular synergy is formed with fluorescent guest molecules, further suppressing their energy loss, enhancing electron delocalization, and improving intersystem crossing efficiency, thus achieving the first level of protection. Second, a highly cross-linked three-dimensional network is formed to physically embed and spatially confine the guest phosphorescent molecules, reducing their molecular vibrational and non-radiative transition probabilities, thus achieving the second level of protection. Finally, the self-enrichment behavior of fluorine-containing segments on the material surface forms an air film layer, significantly reducing surface energy, effectively blocking water molecule penetration, and reducing the interference of external quenchers on phosphorescence, thus achieving the third level of protection, thereby improving the stability of the material in humid or extreme environments.

[0038] Based on the aforementioned core technologies, this disclosure provides a method for preparing the long-lifetime room-temperature phosphorescent material, as follows:

[0039] Epoxy prepolymers containing fluorinated segments are synthesized by copolymerizing epoxy acrylic monomers with fluorinated acrylates.

[0040] Aromatic fluorescent guest molecules are formulated into a suspension and added to a mixture containing epoxy prepolymer, epoxy resin and crosslinking agent to crosslink and cure the mixture, thereby obtaining the long-life room temperature phosphorescent material.

[0041] In a specific embodiment, the epoxy acrylate monomer is one or more of glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3,4-epoxycyclohexyl methacrylate.

[0042] In a specific embodiment, the fluorinated acrylate is one or more of hexafluorobutyl acrylate, 1H,1H,2H,2H-nonafluorohexyl acrylate, tridecafluorooctyl acrylate and 1H,1H,2H,2H-heptafluorodecyl acrylate.

[0043] In a specific embodiment, the mass ratio of the epoxy prepolymer containing fluorinated segments to the epoxy resin is 1:1 to 1:20.

[0044] In specific embodiments, a molecular weight regulator 2,4-diphenyl-4-methyl-1-pentene is added in the copolymerization reaction.

[0045] In specific embodiments, the initiator for the copolymerization reaction is one or more of azobisisobutyronitrile, azobisisoheptyl nitrile and dibenzoyl peroxide.

[0046] In specific embodiments, the method for synthesizing the epoxy prepolymer containing fluorine-containing segments by copolymerization reaction of the epoxy acrylate monomer and the fluorine-containing acrylate ester comprises:

[0047] The epoxy acrylate monomer and the fluorine-containing acrylate monomer are mixed in a mass ratio of 1:1 and an ethyl acetate solution of 2,4-diphenyl-4-methyl-1-pentene is added, N2 is bubbled into the mixed system for a first time, and then the system is heated to a certain temperature for stirring for a second time;

[0048] After the initiator is added into the mixed system in the form of an ethyl acetate solution, the reaction is continued at 60-80°C for 6-8h, and the reaction product is purified to obtain the epoxy prepolymer containing fluorine-containing segments.

[0049] In specific embodiments, the aromatic fluorescent guest molecules are one or more of naphthalene, phenanthrene, perylene, anthracene, pyrene, triphenylene, benz[a]pyrene, fluoranthene, coronene and phenoxazine.

[0050] In specific embodiments, the aromatic fluorescent guest molecules are added in an amount of 0.01-1wt% of the total mass of the host matrix.

[0051] In specific embodiments, the crosslinking agent is a thermosetting crosslinking agent or a light-curing crosslinking agent, the thermosetting crosslinking agent is an acid anhydride curing agent or an amine curing agent, the acid anhydride curing agent is one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and phthalic anhydride, the amine curing agent is diethylenetriamine and / or ethylenediamine, and the light-curing crosslinking agent is triaryl sulfonium phosphorus salt.

[0052] In specific embodiments, the epoxy resin is one or more of E-51, F-51, diphenol hexafluoropropane diglycidyl ether and bisphenol A diglycidyl ether.

[0053] In specific embodiments, the method for crosslinking and curing the mixed system comprises:

[0054] The mixed system is sprayed onto a substrate, the solvent is dried in a 50°C oven for 1h, and then the crosslinking and curing are achieved by keeping the system in a 90-150°C oven for 2-6h or on a track light-curing machine for 1min.

[0055] The following are preferred embodiments of the present disclosure.

[0056] The starting materials, reagents or devices used in the embodiments can be obtained commercially or by known methods unless otherwise specified. The experimental or test methods are conventional methods in the art unless otherwise specified.

[0057] Embodiment 1

[0058] This embodiment 1 provides the synthesis of the epoxy prepolymer containing fluorine-containing segments, and the specific synthesis route is as follows:

[0059] ;

[0060] Wherein: x, y is the degree of polymerization;

[0061]

[0062] The specific synthesis steps are as follows:

[0063] S1. The epoxy acrylic monomer and the fluorine-containing acrylic monomer are weighed according to the mass ratio of 1:1 and then placed in a three-necked flask. Then 4wt% (referring to the total mass of epoxy acrylic and fluorine-containing acrylic) 2,4-diphenyl-4-methyl-1-pentene is dissolved in ethyl acetate and added to the three-necked flask. Bubble with N2 for 20 min, then place the flask in 75℃ and stir for 0.5 h.

[0064] S2. 3wt% (referring to the total mass of epoxy acrylic and fluorine-containing acrylic) initiator azobisisobutyronitrile is dissolved in 10 mL ethyl acetate, and then added dropwise to the mixed system prepared in step S1 using a dropping funnel. It is added dropwise within 1 h. Then continue to react at 70℃ for 7.5 h to obtain the reaction product.

[0065] S3. The reaction product in S2 is added dropwise to petroleum ether to purify the polymer, and vacuum drying at 60℃ obtains white solid powder polymer product, which is the fluorine-containing segment epoxy prepolymer.

[0066] The preparation of the long-life room temperature phosphorescent material and the corresponding comparative examples are described in detail in embodiments 2-17. The epoxy prepolymer involved in each embodiment is prepared in embodiment 1. The composition and amount of the raw materials involved in each embodiment are shown in Table 1.

[0067] Table 1 Composition and amount of raw materials involved in embodiments 2-17

[0068]

[0069]

[0070] Examples 2-4

[0071] The preparation of optically-curable room-temperature phosphorescent materials includes the following steps:

[0072] S1. Weigh 30 mg of benzene and dissolve it in 5 mL of ethyl acetate. Sonicate for 10 min to obtain a homogeneous benzene suspension.

[0073] S2. According to the raw material composition and ratio in Table 1, bisphenol hexafluoropropane diglycidyl ether, epoxy prepolymer, benzene and photocurable crosslinking agent are mixed and dissolved in 3 mL of ethyl acetate and sonicated for 15 min to prepare a solution. Then, the obtained solution is directly sprayed onto the glass substrate by spraying.

[0074] S3. The coating obtained after spraying in S2 above is kept at 50°C in an oven for 1 hour, and then cured under ultraviolet light for 1 minute to obtain room temperature phosphorescent material samples of Cor@PFG (Example 2), Cor@PTADGE (Example 3) and Cor@PTADGE / PFG (Example 4).

[0075] Example 5

[0076] The preparation of thermosetting room temperature phosphorescent materials specifically includes the following steps:

[0077] S1. Weigh 30 mg of benzene and dissolve it in 5 mL of dichloromethane. Sonicate for 10 min to obtain a homogeneous suspension.

[0078] S2. According to the raw material composition and ratio in Table 1, bisphenol hexafluoropropane diglycidyl ether, epoxy prepolymer, benzene and methyl hexahydrophthalic anhydride are mixed and dissolved in 3 mL of ethyl acetate and sonicated for 15 min to prepare a solution. Then, the obtained solution is directly sprayed onto the glass substrate by spraying.

[0079] S3. The coating obtained after spraying in S2 is kept at 50°C for 1 hour and then kept at 150°C for 4 hours to cure, thus obtaining a room temperature phosphorescent material.

[0080] Examples 6-8

[0081] The preparation of thermosetting room temperature phosphorescent materials specifically includes the following steps:

[0082] S1. Weigh 30 mg of perylene and dissolve it in 5 mL of dichloromethane. Sonicate for 10 min to obtain a homogeneous suspension.

[0083] S2. According to the raw material composition and ratio in Table 1, diphenol hexafluoropropane diglycidyl ether, epoxy prepolymer, perylene and methylhexahydrophthalic anhydride were mixed, dissolved in 3 mL of ethyl acetate and ultrasonically treated for 15 min to prepare a solution, and then the obtained solution was directly sprayed on a glass substrate by a spray coating method.

[0084] S3. The coating layer obtained after the spray coating in S2 was incubated in a 50°C oven for 1 h, and then incubated at 150°C for 4 h for curing, to obtain Py@PFG (Example 6), Py@PTADGE (Example 7) and Py@PTADGE / PFG (Example 8) room-temperature phosphorescent material samples, respectively.

[0085] Examples 9-11

[0086] The thermosetting room-temperature phosphorescent material was prepared, specifically including the following steps:

[0087] S1. Anthracene 30 mg was weighed and dissolved in 5 mL of dichloromethane, and ultrasonically treated for 10 min to obtain a uniform suspension.

[0088] S2. According to the raw material composition and ratio in Table 1, diphenol hexafluoropropane diglycidyl ether, epoxy prepolymer, anthracene and methylhexahydrophthalic anhydride were mixed, dissolved in 3 mL of ethyl acetate and ultrasonically treated for 15 min to prepare a solution, and then the obtained solution was directly sprayed on a glass substrate by a spray coating method.

[0089] S3. The coating layer obtained after the spray coating in S2 was incubated in a 50°C oven for 1 h, and then incubated at 150°C for 4 h for curing, to obtain Ant@PFG (Example 9), Ant@PTADGE (Example 10) and Ant@PTADGE / PFG (Example 11) room-temperature phosphorescent material samples, respectively.

[0090] Examples 12-14

[0091] S1. Phenanthrene 30 mg was weighed and dissolved in 5 mL of dichloromethane, and ultrasonically treated for 10 min to obtain a uniform suspension.

[0092] S2. According to the raw material composition and ratio in Table 1, diphenol hexafluoropropane diglycidyl ether, epoxy prepolymer, phenanthrene and methylhexahydrophthalic anhydride were mixed, dissolved in 3 mL of ethyl acetate and ultrasonically treated for 15 min to prepare a solution, and then the obtained solution was directly sprayed on a glass substrate by a spray coating method.

[0093] S3. The coating obtained after spraying in S2 above is kept at 50°C for 1 hour and then cured at 150°C for 4 hours to obtain room temperature phosphorescent material samples of Phen@PFG (Example 12), Phen@PTADGE (Example 13) and Phen@PTADGE / PFG (Example 14).

[0094] Examples 15-17

[0095] S1. Weigh 30 mg of triphenylene and dissolve it in 5 mL of dichloromethane. Sonicate for 10 min to obtain a homogeneous suspension.

[0096] S2. According to the raw material composition and ratio in Table 1, bisphenol hexafluoropropane diglycidyl ether, epoxy prepolymer, triphenylene oxide and methyl hexahydrophthalic anhydride are mixed and dissolved in 3 mL of ethyl acetate and sonicated for 15 min to prepare a solution. Then, the obtained solution is directly sprayed onto the glass substrate by spraying.

[0097] S3. The coating obtained after spraying in S2 above is kept at 50°C for 1 hour and then kept at 150°C for 4 hours to cure, thereby obtaining room temperature phosphorescent material samples of TP@PFG (Example 15), TP@PTADGE (Example 16) and TP@PTADGE / PFG (Example 17).

[0098] The room-temperature phosphorescent material samples from Examples 2-17 were tested, and the results are as follows:

[0099] Figure 1 The images show the afterglow of different epoxy-based phosphorescent materials prepared according to Examples 2-4 after excitation with 365 nm ultraviolet light. Figure 1 As can be seen, the materials exhibit room-temperature phosphorescence durations of approximately 20 seconds, 25 seconds, and 30 seconds after excitation. The phosphorescence lifetime of the Cor@PTADGE / PFG sample is significantly longer than that of the Cor@PFG and Cor@PTADGE samples. This difference indicates that the simultaneous presence of F-π and π-π interactions between the epoxy substrate and the small molecule guest can synergistically enhance phosphorescence performance. Specifically, the Cor@PTADGE system primarily relies on π-π interactions, while the Cor@PFG system is dominated by F-π interactions. In the Cor@PTADGE / PFG system, both interactions coexist, jointly promoting molecular order and electronic delocalization, thereby effectively improving intersystem crossing efficiency and extending phosphorescence lifetime. This result fully verifies the significant synergistic effect of F-π and π-π interactions in this invention.

[0100] Figure 2The phosphorescence time data of the thermally cured room temperature phosphorescent materials obtained in the above examples 6-17 after photoexcitation at 365 nm showed the same regularity as examples 2-4, which verified that the regularity of F-π and π-π synergistic interaction on phosphorescence enhancement was universal.

[0101] Figure 3 The phosphorescence time data of the thermally cured room temperature phosphorescent materials obtained in the above examples 6-17 after photoexcitation at 365 nm showed the same regularity as examples 2-4, which verified that the regularity of F-π and π-π synergistic interaction on phosphorescence enhancement was universal.

[0102] Figure 4 The phosphorescence time data of the thermally cured room temperature phosphorescent materials obtained in the above examples 6-17 after photoexcitation at 365 nm showed the same regularity as examples 2-4, which verified that the regularity of F-π and π-π synergistic interaction on phosphorescence enhancement was universal.

[0103] As Figure 5 The phosphorescence time data of the thermally cured room temperature phosphorescent materials obtained in the above examples 6-17 after photoexcitation at 365 nm showed the same regularity as examples 2-4, which verified that the regularity of F-π and π-π synergistic interaction on phosphorescence enhancement was universal. -2 ) for 2 min. After removing the mold, a two-dimensional code pattern was printed on the coating. It is worth noting that this pattern is invisible to the naked eye under ambient conditions. However, after excitation by 365 nm ultraviolet light, the pattern and the background turned black and yellow, respectively. In addition, the coating showed a two-dimensional code pattern, which could be maintained for several seconds and the information therein could be identified by scanning the code. Then, the pattern was erased by annealing at 90 °C for 6 min to obtain a new coating. Repeating the above steps with the A mold replaced by the B, C, and D molds, the numbers “123”, the letters “Tian Jin University”, and the logo of Tianjin University were clearly printed in sequence, thereby realizing the functions of anti-counterfeiting and information encryption.

[0104] The anti-fouling test results of the Cor@PTADGE / PFG sample of example 4 are as follows Figure 6 After 365 nm ultraviolet excitation, the light source was stopped, and some sewage was dropped on the glass plate coated with the coating which was placed obliquely. The sewage directly flowed down and did not contaminate the coating. When the glass plate was placed horizontally, the sewage could also be easily wiped off. After writing with a permanent marker and wiping with a paper towel, the ink on the glass plate could be completely removed. When the aqueous solution of dye or mud was dropped on the coating, the coating showed good water repellency, and the dirt could be simply wiped off with a paper towel. Similarly, the coating also had good oil repellency, and when hexadecane was dropped on the coating, the dirt could also be simply wiped off with a paper towel. When water droplets rolled on the surface of the coating, dust would be taken away with the flow of the droplets, leaving no traces and being uncontaminated. After removal by 365 nm ultraviolet excitation, the pattern of the two-dimensional code could still be displayed and identified, which indicated that the material had excellent anti-fouling performance.

[0105] The chemical stability test results of the Cor@PTADGE / PFG sample in Example 4 are as follows: Figure 7 When the coating is exposed to various contaminants, such as water, milk, coffee, HCl solution (pH=1), NaOH solution (pH=13), and glycerin, the surface can still be wiped clean after contamination. After UV irradiation, the QR code pattern remains visible and the information can be identified. Even after immersion in solution and UV excitation, the pattern remains visible and identifiable. The phosphorescence performance remains unchanged after immersion in water for 6 weeks. It also retains its phosphorescence performance after immersion in hydrochloric acid (aq., 0.1 M), sodium hydroxide (aq., 0.1 M), and sodium chloride (aq., 1 M) for 6 weeks. Even after immersion in concentrated hydrochloric acid (aq., 1 M) for 6 weeks, the phosphorescence performance is still maintained, demonstrating the excellent water resistance and chemical stability of this room-temperature phosphorescent material.

[0106] The various embodiments of this disclosure have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A long-life room-temperature phosphorescent material, characterized in that, include: Aromatic fluorescent guest molecules and host matrix, wherein an epoxy prepolymer containing fluorine segments is doped into an epoxy resin as the host matrix; The aromatic fluorescent guest molecules are cross-linked and cured with the host matrix to form the long-life room temperature phosphorescent material.

2. The long-life room-temperature phosphorescent material according to claim 1, characterized in that: The aromatic fluorescent guest molecules are one or more of naphthalene, phenanthrene, perylene, anthracene, pyrene, triphenylene, benzo[a]pyrene, fluoranthene, halobenzene, and phenoxazine.

3. The long-life room-temperature phosphorescent material according to claim 1 or 2, characterized in that: The aromatic fluorescent guest molecule accounts for 0.01 to 1 wt% of the total mass of the host matrix.

4. The long-life room-temperature phosphorescent material according to claim 3, characterized in that: The crosslinking agent for crosslinking curing includes thermosetting crosslinking agents and photosetting crosslinking agents; The thermosetting crosslinking agent includes anhydride curing agents and amine curing agents. The anhydride curing agent is one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and phthalic anhydride. The amine curing agent is diethylenetriamine and / or ethylenediamine. The photocuring crosslinking agent is triarylthiophosphate salt.

5. A method for preparing the long-lifetime room-temperature phosphorescent material according to any one of claims 1-4, characterized in that, include: Epoxy prepolymers containing fluorinated segments are synthesized by copolymerizing epoxy acrylic monomers with fluorinated acrylates. Aromatic fluorescent guest molecules are formulated into a suspension and added to a mixture containing epoxy prepolymer, epoxy resin and crosslinking agent to crosslink and cure the mixture, thereby obtaining the long-life room temperature phosphorescent material.

6. The method for preparing the long-lifetime room-temperature phosphorescent material according to claim 5, characterized in that: The epoxy acrylate monomer is one or more of glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3,4-epoxycyclohexyl methacrylate.

7. The method for preparing the long-lifetime room-temperature phosphorescent material according to claim 5 or 6, characterized in that: The fluorinated acrylate is one or more of the following: hexafluorobutyl acrylate, 1H,1H,2H,2H-nonafluorohexyl acrylate, tridecafluorooctyl acrylate, and 1H,1H,2H,2H-heptafluorodecyl acrylate.

8. The method for preparing the long-lifetime room-temperature phosphorescent material according to claim 7, characterized in that: The mass ratio of the epoxy prepolymer containing fluorinated segments to the epoxy resin is 1:1 to 1:

20.

9. The method for preparing the long-lifetime room-temperature phosphorescent material according to claim 5, 6, or 8, characterized in that: The epoxy resin is one or more selected from E-51, F-51, bisphenol A difluoropropane diglycidyl ether, and bisphenol A diglycidyl ether; and / or The initiator used in the copolymerization reaction is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, and benzoyl peroxide.

10. The application of the long-life room temperature phosphorescent material according to any one of claims 1-4 in the fields of information encryption, anti-counterfeiting and anti-fouling.

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