An organic glass scintillator material, a method for preparing the same, and an application thereof

Abstract

The application discloses an organic glass body scintillator material and a preparation method and application thereof. The material comprises a dynamic covalent cross-linked polymer network formed by reaction of an epoxy monomer containing a halogenated conjugated group, a multifunctional carboxylic acid curing agent or a multifunctional anhydride curing agent and an ester exchange catalyst. The application makes the cross-linked network unit have intrinsic radiation light emitting characteristics through molecular structure design, and does not need to be physically doped with a light emitting guest, thus fundamentally solving the bottlenecks of easy precipitation, easy phase separation and low optical transparency of a traditional doped scintillator. The obtained material has high efficient radiation light emission and high transparency, and significantly improves imaging spatial resolution. Meanwhile, by using the topological rearrangement characteristics of a dynamic ester bond, the defect of non-recyclability of a thermosetting scintillator is overcome, and self-repair, morphology customization and cyclic reshaping of a device are realized. The preparation process of the application is simple, and the application has important significance in the fields of X-ray imaging, nondestructive testing and the like.

Description

Technical Field

[0001] This application relates to the fields of optoelectronic functional materials and X-ray detection technology, and mainly to an organic glass scintillator material, its preparation method and application. Background Technology

[0002] X-ray detection technology has wide applications in cutting-edge fields such as clinical medical diagnosis, industrial non-destructive testing (NDT), public safety inspection, and astrophysical exploration. Scintillator materials, as the core energy conversion medium for converting high-energy X-rays into low-energy visible light, directly determine the sensitivity and imaging quality of the detector. With the development of modern imaging technology towards portability, flexibility, and large-area fabrication, the development of highly flexible, low-cost, and easily fabricated large-area scintillator thin films has become a current research hotspot.

[0003] Currently, commercially available scintillator materials are mainly inorganic crystals or ceramics. However, the fabrication process for these materials is cumbersome and costly, and their inherent brittleness and rigidity make them difficult to process into flexible devices and large-area fabrication. To overcome these limitations, researchers typically physically mix scintillator microcrystals or fluorescent molecules into polymer matrices to form composite films. However, this physical doping technique faces severe bottlenecks: First, phase separation or particle agglomeration easily occurs during the fabrication process, leading to severe light scattering, which reduces film transparency and deteriorates imaging spatial resolution; second, increasing the loading to enhance X-ray interception capability further exacerbates phase separation; finally, once the traditional polymer matrix is ​​cross-linked, it forms a permanent chemical structure that cannot be repaired after damage, and the device cannot be recycled by remodeling after it is scrapped.

[0004] In summary, developing a novel intrinsically luminescent organic scintillator material, overcoming phase separation and transparency issues caused by physical doping through molecular structure design, breaking through the bottlenecks of sensitivity and resolution, and simultaneously possessing excellent mechanical flexibility, processability, and recyclable repair capabilities, is of great significance and has promising application prospects. Summary of the Invention

[0005] To address the technical problems in existing technologies, such as phase separation and poor transparency caused by physical doping, and the inability to recycle and reuse traditional thermosetting matrices, this application proposes an organic glass scintillator material, its preparation method, and its application.

[0006] According to one aspect of the present invention, an organic glass scintillator material is provided, comprising a dynamic covalently cross-linked polymer network; the dynamic covalently cross-linked polymer network is formed by reacting an epoxy monomer containing a halogenated conjugated group, a multifunctional carboxylic acid curing agent or a multifunctional acid anhydride curing agent, and an ester exchange catalyst; the structural units in the dynamic covalently cross-linked polymer network possess radiative emission characteristics; the raw materials of the dynamic covalently cross-linked polymer network, by molar parts, include: 100 parts of an epoxy monomer containing a halogenated conjugated group, 30-120 parts of a multifunctional carboxylic acid curing agent or a multifunctional acid anhydride curing agent, and 0.1-5 parts of an ester exchange catalyst; the epoxy monomer containing a halogenated conjugated group includes a halogenated bisphenol A type epoxy resin or a halogenated resorcinol type epoxy resin.

[0007] This invention constructs a cross-linked polymer network with dynamic covalent properties through specific monomer design and catalytic system. This network covalently bonds epoxy monomers containing halogenated conjugated groups and conjugated carboxylic acid monomers with phosphorescent emission properties as structural units within the framework. Under X-ray irradiation, the heavy atom effect efficiently intercepts X-ray energy and transfers it to the conjugated carboxylic acid center. By fully utilizing the triplet excitons, which account for 75% of the total excited states, for radiative transitions, the material is endowed with excellent intrinsic radiative emission properties. Simultaneously, based on the reversible exchange mechanism of dynamic covalent bonds, the material maintains high luminescence efficiency while achieving self-repair and remodeling after damage, achieving a high degree of integration of "structure-function" in scintillator materials.

[0008] Epoxy monomers containing halogenated conjugated groups serve as radiation energy-harvesting units in a polymer network, achieving efficient energy conversion synergy through the heavy atom effect and covalent network energy transfer pathways. The introduction of heavy atoms significantly increases the material's interception cross-section for high-energy X-ray photons, improving energy conversion efficiency. Simultaneously, since both the harvesting and emitting units (multifunctional carboxylic acids / anhydrides) are covalently bonded within the framework, an extremely short energy transfer path is constructed, effectively avoiding energy loss during matrix-guest transfer. This results in high-contrast imaging effects under X-ray excitation.

[0009] Preferably, the halogenated bisphenol A type epoxy resin includes tetrabromobisphenol A diglycidyl ether or tetraiodobisphenol A diglycidyl ether; the halogenated hydroquinone type epoxy resin includes dibromohydroxyl diglycidyl ether or tetrabromohydroxyl diglycidyl ether.

[0010] Preferably, the multifunctional carboxylic acid curing agent includes one or more of aliphatic multifunctional carboxylic acids and aromatic multifunctional carboxylic acids with phosphorescent emission properties, and the multifunctional anhydride curing agent includes one or more of aliphatic multifunctional anhydrides and aromatic multifunctional anhydrides with phosphorescent emission properties.

[0011] By introducing multifunctional carboxylic acid curing agents or multifunctional anhydride curing agents, radiative emission centers are formed in the cross-linked polymer network, enabling precise control over the mechanical and luminescent properties of the scintillator material. In the energy transfer mechanism of this application, the curing agent monomer acts as the final energy receiver and emitter, and its conjugated skeleton can effectively capture the excited state energy transferred from the heavy atom centers of the epoxy monomer. Since approximately 75% of the excitons generated by X-ray excitation are triplet states, this application, by selecting conjugated aromatic carboxylic acid monomers with phosphorescent emission characteristics, can fully utilize the triplet energy for radiative transitions, thereby significantly improving the light yield of the material. Furthermore, by adjusting the structure of the curing agent, differentiated customization of performance can be achieved: aliphatic segments can improve the impact resistance and flexibility of the material, while the aromatic skeleton, while providing rigidity, ensures excellent radiative emission efficiency of the material under high transparency through its intrinsic phosphorescent emission characteristics.

[0012] More preferably, the aliphatic multifunctional carboxylic acid includes succinic acid, adipic acid, sebacic acid, or dodecanoic acid; the aromatic multifunctional carboxylic acid with phosphorescent emission properties includes pyromellitic acid, 4,4',4''-tricarboxylic acid, terephthalic acid or terephthalic acid derivatives, phenyldioxyacetic acid or phenyldioxyacetic acid derivatives.

[0013] Preferably, the transesterification catalyst comprises one or more of zinc acetylacetonate, triazabicyclodecene, zinc octanoate, and 1-methylimidazole. During the curing stage, the transesterification catalyst significantly reduces the activation energy between monomers, inducing rapid and uniform formation of a dynamic network, thereby efficiently locking the luminescent structural units within the framework. In the application stage, the catalyst acts as an active center, endowing the material with excellent topological rearrangement capabilities, enabling the scintillator to activate dynamic bond exchange at relatively low temperatures. This design ensures stable intrinsic radiative luminescence performance while achieving efficient self-healing and remodeling processing, effectively avoiding potential performance damage to the luminescent groups caused by high-temperature treatment.

[0014] According to a second aspect of the present invention, a method for preparing an organic glass scintillator material is provided, comprising the following steps:

[0015] S1. An epoxy monomer containing a halogenated conjugated group, a multifunctional carboxylic acid curing agent or a multifunctional acid anhydride curing agent, and an ester exchange catalyst are mixed in proportion and heated to melt or dissolve to obtain a precursor mixture.

[0016] S2. After degassing the precursor mixture, inject it into a mold and carry out a thermosetting reaction at 80-200℃ to obtain the organic glass scintillator material.

[0017] Preferably, in step S2, the thermosetting reaction adopts a gradient temperature curing method; the organic glass scintillator material can be hot-pressed or annealed after thermosetting.

[0018] The one-step thermosetting molding process employed in this invention achieves a smooth conversion of monomers into a dynamically cross-linked polymer network through gradient heating within a range of 80-200℃. This process is not only simple to operate and requires no complex purification, but also effectively eliminates internal stress generated during molding, preventing optical distortion or microcracks from occurring in the material during curing or demolding.

[0019] According to a third aspect of the present invention, an organic glass scintillator material is proposed for use in X-ray imaging detectors, industrial non-destructive testing screens, three-dimensional dosimetry verification devices, and recyclable and self-healing scintillator devices.

[0020] Compared with the prior art, this application has the following beneficial effects:

[0021] This application abandons the traditional physical doping model of "polymer matrix + luminescent guest," and instead uses molecular structure design to construct a cross-linked network framework where the trapping and luminescent units are covalently bonded to the polymer framework. Since both the trapping and luminescent units are covalently attached to the polymer framework, the light scattering problems caused by guest molecule precipitation, aggregation quenching, and phase separation are effectively solved. In this intrinsic system, the epoxy unit containing halogenated conjugated groups can efficiently trap X-ray energy and precisely transfer it to the conjugated carboxylic acid luminescent center. This allows the material to maintain an optical transparency of approximately 80% while introducing a high loading of heavy atoms to ensure efficient X-ray energy conversion, significantly improving the spatial resolution of imaging.

[0022] The halogenated epoxy monomers and conjugated polyfunctional carboxylic acid monomers selected in this application both possess phosphorescence emission properties. The heavy atom effect promotes the radiative transition process of excitons, enabling the system to exhibit pronounced room-temperature phosphorescence characteristics under X-ray excitation, with a luminescence lifetime on the order of milliseconds. The synergistic effect of phosphorescence from both the epoxy monomer and the curing agent monomer further enhances the material's light yield and radiative energy utilization.

[0023] This application introduces dynamic covalent bonds based on an ester exchange mechanism into the scintillator network. Unlike traditional non-degradable and non-remodelable thermosetting plastic scintillators, the network topology of this material can be rearranged when heated above its topological freezing temperature (Tv). This enables the material to be recycled and reshaped through hot pressing and also achieves surface self-healing of damaged devices. While maintaining efficient radiative emission performance, it significantly extends the service life of scintillator devices and meets the requirements of green environmental protection and sustainable development.

[0024] The preparation process of this application only requires one step of thermosetting molding, without the need for complex synthesis and purification steps, and the raw materials are widely available and inexpensive, making it very easy to achieve customized processing of large-area flexible scintillator screens. Attached Figure Description

[0025] The accompanying drawings are included to provide a further understanding of the embodiments and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments and, together with the description, serve to explain the principles of this application. Other embodiments and many anticipated advantages of these embodiments will be readily recognized as they become better understood through reference to the following detailed description. Elements in the drawings are not necessarily to scale. The same reference numerals refer to corresponding similar parts.

[0026] Figure 1 An X-ray irradiation effect diagram of an organic glass scintillator material according to an embodiment of this application is shown;

[0027] Figure 2 A schematic diagram illustrating the preparation process of an organic glass scintillator material according to an embodiment of this application is shown;

[0028] Figure 3 A schematic diagram of the fabrication process of an organic glass scintillator thin film according to a specific embodiment of this application is shown;

[0029] Figure 4 The XRD pattern of an organic glass scintillator film according to a specific embodiment of this application is shown;

[0030] Figure 5 The UV-Vis transmission spectrum of an organic glass scintillator film according to a specific embodiment of this application is shown.

[0031] Figure 6 The photoluminescence spectrum of an organic glass scintillator thin film according to a specific embodiment of this application is shown;

[0032] Figure 7 A lifetime decay graph of an organic glass scintillator film according to a specific embodiment of this application is shown;

[0033] Figure 8 The X-ray excitation emission spectrum of the organic glass scintillator thin film of Embodiment 1 of this application is shown;

[0034] Figure 9 The X-ray excitation emission spectrum of the organic glass scintillator thin film of Embodiment 2 of this application is shown;

[0035] Figure 10 The X-ray excitation emission spectrum of the organic glass scintillator thin film of Embodiment 3 of this application is shown;

[0036] Figure 11 The X-ray excitation emission spectrum of the organic glass scintillator thin film of Embodiment 4 of this application is shown;

[0037] Figure 12 An X-ray imaging image of an organic glass scintillator film according to a specific embodiment of this application is shown;

[0038] Figure 13 An X-ray imaging resolution diagram of an organic glass scintillator thin film according to a specific embodiment of this application is shown;

[0039] Figure 14 The diagram illustrates the recyclability and reusability of an organic glass scintillator film according to a specific embodiment of this application.

[0040] Figure 15 The X-ray excitation emission spectrum of the scintillator thin film of Comparative Example 1 of this application is shown;

[0041] Figure 16 The image shows the effect of X-ray irradiation on the scintillator film of Comparative Example 1 of this application. Detailed Implementation

[0042] The present application will now be described in further detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention. Furthermore, it should be noted that, for ease of description, only the parts relevant to the invention are shown in the accompanying drawings.

[0043] Where there is no conflict, the embodiments and features described in this application can be combined with each other. This application will now be described in detail with reference to the accompanying drawings and embodiments.

[0044] An organic-based glass scintillator material comprises a dynamically covalently cross-linked polymer network. This network is formed by reacting an epoxy monomer containing halogenated conjugated groups, a multifunctional carboxylic acid curing agent or a multifunctional acid anhydride curing agent, and a transesterification catalyst. Under X-ray excitation, this organic-based glass scintillator exhibits highly efficient radiative luminescence and excellent optical transparency, such as… Figure 1 As shown.

[0045] Specifically, the structural units in the dynamically covalently cross-linked polymer network possess radiative luminescence properties. These structural units refer to repeating cross-linked network units formed by ring-opening polymerization of epoxy monomers containing halogenated conjugated groups and polyfunctional carboxylic acids or polyfunctional anhydrides as curing agents. Because the luminescent groups are covalently bonded to the polymer backbone, each basic chemical unit constituting this dynamically covalently cross-linked network possesses the intrinsic property of absorbing high-energy radiation and converting it into visible light, thus achieving a highly uniform distribution of luminescent centers at the molecular level. Simultaneously, the intrinsic luminescence design avoids energy loss during the transfer of energy from the matrix to the guest, significantly improving radiative luminescence efficiency.

[0046] In specific embodiments, the dynamic covalent crosslinking network utilizes an ester exchange catalyst to induce ester bond breaking and recombination at high temperatures, enabling the material to exhibit processability similar to thermoplastics above the topological freezing temperature (Tv), while maintaining the mechanical strength of thermosetting plastics at room temperature. This effectively solves the drawback of traditional scintillator matrices being unable to change shape after crosslinking, achieving customized device morphology.

[0047] Specifically, the raw materials for the dynamic covalent crosslinked polymer network, by molar parts, include: 100 parts of epoxy monomer containing halogenated conjugated groups, 30-120 parts of polyfunctional carboxylic acid curing agent or polyfunctional acid anhydride curing agent, and 0.1-5 parts of transesterification catalyst. By strictly controlling the molar ratio of epoxy groups to carboxyl / anhydride groups within a near-equivalent range, sufficient free hydroxyl groups can be retained in the cured system, thereby providing the necessary reaction sites for the transesterification reaction, ensuring that the material has optimal crosslinking density, and balancing the hardness of the scintillator with the dynamic repair rate.

[0048] Specifically, epoxy monomers containing halogenated conjugated groups include one or more of the following: halogenated bisphenol A type epoxy resins, halogenated hydroquinone type epoxy resins, and halogenated glycidyl ether compounds containing biphenyl, naphthalene, or anthracene skeletons.

[0049] In specific embodiments, the halogenated bisphenol A type epoxy resin includes tetrabromobisphenol A diglycidyl ether or tetraiodobisphenol A diglycidyl ether; the halogenated hydroquinone type epoxy resin includes dibromohydroxyl diglycidyl ether or tetrabromohydroxyl diglycidyl ether. By introducing a conjugated framework containing bromine or iodine atoms, the photoelectric effect of heavy atoms can be used to significantly increase the material's interception cross-section for high-energy X-ray photons. The intercepted energy is then transferred losslessly to the luminescent center through a covalent network.

[0050] Specifically, multifunctional carboxylic acid curing agents include one or more of aliphatic multifunctional carboxylic acids and aromatic multifunctional carboxylic acids with phosphorescent emission properties, and multifunctional acid anhydride curing agents include one or more of aliphatic multifunctional acid anhydrides and aromatic multifunctional acid anhydrides with phosphorescent emission properties. Aliphatic carboxylic acids can provide flexible segments to adjust the glass transition temperature (Tg), while aromatic carboxylic acids can construct rigid centers. By adjusting the ratio of rigidity to flexibility, various scintillators ranging from rigid bulk materials to flexible, bendable films can be prepared to adapt to different imaging environments.

[0051] In specific embodiments, aliphatic multifunctional carboxylic acids include succinic acid, adipic acid, sebacic acid, or dodecanoic acid; aromatic multifunctional carboxylic acids include pyromellitic acid, 4,4',4''-tricarboxylic acid, terephthalic acid or terephthalic acid derivatives, phenyldioxyacetic acid or phenyldioxyacetic acid derivatives.

[0052] In specific embodiments, the transesterification catalyst includes one or more of zinc acetylacetonate, triazabicyclodecene, zinc octanoate, and 1-methylimidazole. The transesterification catalyst synergistically promotes chemical crosslinking and dynamic exchange. During the initial thermosetting phase of the scintillator material, the catalyst lowers the energy barrier for the esterification reaction between epoxy groups and carboxyl / anhydride groups, enabling halogenated conjugated groups to rapidly participate in network formation and achieve uniform distribution at the molecular level. This is crucial for improving the spatial resolution of the scintillator's imaging. During the use or repair of the material after molding, the catalyst acts as a catalytic medium for the dynamic transesterification reaction, inducing controlled recombination of the polymer network topology under heating conditions. This dynamic characteristic not only endows the scintillator surface with self-healing capabilities for microcracks but also enables the material to undergo thermo-press reshaping and recycling. Furthermore, due to the high catalytic efficiency of the selected catalyst, the material can complete network rearrangement within a relatively low temperature window, thereby maximizing the protection of the structural integrity of the luminescent framework and preventing quenching or attenuation of radiative emission due to overheating.

[0053] Figure 2 This is a schematic diagram of the preparation process of this organic glass scintillator material, for reference. Figure 2 This includes the following steps:

[0054] S1. Mix epoxy monomers containing halogenated conjugated groups and polyfunctional carboxylic acid curing agents or polyfunctional acid anhydride curing agents in proportion, heat to a molten state or dissolve in a solvent, then add transesterification catalyst and stir evenly to obtain a precursor mixture.

[0055] S2. The precursor mixture is placed in a vacuum environment for degassing to remove air bubbles generated during the mixing process. The degassed precursor mixture is then injected into a mold or coated onto a substrate and cured at a gradient temperature of 80-200℃. After the reaction is complete, the mixture is demolded to obtain a transparent organic glass-like scintillator material.

[0056] In a specific embodiment, the solvent in step S1 is N,N-dimethylformamide.

[0057] In practical applications, this organic-based glass scintillator material, with its intrinsic molecular luminescence, can effectively eliminate light scattering centers in traditional doped materials, thereby significantly improving the spatial resolution and contrast of X-ray imaging. In particular, utilizing its dynamic covalent remodeling properties, this organic-based glass scintillator material can be fabricated into flexible curved detectors or large-area seamless splicing screens to adapt to complex non-planar imaging requirements. Simultaneously, through thermally excited transesterification reactions within the material, in-situ self-repair of detector surface damage can be achieved, supporting the hot-pressing recycling and reuse of discarded devices. Furthermore, this material shows broad application prospects in medical imaging diagnostics, precision industrial CT, electronic chip testing, and flexible personal dosimetry monitoring, not only improving detection accuracy but also significantly extending the service life of precision detection equipment and reducing operating costs.

[0058] Example 1

[0059] An organic glass scintillator thin film, reference Figure 3 The specific preparation method is as follows:

[0060] S101. Weigh 3.80 g (10 mmol) of 2,5-dibromohydroquinone diglycidyl ether, 0.5 g (1.5 mmol) of 2-bromo-5-formyl-1,4-phenyldioxyacetic acid and 1.24 g (8.5 mmol) of adipic acid according to the proportion and mix them. Heat the mixture at 140 °C to a molten state, and then add 27 mg of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as an ester exchange catalyst. Stir thoroughly to obtain a homogeneous deep yellow transparent fluid, i.e., the precursor mixture.

[0061] S102. Place the precursor mixture in a vacuum environment to degas for 2 minutes. After the bubbles have completely disappeared, pour it into a mold and place it in a forced-air oven to cure at 150°C for 5 hours. After demolding, an organic glass scintillator film can be obtained.

[0062] In specific embodiments, by adjusting the molar ratio of epoxy monomers containing halogenated conjugated groups to polyfunctional carboxylic acid curing agents or polyfunctional anhydride curing agents, a series of glass-like scintillators with different crosslinking densities and properties can be prepared.

[0063] Figure 4 The image shows the XRD pattern of the organic glass scintillator film. As shown, after curing, the organic glass scintillator material exhibits no obvious sharp crystal diffraction peaks, only a broad and diffuse peak, indicating that it has formed a uniform amorphous structure without monomer precipitation or crystallization. Meanwhile, as... Figure 5 As shown in the UV-Vis transmission spectrum, thanks to this amorphous homogeneous structure, the organic glass scintillator material maintains a transmittance of about 80% in the visible light range of 500 nm-800 nm, exhibiting excellent optical transparency.

[0064] Figure 6 and Figure 7 The figures show the photoluminescence (PL) spectrum and lifetime decay diagram of the organic glass scintillator material. As can be seen from the figures, the emission peak of the organic glass scintillator material is located at 530 nm. Furthermore, the introduction of a high concentration of heavy bromine atoms into the system increases the material's interception cross-section for high-energy rays and promotes the radiative transition process of excitons, resulting in room-temperature phosphorescence properties. Tests show that the luminescence lifetime of the scintillator is approximately 1.79 ms.

[0065] Figure 8 The X-ray excitation emission spectrum of this organic glassy scintillator material is shown. The results show that, under X-ray excitation, its emission peak position is basically consistent with the photoluminescence peak position, proving that the luminescence center originates from the intrinsic radiative transition of the polymer.

[0066] Example 2

[0067] The only difference between this example and Example 1 is that 2-bromo-5-formyl-1,4-phenyldioxyacetic acid is 0.67 g (2 mmol) and adipic acid is 1.17 g (8 mmol).

[0068] Figure 9 The figure shows the X-ray excitation emission spectrum of the organic glass scintillator material prepared in Example 2. As can be seen from the figure, the emission peak position remains stable at about 530 nm, and the peak shape is complete and symmetrical, indicating that the luminescent centers still maintain a uniform molecular-level dispersion at high concentrations, and no aggregation-induced quenching phenomenon caused by excessive concentration occurs.

[0069] Example 3

[0070] The only difference between this example and Example 1 is that 2-bromo-5-formyl-1,4-phenyldioxyacetic acid is 0.33 g (1.0 mmol) and adipic acid is 1.32 g (9.0 mmol).

[0071] Figure 10The X-ray excitation emission spectrum is that of the organic glassy scintillator material prepared in Example 3. (Comparison) Figure 8 , Figure 9 and Figure 10 It can be observed that the intensity of radiative emission decreases synchronously with the decrease in the molar ratio of luminescent monomers. This trend strongly demonstrates that precise linear control of the luminescence brightness of the scintillator can be achieved by adjusting the monomer ratio.

[0072] Example 4

[0073] An organic glass scintillator thin film is prepared by the following method:

[0074] S401. Weigh 6.56 g (10 mmol) tetrabromobisphenol A diglycidyl ether, 0.37 g (1 mmol) tris(4-carboxyphenyl)amine and 1.31 g (9 mmol) adipic acid according to the proportion and mix them. Heat the mixture at 140 °C to a molten state, then add 27 mg of transesterification catalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and stir thoroughly to obtain a homogeneous deep yellow transparent fluid, i.e., the precursor mixture.

[0075] S402. Place the precursor mixture in a vacuum environment to degas for 2 minutes. After the bubbles have completely disappeared, pour it into a mold and place it in a forced-air oven to cure at 150°C for 5 hours. After demolding, an organic glass scintillator film can be obtained.

[0076] Figure 11 The X-ray excitation emission spectrum of the organic glass scintillator material prepared in Example 4 is shown. Its clear and high-intensity emission spectrum demonstrates that even after altering the molecular framework structure, the material can still be successfully cross-linked and maintain efficient radiative emission characteristics. This not only reflects the universality of this approach for different raw material systems but also allows the material to achieve differentiated luminescence brightness by flexibly selecting monomers according to diverse detection requirements.

[0077] Example 5

[0078] Using the organic glass scintillator film prepared in Example 1 as the scintillator screen, and employing chips, metals, etc., as imaging objects, an X-ray source as the excitation source, and a common commercial camera as the image capture device, the organic glass scintillator film absorbs X-rays and converts them into visible light signals, which are then captured by the sensor.

[0079] Figure 12 and Figure 13 The images shown are X-ray images and X-ray resolution diagrams of the organic glass scintillator film. Figure 12 a and Figure 12b represents a physical image and an X-ray image of an industrial fuse, respectively. Figure 12 As can be seen, the scintillator film can penetrate the opaque outer shell of the fuse, clearly and completely revealing the fine fuse wire traces and electrode connection status inside, with no image distortion and sharp edges. Figure 12 c and Figure 12 d represents the physical image and X-ray image of the memory chip, respectively. (From...) Figure 12 As can be seen, this scintillator film can reveal the complex lead frame and arrayed fine gold wire structure inside the chip with extremely high contrast. (In conjunction with...) Figure 13 The imaging resolution test shown demonstrates that the scintillator film, while possessing high sensitivity, can provide extremely high spatial resolution, proving the application potential of this organic glass scintillator in X-ray imaging and non-destructive testing.

[0080] Figure 14 This study demonstrates the remodeling and recyclability of this organic-based glass scintillator film. The film can be cut into fragments and then reassembled into complete films using a hot-pressing method. Furthermore, the film can be molded into various curved surfaces through hot-pressing bending or hot-smoothing processes. This process proves that this type of glass scintillator possesses excellent machinability and recyclability.

[0081] Comparative Example 1

[0082] A scintillator film differs from Example 4 only in that the raw materials used in its preparation are 3.4 g (10 mmol) of bisphenol A diglycidyl ether, 0.41 g (1 mmol) of 4,4'-((4-bromophenyl)amino)dibenzoic acid and 1.31 g (9 mmol) of adipic acid.

[0083] Figure 15 The X-ray excitation emission spectrum of the scintillator thin film prepared in Comparative Example 1 is shown. Figure 16The image shows the actual luminescence effect under X-ray excitation. A comparison with Example 4 shows that the position of heavy atoms in the molecular structure has a decisive influence on the radiative luminescence efficiency. When heavy atoms are covalently modified on epoxy monomers with a conjugated framework (as in Example 4), the material exhibits extremely high radiative luminescence yield; however, when heavy atoms are instead modified on carboxylic acid curing agent monomers (as in Comparative Example 1), the light yield of the material drops drastically, and there is almost no luminescence effect under X-ray excitation. This is because under X-ray radiation, the excited products typically include 75% triplet excitons and 25% singlet excitons. In this application, the epoxy monomer, as the core unit for capturing X-rays and generating primary excited states, must directly carry heavy atoms to effectively convert the dominant triplet energy into a radiative luminescence path through strong spin-orbit coupling effects. The failure of Comparative Example 1 strongly demonstrates that if heavy atoms deviate from the excitation source center of the epoxy monomer, they will be unable to achieve effective physical coordination with the generated excited state, resulting in the triplet energy being dissipated in vain through nonradiative transitions. Heavy atoms must be covalently bonded to the epoxy monomer of a specific conjugated framework in order to construct efficient heavy atom trapping centers and radiative emission centers in the dynamic covalent network.

[0084] In summary, this invention successfully developed an organic glass-like scintillator material with both high-efficiency luminescence and dynamic reshaping properties through a combination of molecular design and dynamic covalent chemistry. Experimental data show that this approach, utilizing the covalently bonded "intrinsic luminescence" mode, fundamentally solves the optical inhomogeneity caused by phase separation in traditional doped systems. The resulting material maintains approximately 80% high transparency while significantly improving radiative luminescence intensity and spatial resolution. Furthermore, thanks to the transesterification-driven dynamic network, this scintillator not only possesses excellent flexibility to adapt to various curved surface detection scenarios but also exhibits outstanding self-healing properties and recyclability potential; damaged devices show no significant performance degradation after hot-pressing. This invention not only provides a new pathway for the preparation of high-performance organic scintillators but also meets the urgent needs of modern precision detectors towards flexibility, long lifespan, and environmental friendliness, possessing extremely high practical application value and economic benefits.

[0085] The specific embodiments of this application have been described above, but the scope of protection of this application is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application.

Claims

1. An organic glass scintillator material, characterized in that, The invention includes a dynamically covalently cross-linked polymer network; the dynamically covalently cross-linked polymer network is formed by reacting an epoxy monomer containing a halogenated conjugated group, a multifunctional carboxylic acid curing agent, and an ester exchange catalyst; the structural units in the dynamically covalently cross-linked polymer network are fixed to the polymer backbone through covalent bonds and thus possess radiative emission characteristics, and the organic glass scintillator material generates radiative emission under X-ray excitation; the structural unit includes a trapping unit and a luminescent unit, the trapping unit being an epoxy monomer containing a halogenated conjugated group, and the luminescent unit being a multifunctional carboxylic acid; The raw materials of the dynamic covalent crosslinked polymer network, by molar amount, include: 100 parts of epoxy monomer containing halogenated conjugated groups, 30-120 parts of multifunctional carboxylic acid curing agent, and 0.1-5 parts of transesterification catalyst; the epoxy monomer containing halogenated conjugated groups includes halogenated bisphenol A type epoxy resin or halogenated resorcinol type epoxy resin; the multifunctional carboxylic acid curing agent includes aliphatic multifunctional carboxylic acids and aromatic multifunctional carboxylic acids with phosphorescence emission properties.

2. The organic glass scintillator material according to claim 1, characterized in that, The halogenated bisphenol A type epoxy resin includes tetrabromobisphenol A diglycidyl ether or tetraiodobisphenol A diglycidyl ether; the halogenated hydroquinone type epoxy resin includes dibromohydroxyl diglycidyl ether or tetrabromohydroxyl diglycidyl ether.

3. The organic glass scintillator material according to claim 1, characterized in that, The aliphatic multifunctional carboxylic acids include succinic acid, adipic acid, sebacic acid, or dodecanoic acid; the aromatic multifunctional carboxylic acids with phosphorescent emission properties include pyromellitic acid, 4,4',4''-tricarboxylic acid or terephthalic acid and its derivatives, phenyldioxyacetic acid and its derivatives.

4. The organic glass scintillator material according to claim 1, characterized in that, The transesterification catalyst includes one or more of zinc acetylacetonate, triazabicyclodecene, zinc octanoate, and 1-methylimidazole.

5. A method for preparing an organic glass scintillator material as described in any one of claims 1-4, characterized in that, Includes the following steps: S1. An epoxy monomer containing a halogenated conjugated group, a multifunctional carboxylic acid curing agent, and an ester exchange catalyst are mixed in proportion and heated to melt or dissolve to obtain a precursor mixture; S2. After degassing the precursor mixture, inject it into a mold and carry out a thermosetting reaction at 80-200℃ to obtain the organic glass scintillator material.

6. The method for preparing the organic glass scintillator material according to claim 5, characterized in that, In S2, the thermosetting reaction adopts a gradient temperature rise curing method; the organic glass scintillator material can be hot-pressed or annealed after thermosetting.

7. The application of an organic glass scintillator material as described in any one of claims 1-4 in X-ray imaging detectors, industrial non-destructive testing screens, three-dimensional dose verification devices, and recyclable and self-healing scintillator devices.

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