Polymerizable organic-inorganic hybrid flexible gel scintillator material and preparation method and application thereof
By preparing organic-inorganic hybrid flexible gel scintillator materials, the brittleness and processing difficulties of traditional scintillator materials have been solved, enabling flexible and high-resolution radiation imaging applications suitable for various scenarios.
Patent Information
- Application Number
- CN202610190919.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-02-10
- Publication Date
- 2026-05-19
AI Technical Summary
Existing scintillator materials suffer from problems such as high brittleness, inflexibility, difficulty in high-temperature processing, difficulty in large-area fabrication, particle aggregation, large light scattering, and structural instability, making it difficult to combine flexibility and radiation stability.
Organic cationic monomers and inorganic metal halides are dissolved and then a crystalline scintillator is formed by solvent diffusion. A crosslinking agent and a photoinitiator are added, and the mixture is then cured and polymerized by ultraviolet light irradiation to form an organic-inorganic hybrid flexible gel scintillator material.
Flexible, stretchable, and large-area fabrication gel or thin-film scintillators were developed, avoiding agglomeration and interface scattering problems, improving imaging resolution, and making them suitable for medical X-ray imaging, industrial non-destructive testing, wearable radiation detectors and other applications.
Smart Images
Figure CN122060110A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of optoelectronic functional materials and radiation detection materials, specifically to a polymerizable organic-inorganic hybrid flexible gel scintillator material, its preparation method, and its applications. Background Technology
[0002] With the rapid development of medical imaging diagnostics, industrial non-destructive testing, security inspection, and radiation monitoring technologies, the demand for high-performance scintillator materials is constantly increasing. Traditional inorganic scintillators, such as CsI:Tl, suffer from problems such as high brittleness, inflexibility, difficulty in high-temperature processing, and difficulty in large-area fabrication. Although metal halide luminescent materials possess excellent optical properties, problems such as crystallization, deliquescence, and poor processability remain unresolved, and it is difficult to combine flexibility and radiation stability. Existing composite scintillator systems, such as nanoparticle composite films and ion gels, still suffer from problems such as particle aggregation, large light scattering, structural instability, and easy destruction of luminescent centers.
[0003] Therefore, there is an urgent need in this field for a polymerizable scintillator material system that can be prepared at low temperatures, can be directly photopolymerized, and is structurally stable and flexible. Summary of the Invention
[0004] The purpose of this invention is to provide a polymerizable organic-inorganic hybrid flexible gel scintillator material, its preparation method, and its application.
[0005] To achieve the above objectives, the present invention adopts the following technical solution: A polymerizable organic-inorganic hybrid flexible gel scintillator material and its preparation method, comprising the following steps: (1) The organic cationic monomer A and the inorganic metal halide MX are reacted. n A crystalline scintillator A2MX was obtained by dissolving it in a solvent at a specific molar ratio and then diffusing it using a solvent diffusion method. n ; (2) The crystalline scintillator obtained in step (1) is first dissolved in deionized water, and then crosslinking agent, photoinitiator and solvent are added and ultrasonically dissolved to obtain a gel scintillator precursor solution; (3) The gel scintillator precursor solution obtained in step (2) is subjected to ultraviolet light irradiation to solidify and polymerize, thereby obtaining organic-inorganic hybrid flexible gel scintillator material; The organic cationic monomer has the structure R1-C=C-R2-Z. + (X) - ), where R1 and R2 are selected from any one of alkyl, alkenyl, ester, ether, and amino substituents, Z + The organic positive ion center is selected from imidazolium, quaternary ammonium, phosphonium, pyridinium, or their derivatives; X - It is a halide anion.
[0006] Furthermore, the organic cationic monomer is one or more of the following: [2-(methacryloyloxy)ethyl]trimethylammonium bromide, [2-(methacryloyloxy)ethyl]trimethylammonium chloride, 1-methyl-3-vinylimidazolium bromide, 1-butyl-3-vinylimidazolium bromide, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, (3-methacrylamidopropyl)trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, 1-tetradecyl-3-vinylimidazolium bromide, (2-(methacryloyloxy)ethyl)triphenylphosphonium bromide, acryloyloxyethyl-triphenylphosphine chloride, 4-vinylpyridine chloride / bromide, and 1-(2-methacryloyloxyethyl)-3-methylimidazolium chloride.
[0007] Furthermore, the inorganic metal halide MX described in step (1) n The metal ion M is selected from at least one of Mn, Pb, Sb, Sn, In, Bi, and Cu, and the halogen X is selected from Cl, Br, or I.
[0008] Furthermore, in step (1), the molar ratio of the organic cationic monomer to the inorganic metal halide is 2:(0.8~1.2); the solvent is one of acetonitrile, methanol, N,N-dimethylformamide, and dimethyl sulfoxide.
[0009] Furthermore, in step (1), the crystalline scintillator A2MX n It is any one of (MTAC)2MnCl4, (MTAC)2MnBr4, (BVIB)2MnBr4, and (MTAB)2MnBr4.
[0010] Furthermore, in step (2), the crosslinking agent is N,N'-methylenebisacrylamide; the photoinitiator is one or a combination of several of the following: hydroxycyclohexylphenyl ketone, benzophenone, acylphosphonate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-phenyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)-1-butanone; and the solvent is anhydrous ethanol.
[0011] Furthermore, in step (2), the ratio of the amount of crystal scintillator, deionized water, crosslinking agent, photoinitiator and solvent is (0.75~1.3mg): (0.2~0.3mL): (5.7~10mg): (7.6~12mg): (100~150μL).
[0012] Furthermore, in step (3), the wavelength of the ultraviolet lamp is 365-395 nm, and the curing reaction time is 3-15 min.
[0013] The present invention also provides organic-inorganic hybrid flexible gel scintillator materials prepared by the above preparation method and their applications in medical X-ray imaging, industrial non-destructive testing digital imaging, and portable real-time monitoring of γ / X-rays; or their applications in the preparation of wearable radiation detectors, flexible detection devices or curved surface detection devices.
[0014] Compared with the prior art, the present invention has the following beneficial effects: (1) Traditional inorganic scintillators generally have disadvantages such as high brittleness, inflexibility, and difficulty in forming thin films. This invention introduces organic cations with polymerizable double bonds, enabling metal halides to exist stably in the photopolymerization network, thereby preparing flexible, stretchable, and large-area gel or thin-film scintillators. Compared with traditional high-temperature sintered metal halide scintillators, the system of this invention can maintain a stable light-emitting structure at room temperature, which is simpler and more efficient than the preparation of traditional metal halide scintillators. It can be extended to continuous coating and printing processing, which is conducive to large-area industrial production. (2) The present invention forms a uniform network structure through in-situ photopolymerization, which avoids the agglomeration and interface scattering problems that are common in nanoparticle composite systems. The resulting material has low light scattering and can clearly present X-ray images. Under the same conditions, the imaging resolution of the material of the present invention can reach 20 lp / mm, which is significantly better than the scintillator film doped with polymers (generally 14.4~18 lp / mm). Therefore, the material prepared by the present invention can be well applied to medical X-ray imaging, industrial non-destructive testing digital imaging, wearable radiation detectors, flexible and curved surface detection equipment, portable γ / X-ray real-time monitoring, and traditional inorganic scintillators are difficult to use in flexible and wearable scenarios. Attached Figure Description
[0015] Figure 1 The images show the actual flexible gel scintillator materials prepared in Examples 1-4.
[0016] Figure 2 The crystal structure diagrams are of the crystal scintillator materials prepared in Examples 1-4, where purple represents Mn, green represents Cl or Br, pink represents O, yellow represents N, and gray represents C.
[0017] Figure 3 The images show the XRD spectra of the crystalline scintillator and the flexible gel scintillator prepared in Example 4.
[0018] Figure 4 The images show the excitation and emission spectra of the crystalline scintillator and the flexible gel scintillator prepared in Example 4.
[0019] Figure 5 The images show the stretched physical and test results of the flexible gel scintillator prepared in Example 4.
[0020] Figure 6 This is an X-ray imaging image of the flexible gel scintillator prepared in Example 4. Detailed Implementation
[0021] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.
[0022] In the following examples, MTAC is [2-(methacryloyloxy)ethyl]trimethylammonium chloride; BVIB is 1-butyl-3-vinylimidazolium bromide (CAS: 34311-90-5); MTAB is [2-(methacryloyloxy)ethyl]trimethylammonium bromide (synthesis process referred to...). Synthesis of Arsenocholine-Type Polycation Brush and Its Hydration Structure in Aqueous Solution ); MBA is N,N'-methylenebisacrylamide; HCPK is hydroxycyclohexylphenyl ketone.
[0023] Example 1
[0024] A polymerizable organic-inorganic hybrid flexible gel scintillator material, its preparation method, and its application are disclosed below: (1) Synthesis of organic-inorganic ionic compound crystal scintillator: The organic cationic monomer MTAC and the inorganic metal halide MnCl2 were dissolved in acetonitrile at a molar ratio of 2:1.1. Cyclohexane or n-hexane was added as a poor solvent (the volume ratio of good solvent to poor solvent was about 1:3). The crystal scintillator (MTAC)2MnCl4 was obtained by diffusion at room temperature for 5 to 8 days. (2) Preparation of gel scintillator precursor solution: Weigh 0.75 g of (MTAC)2MnCl4 crystalline scintillator and dissolve it in 0.25 mL of deionized water. Then add 5.7 mg of crosslinking agent MBA, 7.6 mg of photoinitiator HCPK and 100 μL of anhydrous ethanol. After ultrasonic dissolution, the gel scintillator precursor solution is obtained. (3) The above gel scintillator precursor solution was poured into a mold (diameter 25 mm, height 0.5 mm) and cured by UV 365 nm, 20 W ultraviolet lamp for 4 min to obtain organic-inorganic hybrid flexible gel scintillator material.
[0025] Example 2
[0026] A polymerizable organic-inorganic hybrid flexible gel scintillator material, its preparation method, and its application are disclosed below: (1) Synthesis of organic-inorganic ionic compound crystal scintillator: The organic cationic monomer MTAC and the inorganic metal halide MnBr2 were dissolved in acetonitrile at a molar ratio of 2:1.05. Cyclohexane or n-hexane was added as a poor solvent (the volume ratio of good solvent to poor solvent was about 1:3). The crystal scintillator (MTAC)2MnBr4 was obtained by diffusion at room temperature for 5 to 8 days. (2) Preparation of gel scintillator precursor solution: Weigh 0.80 g of (MTAC)2MnBr4 crystalline scintillator and dissolve it in 0.20 mL of deionized water. Then add 6.0 mg of crosslinking agent MBA, 8.3 mg of photoinitiator HCPK and 110 μL of anhydrous ethanol. After ultrasonic dissolution, the gel scintillator precursor solution is obtained. (3) The above gel scintillator precursor solution was poured into a silicone mold and cured by UV 365 nm, 20 W ultraviolet lamp irradiation for 6 min to obtain organic-inorganic hybrid flexible gel scintillator material.
[0027] Example 3
[0028] A polymerizable organic-inorganic hybrid flexible gel scintillator material, its preparation method, and its application are disclosed below: (1) Synthesis of organic-inorganic ionic compound crystal scintillator: The organic cationic monomer BVIB and the inorganic metal halide MnBr2 were dissolved in methanol at a molar ratio of 2:1. Diethyl ether was added as a poor solvent (the volume ratio of good solvent to poor solvent was about 1:4). The crystal scintillator (BVIB)2MnBr4 was obtained by diffusion at room temperature for 3-7 days. (2) Preparation of gel scintillator precursor solution: Weigh 1.0 g of (BVIB)2MnBr4 crystalline scintillator and dissolve it in 0.30 mL of deionized water. Then add 6.5 mg of crosslinking agent MBA, 8.7 mg of photoinitiator HCPK and 150 μL of anhydrous ethanol. After ultrasonic dissolution, the gel scintillator precursor solution is obtained. (3) The above gel scintillator precursor solution is coated on a glass substrate and cured by UV 365 nm, 20 W ultraviolet lamp irradiation for 10 min to obtain organic-inorganic hybrid flexible gel scintillator material (the thickness of the obtained film can be 500-1200 μm).
[0029] Example 4
[0030] A polymerizable organic-inorganic hybrid flexible gel scintillator material, its preparation method, and its application are disclosed below: (1) Synthesis of organic-inorganic ionic compound crystal scintillator: The organic cationic monomer MTAB and the inorganic metal halide MnBr2 were dissolved in dimethyl sulfoxide at a molar ratio of 2:0.95. Cyclohexane or n-hexane was added as a poor solvent, and the crystal scintillator (MTAB)2MnBr4 was obtained by diffusion at room temperature for 5 to 8 days. (2) Preparation of gel scintillator precursor solution: Weigh 1.3 g of (MTAB)2MnBr4 crystalline scintillator and dissolve it in 0.20 mL of deionized water. Then add 10 mg of crosslinking agent MBA, 12 mg of photoinitiator HCPK and 100 μL of anhydrous ethanol. After ultrasonic dissolution, the gel scintillator precursor solution is obtained. (3) Pour the above gel scintillator precursor solution into a mold or coat it onto a substrate, and cure and polymerize it by UV 365 nm, 20 W ultraviolet lamp irradiation for 15 min to obtain organic-inorganic hybrid flexible gel scintillator material.
[0031] Figure 1 Physical images of the flexible gel scintillator materials from Examples 1 to 4 are shown. As can be seen from the images, the prepared scintillator materials exhibit good transparency and a uniform surface, without obvious defects or bubbles, making them suitable for use as scintillator screens in X-ray detectors.
[0032] Figure 2 The images show the crystal structure diagrams of the scintillator materials prepared in Examples 1-4. The data for each crystal are as follows: (MTAC)2MnCl4: a=10.3345(9), b=10.3880(9), c=25.026(2), alpha=90, beta=90, gamma=90, Volume=2686.7(4), P 21 21 21.
[0033] (MTAC)2MnBr4: a=10.4103(10), b=10.4799(9), c=25.428(3), alpha=90, beta=90, gamma=90, Volume=2774.2(5), P 21 21 21.
[0034] (BVIB)2MnBr4: a=14.1405(12), b=13.0786(10), c=15.3212(14), alpha=90 beta=107.758(8), gamma=90, Volume=2698.5(4), P121 / c1.
[0035] (MTAB)2MnBr4: a=10.472(4), b=10.485(3), c=25.294(5), alpha=90, beta=90, gamma=90, Volume=2777.3(14), P21 21 21.
[0036] Figure 3 The X-ray diffraction (XRD) spectra of the crystalline scintillator (MTAB)2MnBr4 and the flexible gel scintillator material in Example 4 were compared. It can be observed that the crystalline scintillator exhibits clear and sharp diffraction peaks, indicating its highly crystalline structure; while the flexible gel scintillator material shows a broad diffraction peak, indicating its amorphous structure. This amorphous structure helps improve the flexibility of the material without affecting its luminescent properties.
[0037] Figure 4 The excitation and emission spectra of the crystalline scintillator and the flexible gel scintillator in Example 4 are compared. In the excitation spectrum, the excitation peak position at approximately 365 nm is the same for both, indicating that their excitation wavelengths are consistent. The emission spectrum shows that both the crystalline scintillator and the flexible gel scintillator have significant emission peaks in the 520-560 nm range, and the intensity and position of the emission peaks are consistent, proving that the luminescent performance of the luminescent center is not affected after polymerization.
[0038] Figure 5 Tensile tests were performed on the flexible gel scintillator material prepared in Example 4. The material had a diameter of 13.54 mm in its original state and reached 150.00 mm after stretching, demonstrating its excellent flexibility and stretchability. Further quantitative stress-strain curves showed that the flexible membrane had a tensile strength of 0.58 MPa and a maximum strain of 164% during stretching, exhibiting good mechanical strength and high ductility.
[0039] Figure 6 The imaging effect of the flexible gel scintillator material of Example 4 under X-ray excitation is demonstrated. Using this material as a scintillator screen, the X-rays passing through the material can clearly present the image of the target object. Figure 6 The imaging resolution can reach 20 lp / mm, indicating that the material has high resolution in practical applications and is suitable for high-precision X-ray imaging systems.
[0040] Although the present invention has been described in detail through specific embodiments, it should be understood that these embodiments are merely illustrative and should not be considered as limiting the scope of the invention. The scope of protection of the present invention should include all equivalent modifications and variations made based on the basic ideas of the present invention, and all such equivalent modifications and variations should fall within the scope of protection of the claims of the present invention. Those skilled in the art can make corresponding adjustments and optimizations based on the spirit and technical solutions of the present invention without creative effort.
Claims
1. A polymerizable organic-inorganic hybrid flexible gel scintillator material and its preparation method, characterized in that: Includes the following steps: (1) The organic cationic monomer A and the inorganic metal halide MX are reacted. n A crystalline scintillator A2MX was obtained by dissolving it in a solvent at a specific molar ratio and then diffusing it using a solvent diffusion method. n ; (2) The crystalline scintillator obtained in step (1) is first dissolved in deionized water, and then crosslinking agent, photoinitiator and solvent are added and ultrasonically dissolved to obtain a gel scintillator precursor solution; (3) The gel scintillator precursor solution obtained in step (2) is subjected to ultraviolet light irradiation to solidify and polymerize, thereby obtaining organic-inorganic hybrid flexible gel scintillator material; The organic cationic monomer has the structure R1-C=C-R2-Z. + (X) - ), where R1 and R2 are selected from any one of alkyl, alkenyl, ester, ether, and amino substituents, Z + The organic positive ion center is selected from imidazolium, quaternary ammonium, phosphonium, pyridinium, or their derivatives; X - It is a halide anion.
2. The preparation method according to claim 1, characterized in that: The organic cationic monomer is one or more of the following: [2-(methacryloyloxy)ethyl]trimethylammonium bromide, [2-(methacryloyloxy)ethyl]trimethylammonium chloride, 1-methyl-3-vinylimidazolium bromide, 1-butyl-3-vinylimidazolium bromide, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, (3-methacrylamidopropyl)trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, 1-tetradecyl-3-vinylimidazolium bromide, (2-(methacryloyloxy)ethyl)triphenylphosphonium bromide, acryloyloxyethyl-triphenylphosphine chloride, 4-vinylpyridine chloride / bromide, and 1-(2-methacryloyloxyethyl)-3-methylimidazolium chloride.
3. The preparation method according to claim 1, characterized in that: The inorganic metal halide MX described in step (1) n The metal ion M is selected from at least one of Mn, Pb, Sb, Sn, In, Bi, and Cu, and the halogen X is selected from Cl, Br, or I.
4. The preparation method according to claim 1, characterized in that: In step (1), the molar ratio of organic cationic monomer to inorganic metal halide is 2:(0.8~1.2); the solvent is one of acetonitrile, methanol, N,N-dimethylformamide, and dimethyl sulfoxide.
5. The preparation method according to claim 1, characterized in that: In step (1), the crystalline scintillator A2MX n It is any one of (MTAC)2MnCl4, (MTAC)2MnBr4, (BVIB)2MnBr4, and (MTAB)2MnBr4.
6. The preparation method according to claim 1, characterized in that: In step (2), the crosslinking agent is N,N'-methylenebisacrylamide; the photoinitiator is one or a combination of several of the following: hydroxycyclohexylphenyl ketone, benzophenone, acylphosphonate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-phenyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)-1-butanone; and the solvent is anhydrous ethanol.
7. The preparation method according to claim 1, characterized in that: In step (2), the ratio of the amount of crystal scintillator, deionized water, crosslinking agent, photoinitiator and solvent is (0.75~1.3mg): (0.2~0.3mL): (5.7~10mg): (7.6~12mg): (100~150μL).
8. The preparation method according to claim 1, characterized in that: In step (3), the wavelength of the ultraviolet lamp is 365-395nm, and the curing reaction time is 3-15 min.
9. An organic-inorganic hybrid flexible gel scintillator material prepared by the preparation method according to any one of claims 1 to 8.
10. The application of the organic-inorganic hybrid flexible gel scintillator material as described in claim 9 in the following aspects: 1) Applications in medical X-ray imaging, industrial non-destructive testing digital imaging, and portable real-time γ / X-ray monitoring; 2) Applications in the fabrication of wearable radiation detectors, flexible detection devices, or curved surface detection devices.