A pure organic carbon borane-containing X-ray scintillator material, its preparation method and application

Abstract

This invention discloses a pure organic carbon borane-containing X-ray scintillator material, its preparation method, and its applications, belonging to the fields of optical functional materials and X-ray radiation measurement technology. The chemical structural formula of the above-mentioned scintillator material is: [Formula omitted for brevity], where the hollow dot represents BH. The X-ray scintillator material provided by this invention has a novel structure, excellent luminescence performance and radiative luminescence characteristics, with a detection limit as low as 87.9 nGy / s. It exhibits high sensitivity and high chemical and environmental stability. After being prepared into a thin film, it can clearly image X-rays, achieving an imaging resolution greater than 20 lp / mm. This provides a feasible materials science basis for X-ray imaging technology and shows good application prospects in fields such as medical X-ray imaging, X-ray radiation detection, and security inspection. It solves the problems of complex preparation conditions, high cost, low sensitivity, and poor chemical and environmental stability of existing scintillator materials.

Description

Technical Field

[0001] This invention relates to the field of optical functional materials and X-ray radiation measurement technology, specifically to a pure organic carbon borane X-ray scintillator material, its preparation method, and its application. Background Technology

[0002] X-ray detection has been widely studied and applied in industrial and medical fields (including radiography, computed tomography, and scientific research). Generally speaking, X-ray detectors can be divided into two categories: direct and indirect. Indirect detectors are less expensive and more stable. Scintillators, as key materials in indirect X-ray imaging and computed tomography, can convert high-energy X-rays and other radiation into low-energy visible light.

[0003] Currently, a series of inorganic scintillators (such as NaI:Tl, CsI:Tl and bismuth germanate Bi4Ge3O) are available. 12 While these materials have been successfully applied to X-ray imaging, they typically require ultra-high temperatures of approximately 1700°C to grow via the Czeklaussky method, and their hygroscopic and air-degradable nature necessitates complex encapsulation processes. Therefore, developing novel scintillators with low growth temperatures, low costs, high sensitivity, and high chemical and environmental stability is of paramount importance. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide a pure organic carbon borane X-ray scintillator material, its preparation method, and its application, thereby solving the problems of complex preparation conditions, high cost, low sensitivity, and poor chemical and environmental stability of existing scintillator materials.

[0005] The technical solution of the present invention to solve the above-mentioned technical problems is as follows:

[0006] In a first aspect, the present invention provides a pure organic carbon borane-containing X-ray scintillator material, the chemical structural formula of which is: In the formula, the hollow dot is BH.

[0007] The beneficial effects of this invention are as follows: This invention provides an X-ray scintillator material based on pure organic carborane, which has a novel structure, excellent luminescence performance and radiation luminescence characteristics, and a detection limit as low as 87.9 nGy / s. The scintillator thin film screen prepared from it can achieve an imaging resolution greater than 20 lp / mm, and has high sensitivity and high chemical and environmental stability.

[0008] A second aspect of the present invention provides a method for preparing the above-mentioned pure organic carbon borane X-ray scintillator material, comprising the following steps:

[0009] S1: Halogenation reaction is carried out by mixing o-carborane, anhydrous aluminum trichloride and elemental iodine in a solvent;

[0010] S2: Prepare Grignard reagents by mixing magnesium, iodine and 1-bromopyrene in a solvent and carrying out a free radical reaction;

[0011] S3: The products obtained from reaction S1 and reaction S2 are mixed with the palladium catalyst in a solvent to carry out a nucleophilic substitution reaction;

[0012] S4: First, mix n-butyllithium, cuprous chloride and the product obtained from the reaction of S3 in a solvent to carry out a nucleophilic substitution reaction. Then, add 4-n-butyliodobenzene and pyridine to continue the nucleophilic substitution reaction.

[0013] S5: First, n-butyllithium and the final product obtained from the reaction of S4 are mixed in a solvent to carry out a nucleophilic substitution reaction. Then, trimethylchlorosilane is added to continue the nucleophilic substitution reaction to obtain a pure organic carborane X-ray scintillator material.

[0014] Furthermore, the molar ratio of o-carborane, anhydrous aluminum trichloride, and elemental iodine in S1 is (1-3):(0.1-0.15):(1-3).

[0015] The beneficial effects of this invention are as follows: This invention provides a method for preparing pure organic carbon borane X-ray scintillator materials. The raw materials used in this preparation method are inexpensive, the preparation conditions are mild, and there is no need for ultra-high temperature growth. It has broad application prospects and practical value.

[0016] Preferably, the molar ratio of o-carborane, anhydrous aluminum trichloride and elemental iodine in S1 is 2:0.12:2.

[0017] Furthermore, the solvent in S1 includes dichloromethane.

[0018] Furthermore, the halogenation reaction in S1 is carried out at a temperature of 30-50 °C for a time of 30-60 h.

[0019] Preferably, the halogenation reaction in S1 is carried out at a temperature of 40 °C for 48 h.

[0020] Furthermore, the molar ratio of magnesium, iodine and 1-bromopyrene in S2 is (1-3):(0.0005-0.002):(1-3).

[0021] Preferably, the molar ratio of magnesium, iodine and 1-bromopyrene in S2 is 2:0.001:2.

[0022] Furthermore, the solvent in S2 includes tetrahydrofuran.

[0023] Furthermore, the free radical reaction in S2 is carried out at a temperature of 60-80 °C for 1-3 h.

[0024] Preferably, the free radical reaction in S2 is carried out at a temperature of 70 °C for 2 h.

[0025] Furthermore, the molar ratio of the product obtained from reaction S1, the product obtained from reaction S2, and the palladium catalyst in S3 is (0.5-2):(3-7):(0.001-0.003).

[0026] Preferably, the molar ratio of the product obtained from reaction S1, the product obtained from reaction S2, and the palladium catalyst in S3 is 1:5:0.002.

[0027] Furthermore, the solvent in S3 includes tetrahydrofuran.

[0028] Furthermore, the palladium catalyst in S3 includes palladium acetate or palladium dichloride bis(triphenylphosphine) chloride.

[0029] Furthermore, the nucleophilic substitution reaction in S3 is carried out at a temperature of 45-65 °C for a time of 30-60 h.

[0030] Preferably, the nucleophilic substitution reaction in S3 is carried out at a temperature of 55 °C for 48 h.

[0031] Furthermore, the molar ratio of n-butyllithium, cuprous chloride, the product obtained from the S3 reaction, 4-n-butyliodobenzene, and pyridine in S4 is (1-3):(1-1.5):(0.5-2):(1-3):(5-10).

[0032] Preferably, the molar ratio of n-butyllithium, cuprous chloride, the product obtained from the reaction in S3, 4-n-butyliodobenzene, and pyridine in S4 is 2:1.2:1:2:7.4.

[0033] Furthermore, the solvent in S4 is ethylene glycol dimethyl ether.

[0034] Furthermore, the nucleophilic substitution reaction in S4 is carried out at a temperature of 20-30 °C for 1-3 h; the nucleophilic substitution reaction is continued at a temperature of 80-100 °C for 30-60 h.

[0035] Preferably, the nucleophilic substitution reaction in S4 is carried out at a temperature of 25 °C for 2 h; the nucleophilic substitution reaction is continued at a temperature of 9 °C for 48 h.

[0036] Furthermore, the molar ratio of n-butyllithium in S5, the final product obtained from the S4 reaction, and trimethylchlorosilane is (0.5-2):(0.5-1):(0.5-1).

[0037] Preferably, the molar ratio of n-butyllithium in S5, the final product obtained from the reaction in S4, and trimethylchlorosilane is 1:0.8:0.8.

[0038] Furthermore, the solvent in S5 includes tetrahydrofuran.

[0039] Furthermore, the nucleophilic substitution reaction in S5 was carried out at a temperature of -5 to 5 °C for 30 to 90 min; the nucleophilic substitution reaction was continued at a temperature of 80 to 100 °C for 10 to 15 h.

[0040] Preferably, the nucleophilic substitution reaction in S5 is carried out at 0 °C for 60 min; the nucleophilic substitution reaction is continued at 90 °C for 12 h.

[0041] Furthermore, the reactions in S1 to S5 are all carried out under a protective gas atmosphere.

[0042] A third aspect of the present invention provides the application of the above-mentioned pure organic carborane X-ray scintillator material in X-ray imaging, X-ray radiation detection and X-ray security inspection for non-disease diagnostic purposes.

[0043] The present invention has the following beneficial effects:

[0044] This invention provides an X-ray scintillator material based on pure organic carborane. This material has a novel structure, excellent luminescence performance and radiative luminescence characteristics, with a detection limit as low as 87.9 nGy / s. It also exhibits high sensitivity and high chemical and environmental stability. When prepared into a thin film, it can clearly image X-rays, achieving an imaging resolution greater than 20 lp / mm. This provides a feasible material science basis for X-ray imaging technology and shows promising application prospects in fields such as medical X-ray imaging, X-ray radiation detection, and security inspection. Attached Figure Description

[0045] Figure 1 The specific structural formula of ortho-carborane;

[0046] Figure 2 The 1H NMR spectrum of compound S3 obtained in Example 1;

[0047] Figure 3 The carbon NMR spectrum of compound S3 obtained in Example 1;

[0048] Figure 4 The 1H NMR spectrum of compound S4 obtained in Example 1;

[0049] Figure 5 The carbon NMR spectrum of compound S4 obtained in Example 1;

[0050] Figure 6 The 1H NMR spectrum of the scintillator material prepared in Example 1;

[0051] Figure 7 The carbon NMR spectrum of the scintillator material prepared in Example 1;

[0052] Figure 8 The images show the UV-Vis absorption spectrum and fluorescence emission spectrum of the scintillator material prepared in Example 1, where (a) is the UV-Vis absorption spectrum and (b) is the fluorescence emission spectrum.

[0053] Figure 9 The image shows the X-ray detection limit of the scintillator material prepared in Example 1.

[0054] Figure 10 The images shown are of the scintillator thin film material prepared in Example 3, where (a) is an image of the spring inside the capsule and (b) is an image of the chip.

[0055] Figure 11 This is a resolution card image of the scintillator thin film material prepared in Example 3. Detailed Implementation

[0056] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0057] Example 1: Preparation of pure organic carbon borane X-ray scintillator materials

[0058] A method for preparing a pure organic carbon borane X-ray scintillator material includes the following steps:

[0059] S1: Preparation of compound S1

[0060] The preparation reaction formula is shown below:

[0061] ;

[0062] In the formula, the hollow dot is BH.

[0063] Specifically, the following steps are included:

[0064] Under a nitrogen atmosphere, first, o-carborane (288 mg, 2 mmol, specific structural formula as shown) was added. Figure 1The mixture (as shown) was dissolved in dichloromethane (50 mL), and anhydrous aluminum trichloride (16 mg, 12 μmol) and elemental iodine (508 mg, 1 mmol) were added sequentially. The reaction system was then heated in an oil bath at 40 °C until the color of the iodine completely disappeared. Heating was stopped and the mixture was cooled to room temperature. Then, under nitrogen protection, elemental iodine (508 mg, 1 mmol) was added again, and the mixture was reheated to 40 °C with stirring for two days. After the reaction was completed, the mixture was poured into a separatory funnel, and an appropriate amount of distilled water was added for extraction. The organic phase was separated. The aqueous phase was extracted three times with diethyl ether, and all organic phases were combined and dried with anhydrous magnesium sulfate. The dried organic liquid was filtered through defatted cotton, and the filtrate was collected in a round-bottom flask. The solvent was removed by rotary evaporation to obtain a grayish-white solid. An appropriate amount of petroleum ether and a small amount of dichloromethane were added to the solid, and the mixture was heated until completely dissolved. The solution was then recrystallized in a -40 °C refrigerator to obtain a white crystalline compound S1 (635 mg, yield 80%).

[0065] Preparation of S2: 1-Bromopyrene Grignard reagent solution

[0066] The preparation reaction formula is shown below:

[0067] .

[0068] Specifically, the following steps are included:

[0069] First, weigh 2.4 g (0.1 mol) of magnesium shavings and two grains of iodine (0.00005 mol) and place them in a dry three-necked flask. Apply high-vacuum silicone grease evenly to the interfaces of the three-necked flask, the constant-pressure dropping funnel, and the condenser, and assemble the reaction apparatus. Connect the entire apparatus to the vacuum line and perform three purging and purging operations to remove internal oxygen, then purge with nitrogen as a protective atmosphere. Then, using a double-ended needle, transfer 30 mL of dry tetrahydrofuran to a constant-pressure dropping funnel containing 28.1 g (0.1 mol) of 1-bromopyrene. Under a nitrogen atmosphere, slowly add the solution from the funnel to the three-necked flask, simultaneously gently heating with a hot torch to initiate the reaction until the liquid in the flask gently boils and refluxes. After the final addition is complete, continue heating under reflux for 2 hours to obtain a 1-bromopyrene Grignard reagent solution. The obtained product is used directly in subsequent reactions without purification.

[0070] S3: Preparation of compound S3

[0071] The preparation reaction formula is shown below:

[0072] ;

[0073] In the formula, the hollow dot is BH.

[0074] Specifically, the following steps are included:

[0075] First, a magnetic stir bar was placed in a Young's reaction tube and a PTFE stopcock was installed. Three cycles of vacuuming and nitrogen purging were performed using a double-row tube to ensure the system was under nitrogen protection. Then, accurately weighed compound S1 (400 mg, 1 mmol) and freshly prepared 1-bromopyrene Grignard reagent solution (5 mL, 5 mmol) were added. After tightening the stopcock again, the Young's tube was transferred to a glove box, where catalyst (Ph3P)2PdCl2 (15 mg, 2 μmol) and 10 mL of dry tetrahydrofuran were added. The reaction tube was then removed from the glove box and stirred and refluxed at 55 °C for two days. After the reaction solution cooled to room temperature, a small sample was taken for gas chromatography-mass spectrometry (GC-MS) monitoring until the 1-bromopyrene Grignard reagent completely disappeared, at which point the reaction was stopped. Finally, an appropriate amount of deionized water was added to quench any remaining Grignard reagent, and extraction was performed to separate the organic phase. The aqueous phase was further extracted three times with diethyl ether, and all organic phases were combined in a round-bottom flask. The solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by column chromatography using a dichloromethane / petroleum ether (volume ratio 1:4) mixture as the eluent. The target fraction was collected and recrystallized from n-hexane to give compound S3 (295 mg, yield 54.3%), a pale yellow-white solid.

[0076] Compound S3 was characterized by nuclear magnetic resonance imaging, and the characterization results are as follows: Figure 2 and Figure 3 As shown:

[0077] 1 ¹H NMR (500 MHz, CDCl₃·ppm) δ = 9.03 (d, J = 9.3 Hz, 2H), 8.07-8.01 (m,6H), 7.93-7.85 (m, 6H), 7.76 (d, J = 8.8 Hz, 2H), 7.68 (d, J = 8.0 Hz, 2H), 3.92 (s, 2H), 3.46-2.04 (m, 8H).

[0078] 13 C10 NMR (125 MHz, CDC13.ppm) δ = 132.83, 132.53, 130.60, 130.30, 129.60, 129.50, 126.53, 126.40, 126.02, 125.20, 124.29, 123.92, 123.45, 123.23, 122.93, 118.02.

[0079] S4: Preparation of compound S4

[0080] The preparation reaction formula is shown below:

[0081] ;

[0082] In the formula, the hollow dot is BH.

[0083] Specifically, the following steps are included:

[0084] First, compound S3 (281 mg, 0.5 mmol) was weighed into a Young's reaction tube, a magnetic stir bar was added, and ethylene glycol dimethyl ether (5 mL) was added in a glove box and stirred until completely dissolved. The tube was then sealed with a polytetrafluoroethylene stopcock and removed. Next, under a nitrogen atmosphere, a solution of n-butyllithium (0.4 mL, 1 mmol, 2.5 mol / L) was slowly added to the reaction tube, and the mixture was stirred for 1 hour. Then, under nitrogen protection, cuprous chloride (60 mg, 0.6 mmol) was added, and stirring continued at room temperature for 1 hour. Finally, 4-n-butyliodobenzene (148 mg, 1 mmol) was added under a nitrogen atmosphere, and pyridine (0.3 mL, 3.7 mmol) was injected using a dry syringe. The mixture was stirred at 90 °C for 2 days. After the reaction was complete, a suitable amount of distilled water was added to quench the reaction, and the solvent was removed by rotary evaporation to obtain a yellow oily crude product. The crude product was separated by column chromatography using a dichloromethane / petroleum ether (volume ratio 1:5) mixture as the eluent. The fractions containing the target component were collected, combined, and concentrated under reduced pressure to obtain a white flocculent solid. Further recrystallization from n-hexane yielded a white solid compound S4 (113 mg, yield 32%).

[0085] Compound S4 was characterized by its nuclear magnetic resonance spectrum. The characterization results are as follows: Figure 4 and Figure 5 As shown:

[0086] 1 ¹H NMR (500 MHz, CDCl₃·ppm) δ = 9.09 (d, J = 9.3 Hz, 1H), 9.04 (d, J =9.4 Hz, 1H), 8.12 (dd, J = 10.0, 7.9 Hz, 2H), 8.07-8.02 (m, 4H), 7.95-7.86 (m,6H), 7.77 (dd, J = 8.8, 1.3 Hz, 2H), 7.70 (dd, J= 8.0, 6.0 Hz, 2H), 7.57-7.52(m, 2H), 7.20-7.16 (m, 2H), 4.25 (s, 1H), 4.20-2.59 (m, 10H).

[0087] 13 C10 NMR (125 MHz, CDC13.ppm) δ = 145.42, 136.32, 134.02, 133.89, 133.71, 133.61, 132.89, 131.52, 131.35, 130.96, 130.64, 130.58, 130.11, 128.95, 128.86, 127.74, 127.72, 127.63, 127.46, 127.03, 126.22, 126.13, 125.82, 125.32, 125.10, 124.99, 124.98, 124.84, 126.64, 124.62, 124.56, 124.46, 124.26, 124.00, 123.98, 73.13, 56.92, 35.10, 33.25, 26.95, 22.33, 13.91.

[0088] S5: Preparation of pure organic carbon borane-containing X-ray scintillator materials

[0089] The preparation reaction formula is shown below:

[0090] ;

[0091] In the formula, the hollow dot is BH.

[0092] Specifically, the following steps are included:

[0093] First, compound S4 (140 mg, 0.2 mmol) was weighed into a Young's reaction tube, a magnetic stir bar was added, and dry tetrahydrofuran (5 mL) was added in a glove box. The reaction tube was then removed from the glove box and cooled in an ice-water bath. While stirring, a solution of n-butyllithium hexane (0.1 mL, 0.25 mmol, 2.5 mol / L) was slowly added, and the reaction was continued for 1 hour. Subsequently, TMSCl (38 mg, 0.2 mmol) was added under nitrogen protection, and the reaction was stirred overnight at 90 °C. After the reaction was complete, the reaction mixture was initially filtered through a 5 cm silica gel column, using dichloromethane as the eluent to remove insoluble matter. The filtrate was collected in a round-bottom flask and concentrated under reduced pressure to remove the solvent. The crude product was purified by column chromatography using a dichloromethane / petroleum ether (1:5 v / v) mixture as the eluent. The fraction containing the target compound was collected, evaporated to dryness under reduced pressure, and the crude product was obtained. Finally, recrystallization with n-hexane yielded a white solid product, pure organic carbon borane X-ray scintillator material (S5) (98 mg, yield 63%).

[0094] The pure organic carbon borane X-ray scintillator material was characterized by nuclear magnetic resonance spectroscopy. The characterization results are as follows: Figure 6 and Figure 7 As shown:

[0095] 1 ¹H NMR (500 MHz, CDCl₃·ppm) δ = 9.15 (d, J = 9.3 Hz, 1H), 9.09 (d, J =9.3 Hz, 1H), 8.18 (d, J = 8.0 Hz, 1H), 8.13 (d, J = 7.9 Hz, 1H), 8.09 - 7.95(m, 5H), 7.92 - 7.83 (m, 5H), 7.80 - 7.68 (m, 6H), 7.21 - 7.16 (m, 2H), 4.45- 1.92 (m, 10H).

[0096] 13 C10 NMR (125 MHz, CDC13.ppm) δ= 146.39, 134.20, 134.01, 133.93, 133.70, 131.63, 131.59, 131.56, 130.88, 130.84, 130.77, 130.71, 129.85, 128.90, 128.24, 128.12, 127.99, 127.74, 127.69, 127.28, 127.15, 127.13, 126.35, 126.25, 125.51, 125.43, 125.27, 125.23, 124.86, 124.80, 124.60, 124.55, 124.42, 124.37, 124.22, 124.16, 79.96, 71.69, 35.37, 33.47, 22.47, 14.14, 0.97, 0.22, -0.23.

[0097] Example 2: Photophysical properties of pure organic carbon borane X-ray scintillator materials

[0098] The pure organic carbon borane X-ray scintillator material prepared in Example 1 was subjected to photophysical property tests, specifically including ultraviolet-visible absorption spectroscopy and fluorescence emission spectroscopy tests.

[0099] Experimental results are as follows Figure 8 As shown. Figure 8 As shown in Figure (a), the absorption spectrum of the scintillator material exhibits -* transition absorption with the aromatic group attached to the ortho-carborane, i.e., pyrene transition absorption. The peak shapes of its absorption spectra in solvents of different polarities almost completely overlap. Solvent polarity has a relatively small effect on the molecular absorption spectrum; therefore, the absorption spectrum of the scintillator material is not solvent-dependent. Figure 8As shown in Figure (b), the scintillator material has two emission bands. One emission band has a peak at 422 nm. As the solvent polarity decreases, a shoulder peak appears at its longer wavelength. Therefore, this emission band originates from the localized excited (LE) state emission of pyrene and the excimer emission. Moreover, the excimer peak gradually disappears as the solvent polarity increases. Another emission band is the one with a peak at 794 nm. It has a broad peak shape and no fine structure, and it only appears in low polar solvents such as hexane and toluene. The reason for this phenomenon is that a new group TMS (trimethylsilane) is introduced at the carbon terminus of the 2-position of the 1,000-carborane. Although this group itself does not have electron-withdrawing ability, it can rotate around the CC bond of the 1,000-carborane. When the angle between the TMS plane and the CC bond of the 1,000-carborane increases, the CC bond of the 1,000-carborane will exhibit strong electron-withdrawing behavior. At this time, intramolecular charge transfer will occur between the pyrene group and the 1,000-carborane, so the ICT peak appears. When the plane of the TMS molecule is parallel to the CC bond of the 1,000-carborane, the fluorescence emission spectrum of the molecule still only shows the LE peak originating from pyrene. Therefore, scintillator materials exhibit dual emission properties. Furthermore, the ICT state peak is not observed with increasing solution polarity. This is because the molecular configuration of the ICT state differs significantly from the ground state. In highly polar solvents, the radiative transition rate of the ICT state decreases, hindering its ICT luminescence. Conversely, in less polar solvents, the ICT state becomes more stable, making the ICT state peak easier to observe. It is noteworthy that since the internal transformation between these two emission states is irreversible, the appearance of the ICT state peak in certain solutions can cause a degree of quenching in the LE state peak.

[0100] Example 3: X-ray radiation performance test of pure organic carbon borane X-ray scintillator material

[0101] Take 50 mg of the pure organic carbon borane X-ray scintillator material prepared in Example 1, and calculate its X-ray detection limit using the three-fold signal-to-noise ratio method.

[0102] Experimental results are as follows Figure 9 As shown, the results indicate that the pure organic carbon-borane X-ray scintillator material prepared in Example 1 of the present invention exhibits a good detection limit value, specifically 87.9 nGy / s.

[0103] Example 4: X-ray imaging performance test of thin films based on scintillator materials

[0104] 20 mg of the pure organic carborane X-ray scintillator material prepared in Example 1 and 1000 mg of polymethyl methacrylate (PMMA) were placed in a sample vial, and 30 mL of spectrally pure dichloromethane was added. After thorough ultrasonic dissolution, a homogeneous mixture was obtained. Then, an appropriate amount of solution was taken with a glass dropper and spin-coated onto a 10 cm × 10 cm standard quartz plate to prepare a PMMA film with a scintillator material doping mass fraction of 2%. The instruments used in the preparation included a JT-410HTD ultrasonic cleaner and an EZ4-S spin coater. The film material prepared in this example was then used for X-ray imaging testing and imaging on a self-built X-ray imaging system.

[0105] Experimental results are as follows Figure 10 and Figure 11 As shown. Figure 10 The images presented clearly show the textured patterns of the springs and chips inside the capsule. Figure 11 The resolution of scintillator thin film materials was demonstrated, showing that the resolution can reach 20 lp / mm, demonstrating great potential in X-ray imaging.

[0106] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A pure organic carbon borane-containing X-ray scintillator material, characterized in that, The chemical structural formula is: In the formula, the hollow dot is BH.

2. The method for preparing the pure organic carbon-borane X-ray scintillator material according to claim 1, characterized in that, Includes the following steps: S1: Halogenation reaction is carried out by mixing o-carborane, anhydrous aluminum trichloride and elemental iodine in a solvent; S2: Prepare Grignard reagents by mixing magnesium, iodine and 1-bromopyrene in a solvent and carrying out a free radical reaction; S3: The products obtained from reaction S1 and reaction S2 are mixed with the palladium catalyst in a solvent to carry out a nucleophilic substitution reaction; S4: First, mix n-butyllithium, cuprous chloride and the product obtained from the reaction of S3 in a solvent to carry out a nucleophilic substitution reaction. Then, add 4-n-butyliodobenzene and pyridine to continue the nucleophilic substitution reaction. S5: First, n-butyllithium and the final product obtained from the reaction of S4 are mixed in a solvent to carry out a nucleophilic substitution reaction. Then, trimethylchlorosilane is added to continue the nucleophilic substitution reaction to obtain a pure organic carborane X-ray scintillator material.

3. The method for preparing the pure organic carbon-borane X-ray scintillator material according to claim 2, characterized in that, The molar ratio of o-carborane, anhydrous aluminum trichloride, and elemental iodine in S1 is (1-3):(0.1-0.15):(1-3); the solvent includes dichloromethane; the halogenation reaction is carried out at a temperature of 30-50 °C for 30-60 h.

4. The method for preparing the pure organic carbon borane X-ray scintillator material according to claim 2, characterized in that, The molar ratio of magnesium, iodine and 1-bromopyrene in S2 is (1-3):(0.0005-0.002):(1-3); the solvent includes tetrahydrofuran; the free radical reaction temperature is 60-80 °C and the time is 1-3 h.

5. The method for preparing the pure organic carbon-borane X-ray scintillator material according to claim 2, characterized in that, The molar ratio of the product obtained from reaction S1, the product obtained from reaction S2, and the palladium catalyst in S3 is (0.5-2):(3-7):(0.001-0.003); the solvent includes tetrahydrofuran; the palladium catalyst includes palladium acetate or palladium dichloride bis(triphenylphosphine); the nucleophilic substitution reaction is carried out at a temperature of 45-65 °C for a time of 30-60 h.

6. The method for preparing the pure organic carbon-borane X-ray scintillator material according to claim 2, characterized in that, The molar ratio of n-butyllithium, cuprous chloride, the product obtained from the S3 reaction, 4-n-butyliodobenzene, and pyridine in S4 is (1-3):(1-1.5):(0.5-2):(1-3):(5-10); the solvent is ethylene glycol dimethyl ether; the temperature for the nucleophilic substitution reaction is 20-30 °C, and the time is 1-3 h; the temperature for the continued nucleophilic substitution reaction is 80-100 °C, and the time is 30-60 h.

7. The method for preparing the pure organic carbon-borane X-ray scintillator material according to claim 2, characterized in that, The molar ratio of n-butyllithium in S5, the final product obtained from S4, and trimethylchlorosilane is (0.5-2):(0.5-1):(0.5-1); the solvent includes tetrahydrofuran; the temperature for the nucleophilic substitution reaction is -5 to 5 °C, and the time is 30 to 90 min; the temperature for the continued nucleophilic substitution reaction is 80 to 100 °C, and the time is 10 to 15 h.

8. The method for preparing the pure organic carbon-borane X-ray scintillator material according to claim 2, characterized in that, The reactions in S1 to S5 are all carried out under a protective gas atmosphere.

9. The application of the pure organic carboborane X-ray scintillator material of claim 1 in X-ray imaging, X-ray radiation detection or X-ray security inspection for non-disease diagnosis purposes.

Images