A fused ring aromatic hydrocarbon double coupling molecule and ethylene-vinyl acetate copolymer composite film, and a preparation method and application thereof

Abstract

The application belongs to the technical field of force stimulation response room temperature phosphor, and more particularly relates to a fused ring aromatic hydrocarbon double coupling molecule and ethylene-vinyl acetate copolymer composite film and a preparation method and application thereof. The fused ring aromatic hydrocarbon double coupling molecule with a specific structure is compounded with ethylene-vinyl acetate copolymer to prepare a composite film which has enhanced room temperature phosphor intensity and prolonged luminescence lifetime with the increase of applied mechanical force under low pressure. The composite film has excellent low pressure sensitivity and can exhibit excellent room temperature phosphor performance under lower pressure, has excellent phosphor intensity and lifetime, and has broad application prospects in the field of pressure sensing and the like.

Description

Technical Field

[0001] This invention belongs to the technical field of force-stimulated room temperature phosphorescence, and more specifically, relates to a composite film of a fused-ring aromatic hydrocarbon dual-coupling molecule and an ethylene-vinyl acetate copolymer, its preparation method and application. Background Technology

[0002] Organic optoelectronic materials have lower costs compared to inorganic optoelectronic materials because their raw materials are more widely available and inexpensive. Furthermore, organic structures are easier to design and modify, and the resulting materials have simpler manufacturing processes. Among them, organic phosphorescent materials have attracted particular attention from academia and industry due to their unique long-lifetime luminescence characteristics and excellent optical properties. The luminescence mechanism of phosphorescence is mainly based on the Jabrunsky law. When matter is excited, the exciton in the singlet ground state (S0) absorbs energy (mainly photons) and transitions to the singlet excited state (S...). n After internal conversion relaxation, the exciton reaches a relatively stable singlet excited state (S1). If the exciton is released in the form of photoradiation to reach S0, fluorescence (FL) is produced, with a luminescence lifetime typically on the nanosecond scale. However, when it passes through intersystem crossing (ISC) to the triplet excited state (T... n After internal conversion to a relatively stable triplet excited state (T1), the release of energy to S0 via light radiation is accompanied by phosphorescence (PL). Because this process is forbidden, phosphorescence has a long lifetime, typically on the order of microseconds or sub-milliseconds. As a result, phosphorescent materials have a significantly longer luminescence lifetime than fluorescence, and also exhibit higher signal-to-noise ratios and sensitivity. Compared to fluorescence, phosphorescent materials retain their luminescence for a longer period after leaving the excitation source, avoiding the influence of the excitation light and thus having broader applications in optoelectronics, sensing, and information encryption.

[0003] With the continuous development of optoelectronic materials science, research on stimulus-responsive phosphorescence is also increasing. Among them, pressure-responsive materials have attracted much attention due to their important applications in stress sensing, intelligent monitoring and information storage. Patent application CN118388954A discloses a polyurethane composite material that can enhance room temperature phosphorescence and extend lifespan with increasing pressure. This invention uses a simple solution blending method to prepare a polyurethane composite film. Before and after the material is subjected to pressure, the phosphorescence emission changes from almost invisible to the naked eye before pressure to bright phosphorescence emission after pressure. After the pressure is removed, the phosphorescence emission returns to the level of being invisible to the naked eye. However, the above solution still has the following problems: (1) It is difficult for the polyurethane composite film to achieve pressure-responsive room temperature phosphorescence under low pressure (0-40MPa). It needs to be under higher pressure to exhibit a certain phosphorescence intensity; (2) It has poor toughness and low-temperature brittleness, making it difficult to meet more application scenarios; (3) Based on the application scenarios of artificial intelligence and low-pressure damage detection, higher requirements are put forward for the phosphorescence intensity change rate of composite materials under low pressure.

[0004] Therefore, further development of a series of polymeric materials composed of different polymer substrates and organic phosphorescent molecules, which can exhibit superior phosphorescence intensity under low pressure, improve the low-pressure sensitivity response of the materials, and fill existing application gaps, is of profound and significant importance for the further development of the field of force-responsive luminescent materials. Summary of the Invention

[0005] To address the aforementioned problems in the existing technology, the primary objective of this invention is to provide a composite membrane of a fused-ring aromatic hydrocarbon dual coupling molecule and an ethylene-vinyl acetate copolymer.

[0006] The second objective of this invention is to provide a method for preparing a composite film of a fused-ring aromatic hydrocarbon dual coupling molecule and an ethylene-vinyl acetate copolymer.

[0007] The third objective of this invention is to provide an application of a composite membrane of a polycyclic aromatic hydrocarbon dual coupling molecule and an ethylene-vinyl acetate copolymer in the fields of pressure sensing, artificial intelligence, and low-pressure damage detection.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solution: This invention claims protection for a composite film of a polycyclic aromatic hydrocarbon dual coupling molecule and an ethylene-vinyl acetate copolymer, comprising: a polycyclic aromatic hydrocarbon dual coupling molecule and an ethylene-vinyl acetate copolymer; The structural formula of the polycyclic aromatic hydrocarbon dual-coupling molecule is shown below: ; In the formula, X is selected from or Y is selected from , , , , or ; R1 and R2 are each independently selected from H, , , or .

[0009] This invention utilizes a fused-ring aromatic double-coupled molecule with a specific structure to composite with an ethylene-vinyl acetate copolymer, preparing a composite film whose room-temperature phosphorescence intensity and luminescence lifetime increase with increasing mechanical force under low pressure. The room-temperature phosphorescence intensity and lifetime of the composite film are positively correlated with the applied pressure: under no pressure, it exhibits only weak phosphorescence emission invisible to the naked eye; after applying a small pressure, it rapidly transforms into bright phosphorescence emission; after the pressure is removed, the phosphorescence emission returns to the initial level. This change is reversible, demonstrating excellent mechanical stability and in-situ recovery capability.

[0010] The composite film provided by this invention uses ethylene-vinyl acetate copolymer (EVA) elastomer as a base. Compared with polyurethane, it has extremely high flexibility and low-temperature toughness: EVA has an extremely low glass transition temperature, and can maintain excellent softness and elasticity even in cold environments, and is not easy to harden or become brittle; secondly, it has an extremely low density, making it easy to achieve lightweighting; finally, EVA also has the advantages of simple processing and low cost.

[0011] The composite membrane provided by this invention exhibits excellent low-pressure sensitivity, demonstrating superior room-temperature phosphorescence performance even at relatively low pressures. It also exhibits excellent phosphorescence intensity and lifetime, showing broad application prospects in pressure sensing and other fields. Furthermore, the composite membrane provided by this invention shows a greater variation in phosphorescence intensity under low-pressure conditions, exhibiting a superior rate of phosphorescence intensity change, making it more suitable for fields such as artificial intelligence and low-pressure damage detection.

[0012] Preferably, the low pressure ranges from 1 to 50 MPa; more preferably, the low pressure ranges from 10 to 40 MPa; even more preferably, the low pressure ranges from 20 to 40 MPa. Under the above-mentioned low pressure, the composite membrane provided by the present invention exhibits superior room temperature phosphorescence performance.

[0013] Preferably, the mass ratio of the polycyclic aromatic hydrocarbon (PAH) dicoupler to the ethylene-vinyl acetate copolymer is 0.01-10:100. Specifically, the mass ratio of the PAH dicoupler to the ethylene-vinyl acetate copolymer can be 0.03:100, 0.05:100, 0.08:100, 0.1:100, 0.3:100, 0.5:100, 0.8:100, 1:100, 3:100, 5:100, 8:100, etc., or any range formed by the above values, such as 0.01-1:100, 0.02-0.08:100, 0.05-0.1:100, etc., and the present invention is not limited thereto.

[0014] More preferably, the mass ratio of the polycyclic aromatic hydrocarbon bis-coupled molecule to the ethylene-vinyl acetate copolymer is 0.05-0.5:100.

[0015] Preferably, X is selected from... Y is selected from or .

[0016] Preferably, R1 and R2 are independently selected from H, or .

[0017] Preferably, the structural formula of the polycyclic aromatic hydrocarbon bis-coupled molecule is selected from any of the following: .

[0018] More preferably, the structural formula of the polycyclic aromatic hydrocarbon bis-coupled molecule is selected from any of the following: Under these preferred conditions, the prepared composite film exhibits superior room-temperature phosphorescence properties at low pressure.

[0019] Preferably, the number-average molecular weight of the ethylene-vinyl acetate copolymer is 20,000 to 1,000,000. Specifically, the number-average molecular weight of the ethylene-vinyl acetate copolymer can be 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 150,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000, 900,000, or any range formed by the above values, such as 20,000-80,000, 40,000-60,000, 30,000-50,000, 30,000-100,000, etc., and the present invention is not limited thereto. More preferably, the number-average molecular weight of the ethylene-vinyl acetate copolymer is 40,000 to 50,000.

[0020] Preferably, the structural formula of the ethylene-vinyl acetate copolymer is as follows: y is 15-30; more preferably y is 20-25.

[0021] Preferably, the vinyl acetate content in the ethylene-vinyl acetate copolymer is 5-50% by mass. Specifically, the vinyl acetate content is 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc., or any range formed by the above values, such as 14-40%, 25-40%, 30-35%, 30-38%, 28-35%, etc., and the present invention is not limited thereto.

[0022] Preferably, the thickness of the composite film of the polycyclic aromatic hydrocarbon dual coupling molecule and the ethylene-vinyl acetate copolymer is 10-1000 μm. Specifically, the thickness of the composite film can be 80 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, etc., or any range formed by the above values, such as 50-500 μm, 100-400 μm, 300-500 μm, 150-250 μm, etc., and the present invention is not limited thereto.

[0023] Furthermore, this invention claims protection for a method for preparing a composite membrane of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer, wherein the polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer are dissolved in an organic solvent, blended, and the solvent is removed, and then pressed into a membrane to obtain the composite membrane of the polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer.

[0024] Preferably, the organic solvent includes, but is not limited to, dichloromethane, tetrahydrofuran, toluene, etc.

[0025] Preferably, the blending time is 3-5 hours.

[0026] Preferably, the pressing temperature is 150-200℃.

[0027] Furthermore, this invention claims protection for the application of a composite membrane of a polycyclic aromatic hydrocarbon dual coupling molecule and ethylene-vinyl acetate copolymer in the fields of pressure sensing, artificial intelligence, and low-pressure damage detection.

[0028] Compared with the prior art, the present invention has the following beneficial effects: This invention uses a polycyclic aromatic hydrocarbon dual-coupling molecule with a specific structure to composite with an ethylene-vinyl acetate copolymer to prepare a composite film whose room temperature phosphorescence intensity increases and luminescence lifetime is extended with increasing mechanical force under low pressure. The composite film has excellent low-pressure sensitivity and can exhibit excellent room temperature phosphorescence performance at low pressure. It has excellent phosphorescence intensity and lifetime and shows broad application prospects in pressure sensing and other fields. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the apparatus and forces applied during the pressure test of the composite membrane.

[0030] Figure 2 The image shows the phosphorescence effect of the composite film prepared in Example 1 under pressure.

[0031] Figure 3 The time-delayed spectral changes of the composite membrane prepared in Example 1 during the pressurization process; wherein, Figure 3 (a) shows the spectral changes of the composite membrane under different pressures. Figure 3 (b) shows the spectral changes of the composite membrane after multiple cycles.

[0032] Figure 4 The spectral changes of the composite membranes prepared in Examples 2 and 3 under different pressures are shown; wherein, Figure 4 (a) shows the spectral changes of the NpTA@EVA composite film prepared in Example 3 under different pressures. Figure 4 (b) shows the spectral changes of the TpPX@EVA composite membrane prepared in Example 2 under different pressures.

[0033] Figure 5 The lifespan of TpTA@EVA and TpPX@EVA composite membranes under pressurized or depressurized conditions is shown; among them, Figure 5 (a) and (b) show the lifespan of the TpTA@EVA composite membrane under pressurized and depressurized conditions, respectively. Figure 5 (c) and (d) in the figure represent the lifespan of the TpPX@EVA composite membrane under pressurized and depressurized conditions.

[0034] Figure 6 The spectral changes of the TA@EVA composite film under different pressures are shown under pressurized or depressurized conditions; among them, Figure 6 (a) shows the spectral changes of the TA@EVA composite membrane under pressure. Figure 6 (b) shows the spectral changes of the TA@EVA composite membrane under depressurization.

[0035] Figure 7 The spectral changes of the TpTA@PU composite film under different pressures during pressurization or depressurization are shown; among them, Figure 7 (a) shows the spectral changes of the TpTA@PU composite film under pressure. Figure 7 (b) shows the spectral changes of the TpTA@PU composite film under depressurization conditions.

[0036] Figure 8 The spectral changes of the PhaTA@EVA composite membrane under pressure are shown. Detailed Implementation

[0037] The present invention will be further described below with reference to the specification and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0038] Example 1: A composite membrane of a polycyclic aromatic hydrocarbon dual coupling molecule and an ethylene-vinyl acetate copolymer (1) Synthesis of polycyclic aromatic hydrocarbon dicoupled molecules The reaction formula is shown below:

[0039] The specific preparation method includes the following steps: Prepare a clean 250 mL three-necked flask. Add the starting materials triphenyl-2-boronic acid (500 mg, 1.63 mmol) and 2-bromodithionanthracene (420 mg, 1.63 mmol), followed by the catalyst tetra(triphenylphosphine)palladium (188 mg, 0.16 mmol) and potassium carbonate (450 mg, 3.26 mmol). Measure 40 mL of toluene, 5 mL of anhydrous ethanol, and 5 mL of deionized water into the reaction system. First, purge the system with nitrogen for 30 min to remove air. Then, heat to 110 °C and stir the reaction mixture at this temperature under a nitrogen atmosphere for 24 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The product was concentrated at room temperature and separated by silica gel column chromatography (using hexane and dichloromethane as solvents, with a volume ratio of hexane to dichloromethane of 1:1). The product obtained by column chromatography was dissolved in tetrahydrofuran solution to obtain a saturated solution of tetrahydrofuran. Anhydrous ethanol was then added to make the solution appear turbid (the volume ratio of tetrahydrofuran to anhydrous ethanol was 1:1). This mixture was placed in a refrigerator at -10 °C and recrystallized for 24 h to obtain a purified product with a yield of 50%. The purified product was dried in a vacuum oven at 65 °C for 4 h to obtain a dry powder, which is the final product TpTA.

[0040] The NMR data for the final product TpTA are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 8.81 (d, J= 1.9 Hz, 1H), 8.78–8.60 (m, 5H), 7.93 (d, J = 1.9 Hz, 1H), 7.86 (dd, J =8.4, 1.9 Hz, 1H), 7.79–7.59 (m, 6H), 7.54 (td, J = 5.3, 3.4 Hz, 2H), 7.28 (dd, J = 5.8, 3.3 Hz, 2H).

[0041] (2) Preparation of composite membrane 100 mg of ethylene-vinyl acetate copolymer (Mn = 42700, vinyl acetate (VA): 32 wt%, EVA32, Aladdin) and 0.5 mg of polycyclic aromatic hydrocarbon (PAH) dicoupler TpTA were dissolved in 5 mL of tetrahydrofuran and stirred at room temperature for 4 h for physical blending. The resulting mixture was poured into a glass bottle, air-dried in a fume hood for 12 h, and then dried in a 65℃ forced-air oven for 3 h to further remove the solvent, yielding a film. The film was then pressed at 180℃ for 5 min using a hot press (Dongguan Zhuosheng Machinery Equipment Co., Ltd., ZS-406BE-30-310), and after cooling, a composite film (TpTA@EVA) with a thickness of 200 μm was obtained.

[0042] Example 2: A composite membrane of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer The difference between this embodiment and Example 1 is that in step (1), 4-bromophenoxathia (394 mg, 1.63 mmol) was used to replace 2-bromodithionanthracene. The final product was a polycyclic aromatic hydrocarbon bis-coupled molecule TpPX with a yield of 50%. In step (2), a composite membrane (TpPX@EVA) was prepared.

[0043] The reaction formula is shown below:

[0044] The NMR data for TpPX are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 8.85 (d, J = 1.9Hz, 1H), 8.80–8.55 (m, 5H), 7.87 (dd, J = 8.4, 1.8 Hz, 1H), 7.68 (ddd, J =12.6, 8.3, 6.1 Hz, 4H), 7.40 (dd, J = 7.2, 2.0 Hz, 1H), 7.25–7.14 (m, 3H), 7.14–7.01 (m, 2H), 6.96–6.87 (m, 1H).

[0045] Example 3: A composite membrane of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer The difference between this embodiment and Example 1 is that in step (1), 2-naphthoboric acid (291 mg, 1.63 mmol) was used instead of triphenyl-2-boric acid. The final product was a polycyclic aromatic hydrocarbon dual-coupling molecule NpTA with a yield of 50%. In step (2), a composite membrane (NpTA@EVA) was prepared.

[0046] The reaction formula is shown below:

[0047] The NpTA NMR data are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 8.04 (s, 1H), 7.91 (dd, J = 19.2, 10.8 Hz, 4H), 7.72 (dd, J = 8.4, 1.9 Hz, 1H), 7.61 (d, J= 2.1 Hz, 2H), 7.61 – 7.51 (m, 3H), 7.52 (d, J = 4.7 Hz, 1H), 7.29 (d, J =4.1 Hz, 5H).

[0048] Comparative Example 1 The difference between this comparative example and Example 1 is as follows: (1) Obtain TpTA; (2) 100 mg of polyurethane (MDI / BDO / PBA-PU, purchased from Zhejiang Huafeng Thermoplastic Polyurethane Co., Ltd., Mn = 30783, PDI = 1.92, MDI: 38 wt.%, BDO: 12 wt.%, PBA: 50 wt.%) and 0.5 mg of polycyclic aromatic hydrocarbon (PAH) dicoupled molecule TpTA were dissolved in 5 mL of tetrahydrofuran and stirred at room temperature for 4 h for physical blending. The resulting mixed solution was poured into a glass bottle, placed in a fume hood to air dry for 12 h, and then placed in a 65℃ forced-air oven to dry for 3 h to further remove the solvent, thus obtaining a film. Next, the film was pressed at 180℃ for 5 min using a hot press (Dongguan Zhuosheng Machinery Equipment Co., Ltd., ZS-406BE-30-310), and after cooling, a TpTA@PU with a thickness of 200 μm was obtained.

[0049] Comparative Example 2 The difference between this comparative example and Example 1 is that step (1) is not performed; in step (2), thiaanthracene TA (98%, Guangzhou Muran Biochemical Technology Co., Ltd., structural formula as follows) is used to replace the polycyclic aromatic hydrocarbon dual coupling molecule TpTA to prepare a composite membrane (TA@EVA).

[0050]

[0051] Comparative Example 3 The difference between this comparative example and Example 1 is as follows: The difference between this embodiment and Example 1 is that in step (1), 9-phenanthroline boric acid (376 mg, 1.63 mmol) was used to replace triphenyl-2-boronic acid. The final product was a polycyclic aromatic hydrocarbon dual-coupling molecule, PhaTA, with a yield of 50%. In step (2), a composite membrane (PhaTA@EVA) was prepared.

[0052] The reaction formula is shown below:

[0053] The NMR data for PhaTA are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 8.80 (d, J = 8.3Hz, 1H), 8.75 (d, J = 8.2 Hz, 1H), 7.89 (dd, J = 14.0, 8.0 Hz, 2H), 7.76 –7.61 (m, 6H), 7.61 – 7.51 (m, 3H), 7.45 (dt, J = 7.9, 1.6 Hz, 1H), 7.35 –7.26 (m, 2H).

[0054] Test case (1) Using quartz glass as the pressure transmission carrier, the composite films (TpTA@EVA, NpTA@EVA and TpPX@EVA) prepared in the examples were pressurized or depressurized (the pressure application device was a BJ-15 powder tablet press, Tianjin Bojun Technology Co., Ltd.) to study the phosphorescence emission of the composite films under different pressures (0 MPa, 5 MPa, 10 MPa, 15 MPa, 20 MPa). The delayed spectrum (phosphorescence spectrum) of the composite films under pressure was tested through quartz glass using a miniature fiber optic spectrometer (Ocean Optics QE65PRO), and the wavelength of the excitation source was found to be 405 nm.

[0055] Figure 1 This is a schematic diagram of the apparatus and forces applied during the pressure test of the composite membrane. Figure 2 The image shows the phosphorescence effect of the composite film prepared in Example 1 under pressure. Figure 2 As shown, under 405 nm visible light excitation, the phosphorescence emission of the composite film prepared in Example 1 varies under different pressures. At 0 MPa, the luminescence of the composite film is weak. As the pressure gradually increases, the luminescence intensity and lifetime of the composite film show a monotonically increasing trend. When the pressure is released to 0 MPa, the phosphorescence intensity and lifetime return to their original state.

[0056] Figure 3 The time-delayed spectral changes of the composite membrane prepared in Example 1 during the pressurization process; wherein, Figure 3 (a) shows the spectral changes of the composite membrane under different pressures. Figure 3 (b) shows the spectral changes of the composite membrane after multiple cycles. Figure 3 It can be seen that as the pressure increases, the intensity of the phosphorescence spectrum of the composite film TpTA@EVA prepared in Example 1 gradually increases, and multiple cycles show that its correlation with pressure is good. This composite film exhibits excellent low-pressure sensitivity and reversibility under low pressures of 5-20 MPa, especially under low pressures of 10-20 MPa, and possesses very high phosphorescence intensity.

[0057] Figure 4 The spectral changes of the composite membranes prepared in Examples 2 and 3 under different pressures are shown; wherein, Figure 4 (a) shows the spectral changes of the NpTA@EVA composite film prepared in Example 3 under different pressures. Figure 4 (b) shows the spectral changes of the TpPX@EVA composite membrane prepared in Example 2 under different pressures. Figure 4 It is evident that the NpTA@EVA and TpPX@EVA composite films also exhibit the same pressure-responsive room-temperature phosphorescence properties. Both NpTA@EVA and TpPX@EVA composite films demonstrate excellent low-pressure sensitivity and reversibility, particularly at 10-20 MPa. Specifically, the NpTA@EVA composite film exhibits superior phosphorescence intensity at low pressure, while the TpPX@EVA composite film also shows a significant change in phosphorescence intensity under low pressure, demonstrating excellent low-pressure sensitivity.

[0058] (2) The composite membrane was pressurized using an anvil pressurization device, and the pressurization device was placed in the measurement section of the Horiba JY FL instrument to test the phosphorescence lifetime.

[0059] Figure 5 The lifespan of TpTA@EVA and TpPX@EVA composite membranes under pressurized or depressurized conditions is shown; among them, Figure 5 (a) and (b) show the lifespan of the TpTA@EVA composite membrane under pressurized and depressurized conditions, respectively. Figure 5 Figures (c) and (d) show the lifespan of the TpPX@EVA composite membrane under pressurized and depressurized conditions. Figure 5 It can be seen that as pressure increases, lifespan increases, and this phenomenon is also reversible.

[0060] (3) The above test methods were used to test the TA@EVA, TpTA@PU and PhaTA@EVA prepared in the comparative example under pressure or pressure relief to study the time delay spectrum changes of the composite film under different pressures.

[0061] Figure 6 The spectral changes of the TA@EVA composite film under different pressures are shown under pressurized or depressurized conditions; among them, Figure 6 (a) shows the spectral changes of the TA@EVA composite membrane under pressure. Figure 6 (b) shows the spectral changes of the TA@EVA composite membrane under depressurization. Figure 7 The spectral changes of the TpTA@PU composite film under different pressures during pressurization or depressurization are shown; among them, Figure 7 (a) shows the spectral changes of the TpTA@PU composite film under pressure. Figure 7 (b) shows the spectral changes of the TpTA@PU composite film under depressurization conditions. Figure 8 The spectral changes of the PhaTA@EVA composite membrane under pressure are shown.

[0062] Depend on Figure 6 , Figure 7 and Figure 8 It can be seen that the TA@EVA composite film, TpTA@PU composite film and PhaTA@EVA composite film have poor sensitivity and response characteristics under low pressure, and low phosphorescence intensity under low pressure, which is significantly different from the composite film prepared in the example.

[0063] A comparison of the phosphorescence intensity data of the composite films prepared in the above embodiments and comparative examples under low pressure shows that the composite film formed by solvent blending of the specific molecular structure formed by coupling polycyclic aromatic hydrocarbons and thiophene molecules with the EVA system exhibits excellent low-pressure sensitivity and response characteristics. When the polycyclic aromatic hydrocarbon dual-coupling molecules of this invention are replaced with other molecules in the EVA system, or when EVA is replaced with polyamide as the matrix resin, it is difficult to achieve excellent low-pressure sensitivity, resulting in lower phosphorescence intensity under low pressure.

[0064] The foregoing examples are merely illustrative, used to explain some features of the method described in this invention. The appended claims are intended to claim the broadest possible scope, and the embodiments presented herein are demonstrated by the applicant's actual experimental results. Therefore, the applicant intends that the appended claims are not limited by the selection of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be interpreted as being covered by the appended claims where possible.

Claims

1. A composite film of a polycyclic aromatic hydrocarbon dual-coupling molecule and an ethylene-vinyl acetate copolymer, characterized in that, include: Polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymers; The structural formula of the polycyclic aromatic hydrocarbon dual-coupling molecule is shown below: ； In the formula, X is selected from or Y is selected from , , , , or ; R1 and R2 are each independently selected from H, , , or .

2. The composite film of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer according to claim 1, characterized in that, The mass ratio of the polycyclic aromatic hydrocarbon bis-coupled molecule to the ethylene-vinyl acetate copolymer is 0.01-10:

100.

3. The composite film of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer according to claim 1, characterized in that, X is selected from Y is selected from or .

4. The composite film of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer according to claim 1, characterized in that, R1 and R2 are independently selected from H, or .

5. The composite film of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer according to claim 1, characterized in that, The structural formula of the polycyclic aromatic hydrocarbon dual-coupling molecule is selected from any of the following: 。 6. The composite film of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer according to claim 1, characterized in that, The number average molecular weight of the ethylene-vinyl acetate copolymer is 2-1,000,000.

7. The composite film of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer according to claim 1, characterized in that, The ethylene-vinyl acetate copolymer contains 5-50% vinyl acetate by mass.

8. The composite film of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer according to claim 1, characterized in that, The thickness of the composite film of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer is 10-1000 μm.

9. A method for preparing a composite film of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer according to any one of claims 1-8, characterized in that, The polycyclic aromatic hydrocarbon dual coupling molecule and the ethylene-vinyl acetate copolymer are dissolved in an organic solvent, blended, and the solvent is removed. The mixture is then pressed into a film to obtain the composite film of the polycyclic aromatic hydrocarbon dual coupling molecule and the ethylene-vinyl acetate copolymer.

10. The application of the composite membrane of polycyclic aromatic hydrocarbon dual coupling molecules and ethylene-vinyl acetate copolymer as described in any one of claims 1-8 in the fields of pressure sensing, artificial intelligence and low-pressure damage detection.

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