Spontaneous phase change luminescent materials, thermal exposure monitoring materials, their preparation methods and applications

Abstract

This invention discloses a spontaneous phase-change luminescent material, a heat exposure monitoring material, its preparation method, and its application, relating to the field of smart materials technology. The structural formula of the spontaneous phase-change luminescent material is: [Formula omitted for brevity]; where R is an alkyl group with 4-6 carbon atoms. After the spontaneous phase-change luminescent material provided by this invention is prepared into a film, a phase transition occurs at a certain temperature, and the phase transition rate varies at different temperatures; the higher the temperature, the faster the phase transition. As the phase transition proceeds, the luminescence (specifically photoluminescence) color changes, and this color change can be completed within minutes or hours. Therefore, it has a heat exposure monitoring function and a fast response rate.

Description

Technical Field

[0001] This invention relates to the field of smart materials technology, and in particular to spontaneous phase change luminescent materials, thermal exposure monitoring materials, their preparation methods and applications. Background Technology

[0002] Currently, vaccine vial monitors (VVMs) technology, through their irreversible color-changing reaction, has become a key tool for ensuring the safety of vaccines during storage and transportation at the end of the cold chain. VVMs have formed standardized time-temperature response systems, mainly divided into types such as VVM2 (reaching the endpoint in approximately 2 days at 37°C) and VVM14 (reaching the endpoint in approximately 14 days at 37°C), to match the thermal stability of different vaccines. In practical applications, vaccines with short heat exposure tolerance windows (such as oral polio vaccines) must be monitored using the faster-responding VVM2, while most other live vaccines (such as measles and rubella vaccines) use VVM14. However, for some vaccines with heat exposure tolerance windows only on the order of hours (such as the G3 strain of rotavirus vaccines, whose half-life at 37°C is less than 2 hours), there is a lack of VVMs with corresponding response rates.

[0003] The core color-changing material used in current VVMs is a substituted diyne monomer. The color change mechanism of VVMs is mainly based on the solid-state chemical polymerization reaction of the substituted diyne monomer. This monomer undergoes irreversible solid-state polymerization upon heating, gradually changing from a light color to a dark color. The rate of color change is positively correlated with temperature; the higher the temperature, the faster the color deepens, thus visually reflecting the cumulative heat exposure of the vaccine. By changing the substituents on the diyne monomer molecule, its stacking pattern in the crystal lattice and the distance between molecules can be precisely controlled, thereby finely controlling the activation energy and rate of the polymerization reaction. However, the reaction rate of this substituted diyne monomer is limited, making it difficult to achieve VVM preparation with a short response cycle.

[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0005] Based on the shortcomings of the existing technology, the purpose of this invention is to provide spontaneous phase change luminescent materials, thermal exposure monitoring materials, their preparation methods and applications, in order to solve the problem that existing color-changing materials for VVMs are difficult to achieve minute or hour-level color-changing responses.

[0006] The technical solution of the present invention is as follows: In a first aspect, the present invention provides a spontaneous phase change luminescent material, wherein the structural formula of the spontaneous phase change luminescent material is: ; Wherein, R is an alkyl group having 4 to 6 carbon atoms.

[0007] Optionally, R is selected from one of the following groups: -CH2CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -C(CH3)3, -CH2CH2CH2CH2CH3, -CH(CH3)CH2CH2CH3, -CH2CH(CH3)CH2CH3, -CH2CH2CH(CH3)2, -CH(CH3)CH(CH3)2, -C(CH3)2CH2CH3, -CH(C2H5)CH2CH3, -CH2C(CH3)3, -CH2CH2CH2CH2CH2CH3, -CH2CH2CH2CH(CH3)2, -CH2CH2CH(CH3)CH2CH3, -CH2CH2C(CH3)2CH3, -CH2CH2CH(C2H5)CH3, -CH2CH(CH3)CH2CH2CH3, -CH2C(CH3)2CH2CH3, -CH2CH(CH3)CH(CH3)CH3, -CH2CH(C2H5)CH2CH3, -CH(CH3)CH2CH2CH2CH3, -CH(CH3)CH(CH3)CH2CH3, -CH(CH3)CH2CH(CH3)CH3, -CH(C2H5)CH2CH2CH3, -CH(C2H5)CH(CH3)CH3, -C(CH3)2CH2CH2CH3, -C(CH3)2CH(CH3)CH3 and -C(C2H5)2CH3.

[0008] A second aspect of the present invention provides a method for preparing the spontaneous phase change luminescent material as described above, comprising the following steps: Will and After the reaction, the spontaneous phase change luminescent material is obtained.

[0009] Optionally, The preparation method includes the following steps: Will and After the reaction, we get .

[0010] Optionally, The preparation method includes the following steps: Will After reacting with a chlorinating agent, the following is obtained: .

[0011] Optionally, The preparation method includes the following steps: Will and After the reaction, we get ; Will After reacting with a reducing agent, the following is obtained: ; Where X is a halogen.

[0012] A third aspect of the present invention provides a method for preparing a heat exposure monitoring material, comprising the following steps: The spontaneous phase change luminescent material of the present invention, as described above, is mixed with the sixth solvent to prepare a solution. After coating, the solvent is removed to obtain the heat exposure monitoring material.

[0013] Optionally, the sixth solvent includes at least one selected from dichloromethane, petroleum ether, ethyl acetate, tetrahydrofuran, dioxane, diethyl ether, and acetone; and / or, The concentration of the spontaneous phase change luminescent material in the solution is 1.0 × 10⁻⁶. -4 mol / L~1.0mol / L.

[0014] In a fourth aspect, the present invention provides a heat exposure monitoring material, wherein it is prepared by the preparation method of the present invention as described above.

[0015] A fifth aspect of the present invention provides the application of the spontaneous phase change luminescent material of the present invention as described above or the heat exposure monitoring material of the present invention as described above in a vaccine vial monitor.

[0016] Beneficial effects: After the spontaneous phase-change luminescent material provided by this invention is prepared into a film, a phase transition occurs at a certain temperature, and the phase transition rate varies at different temperatures. The higher the temperature, the faster the phase transition. As the phase transition proceeds, the luminescence (specifically photoluminescence) color changes. The color change can be completed within minutes or hours, thus providing a heat exposure monitoring function with a fast response rate. The spontaneous phase-change luminescent material can be used to prepare a vaccine vial monitor, which can monitor vaccines with heat exposure tolerance windows of only hours (such as the G3 strain of rotavirus vaccine, which has a half-life of less than 2 hours at 37°C).

[0017] Specifically, the spontaneous phase change of the spontaneous phase change luminescent material is from an amorphous state to a crystalline state, approximating a cold crystallization process. Luminescence refers to photoluminescence. After the spontaneous phase change luminescent material provided by this invention is prepared into a film, it forms an amorphous aggregate. At this point, the photoluminescence color is yellow (i.e., the luminescence color under ultraviolet excitation is yellow). At a certain temperature (such as room temperature or higher), the amorphous aggregate undergoes solid-state molecular motion and gradually crystallizes spontaneously within half an hour to two hours (the specific time depends on the R group and temperature). After crystallization, the photoluminescence color is green (i.e., the luminescence color under ultraviolet excitation is green). Thus, the color change reflects the cumulative heat exposure. Attached Figure Description

[0018] Figure 1 The image shows the hydrogen nuclear magnetic resonance spectrum of the spontaneous phase change luminescent material (R is n-pentyl) prepared in Example 1.

[0019] Figure 2 The image shows the carbon NMR spectrum of the spontaneous phase change luminescent material (R is n-pentyl) prepared in Example 1.

[0020] Figure 3 This is a high-resolution mass spectrum of the spontaneous phase change luminescent material (R is n-pentyl) prepared in Example 1.

[0021] Figure 4 This is an ultraviolet-excited emission diagram of the heat exposure monitoring material in its initial state in Example 1.

[0022] Figure 5 This is an ultraviolet-excited emission diagram of the thermal exposure monitoring material after phase transition in Example 1.

[0023] Figure 6 The images show the X-ray diffraction patterns of the heat exposure monitoring material in its initial state and the heat exposure monitoring material after phase change in Example 1.

[0024] Figure 7 The image shows the hydrogen nuclear magnetic resonance spectrum of the spontaneous phase change luminescent material (R is n-butyl) prepared in Example 2.

[0025] Figure 8 The image shows the carbon NMR spectrum of the spontaneous phase change luminescent material (R is n-butyl) prepared in Example 2.

[0026] Figure 9 This is a high-resolution mass spectrum of the spontaneous phase change luminescent material (R is n-butyl) prepared in Example 2.

[0027] Figure 10 This is an ultraviolet-excited emission diagram of the heat exposure monitoring material in its initial state in Example 2.

[0028] Figure 11This is an ultraviolet-excited emission diagram of the thermal exposure monitoring material after phase transition in Example 2.

[0029] Figure 12 The image shows the hydrogen nuclear magnetic resonance spectrum of the spontaneous phase change luminescent material (R is n-hexyl) prepared in Example 3.

[0030] Figure 13 The image shows the carbon NMR spectrum of the spontaneous phase change luminescent material (R is n-hexyl) prepared in Example 3.

[0031] Figure 14 This is a high-resolution mass spectrum of the spontaneous phase change luminescent material (R is n-hexyl) prepared in Example 3.

[0032] Figure 15 This is an ultraviolet-excited emission diagram of the heat exposure monitoring material in its initial state in Example 3.

[0033] Figure 16 This is an ultraviolet-excited emission diagram of the thermal exposure monitoring material after phase transition in Example 3. Detailed Implementation

[0034] This invention provides spontaneous phase change luminescent materials, thermal exposure monitoring materials, their preparation methods, and applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0036] If the embodiments of the present invention involve descriptions such as "first" or "second", such descriptions are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated.

[0037] This invention provides a spontaneous phase change luminescent material, wherein the structural formula of the spontaneous phase change luminescent material is: ; Wherein, R is an alkyl group having 4 to 6 carbon atoms.

[0038] After the spontaneous phase-change luminescent material provided in this embodiment of the invention is prepared into a film, a phase transition occurs at a certain temperature, and the phase transition rate varies at different temperatures. The higher the temperature, the faster the phase transition. As the phase transition proceeds, the color of the luminescence (specifically photoluminescence) changes. The color change can be completed within minutes or hours, thus providing a heat exposure monitoring function with a fast response rate. The spontaneous phase-change luminescent material is used to prepare a vaccine vial monitor, which can monitor vaccines with a heat exposure tolerance window of only hours (such as the G3 strain of rotavirus vaccine, which has a half-life of less than 2 hours at 37°C).

[0039] Specifically, the spontaneous phase change of the spontaneous phase change luminescent material is from an amorphous state to a crystalline state, approximating a cold crystallization process. Luminescence refers to photoluminescence. After the spontaneous phase change luminescent material provided by this invention is prepared into a film, it forms an amorphous aggregate. At this point, the photoluminescence color is yellow (i.e., the emission color under ultraviolet excitation is yellow). At a certain temperature (such as room temperature or higher), the amorphous aggregate undergoes solid-state molecular motion and gradually crystallizes spontaneously within half an hour to two hours (the specific time depends on the R group and temperature). After crystallization, the photoluminescence color is green (i.e., the emission color under ultraviolet excitation is green). Thus, the color change reflects the cumulative heat exposure. At low temperatures (such as 0°C), molecular thermal motion is restricted, and solid-state molecular motion cannot occur, thus the spontaneous phase change is suppressed.

[0040] In some embodiments, R is selected from one of the following groups: -CH2CH2CH2CH3 (n-butyl), -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -C(CH3)3 -CH2CH2CH2CH2CH3 (n-pentyl), -CH(CH3)CH2CH2CH3, -CH2CH(CH3)CH2CH3, -CH2CH2CH(CH3)2, -CH(CH3)CH(CH3)2, -C(CH3)2CH2CH3, -CH(C2H5)CH2CH3, -CH2C(CH3)3, -CH2CH2CH2CH2CH2CH3 (n-hexyl), -CH2CH2CH2CH(CH3)2, -CH2CH2CH(CH3)CH2CH3, -CH2CH2C(CH3)2CH3, -CH2CH2CH(C2H5)CH3, -CH2CH(CH3)CH2CH2CH3, -CH2C(CH3)2CH2CH3, -CH2CH(CH3)CH(CH3)CH3, -CH2CH(C2H5)CH2CH3, -CH(CH3)CH2CH2CH2CH3, -CH(CH3)CH(CH3)CH2CH3, -CH(CH3)CH2CH(CH3)CH3, -CH(C2H5)CH2CH2CH3, -CH(C2H5)CH(CH3)CH3, -C(CH3)2CH2CH2CH3, -C(CH3)2CH(CH3)CH3 and -C(C2H5)2CH3.

[0041] This invention also provides a method for preparing the spontaneous phase change luminescent material as described above, comprising the following steps: Will (The choice of R in this context is the same as that in the spontaneous phase change luminescent materials section above. The choice of R in the different structural formulas below is also the same as that in the spontaneous phase change luminescent materials section above. When R appears again in the different structural formulas below, it will not be repeated.) After the reaction, the spontaneous phase change luminescent material is obtained.

[0042] The spontaneous phase-change luminescent material prepared by the method provided in this embodiment has a heat exposure monitoring function. After being prepared into a film, it undergoes a phase transition at a certain temperature, and the phase transition rate varies at different temperatures. The higher the temperature, the faster the phase transition. As the phase transition proceeds, the luminescence (specifically photoluminescence) color changes. The color change can be completed within minutes or hours, exhibiting a fast color change response speed. The color change can reflect the cumulative heat exposure. The spontaneous phase-change luminescent material is used to prepare a vaccine vial monitor, which can monitor vaccines with a heat exposure tolerance window of only hours (such as the G3 strain of rotavirus vaccine, which has a half-life of less than 2 hours at 37°C).

[0043] Specifically, the spontaneous phase change of the spontaneous phase change luminescent material is from an amorphous state to a crystalline state, approximating a cold crystallization process. Luminescence refers to photoluminescence. After the spontaneous phase change luminescent material provided by this invention is prepared into a film, it forms an amorphous aggregate. At this point, the photoluminescence color is yellow (i.e., the luminescence color under ultraviolet excitation is yellow). At a certain temperature (such as room temperature or higher), the amorphous aggregate undergoes solid-state molecular motion and gradually crystallizes spontaneously within half an hour to two hours (the specific time depends on the R group and temperature). After crystallization, the photoluminescence color is green (i.e., the luminescence color under ultraviolet excitation is green). Thus, the color change reflects the cumulative heat exposure.

[0044] In some implementations... The preparation method includes the following steps: Will and After the reaction, we get .

[0045] In some implementations... The preparation method includes the following steps: Will After reacting with a chlorinating agent, the following is obtained: .

[0046] In some implementations... The preparation method includes the following steps: Will and After the reaction, we get ; Will After reacting with a reducing agent, the following is obtained: ; Where X is a halogen, specifically Cl, Br, or I.

[0047] The preparation method of spontaneous phase change luminescent materials is described in detail below, and the synthesis route is as follows: .

[0048] According to the above synthetic route, the preparation method of the spontaneous phase change luminescent material includes the following steps: S1. The compound shown in Formula I is mixed with RX (X is a halogen, specifically Cl, Br or I), a first base and a first solvent, and after a first reaction, the compound shown in Formula II is obtained.

[0049] Specifically, the molar ratio of the compound shown in Formula I to RX is 1:(1~4), for example, it can be 1:1, 1:2, 1:3 or 1:4, etc.

[0050] The molar ratio of the compound shown in Formula I to the first base is 1:(1~4), for example, it can be 1:1, 1:2, 1:3 or 1:4, etc.

[0051] The ratio of the compound shown in Formula I to the first solvent is 1 mmol: (5~20) mL, for example, it can be 1 mmol: 5 mL, 1 mmol: 8 mL, 1 mmol: 10 mL, 1 mmol: 12 mL, 1 mmol: 15 mL, 1 mmol: 18 mL or 1 mmol: 20 mL, etc.

[0052] The first alkali includes, but is not limited to, at least one of potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, potassium phosphate, sodium phosphate, sodium hydroxide, and potassium hydroxide.

[0053] The first solvent includes, but is not limited to, at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, and tetrahydrofuran.

[0054] The reaction temperature of the first reaction is 50~190℃ (for example, it can be 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, etc.). The reaction time of the first reaction is 0.5 to 24 hours (e.g., 175℃, 180℃, 185℃ or 190℃, etc.).

[0055] S2. The compound shown in Formula II, the reducing agent, and the second solvent are mixed and subjected to a second reaction to obtain the compound shown in Formula III.

[0056] Specifically, the molar ratio of the compound shown in Formula II to the reducing agent is 1:(2~5), for example, it can be 1:2, 1:3, 1:4 or 1:5, etc.

[0057] The ratio of the compound shown in Formula II to the second solvent is 1 mmol: (10~50) mL, for example, it can be 1 mmol: 10 mL, 1 mmol: 20 mL, 1 mmol: 30 mL, 1 mmol: 40 mL or 1 mmol: 50 mL, etc.

[0058] The reducing agent includes, but is not limited to, at least one of lithium aluminum hydride, sodium borohydride, and diisopropylaminoaluminum hydride.

[0059] The second solvent includes, but is not limited to, dioxane, tetrahydrofuran, and diethyl ether.

[0060] The reaction temperature of the second reaction is 0~80℃ (e.g., it can be 0℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75 or 80℃, etc.), and the reaction time of the second reaction is 6~24h (e.g., it can be 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, etc.).

[0061] S3. The compound shown in Formula III, the chlorinating agent, and the third solvent are mixed and subjected to a third reaction to obtain the compound shown in Formula IV.

[0062] Specifically, the molar ratio of the compound shown in Formula III to the chlorinating agent is 1:(1~5), for example, it can be 1:1, 1:2, 1:3, 1:4 or 1:5, etc.

[0063] The ratio of the compound shown in Formula III to the third solvent is 1 mmol: (1~5) mL, for example, it can be 1 mmol: 1 mL, 1 mmol: 2 mL, 1 mmol: 3 mL, 1 mmol: 4 mL or 1 mmol: 5 mL, etc.

[0064] The chlorinating agent includes, but is not limited to, at least one of thionyl chloride, N-chlorosuccinimide, thioyl chloride, phosphorus trichloride, phosphorus pentachloride, and hypochlorite.

[0065] The third solvent includes, but is not limited to, dioxane, tetrahydrofuran, and diethyl ether.

[0066] The reaction temperature of the third reaction is 0~80℃ (for example, it can be 0℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75 or 80℃, etc.), and the reaction time of the third reaction is 0.5~6h (for example, it can be 0.5h, 1h, 2h, 3h, 4h, 5h or 6h, etc.).

[0067] S4, the compound shown in Formula IV, p-hydroxyphenylacetonitrile ( The second base and the fourth solvent are mixed and subjected to a fourth reaction to obtain the compound shown in formula V.

[0068] Specifically, the molar ratio of the compound shown in Formula IV to p-hydroxyphenylacetonitrile is 1:(0.8~2), for example, it can be 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8 or 1:2, etc.

[0069] The molar ratio of the compound shown in Formula IV to the second base is 1:(1~3), for example, it can be 1:1, 1:2 or 1:3, etc.

[0070] The ratio of the compound shown in Formula IV to the fourth solvent is 1 mmol: (5~10) mL, for example, it can be 1 mmol: 5 mL, 1 mmol: 6 mL, 1 mmol: 7 mL, 1 mmol: 8 mL, 1 mmol: 9 mL or 1 mmol: 10 mL, etc.

[0071] The second alkali includes, but is not limited to, at least one of potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, potassium phosphate, sodium phosphate, sodium hydroxide, and potassium hydroxide.

[0072] The fourth solvent includes, but is not limited to, at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, and tetrahydrofuran.

[0073] The reaction temperature of the fourth reaction is 50~190℃ (e.g., it can be 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, or 190℃, etc.), and the reaction time of the fourth reaction is 6~4 8h (e.g., it can be 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h, or 48h, etc.).

[0074] S5, the compound shown in formula V, terephthalaldehyde ( The third base and the fifth solvent are mixed and subjected to the fifth reaction to obtain the compound shown in Formula VI (i.e., the spontaneous phase change luminescent material).

[0075] Specifically, the molar ratio of the compound shown in Formula V to terephthalaldehyde is 1:(0.3~0.6), for example, it can be 1:0.3, 1:0.4, 1:0.5 or 1:0.6, etc.

[0076] The molar ratio of the compound shown in Formula V to the third base is 1:(1~2), for example, it can be 1:1, 1:1.2, 1:1.5, 1:1.8 or 1:2, etc.

[0077] The ratio of the compound shown in Formula V to the fifth solvent is 1 mmol: (10~20) mL, for example, it can be 1 mmol: 10 mL, 1 mmol: 12 mL, 1 mmol: 15 mL, 1 mmol: 18 mL or 1 mmol: 20 mL, etc.

[0078] The third alkali includes, but is not limited to, at least one of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide.

[0079] The fifth solvent includes, but is not limited to, at least one of acetonitrile, methanol, ethanol, and tert-butanol.

[0080] The reaction temperature of the fifth reaction is 0~60℃ (for example, it can be 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃ or 60℃, etc.), and the reaction time of the fifth reaction is 0.5~12h (for example, it can be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, etc.).

[0081] This invention also provides a method for preparing a heat exposure monitoring material, comprising the following steps: The spontaneous phase change luminescent material described in the embodiments of the present invention is mixed with the sixth solvent to prepare a solution. After coating, the solvent is removed (e.g., the solvent evaporates naturally) to obtain the heat exposure monitoring material (film).

[0082] Specifically, the solution can be coated onto a substrate, which includes, but is not limited to, one of quartz glass, ordinary glass, polymer film, paper, and textiles.

[0083] In this embodiment, the heat exposure monitoring material undergoes a phase transition at a certain temperature, and the phase transition rate is different at different temperatures. The higher the temperature, the faster the phase transition. As the phase transition proceeds, the color of the emitted light (specifically photoluminescence) changes. The color change can be completed within minutes or hours, thus it has a heat exposure monitoring function and a fast response rate.

[0084] In this embodiment, the photoluminescence color of the prepared heat exposure monitoring material (i.e., before phase transition) is yellow. After exposure to room temperature for half an hour to two hours, a phase transition occurs, and the photoluminescence color gradually changes to green. Specifically, the freshly prepared heat exposure monitoring material is an amorphous aggregate, and its photoluminescence color under ultraviolet excitation is yellow. At a certain temperature (such as room temperature or higher), the amorphous aggregate undergoes solid-state molecular motion and gradually crystallizes spontaneously within half an hour to two hours (the specific time depends on the R group and temperature). After crystallization, the photoluminescence color is green (i.e., the photoluminescence color under ultraviolet excitation is green). Therefore, the cumulative heat exposure can be reflected by the color change.

[0085] In some embodiments, the sixth solvent includes, but is not limited to, at least one of dichloromethane, petroleum ether, ethyl acetate, tetrahydrofuran, dioxane, diethyl ether, and acetone.

[0086] In some embodiments, the concentration of the spontaneous phase change luminescent material in the solution is 1.0 × 10⁻⁶. -4 mol / L to 1.0 mol / L, for example, 1.0 × 10⁻⁶. -4 mol / L, 1.0×10 -3 mol / L, 1.0×10 -2 mol / L, 0.1mol / L, or 1mol / L, etc.

[0087] This invention also provides a heat exposure monitoring material, which is prepared using the preparation method described above.

[0088] This invention also provides an application of the spontaneous phase change luminescent material or the heat exposure monitoring material described above in a vaccine vial monitor.

[0089] In this embodiment, the photoluminescence color of the heat exposure monitoring material before phase change is yellow. After exposure to room temperature for half an hour to two hours, a phase change occurs, and the photoluminescence color gradually changes to green. Therefore, during the phase change process, by comparing with a standard color chart, the current phase change progress can be determined, thereby obtaining its cumulative heat exposure information. Therefore, it can be used to prepare a vaccine vial monitor that can monitor vaccines with heat exposure tolerance windows on the order of hours (such as the G3 strain of rotavirus vaccine, which has a half-life of less than 2 hours at 37°C).

[0090] The present invention will be further described below through specific embodiments.

[0091] Unless otherwise specified, all raw materials used in the following embodiments are commercially available products. Room temperature in the following embodiments refers to 25°C.

[0092] Example 1 This embodiment provides a method for preparing spontaneous phase change luminescent materials and thermal exposure monitoring materials.

[0093] The synthesis route for spontaneous phase change luminescent materials is as follows: ; Where R stands for n-pentyl.

[0094] According to the above synthetic route, the preparation method of spontaneous phase change luminescent materials includes the following steps: (1) 1 mmol of the compound shown in Formula I, 3 mmol of n-pentyl chloride and 3 mmol of potassium carbonate were added to 10 mL of N,N-dimethylformamide and reacted at 90 °C for 2 hours. The mixture of reactants was filtered, the filtrate was dried with sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in Formula II.

[0095] (2) 1 mmol of the compound shown in Formula II and 3 mmol of lithium aluminum hydride were added to 20 mL of tetrahydrofuran and reacted at 80 °C for 12 hours. The reaction was quenched with water, the reaction mixture was filtered, the filtrate was dried with sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in Formula III.

[0096] (3) Add 1 mmol of the compound shown in Formula III and 2 mmol of thionyl chloride to 4 mL of tetrahydrofuran, react at 25 °C for 2 hours, and directly evaporate the reaction mixture to dryness without further treatment and directly add it to the next reaction to obtain the compound shown in Formula IV.

[0097] (4) Mix 1 mmol of the compound shown in Formula IV and 1.1 mmol of p-hydroxyphenylacetonitrile ( ) and 2 mmol of potassium carbonate were added to 8 mL of N,N-dimethylformamide, and the mixture was reacted at 85 °C for 12 hours. The reaction mixture was filtered, the filtrate was dried with sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in formula V. (5) Add 1 mmol of the compound shown in formula V and 0.5 mmol of terephthalaldehyde ( 2 mmol of potassium carbonate was added to 10 mL of acetonitrile, and the mixture was reacted at 25 °C for 5 hours. The reaction mixture was filtered, and the filtrate was dried over sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in Formula VI, which is the spontaneous phase change luminescent material. The 1H NMR spectrum of the prepared spontaneous phase change luminescent material is shown below. Figure 1 As shown, the carbon NMR spectrum is as follows: Figure 2 As shown, the high-resolution mass spectrum is as follows: Figure 3 As shown.

[0098] The preparation method of thermally exposed phase change materials includes the following steps: (1) The spontaneous phase change luminescent material prepared above was mixed with dichloromethane to prepare a solution with a concentration of 1.0 × 10⁻⁶. -3 A solution of mol / L; (2) The above solution was dripped onto the surface of quartz glass (1cm×2cm). After the dichloromethane evaporated, the heat exposure monitoring material was obtained.

[0099] At room temperature, the freshly prepared heat exposure monitoring material was immediately excited with ultraviolet light (wavelength 365nm, all ultraviolet light mentioned below refers to this wavelength), and it emitted yellow light (e.g., Figure 4 As shown, the freshly prepared heat exposure monitoring material is in its initial state, i.e., it has not undergone a phase change. After placing the heat exposure monitoring material at room temperature for 30 minutes, it is excited again with ultraviolet light, and its emission color is green (e.g., ...). Figure 5 As shown, the heat exposure monitoring material placed at room temperature for 30 minutes is the heat exposure monitoring material after phase change.

[0100] X-ray diffraction patterns of the initial state and the phase-transformed state of the heat exposure monitoring material are shown below. Figure 6 As shown (where "initial state" refers to the initial state of the heat exposure monitoring material, and "after phase change" refers to the heat exposure monitoring material after the phase change), it can be seen that the heat exposure monitoring material undergoes a phase change after being placed at room temperature for 30 minutes, and a new phase is generated.

[0101] Example 2 This embodiment provides a method for preparing spontaneous phase change luminescent materials and thermal exposure monitoring materials.

[0102] The synthesis route for spontaneous phase change luminescent materials is as follows: ; Wherein, R is n-butyl.

[0103] According to the above synthetic route, the preparation method of spontaneous phase change luminescent materials includes the following steps: (1) 1 mmol of the compound shown in Formula I, 3 mmol of n-butyl chloride and 3 mmol of potassium carbonate were added to 10 mL of N,N-dimethylformamide and reacted at 90 °C for 2 hours. The mixture of reactants was filtered, the filtrate was dried with sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in Formula II.

[0104] (2) 1 mmol of the compound shown in Formula II and 3 mmol of lithium aluminum hydride were added to 20 mL of tetrahydrofuran and reacted at 80 °C for 12 hours. The reaction was quenched with water, the reaction mixture was filtered, the filtrate was dried with sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in Formula III.

[0105] (3) Add 1 mmol of the compound shown in Formula III and 2 mmol of thionyl chloride to 4 mL of tetrahydrofuran, react at 25 °C for 2 hours, and directly evaporate the reaction mixture to dryness without further treatment and directly add it to the next reaction to obtain the compound shown in Formula IV.

[0106] (4) Mix 1 mmol of the compound shown in Formula IV and 1.1 mmol of p-hydroxyphenylacetonitrile ( ) and 2 mmol of potassium carbonate were added to 8 mL of N,N-dimethylformamide, and the mixture was reacted at 85 °C for 12 hours. The reaction mixture was filtered, the filtrate was dried with sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in formula V. (5) Add 1 mmol of the compound shown in formula V and 0.5 mmol of terephthalaldehyde ( 2 mmol of potassium carbonate was added to 10 mL of acetonitrile, and the mixture was reacted at 25 °C for 5 hours. The reaction mixture was filtered, and the filtrate was dried over sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in Formula VI, which is the spontaneous phase change luminescent material. The 1H NMR spectrum of the prepared spontaneous phase change luminescent material is shown below. Figure 7 As shown, the carbon NMR spectrum is as follows: Figure 8 As shown, the high-resolution mass spectrum is as follows: Figure 9 As shown.

[0107] The preparation method of thermally exposed phase change materials includes the following steps: (1) The spontaneous phase change luminescent material prepared above was mixed with dichloromethane to prepare a solution with a concentration of 1.0 × 10⁻⁶. -3 A solution of mol / L; (2) The above solution was dripped onto the surface of quartz glass (1cm×2cm). After the dichloromethane evaporated, the heat exposure monitoring material was obtained.

[0108] At room temperature, the freshly prepared heat exposure monitoring material is immediately excited with ultraviolet light, and it emits yellow light (e.g., Figure 10 As shown, the freshly prepared heat exposure monitoring material is in its initial state. After placing the heat exposure monitoring material at room temperature for 30 minutes, it is excited again with ultraviolet light, and its emission color is green (e.g., ...). Figure 11 As shown, the heat exposure monitoring material placed at room temperature for 30 minutes is the heat exposure monitoring material after phase change.

[0109] Example 3 This embodiment provides a method for preparing spontaneous phase change luminescent materials and thermal exposure monitoring materials.

[0110] The synthesis route for spontaneous phase change luminescent materials is as follows: ; Where R is the hexyl group.

[0111] According to the above synthetic route, the preparation method of spontaneous phase change luminescent materials includes the following steps: (1) 1 mmol of the compound shown in Formula I, 3 mmol of n-hexyl chloride and 3 mmol of potassium carbonate were added to 10 mL of N,N-dimethylformamide and reacted at 90 °C for 2 hours. The mixture of reactants was filtered, the filtrate was dried with sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in Formula II.

[0112] (2) 1 mmol of the compound shown in Formula II and 3 mmol of lithium aluminum hydride were added to 20 mL of tetrahydrofuran and reacted at 80 °C for 12 hours. The reaction was quenched with water, the reaction mixture was filtered, the filtrate was dried with sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in Formula III.

[0113] (3) Add 1 mmol of the compound shown in Formula III and 2 mmol of thionyl chloride to 4 mL of tetrahydrofuran, react at 25 °C for 2 hours, and directly evaporate the reaction mixture to dryness without further treatment and directly add it to the next reaction to obtain the compound shown in Formula IV.

[0114] (4) Add 1 mmol of the compound shown in Formula IV and 1.2 mmol of p-hydroxyphenylacetonitrile ( ) and 2 mmol of potassium carbonate were added to 8 mL of N,N-dimethylformamide, and the mixture was reacted at 85 °C for 12 hours. The reaction mixture was filtered, the filtrate was dried with sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in formula V. (5) Add 1 mmol of the compound shown in formula V and 0.45 mmol of terephthalaldehyde ( 2 mmol of potassium carbonate was added to 10 mL of acetonitrile, and the mixture was reacted at 25 °C for 5 hours. The reaction mixture was filtered, and the filtrate was dried over sodium sulfate and then evaporated to dryness. The filtrate was purified by column chromatography to obtain the compound shown in Formula VI, which is the spontaneous phase change luminescent material. The 1H NMR spectrum of the prepared spontaneous phase change luminescent material is shown below. Figure 12 As shown, the carbon NMR spectrum is as follows: Figure 13 As shown, the high-resolution mass spectrum is as follows: Figure 14 As shown.

[0115] The preparation method of thermally exposed phase change materials includes the following steps: (1) The spontaneous phase change luminescent material prepared above was mixed with dichloromethane to prepare a solution with a concentration of 1.0 × 10⁻⁶. -3 A solution of mol / L; (2) The above solution was dripped onto the surface of quartz glass (1cm×2cm). After the dichloromethane evaporated, the heat exposure monitoring material was obtained.

[0116] At room temperature, the freshly prepared heat exposure monitoring material is immediately excited with ultraviolet light, and it emits yellow light (e.g., Figure 15 As shown, the freshly prepared heat exposure monitoring material is in its initial state. After placing the heat exposure monitoring material at room temperature for 30 minutes, it is excited again with ultraviolet light, and its emission color is green (e.g., ...). Figure 16 As shown, the heat exposure monitoring material placed at room temperature for 30 minutes is the heat exposure monitoring material after phase change.

[0117] In summary, this invention provides spontaneous phase-change luminescent materials, heat exposure monitoring materials, their preparation methods, and applications. After the spontaneous phase-change luminescent material provided by this invention is prepared into a film, a phase transition occurs at a certain temperature, and the phase transition rate varies at different temperatures; the higher the temperature, the faster the phase transition. As the phase transition progresses, the luminescence (specifically photoluminescence) color changes, and this color change can be completed within minutes or hours, thus providing a heat exposure monitoring function. Furthermore, during the phase transition process, by comparing with a standard color chart, the current phase transition progress can be determined, thereby obtaining its cumulative heat exposure information. Therefore, it can be used to prepare vaccine vial monitors. This vaccine vial monitor can monitor vaccines with heat exposure tolerance windows of only hours (such as the G3 strain of rotavirus vaccine, whose half-life at 37°C is less than 2 hours).

[0118] Specifically, the spontaneous phase change of the spontaneous phase change luminescent material from an amorphous state to a crystalline state is approximately a cold crystallization process. Luminescence refers to photoluminescence. After the spontaneous phase change luminescent material provided by this invention is prepared into a film, it forms an amorphous aggregate. At this point, the photoluminescence color is yellow (i.e., the emission color under ultraviolet excitation is yellow). At a certain temperature (such as room temperature or higher), the amorphous aggregate undergoes solid-state molecular motion and gradually crystallizes spontaneously within half an hour to two hours (the specific time depends on the R group and temperature). After crystallization, the photoluminescence color is green (i.e., the emission color under ultraviolet excitation is green). Therefore, the cumulative heat exposure can be reflected by the color change.

[0119] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A spontaneous phase change luminescent material, characterized in that, The structural formula of the spontaneous phase change luminescent material is: ； Wherein, R is an alkyl group having 4 to 6 carbon atoms.

2. The spontaneous phase change luminescent material according to claim 1, characterized in that, R is selected from one of the following groups: -CH2CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -C(CH3)3, -CH2CH2CH2CH2CH3, -CH(CH3)CH2CH2CH3, -CH2CH(CH3)CH2CH3, -CH2CH2CH(CH3)2, -CH(CH3)CH(CH3)2, -C(CH3)2CH2CH3, -CH(C2H5)CH2CH3, -CH2C(CH3)3, -CH2CH2CH2CH2CH2CH3, -CH2CH2CH2CH(CH3)2, -CH2CH2CH(CH3)CH2CH3, -CH2CH2C(CH3)2CH3, -CH2CH2CH(C2H5)CH3, -CH2CH(CH3)CH2CH2CH3, -CH2C(CH3)2CH2CH3, -CH2CH(CH3)CH(CH3)CH3, -CH2CH(C2H5)CH2CH3, -CH(CH3)CH2CH2CH2CH3, -CH(CH3)CH(CH3)CH2CH3, -CH(CH3)CH2CH(CH3)CH3, -CH(C2H5)CH2CH2CH3, -CH(C2H5)CH(CH3)CH3, -C(CH3)2CH2CH2CH3, -C(CH3)2CH(CH3)CH3 and -C(C2H5)2CH3.

3. A method for preparing the spontaneous phase change luminescent material according to claim 1, characterized in that, Includes the following steps: Will and After the reaction, the spontaneous phase change luminescent material is obtained.

4. The preparation method according to claim 3, characterized in that, The preparation method includes the following steps: Will and After the reaction, we get .

5. The preparation method according to claim 4, characterized in that, The preparation method includes the following steps: Will After reacting with a chlorinating agent, the following is obtained: .

6. The preparation method according to claim 5, characterized in that, The preparation method includes the following steps: Will and After the reaction, we get ; Will After reacting with a reducing agent, the following is obtained: ; Where X is a halogen.

7. A method for preparing a heat exposure monitoring material, characterized in that, Includes the following steps: The spontaneous phase change luminescent material according to any one of claims 1-2 is mixed with the sixth solvent to prepare a solution, coated, and then the solvent is removed to obtain the heat exposure monitoring material.

8. The preparation method according to claim 7, characterized in that, The sixth solvent includes at least one selected from dichloromethane, petroleum ether, ethyl acetate, tetrahydrofuran, dioxane, diethyl ether, and acetone; and / or, The concentration of the spontaneous phase change luminescent material in the solution is 1.0 × 10⁻⁶. -4 mol / L~1.0mol / L.

9. A heat exposure monitoring material, characterized in that, It is prepared by the preparation method according to any one of claims 7-8.

10. The application of a spontaneous phase change luminescent material according to any one of claims 1-2 or the heat exposure monitoring material according to claim 9 in a vaccine vial monitor.

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