Preparation method of organic phosphorescent temperature-sensitive film and organic phosphorescent temperature-sensitive film

Abstract

The invention provides a preparation method of an organic phosphorescent temperature-sensitive film and the organic phosphorescent temperature-sensitive film, which are used for solving the technical problems that most existing organic phosphorescent materials exist in the form of crystals, carbon dots or clusters and do not have good forming and processing properties. According to the preparation method of the organic phosphorescent temperature-sensitive film provided by the invention, phosphorescent guest molecules, etherified cellulose and water are mixed according to a certain proportion, the mixture is heated and melted, then is coated on a substrate and is dried, and the phosphorescent guest molecules and the etherified cellulose can generate reversible aldehyde acetal, so that the phosphorescent guest molecules and the etherified cellulose can generate reversible aldehyde acetal; therefore, the organic phosphorescent temperature-sensitive film which can respond to phosphorescent emission performance through temperature is obtained, and the phosphorescent emission wavelength can be changed along with temperature change within the range of 77K-298K. The preparation method disclosed by the invention is simple and controllable, high in material regularity and good in reproducibility, has the advantages of large-scale and low-cost synthesis, and also has excellent forming processing capability.

Description

Technical Field

[0001] This invention relates to phosphorescent materials and their preparation methods, specifically to a method for preparing an organic phosphorescent thermosensitive film and the organic phosphorescent thermosensitive film itself. Background Technology

[0002] Organic phosphorescent materials are a class of materials that continue to emit light even after the excitation source has ceased. This characteristic makes them highly valuable in fields such as organic light-emitting diodes (OLEDs), bioimaging, environmental sensing, and anti-counterfeiting encryption. The first artificially prepared phosphorescent material was a sulfide-based long phosphorescent material developed by French scientists, but subsequent widely used phosphorescent materials are mostly inorganic. Currently, organic phosphorescent materials exist primarily in the form of crystals, carbon dots, or clusters, lacking good molding and processing properties, which limits their application range. Developing high-performance organic phosphorescent materials with good molding and processing capabilities is a pressing issue that needs to be addressed in the industry. Summary of the Invention

[0003] To address the technical problem that existing organic phosphorescent materials mostly exist in the form of crystals, carbon dots, or clusters and lack good molding and processing performance, this invention provides a method for preparing an organic phosphorescent thermosensitive film and the organic phosphorescent thermosensitive film itself.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing an organophosphorus photothermal film, characterized by the following steps: Step 1: Mix phosphorescent guest molecules, etherified cellulose, and water at a mass ratio of 1:1000~10000:2000~20000, and heat the mixture until it is completely dissolved to obtain a phosphorescent mixed solution; Step 2: Apply the phosphorescent mixed solution obtained in Step 1 onto the substrate and dry it at a temperature of 40~60℃ for 12~24h to form an organic phosphorescent thermosensitive film on the substrate surface. Remove the organic phosphorescent thermosensitive film from the substrate surface to complete the preparation of the organic phosphorescent thermosensitive film.

[0005] Further, in step 1, the etherified cellulose is one or a mixture of at least two of hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

[0006] Further, in step 1, the phosphorescent guest molecule is one or a mixture of at least two of 3',5'-dimethoxy-4'-hydroxyacetophenone, 3-methoxybenzaldehyde, 4-methoxy-naphthaldehyde, and 3,4-dimethoxybenzaldehyde.

[0007] Furthermore, in step 1, heating the mixed materials until they are completely dissolved specifically involves: Heat the mixed materials to 30~80℃ and maintain for 60~100 minutes.

[0008] Further, in step 1, the phosphorescent guest molecule is 3-methoxybenzaldehyde, the etherified cellulose is hydroxyethyl cellulose, and the mass ratio of 3-methoxybenzaldehyde, hydroxyethyl cellulose, and water is 1:3000:5000; the mixed material is heated to 70°C and held for 75 minutes. In step 2, the phosphorescent mixed solution is applied to the substrate and dried at 60°C for 12 hours.

[0009] Further, in step 1, the phosphorescent guest molecule is 3',5'-dimethoxy-4'-hydroxyacetophenone, the etherified cellulose is hydroxymethyl cellulose, and the mass ratio of 3',5'-dimethoxy-4'-hydroxyacetophenone, hydroxymethyl cellulose, and water is 1:1000:10000; the mixed material is heated to 80°C and held for 60 minutes; In step 2, the phosphorescent mixed solution is applied to the substrate and dried at 60°C for 12 hours.

[0010] Furthermore, the phosphorescent guest molecule is 4-methoxy-naphthaldehyde, the etherified cellulose is hydroxypropyl cellulose, and the mass ratio of 4-methoxy-naphthaldehyde, hydroxypropyl cellulose, and water is 1:4000:5000; the mixed material is heated to 60°C and held for 90 minutes. In step 2, the phosphorescent mixed solution is applied to the substrate and dried at 40°C for 24 hours.

[0011] Furthermore, the phosphorescent guest molecule is 3,4-dimethoxybenzaldehyde, the etherified cellulose is hydroxyethyl cellulose, and the mass ratio of 3,4-dimethoxybenzaldehyde, hydroxyethyl cellulose, and water is 1:10000:20000; the mixed material is heated to 40°C and held for 100 min; In step 2, the phosphorescent mixed solution is applied to the substrate and dried at 50°C for 17 hours.

[0012] Furthermore, in step 2, the substrate is a glass plate.

[0013] In addition, the present invention also provides an organic phosphorescent thermosensitive film, which is special in that it is prepared by the above-mentioned method for preparing organic phosphorescent thermosensitive film; the phosphorescence emission wavelength of the organic phosphorescent thermosensitive film changes with temperature in the range of 77K-298K.

[0014] The advantages of this invention compared to the prior art are: 1. The present invention provides a method for preparing an organic phosphorescent thermosensitive film, wherein phosphorescent guest molecules, etherified cellulose, and water are mixed in a certain proportion, heated and melted, coated onto a substrate and dried. Since reversible acetalization can occur between the phosphorescent guest molecules and etherified cellulose, an organic phosphorescent thermosensitive film with phosphorescence emission performance that can be responded to by temperature is obtained. The preparation method is simple and controllable, the material has high regularity, good reproducibility, and has the advantages of large-scale and low-cost synthesis, while also having excellent molding and processing capabilities.

[0015] 2. The organic phosphorescent thermosensitive film obtained by the preparation method of the present invention has good temperature-responsive phosphorescence emission performance, and can realize the phosphorescence emission wavelength changes with temperature in the range of 77K-298K. Attached Figure Description

[0016] Figure 1 A schematic diagram of the chemical formula when methanol is added to use deuterated chloroform as a solvent for 3-methoxybenzaldehyde. Figure 2 The reaction of 3-methoxybenzaldehyde in deuterated chloroform was carried out. 1 The 1H NMR titration spectrum, where (a) shows the titration of 3-methoxybenzaldehyde in deuterated chloroform without the addition of methanol. 1 (b) is the 1H NMR titration spectrum of 3-methoxybenzaldehyde in deuterated chloroform after the addition of 25 μL of methanol. 1 The 1H NMR titration spectrum, (c) shows the titration of 3-methoxybenzaldehyde in deuterated chloroform with the addition of 100 μL of methanol. 1 The proton spectrum obtained by H nuclear magnetic resonance titration; Figure 3 This invention relates to a method for preparing an organophosphorescent thermosensitive film. In step 1 of Example 1, the phosphorescence emission spectra of the organophosphorescent thermosensitive film at 77K and 298K are obtained under the thermosensitive response of 3-methoxybenzaldehyde and hydroxyethyl cellulose. Figure 4 This invention provides a method for preparing an organic phosphorescent thermosensitive film. In step 1 of Example 2, the phosphorescence emission spectra of the organic phosphorescent thermosensitive film at 77K and 298K under the thermosensitive response of 3',5'-dimethoxy-4'-hydroxyacetophenone and hydroxymethylcellulose are shown. Figure 5 This invention relates to a method for preparing an organophosphorescent thermosensitive film. In step 1 of Example 3, the phosphorescence emission spectra of the organophosphorescent thermosensitive film at 77K and 298K are obtained under the thermosensitive response of 4-methoxy-naphthaldehyde and hydroxypropyl cellulose. Figure 6 This invention relates to a method for preparing an organophosphorescent thermosensitive film. In step 1 of Example 4, the phosphorescence emission spectra of the organophosphorescent thermosensitive film at 77K and 298K are obtained under the thermosensitive response of 3,4-dimethoxybenzaldehyde and hydroxyethyl cellulose. Detailed Implementation

[0017] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Example 1 A method for preparing an organophosphorus photothermal film specifically includes the following steps: Step 1: Mix 3-methoxybenzaldehyde, hydroxyethyl cellulose, and water at a mass ratio of 1:3000:5000, heat to 70°C and maintain for 75 minutes to completely dissolve the mixed materials and obtain a phosphorescent mixed solution.

[0019] Step 2: Apply the phosphorescent mixed solution to a glass plate and dry it at 60°C for 12 hours. An organic phosphorescent thermosensitive film is formed on the glass plate. Remove this organic phosphorescent thermosensitive film from the substrate surface to complete the preparation of the organic phosphorescent thermosensitive film. In other embodiments of the present invention, the dissolved phosphorescent mixed solution can also be applied to other smooth substrate surfaces to facilitate demolding.

[0020] The organic phosphorescent thermosensitive film prepared by the above method can achieve phosphorescence emission wavelength variation with temperature in the range of 77K-298K because the phosphorescent guest molecules can undergo reversible acetalization with etherified cellulose.

[0021] The following experimental verification is conducted using 3-methoxybenzaldehyde and hydroxyethyl cellulose as examples in this embodiment. Deuterated chloroform was used as the solvent for 3-methoxybenzaldehyde, and methanol was continuously added dropwise to the solvent to simulate the polyhydroxyl conditions in hydroxyethyl cellulose. The acetalization ratio was calculated by NMR titration of proton NMR spectra. It was found that 3-methoxybenzaldehyde underwent rapid acetalization with methanol, and the proportion of acetal products increased continuously with the increase of the methanol ratio. When the mass ratio of methanol to deuterated chloroform was 1:16, the proportion of acetal products from 3-methoxybenzaldehyde was 9.6%. When the mass ratio of methanol to deuterated chloroform was 1:4, the proportion of acetal products from 3-methoxybenzaldehyde reached 30.1%. Specific data are shown in Table 1.

[0022] Table 1. Percentage of acetal products of 3-methoxybenzaldehyde at different mass ratios of methanol to deuterated chloroform. Figure 1 A schematic diagram of the chemical formula when methanol is added to use deuterated chloroform as a solvent for 3-methoxybenzaldehyde. Figure 2The reaction of 3-methoxybenzaldehyde in deuterated chloroform was carried out. 1 The proton NMR spectrum obtained from the H NMR titration, in which... Figure 2 (a) in the figure represents the reaction of 3-methoxybenzaldehyde in deuterated chloroform without the addition of methanol. 1 The hydrogen spectrum of the H NMR titration, a, b, c, d, and e represent the five characteristic peaks; Figure 2 (b) shows the concentration of 3-methoxybenzaldehyde in deuterated chloroform after the addition of 25 μL of methanol. 1 The proton spectrum of H NMR titration Figure 2 (c) represents the concentration of 3-methoxybenzaldehyde in deuterated chloroform when 100 μL of methanol is added. 1 Taking the 1H NMR titration as an example, peak d belongs to 3-methoxybenzaldehyde. After adding methanol, peak f appears, which belongs to the acetal product of 3-methoxybenzaldehyde. The ratio of the area of ​​peak d to peak f can be used to calculate the proportion of 3-methoxybenzaldehyde and its acetal product. Therefore, it can be seen that with the increase of methanol, the acetal product of 3-methoxybenzaldehyde also increases significantly.

[0023] In this embodiment, the five characteristic peaks of 3-methoxybenzaldehyde are as follows: 1H NMR (800MHz, chloroform-d) δ9.98 (s, 1H), 7.51-7.44 (m, 2H), 7.39 (dd, J=2.8, 1.3 Hz, 1H), 7.22-7.15 (m, 1H), 3.87 (s, 3H).

[0024] like Figure 3 As shown, the phosphorescence performance of the organic phosphorescent thermosensitive film prepared in this embodiment was analyzed at 298K and 77K using steady-state / transient fluorescence spectroscopy. It was found that the phosphorescence emission of the organic phosphorescent thermosensitive film was 531nm at 298K, and 491nm and 513nm at 77K.

[0025] Example 2 A method for preparing an organophosphorus photothermal coating film specifically includes the following steps: Step 1: Mix 3',5'-dimethoxy-4'-hydroxyacetophenone, hydroxymethylcellulose, and water at a mass ratio of 1:1000:10000, heat to 80°C and maintain for 60 minutes to completely dissolve the mixed materials and obtain a dissolved phosphorescent mixed solution.

[0026] Step 2: Apply the dissolved phosphorescent mixed solution onto a glass plate and dry it at 60°C for 12 hours. At this time, an organic phosphorescent thermosensitive film is formed on the glass plate. Remove the organic phosphorescent thermosensitive film from the substrate surface to complete the preparation of the organic phosphorescent thermosensitive film.

[0027] like Figure 4 As shown, the phosphorescence performance of the organic phosphorescent thermosensitive film prepared in this embodiment was analyzed at 298K and 77K using steady-state / transient fluorescence spectroscopy. It was found that the phosphorescence emission of the organic phosphorescent thermosensitive film was 520nm at 298K and 492nm at 77K.

[0028] Example 3 A method for preparing an organophosphorus photothermal film specifically includes the following steps: Step 1: Mix 4-methoxy-naphthaldehyde, hydroxypropyl cellulose, and water at a mass ratio of 1:4000:5000, heat to 60°C and maintain for 90 minutes to completely dissolve the mixed materials and obtain a dissolved phosphorescent mixed solution.

[0029] Step 2: Apply the dissolved phosphorescent mixed solution to a glass plate and dry it at 40°C for 24 hours. At this time, an organic phosphorescent thermosensitive film is formed on the glass plate. Remove the organic phosphorescent thermosensitive film from the substrate surface to complete the preparation of the organic phosphorescent thermosensitive film.

[0030] like Figure 5 As shown, the phosphorescence performance of the organic phosphorescent thermosensitive film prepared in this embodiment was analyzed at 298K and 77K using steady-state / transient fluorescence spectroscopy. It was found that the phosphorescence emission of the organic phosphorescent thermosensitive film was at 540nm at 298K, and at 543nm and 502nm at 77K.

[0031] Example 4 A method for preparing an organophosphorus photothermal film specifically includes the following steps: Step 1: Mix 3,4-dimethoxybenzaldehyde, hydroxyethyl cellulose, and water at a mass ratio of 1:10000:20000, heat to 40°C and hold for 100 minutes to dissolve all the mixed materials and obtain a dissolved phosphorescent mixed solution.

[0032] Step 2: Apply the dissolved phosphorescent mixed solution onto a glass plate and dry it at 50°C for 17 hours. At this time, an organic phosphorescent thermosensitive film is formed on the glass plate. Remove the organic phosphorescent thermosensitive film from the substrate surface to complete the preparation of the organic phosphorescent thermosensitive film.

[0033] like Figure 6 As shown, the phosphorescence performance of the organic phosphorescent thermosensitive film prepared in this embodiment was analyzed at 298K and 77K using steady-state / transient fluorescence spectroscopy. It was found that the phosphorescence emission of the organic phosphorescent thermosensitive film was 508nm at 298K and 476nm at 77K.

[0034] It is worth noting that the temperature and time for heating the mixed materials and the drying time after the phosphorescent mixed solution is coated on the glass plate can be selected as needed. However, the heating temperature must meet the temperature limit of 30~80℃ and the drying temperature must meet the temperature limit of 40~60℃. Too high or too low a temperature will affect the acetalization effect.

[0035] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions within the technical scope disclosed in the present invention should be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing an organophosphorus photothermal film, characterized in that, Includes the following steps: Step 1: Mix phosphorescent guest molecules, etherified cellulose, and water at a mass ratio of 1:1000~10000:2000~20000, and heat the mixture until it is completely dissolved to obtain a phosphorescent mixed solution; Step 2: Apply the phosphorescent mixed solution obtained in Step 1 onto the substrate and dry it at a temperature of 40~60℃ for 12~24h to form an organic phosphorescent thermosensitive film on the substrate surface. Remove the organic phosphorescent thermosensitive film from the substrate surface to complete the preparation of the organic phosphorescent thermosensitive film.

2. The method for preparing an organophosphorus photothermal film according to claim 1, characterized in that: In step 1, the etherified cellulose is one or a mixture of at least two of hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

3. The method for preparing an organophosphorus photothermal film according to claim 2, characterized in that: In step 1, the phosphorescent guest molecule is one or a mixture of at least two of 3',5'-dimethoxy-4'-hydroxyacetophenone, 3-methoxybenzaldehyde, 4-methoxy-naphthaldehyde, and 3,4-dimethoxybenzaldehyde.

4. The method for preparing an organophosphorus photothermal film according to claim 3, characterized in that: In step 1, heating the mixed materials until they are completely dissolved specifically involves: Heat the mixed materials to 30~80℃ and maintain for 60~100 minutes.

5. The method for preparing an organophosphorus photothermal film according to claim 1, characterized in that: In step 1, the phosphorescent guest molecule is 3-methoxybenzaldehyde, the etherified cellulose is hydroxyethyl cellulose, and the mass ratio of 3-methoxybenzaldehyde, hydroxyethyl cellulose, and water is 1:3000:5000; the mixed material is heated to 70°C and held for 75 minutes. In step 2, the phosphorescent mixed solution is applied to the substrate and dried at 60°C for 12 hours.

6. The method for preparing an organophosphorus photothermal film according to claim 1, characterized in that: In step 1, the phosphorescent guest molecule is 3',5'-dimethoxy-4'-hydroxyacetophenone, the etherified cellulose is hydroxymethyl cellulose, and the mass ratio of 3',5'-dimethoxy-4'-hydroxyacetophenone, hydroxymethyl cellulose, and water is 1:1000:10000; the mixed material is heated to 80°C and held for 60 minutes. In step 2, the phosphorescent mixed solution is applied to the substrate and dried at 60°C for 12 hours.

7. The method for preparing an organophosphorus photothermal film according to claim 1, characterized in that: The phosphorescent guest molecule is 4-methoxy-naphthaldehyde, the etherified cellulose is hydroxypropyl cellulose, and the mass ratio of 4-methoxy-naphthaldehyde, hydroxypropyl cellulose, and water is 1:4000:5000; the mixed material is heated to 60°C and held for 90 minutes. In step 2, the phosphorescent mixed solution is applied to the substrate and dried at 40°C for 24 hours.

8. The method for preparing an organophosphorus photothermal film according to claim 1, characterized in that: The phosphorescent guest molecule is 3,4-dimethoxybenzaldehyde, the etherified cellulose is hydroxyethyl cellulose, and the mass ratio of 3,4-dimethoxybenzaldehyde, hydroxyethyl cellulose, and water is 1:10000:20000; the mixed material is heated to 40°C and held for 100 min. In step 2, the phosphorescent mixed solution is applied to the substrate and dried at 50°C for 17 hours.

9. The method for preparing an organophosphorus photothermal film according to claim 1, characterized in that: In step 2, the substrate is a glass plate.

10. An organophosphorus photothermal film, characterized in that, The organic phosphorescent thermosensitive film is prepared by any of the preparation methods described in claims 1-9; the phosphorescence emission wavelength of the organic phosphorescent thermosensitive film varies with temperature in the range of 77K-298K.

Images