Photochromic high-molecular compound as well as preparation method and application thereof
Through the collaborative design of the photoresponsive unit and the polymer matrix, photochromic polymer compounds are prepared, which solves the shortcomings in accuracy and compatibility of the photochromic polymer film, and achieves high-precision photocopy and excellent adhesion. It is suitable for dynamic information storage and rewritable anti-counterfeiting labels.
Patent Information
- Application Number
- CN202510678896.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-26
- Publication Date
- 2025-07-25
AI Technical Summary
The existing photochromic polymer films have shortcomings in patterning processing accuracy and compatibility with substrates.
Through the collaborative design of photoresponsive units and polymer matrix, a new photochromic polymer compound is prepared for the preparation of high-precision photochromic film materials, with excellent adhesion and compatibility with glass.
It realizes high-precision optical chromatography performance, can meet the high-value-added application needs of dynamic information storage and rewritable anti-counterfeiting labels, and has excellent optical response performance and environmental stability.
Smart Images
Figure CN120365506A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of photochromic polymer materials, and particularly relates to a photochromic polymer compound, a preparation method thereof, and an application thereof. Background Art
[0002] A photochromic polymer film is a functional material that can undergo reversible color changes under light irradiation. Its research background mainly stems from the exploration of light-responsive materials in the mid-20th century. As an intelligent responsive material, the development of photochromic polymer films can be traced back to the cross-integration of photochemistry and polymer science in the mid-20th century. Early research mainly focused on inorganic photochromic systems. It wasn't until the 1960s that with the discovery of organic photochromic molecules (such as spiropyrans, azobenzenes, etc.) and the elucidation of their photoisomerization mechanisms, researchers began to attempt to introduce these functional molecules into polymer matrices. By compounding photochromic units such as spiropyrans and diarylethene with polymer materials such as polymethyl methacrylate (PMMA) and polyurethane (PU), an intelligent thin film system with flexibility and processability was successfully developed.
[0003] However, in the prior art, the patterning processing accuracy of the polymer film is insufficient and the compatibility with the substrate is insufficient. Based on this, it is necessary to develop a new photochromic polymer compound to solve these problems. Summary of the Invention
[0004] In order to solve the problems raised in the above background art, the purpose of the present invention is to provide a photochromic polymer compound, a preparation method thereof, and an application thereof. Through the collaborative design of a light-responsive unit - polymer matrix, the present invention provides a novel photochromic polymer compound. The photochromic thin film material prepared from this photochromic polymer compound can be applied to high-precision light writing and can exhibit excellent adhesion to glass, solving the technical problems of low precision of traditional light writing materials and insufficient compatibility with substrates.
[0005] In order to achieve the above purpose, the technical solution adopted by the present invention is as follows: On the one hand, the present invention provides a photochromic polymer compound, whose structure is shown in Formula I:
[0006]
[0007] Wherein,
[0008] n = 2 - 7, x = 60 - 90, y = 100 - x.
[0009] On the other hand, the present invention provides a preparation method of the above-mentioned photochromic polymer compound, comprising the following steps:
[0010] (1) React N-methyl-4-piperidone, 2,2,2-trifluoroacetophenone and terphenyl to obtain a compound
[0011]
[0012] (2) React 1-pyrenemethanol and CH2Br(CH2) n Br to obtain a compound
[0013] (3) React to obtain a compound
[0014] Furthermore, step (1) specifically includes the following steps:
[0015] Dissolve N-methyl-4-piperidone, 2,2,2-trifluoroacetophenone and terphenyl in a solvent, and react at 0 °C to 4 °C for 24 h to 48 h to obtain
[0016] The molar ratio of the N-methyl-4-piperidone, 2,2,2-trifluoroacetophenone and terphenyl is (60 - 90):(10 - 40):100.
[0017] Furthermore, step (2) specifically includes the following steps:
[0018] Dissolve 1-pyrenemethanol and sodium hydride in a solvent, react under a protective gas atmosphere for 20 min to 120 min, and then add CH2Br(CH2) n Br and react for 24 h to 72 h to obtain
[0019] The molar ratio of the 1-pyrenemethanol, sodium hydride, CH2Br(CH2) n Br is 1:20:10.
[0020] Furthermore, step (3) specifically includes the following steps:
[0021] Dissolve in a solvent to obtain solution, dissolve in a solvent to obtain solution, and at 60 °C to 80 °C, add the solution to the solution and react for 24 h to 72 h to obtain
[0022] The molar ratio is (3 - 5):1.
[0023] On the other hand, the present invention provides an application of the above-described photochromic polymer compound or a photochromic polymer compound prepared by any of the above-described preparation methods in a photochromic thin film material.
[0024] On yet another aspect, the present invention provides a photochromic thin film material, which is prepared by the following method:
[0025] Dissolve the above-described photochromic polymer compound or a photochromic polymer compound prepared by any of the above-described preparation methods in a solvent to obtain a uniform solution, spread the uniform solution on a substrate, and volatilize it under thermal conditions to obtain the photochromic thin film material.
[0026] Further, the concentration of the uniform solution is 10 mg / mL to 30 mg / mL.
[0027] Further, the temperature of the thermal conditions is 80 °C to 120 °C.
[0028] On yet another aspect, the present invention provides an application of any of the above-described photochromic thin film materials in anti-counterfeiting encryption and light-responsive intelligent coatings.
[0029] Compared with the prior art, the present invention has the following beneficial effects:
[0030] The present invention innovatively combines a light-responsive unit with a polymer matrix to obtain a photochromic polymer compound. The photochromic thin film material prepared from the photochromic polymer compound has excellent light writing performance, is suitable for high-precision light writing applications, and can meet the strict requirements of high-value-added application scenarios such as dynamic information storage and erasable anti-counterfeiting labels for material resolution and stability; and it can exhibit excellent adhesion to glass and good compatibility with the substrate; and it has successfully achieved fast response and excellent environmental stability. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 It is a state diagram of the photochromic thin film material prepared in Example 2 of the present invention under a fluorescent lamp (left) and an ultraviolet lamp (right);
[0032] Figure 2 It is a high-precision light writing performance result diagram of the photochromic thin film material prepared in Example 2 of the present invention;
[0033] Figure 3 It is a patterning treatment result diagram of the photochromic thin film material prepared in Example 4 of the present invention;
[0034] Figure 4 It is a high-precision light writing performance result diagram of the photochromic thin film material prepared in Example 4 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0035] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0036] Example 1
[0037] A photochromic polymer compound, the structure of which is shown as follows:
[0038]
[0039] The preparation of the photochromic polymer compound includes the following steps:
[0040] (1) Dissolve N-methyl-4-piperidone (1 g, 8.8 mmol), 2,2,2-trifluoroacetophenone (0.27 g, 1.55 mmol) and terphenyl (2.4 g, 10.35 mmol) in dichloromethane, react for 24 h in an ice-water bath, and a white solid precipitates. After filtering the precipitated solid, wash it thoroughly with 1 mol / L potassium carbonate solution (50 mL) by stirring at 50 °C for 12 h, then filter and dry to obtain
[0041] (2) Dissolve 1-pyrenemethanol (2.32 g, 10 mmol) and sodium hydride (4.8 g, 200 mmol) in dry tetrahydrofuran (100 mL), react for 30 min under a nitrogen atmosphere, then add 1,4-dibromobutane (21.6 g, 100 mmol), and react at room temperature for 48 h. After the reaction is completed, slowly dropwise add distilled water to quench the reaction, then extract three times with dichloromethane (100 mL), collect the organic phase, and wash it with 5 wt% dilute hydrochloric acid, 10 wt% sodium carbonate solution and distilled water respectively. The obtained organic phase is dried with anhydrous sodium sulfate and then concentrated in vacuo to remove the solvent, and then separated and purified by column chromatography (eluent VPE:VDCM = 1:1) to obtain
[0042] (3) Dissolve (1.2 g) in dimethyl sulfoxide (DMSO) (5 mL) to obtain a solution, dissolve (0.4 g) in dimethyl sulfoxide (DMSO) (5 mL) to obtain a solution, and at 80 °C, The solution was added to the solution and reacted for 24 h. After the reaction, it was cooled to room temperature. Diethyl ether was added to precipitate the product. After filtration, it was washed with diethyl ether and dried to obtain
[0043]
[0044] Example 2
[0045] The photochromic thin film material was prepared by the following method:
[0046] The photochromic polymer compound prepared in Example 1 was dissolved in dimethyl sulfoxide (DMSO) to prepare a uniform solution with a concentration of 20 mg / mL. After spreading this solution on a glass plate, it was allowed to naturally evaporate under hot conditions at 100 °C to form a transparent self-supporting film, namely the photochromic thin film material.
[0047] The photochromic thin film material exhibited excellent light transmission performance in the initial state, being colorless and transparent under a fluorescent lamp, while being blue-green under irradiation with an ultraviolet lamp (365 nm), as shown in Figure 1 shown.
[0048] High-precision light writing performance of the photochromic thin film material: Using a standard QR code pattern as a mask template, after physically masking a partial area on the surface of the photochromic thin film material with the mask template, it was irradiated directionally with a 365 nm ultraviolet light source for 3 minutes, as shown in Figure 2 shown. It can be seen from Figure 2 that an identifiable QR code pattern was successfully formed on the surface of the irradiated photochromic thin film material, and the colored area formed a sharp contrast with the masked area. Testing the photochromic QR code with an ordinary smartphone scanner showed good scanning recognition under ultraviolet light illumination conditions. It is particularly noteworthy that the obtained QR code pattern could be stably maintained for more than 48 hours at room temperature in the dark. This experimental result fully demonstrates that the photochromic thin film material of the present invention has excellent light writing performance and can meet the strict requirements for material resolution and stability in high-value application scenarios such as dynamic information storage and erasable anti-counterfeiting labels.
[0049] Example 3
[0050] The photochromic polymer compound has the following structure:
[0051]
[0052] The preparation of the photochromic polymer compound includes the following steps:
[0053] (1) N-Methyl-4-piperidone (1 g, 8.8 mmol), 2,2,2-Trifluoroacetophenone (1 g, 5.9 mmol) and terphenyl 3.4 g, 14.7 mmol) were dissolved in dichloromethane. After reacting for 24 h in an ice-water bath, a white solid precipitated. After filtering the precipitated solid, it was washed thoroughly by stirring with 1 mol / L potassium carbonate solution (50 mL) at 50 °C for 12 h, and then filtered and dried to obtain
[0054] (2) 1-Pyrenemethanol (2.32 g, 10 mmol) and sodium hydride (4.8 g, 200 mmol) were dissolved in dry tetrahydrofuran (100 mL). After reacting for 30 min under a nitrogen atmosphere, 1,8-dibromooctane (27.2 g, 100 mmol) was added, and the reaction was carried out at room temperature for 48 h. After the reaction was completed, distilled water was slowly added dropwise to quench the reaction, and then it was extracted three times with dichloromethane (100 mL). After collecting the organic phase, it was washed with 5 wt% dilute hydrochloric acid, 10 wt% sodium carbonate solution, and distilled water respectively. The obtained organic phase was dried over anhydrous sodium sulfate and then concentrated in vacuo to remove the solvent, and then separated and purified by column chromatography (eluent VPE:VDCM = 1:1) to obtain
[0055] (3) (2 g) was dissolved in dimethyl sulfoxide (DMSO) (5 mL) to obtain a solution. (0.6 g) was dissolved in dimethyl sulfoxide (DMSO) (5 mL) to obtain a solution. At 120 °C, the solution was added to the solution and reacted for 72 h. After the reaction was completed, the temperature was lowered to room temperature, and diethyl ether was added to precipitate the product. After filtering, it was washed with diethyl ether and dried to obtain
[0056]
[0057] Example 4
[0058] A photochromic thin film material was prepared by the following method:
[0059] The photochromic polymer compound prepared in Example 3 was dissolved in dimethyl sulfoxide (DMSO) to prepare a homogeneous solution with a concentration of 20 mg / mL. After spreading this solution on a glass plate, the solution was naturally volatilized under heating conditions at 100 °C to form a transparent self-supporting film, namely the photochromic thin film material.
[0060] The photochromic thin film material exhibits excellent light transmittance performance in the initial state, is colorless and transparent under a fluorescent lamp, and is blue-green under irradiation with an ultraviolet lamp (365 nm).
[0061] Patterning treatment of the photochromic thin film material: After physically masking a partial area on the surface of the photochromic thin film material using a mask plate, a 365 nm ultraviolet light source is used for 3 minutes of directional irradiation. After irradiation, an obvious patterning contrast effect appears on the surface of the photochromic thin film material: The area directly irradiated by ultraviolet light (the area not physically masked by the mask plate) undergoes a significant color change reaction and turns yellow-green, while the masked protection area remains in the initial blue-green state after ultraviolet light irradiation. The result is as Figure 3 shown.
[0062] High-precision photo-writing performance of the photochromic thin film material: Using a standard QR code pattern as a mask template, after physically masking a partial area on the surface of the photochromic thin film material using the mask template, a 365 nm ultraviolet light source is used for 3 minutes of directional irradiation. The result is as Figure 4 shown. From Figure 4 it can be seen that a recognizable QR code pattern has been successfully formed on the surface of the photochromic thin film material after light irradiation, and its color-developing area forms a sharp contrast with the masked area. The photochromic QR code is tested using an ordinary smartphone scanner, and it has good scanning recognition under ultraviolet light irradiation conditions. It is particularly worth noting that the obtained QR code pattern can be stably maintained for more than 48 hours under room temperature and dark conditions, having excellent environmental stability. This experimental result fully demonstrates that the photochromic thin film material of the present invention has excellent photo-writing performance and can meet the strict requirements of high-value application scenarios such as dynamic information storage and erasable anti-counterfeiting labels for material resolution and stability.
[0063] The above are only specific embodiments of the present invention, not all embodiments. Any equivalent transformation of the technical solution of the present invention by those of ordinary skill in the art by reading the specification of the present invention is covered by the claims of the present invention.
Claims
1. A photochromic polymer compound, the structure of which is shown in Formula I: Wherein, n = 2 - 7, x = 60 - 90, y = 100 - x.
2. The preparation method of the photochromic polymer compound according to claim 1, characterized in that, Comprising the following steps: (1) React N-methyl-4-piperidone, 2,2,2-trifluoroacetophenone and terphenyl to obtain a compound (2) React 1-pyrenemethanol with CH2Br(CH2) n Br to obtain the compound (3) React to obtain compound 3. The preparation method according to claim 2, characterized in that, Step (1) specifically comprises the following steps: Dissolve N-methyl-4-piperidone, 2,2,2-trifluoroacetophenone and terphenyl in a solvent, and react at 0 °C to 4 °C for 24 h to 48 h to obtain The molar ratio of the N-methyl-4-piperidone, 2,2,2-trifluoroacetophenone and terphenyl is (60 - 90):(10 - 40):
100.
4. The preparation method according to claim 2, characterized in that, Step (2) specifically comprises the following steps: Dissolve 1-pyrenemethanol and sodium hydride in a solvent, react for 20 min to 120 min under an inert gas atmosphere, and then add CH2Br(CH2) n Br and react for 24 h to 72 h to obtain The molar ratio of the 1-pyrenemethanol, sodium hydride, and CH2Br(CH2) n Br is 1:20:
10.
5. The preparation method according to claim 2, characterized in that, Step (3) specifically comprises the following steps: Dissolve in a solvent to obtain solution. Dissolve in a solvent to obtain solution. At 60 °C to 80 °C, add solution to solution and react for 24 h to 72 h to obtain The has a molar ratio of (3 to 5):
1.
6. The application of the photochromic polymer compound according to claim 1 or the photochromic polymer compound prepared by the preparation method according to any one of claims 2 - 5 in a photochromic thin film material.
7. A photochromic thin film material, characterized in that, Prepared by the following method: Dissolve the photochromic polymer compound according to claim 1 or the photochromic polymer compound prepared by the preparation method according to any one of claims 2 - 5 in a solvent to obtain a uniform solution, spread the uniform solution on a substrate, and volatilize it under thermal conditions to obtain the photochromic thin film material.
8. The photochromic thin film material according to claim 7, wherein The concentration of the uniform solution is 10mg / mL - 30mg / mL.
9. The photochromic thin film material according to claim 7, characterized in that, The temperature of the thermal conditions is 80°C - 120°C.
10. The application of the photochromic thin film material according to any one of claims 7 - 9 in anti-counterfeiting encryption and light-responsive intelligent coatings.