High-temperature-resistant polyarylate fluorescent film and preparation method thereof

Abstract

The present application belongs to the field of polyester materials, and relates to a high-temperature-resistant polyarylate fluorescent film and a preparation method thereof.The product prepared by the present application comprises reaction monomers, and esterification is carried out under the conditions of a catalyst and a stabilizer;first, diphenol fluorene, 18-crown-6 ether-6 and deionized water are mixed and stirred to prepare a precursor solution;then, part of terephthaloyl chloride solution is gradually added and continuously reacted for 3 hours under alkaline conditions;then, an aqueous solution of bisphenol A is added to the above solution, and the remaining terephthaloyl chloride solution is continuously added and reacted for 5 hours;the PH of the mixed solution is adjusted to be acidic;finally, the product is crushed, suction-filtered, precipitated, dried, and dissolved in an N-methyl pyrrolidone solution for film preparation.The film prepared by the method has good high-temperature resistance, can emit blue fluorescence under ultraviolet light excitation, and can be applied to the field of anti-counterfeiting as a new optical material.

Description

Technical Field

[0001] This invention belongs to the field of polyester materials, specifically a high-temperature resistant polyarylate fluorescent film and its preparation method. Background Technology

[0002] Polyester is an important polymer material, primarily composed of ester bonds, possessing high strength, heat resistance, and chemical stability, and is widely used in beverage bottles, fibers, and films. With technological advancements and increasingly diversified material demands, aromatic polyesters, as novel materials, not only exhibit excellent mechanical and thermal properties but can also be endowed with optical properties by controlling the molecular structure of the reactants.

[0003] Fluorescent polymer materials are mainly prepared through two methods: one is the design and synthesis of main-chain or side-chain polymers containing aromatic rings; the other is the composite of rare-earth or aromatic fused-ring compounds with fluorescent properties with general-purpose polymers that do not possess photoluminescence properties. In recent years, researchers have achieved the preparation of room-temperature optical materials by rationally designing the molecular structures of polymer matrices and chromophores, using methods such as rigid steroidal compounds and covalent cross-linking. Among these methods, the rigid conjugated structure on the polymer chain is key to photoluminescence.

[0004] Currently, optical anti-counterfeiting methods mainly include laser anti-counterfeiting and photo-etching anti-counterfeiting. Although these two methods are effective, they are expensive and mainly used for certificates. In contrast, fluorescent anti-counterfeiting is widely used in banknotes and commodity labels due to its convenience and economy. However, most organic fluorescent polymer materials do not perform well at high temperatures, which limits some of their applications. Summary of the Invention

[0005] To expand the application areas of polyester materials and develop low-cost anti-counterfeiting technologies, this invention, starting from a simple preparation process, introduces bisphenol fluorene into the main chain of traditional polyester using a low-temperature solution method and modifies the aggregated structure of the polyester by adjusting the reaction rate. This invention provides a polyarylate film with excellent thermal properties, exhibiting good blue fluorescence after ultraviolet excitation. It can be used in various anti-counterfeiting fields. Due to its excellent overall performance, it is difficult to be damaged in normal environments, protecting anti-counterfeiting certificates and broadening its applications in the anti-counterfeiting field. The preparation process of this polyarylate film is simple and suitable for future industrial production.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a method for preparing a high-temperature resistant polyarylate fluorescent film, which, by weight, comprises the following components: BPA: 30-95 parts; BPF: 5-55 parts; TPC: 55 parts; 18-crown ether-6: 0.5 parts.

[0007] S1. Add BPF and 18-crown ether-6 to a mixed solution of deionized water and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃. Nitrogen gas needs to be continuously introduced during the reaction process as a protective gas.

[0008] S2. Add a dichloromethane solution containing a portion of TPC to the precursor solution dropwise and continue the reaction for 3 hours.

[0009] S3. Add the aqueous solution containing BPA to the above solution, and continuously add the remaining TPC solution dropwise, and react for 5 hours;

[0010] S4. Add HCl solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a high-speed blender at 25000 rpm and dry it in an oven for 12 hours to obtain the dried polyarylate fluorescent material.

[0011] S5. Dissolve the above polyarylate fluorescent material in NMP solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

[0012] Preferably, the BPA has a purity >99.8%, a melting point of 158°C, and a boiling point of 220°C under low pressure conditions of 4 mm Hg.

[0013] Preferably, the BPF has a purity of 98%, a melting point of 225°C, and a boiling point of 503°C.

[0014] Preferably, the TPC has a purity >97%, a melting point of 83°C, a boiling point of 259°C, a flash point of 180°C, and is soluble in a 99.5% pure dichloromethane solution.

[0015] Preferably, the 18-crown ether-6 has a purity of 99%, a boiling point of 190°C and a melting point of 39°C under a pressure of 0.7 mm Hg.

[0016] Compared with the prior art, the present invention has the following advantages:

[0017] (1) The BPF used in this invention is a compound with a Cardo skeleton. This special structure not only greatly improves the thermal properties of the synthesized polyarylate, but also has a good effect on improving the fluorescence properties.

[0018] (2) This invention successfully obtained a polyarylate fluorescent film by polymerizing BPF and BPA with terephthaloyl chloride. It not only has a high glass transition temperature, but also a high fluorescence quantum yield and fluorescence efficiency.

[0019] (3) The raw materials of this invention are widely available and inexpensive. The synthesized polyarylate materials are made from common small molecules, have simple composition, and are easy to prepare. This provides a new research direction for simple and efficient industrial production of materials and also broadens the application range of fluorescent materials. Detailed Implementation

[0020]

Example 1

[0021] For ease of comparison, the experimental results are listed in Table 1.

[0022] This embodiment provides a high-temperature resistant polyarylate fluorescent film and its preparation method, comprising the following components by weight: BPA: 80 parts; BPF: 20 parts; TPC: 55 parts; 18-crown ether-6: 0.5 parts.

[0023] S1. Add BPF and 18-crown ether-6 parts to a mixed solution of deionized water, and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃, and nitrogen gas needs to be continuously introduced during the reaction process as a protective gas.

[0024] S2. Add a dichloromethane solution containing a portion of TPC to the precursor solution dropwise and continue the reaction for 3 hours.

[0025] S3. Add the aqueous solution containing BPA to the above solution, and continuously add the remaining TPC solution dropwise, and react for 5 hours;

[0026] S4. Add HCl solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a high-speed blender at 25000 rpm and dry it in an oven for 12 hours to obtain the dried polyarylate fluorescent material.

[0027] S5. Dissolve the above polyarylate fluorescent material in NMP solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

[0028]

Example 2

[0029] For ease of comparison, the experimental results are listed in Table 1.

[0030] This embodiment provides a high-temperature resistant polyarylate fluorescent film and its preparation method, comprising the following components by weight: BPA: 70 parts; BPF: 25 parts; TPC: 55 parts; 18-crown ether-6: 0.5 parts.

[0031] S1. Add BPF and 18-crown ether-6 parts to a mixed solution of deionized water, and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃, and nitrogen gas needs to be continuously introduced during the reaction process as a protective gas.

[0032] S2. Add a dichloromethane solution containing a portion of TPC to the precursor solution dropwise and continue the reaction for 3 hours.

[0033] S3. Add the aqueous solution containing BPA to the above solution, and continuously add the remaining TPC solution dropwise, and react for 5 hours;

[0034] S4. Add HCl solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a high-speed blender at 25000 rpm and dry it in an oven for 12 hours to obtain the dried polyarylate fluorescent material.

[0035] S5. Dissolve the above polyarylate fluorescent material in NMP solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

[0036]

Example 3

[0037] For ease of comparison, the experimental results are listed in Table 1.

[0038] This embodiment provides a high-temperature resistant polyarylate fluorescent film and its preparation method, comprising the following components by weight: BPA: 60 parts; BPF: 30 parts; TPC: 55 parts; 18-crown ether-6: 0.5 parts.

[0039] S1. Add BPF and 18-crown ether-6 parts to a mixed solution of deionized water, and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃, and nitrogen gas needs to be continuously introduced during the reaction process as a protective gas.

[0040] S2. Add a dichloromethane solution containing a portion of TPC to the precursor solution dropwise and continue the reaction for 3 hours.

[0041] S3. Add the aqueous solution containing BPA to the above solution, and continuously add the remaining TPC solution dropwise, and react for 5 hours;

[0042] S4. Add HCl solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a high-speed blender at 25000 rpm and dry it in an oven for 12 hours to obtain the dried polyarylate fluorescent material.

[0043] S5. Dissolve the above polyarylate fluorescent material in NMP solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

[0044]

Example 4

[0045] For ease of comparison, the experimental results are listed in Table 1.

[0046] This embodiment provides a high-temperature resistant polyarylate fluorescent film and its preparation method, comprising the following components by weight: BPA: 50 parts; BPF: 35 parts; TPC: 55 parts; 18-crown ether-6: 0.5 parts.

[0047] S1. Add BPF and 18-crown ether-6 parts to a mixed solution of deionized water, and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃, and nitrogen gas needs to be continuously introduced during the reaction process as a protective gas.

[0048] S2. Add a dichloromethane solution containing a portion of TPC to the precursor solution dropwise and continue the reaction for 3 hours.

[0049] S3. Add the aqueous solution containing BPA to the above solution, and continuously add the remaining TPC solution dropwise, and react for 5 hours;

[0050] S4. Add HCl solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a high-speed blender at 25000 rpm and dry it in an oven for 12 hours to obtain the dried polyarylate fluorescent material.

[0051] S5. Dissolve the above polyarylate fluorescent material in NMP solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

[0052]

Example 5

[0053] For ease of comparison, the experimental results are listed in Table 1.

[0054] This embodiment provides a high-temperature resistant polyarylate fluorescent film and its preparation method, comprising the following components by weight: BPA: 30 parts; BPF: 55 parts; TPC: 55 parts; 18-crown ether-6: 0.5 parts.

[0055] S1. Add BPF and 18-crown ether-6 parts to a mixed solution of deionized water, and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃, and nitrogen gas needs to be continuously introduced during the reaction process as a protective gas.

[0056] S2. Add a dichloromethane solution containing a portion of TPC to the precursor solution dropwise and continue the reaction for 3 hours.

[0057] S3. Add the aqueous solution containing BPA to the above solution, and continuously add the remaining TPC solution dropwise, and react for 5 hours;

[0058] S4. Add HCl solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a high-speed blender at 25000 rpm and dry it in an oven for 12 hours to obtain the dried polyarylate fluorescent material.

[0059] S5. Dissolve the above polyarylate fluorescent material in NMP solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

[0060] Comparative Example 1

[0061] For ease of comparison, the experimental results are listed in Table 1.

[0062] This embodiment provides a high-temperature resistant polyarylate fluorescent film and its preparation method, comprising the following components by weight: BPA: 85 parts; BPF: 15 parts; TPC: 55 parts; 18-crown ether-6: 0.5 parts.

[0063] S1. Add BPF and 18-crown ether-6 parts to a mixed solution of deionized water, and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃, and nitrogen gas needs to be continuously introduced during the reaction process as a protective gas.

[0064] S2. Add a dichloromethane solution containing a portion of TPC to the precursor solution dropwise and continue the reaction for 3 hours.

[0065] S3. Add the aqueous solution containing BPA to the above solution, and continuously add the remaining TPC solution dropwise, and react for 5 hours;

[0066] S4. Add HCl solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a high-speed blender at 25000 rpm and dry it in an oven for 12 hours to obtain the dried polyarylate fluorescent material.

[0067] S5. Dissolve the above polyarylate fluorescent material in NMP solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

[0068] Comparative Example 2

[0069] For ease of comparison, the experimental results are listed in Table 1.

[0070] This embodiment provides a high-temperature resistant polyarylate fluorescent film and its preparation method, comprising the following components by weight: BPA: 90 parts; BPF: 10 parts; TPC: 55 parts; 18-crown ether-6: 0.5 parts.

[0071] S1. Add BPF and 18-crown ether-6 parts to a mixed solution of deionized water, and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃, and nitrogen gas needs to be continuously introduced during the reaction process as a protective gas.

[0072] S2. Add a dichloromethane solution containing a portion of TPC to the precursor solution dropwise and continue the reaction for 3 hours.

[0073] S3. Add the aqueous solution containing BPA to the above solution, and continuously add the remaining TPC solution dropwise, and react for 5 hours;

[0074] S4. Add HCl solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a high-speed blender at 25000 rpm and dry it in an oven for 12 hours to obtain the dried polyarylate fluorescent material.

[0075] S5. Dissolve the above polyarylate fluorescent material in NMP solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

[0076] Comparative Example 3

[0077] For ease of comparison, the experimental results are listed in Table 1.

[0078] This embodiment provides a high-temperature resistant polyarylate fluorescent film and its preparation method, comprising the following components by weight: BPA: 95 parts; BPF: 5 parts; TPC: 55 parts; 18-crown ether-6: 0.5 parts.

[0079] S1. Add BPF and 18-crown ether-6 parts to a mixed solution of deionized water, and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃, and nitrogen gas needs to be continuously introduced during the reaction process as a protective gas.

[0080] S2. Add a dichloromethane solution containing a portion of TPC to the precursor solution dropwise and continue the reaction for 3 hours.

[0081] S3. Add the aqueous solution containing BPA to the above solution, and continuously add the remaining TPC solution dropwise, and react for 5 hours;

[0082] S4. Add HCl solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a high-speed blender at 25000 rpm and dry it in an oven for 12 hours to obtain the dried polyarylate fluorescent material.

[0083] S5. Dissolve the above polyarylate fluorescent material in NMP solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

[0084] Table 1

[0085] BPF BPA TPC 18-crown ether-6 Example 1 20 80 55 0.5 Example 2 25 70 55 0.5 Example 3 30 60 55 0.5 Example 4 35 50 55 0.5 Example 5 55 30 55 0.5 Comparative Example 1 15 85 55 0.5 Comparative Example 2 10 90 55 0.5 Comparative Example 3 5 95 55 0.5

[0086] Table 1 (continued)

[0087]

[0088] As shown in Table 1, compared with Example 3 of the present invention, Comparative Example 1 used less BPF in the preparation process, so the thermal properties of the resulting product were worse. g With T 5％ Lower (T) g The temperature was 279.8℃, T 5％ (458℃); In Comparative Example 2, the amount of BPF used was further reduced compared to Comparative Example 1 during the preparation process, resulting in a product with poorer thermal properties. g With T 5％ Lower (T) g The temperature was 277.8℃, T 5％ (456℃); Comparative Example 3 used the least amount of BPF during the preparation process, therefore the resulting product had the worst thermal properties, Tg With T 5％ Lower (T) g The temperature was 273.6℃, ​​T 5％ (453℃).

[0089] As shown in Table 1, the wavelengths of the maximum UV absorption peaks in all cases are similar, indicating that due to the similar molecular structures, the products can all emit fluorescence better under the same UV light excitation wavelength. Furthermore, the maximum fluorescence emission wavelengths in all cases are within the wavelength range of blue fluorescence, further demonstrating that all products can emit blue fluorescence. Depending on the block ratio of BPF to BPA, as in Example 3, its T... g With T 5％ It is the highest (T) g The temperature was 313.3℃, ​​T 5％ Since the temperature is 487℃, when the raw material dosage is close to that of BPF (30 parts) and BPA (60 parts), the product with the best thermal properties can be obtained.

[0090] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention; although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for preparing a high-temperature resistant polyarylate fluorescent film, characterized in that, Includes the following steps: S1. Add 25-30 parts of bisphenol fluorene and 0.5 parts of 18-crown ether-6 to a mixed solution of deionized water, and stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20℃, and nitrogen gas needs to be continuously introduced during the reaction process as a protective gas. S2. Add a solution of dichloromethane containing 55 parts of terephthaloyl chloride dropwise to the precursor solution and continue the reaction for 3 hours. S3. Add an aqueous solution containing 60-70 parts of bisphenol A to the above solution, and continuously add the remaining terephthaloyl chloride solution dropwise, and react for 5 hours. S4. Add hydrochloric acid solution dropwise to the mixed solution until the pH value is 3. Then, let it stand in acetone solution to precipitate, wash it repeatedly with deionized water 5 times, and finally crush it with a wall-breaking machine at a speed of 25000 rpm and dry it in an oven for 12 hours to obtain dried polyarylate fluorescent material. S5. Dissolve the above-mentioned polyarylate fluorescent material in N-methylpyrrolidone solution with a solid content of 20%, coat the solution onto a clean glass plate, and dry it in a vacuum oven at a vacuum degree of -0.1MPa and a temperature of 120℃ for 9 hours to obtain a high-temperature resistant polyarylate fluorescent film.

2. The method for preparing a high-temperature resistant polyarylate fluorescent film according to claim 1, characterized in that, The bisphenol A, abbreviated as BPA, has a purity >99.8%, a melting point of 158℃, and a boiling point of 220℃ under low pressure conditions of 4 mm Hg.

3. The method for preparing a high-temperature resistant polyarylate fluorescent film according to claim 1, characterized in that, The bisphenol fluorene, abbreviated as BPF, has a purity of 98%, a melting point of 225°C, and a boiling point of 503°C.

4. The method for preparing a high-temperature resistant polyarylate fluorescent film according to claim 1, characterized in that, The terephthaloyl chloride, abbreviated as TPC, has a purity >97%, a melting point of 83°C, a boiling point of 259°C, a flash point of 180°C, and is soluble in a 99.5% pure dichloromethane solution.

5. The method for preparing a high-temperature resistant polyarylate fluorescent film according to claim 1, characterized in that, The 18-crown ether-6 has a purity of 99%, a boiling point of 190°C and a melting point of 39°C under a pressure of 0.7 mm Hg.

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