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

Abstract

The invention belongs to the field of polyester materials, and relates to a high-temperature-resistant polyarylester fluorescent film and a preparation method thereof. The preparation method comprises the following steps: carrying out esterification reaction on a reaction monomer under the conditions of a catalyst and a stabilizer, firstly mixing and stirring bisphenol fluorene, 18-crown ether-6 and deionized water to prepare a precursor solution, then gradually dropwise adding part of a paraphthaloyl chloride solution, continuously reacting for 3 hours under an alkaline condition, then adding an aqueous solution of bisphenol A into the solution, continuously reacting for 3 hours under an alkaline condition, and carrying out vacuum drying, so as to obtain the bisphenol fluorene / 18-crown ether-6 composite material. And continuously dropwise adding the residual paraphthaloyl chloride solution, reacting for 5 hours, adjusting the pH value of the mixed solution to be acidic, finally crushing, suction-filtering, precipitating and drying the product, and dissolving the product in an N-methyl pyrrolidone solution to prepare the film. The film prepared by the method has better high-temperature resistance, can emit blue fluorescence under the excitation of ultraviolet light, and can be used as a new optical material to be applied to the anti-counterfeiting field.

Description

Technical Field

[0001] The invention belongs to the field of polyester materials, and in particular relates to a high-temperature resistant polyarylate fluorescent film and a preparation method thereof. Background Art

[0002] Polyester is an important polymer material, mainly composed of ester bonds, with high strength, heat resistance and chemical stability. It is widely used in beverage bottles, fibers and films. With the advancement of science and technology, the demand for materials is becoming increasingly diversified. Aromatic polyester, as a new material, not only has excellent mechanical and thermal properties, but also can be endowed with optical properties by regulating the molecular structure of the reaction monomer.

[0003] Fluorescent polymer materials are mainly prepared in two ways: one is to design and synthesize main chain or side chain polymers containing aromatic rings; the other is to combine rare earth or aromatic condensed ring compounds with fluorescent properties with general polymer materials that do not have photoluminescence properties. In recent years, researchers have achieved the preparation of room temperature optical materials by rationally designing the molecular structure of polymer matrix and chromophore, using rigid steroid compounds, covalent cross-linking and other methods. Among them, the rigid conjugated structure on the polymer chain is the key to photoluminescence.

[0004] At present, optical anti-counterfeiting methods mainly include laser anti-counterfeiting and photo-etching anti-counterfeiting. Although these two methods are effective, they are expensive and are mainly used for documents. In contrast, fluorescent anti-counterfeiting is widely used in banknotes and product labels due to its convenience and economy. However, most organic fluorescent polymer materials perform poorly at high temperatures, which limits some of their applications. Summary of the invention

[0005] In order to improve the application field of polyester materials and develop low-cost anti-counterfeiting technology, bisphenol fluorene is introduced into the main chain of traditional polyester from the perspective of simple preparation process, and the aggregation structure of polyester is changed by adjusting the reaction rate by using a low-temperature solution method. The present invention provides a polyarylate film with excellent thermal properties, which has good blue fluorescence characteristics after ultraviolet excitation and can be used in various anti-counterfeiting fields. Due to its excellent comprehensive performance, it is difficult to be damaged in a general environment, protecting anti-counterfeiting proofs and broadening its application in the anti-counterfeiting field. The preparation process of the polyarylate film is simple and is also suitable for future industrial production.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is: a method for preparing a high temperature resistant polyarylate fluorescent film, which comprises the following components by weight: 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 into a mixed solution of deionized water, stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20°C. Nitrogen needs to be continuously introduced during the reaction as a protective gas.

[0008] S2, adding a portion of the dichloromethane solution containing some TPC to the precursor solution, and continuing the reaction for 3 hours;

[0009] S3, adding the aqueous solution containing BPA to the above solution, and continuously adding the remaining TPC solution dropwise, and reacting for 5 hours;

[0010] S4, adding HCl solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material;

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

[0012] Preferably, the BPA has a purity of >99.8%, a melting point of 158° C., and a boiling point of 220° C. under a low pressure 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 of >97%, a melting point of 83° C., a boiling point of 259° C., a flash point of 180° C., and is dissolved in a dichloromethane solution with a purity of 99.5%.

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

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

[0017] (1) The BPF used in the present 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 in improving the fluorescence properties.

[0018] (2) The present invention successfully obtains a polyarylate fluorescent film by polymerization of BPF and BPA with terephthaloyl chloride, which not only has a high glass transition temperature, but also has a high fluorescence quantum yield and fluorescence efficiency.

[0019] (3) The raw materials of the present invention are widely available and inexpensive. The synthesized polyarylate material uses common small molecules as raw materials, has simple ingredients, and is easy to prepare by a simple and controllable method. This provides a new research direction for simple and efficient industrial production of materials and also broadens the application scope of fluorescent materials. DETAILED DESCRIPTION

[0020] [Example 1]

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

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

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

[0024] S2, adding a portion of the dichloromethane solution containing some TPC to the precursor solution, and continuing the reaction for 3 hours;

[0025] S3, adding the aqueous solution containing BPA to the above solution, and continuously adding the remaining TPC solution dropwise, and reacting for 5 hours;

[0026] S4, adding HCl solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material;

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

[0028] [Example 2]

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

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

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

[0032] S2, adding a portion of the dichloromethane solution containing some TPC to the precursor solution, and continuing the reaction for 3 hours;

[0033] S3, adding the aqueous solution containing BPA to the above solution, and continuously adding the remaining TPC solution dropwise, and reacting for 5 hours;

[0034] S4, adding HCl solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material;

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

[0036] [Example 3]

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

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

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

[0040] S2, adding a portion of the dichloromethane solution containing some TPC to the precursor solution, and continuing the reaction for 3 hours;

[0041] S3, adding the aqueous solution containing BPA to the above solution, and continuously adding the remaining TPC solution dropwise, and reacting for 5 hours;

[0042] S4, adding HCl solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material;

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

[0044] [Example 4]

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

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

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

[0048] S2, adding a portion of the dichloromethane solution containing some TPC to the precursor solution, and continuing the reaction for 3 hours;

[0049] S3, adding the aqueous solution containing BPA to the above solution, and continuously adding the remaining TPC solution dropwise, and reacting for 5 hours;

[0050] S4, adding HCl solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material;

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

[0052] [Example 5]

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

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

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

[0056] S2, adding a portion of the dichloromethane solution containing some TPC to the precursor solution, and continuing the reaction for 3 hours;

[0057] S3, adding the aqueous solution containing BPA to the above solution, and continuously adding the remaining TPC solution dropwise, and reacting for 5 hours;

[0058] S4, adding HCl solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material;

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

[0060] [Comparative Example 1]

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

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

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

[0064] S2, adding a portion of the dichloromethane solution containing some TPC to the precursor solution, and continuing the reaction for 3 hours;

[0065] S3, adding the aqueous solution containing BPA to the above solution, and continuously adding the remaining TPC solution dropwise, and reacting for 5 hours;

[0066] S4, adding HCl solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material;

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

[0068] [Comparative Example 2]

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

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

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

[0072] S2, adding a portion of the dichloromethane solution containing some TPC to the precursor solution, and continuing the reaction for 3 hours;

[0073] S3, adding the aqueous solution containing BPA to the above solution, and continuously adding the remaining TPC solution dropwise, and reacting for 5 hours;

[0074] S4, adding HCl solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material;

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

[0076] [Comparative Example 3]

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

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

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

[0080] S2, adding a portion of the dichloromethane solution containing some TPC to the precursor solution, and continuing the reaction for 3 hours;

[0081] S3, adding the aqueous solution containing BPA to the above solution, and continuously adding the remaining TPC solution dropwise, and reacting for 5 hours;

[0082] S4, adding HCl solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material;

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

[0084] Table 1

[0085] BPF BPA TPC 18-Crown-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, the amount of BPF used in Comparative Example 1 during the preparation process is relatively small, so the thermal properties of the obtained product are relatively poor, T g With T 5％ Lower (T g is 279.8℃, T 5％ 458°C); in the preparation process of Comparative Example 2, the amount of BPF used was further reduced on the basis of Comparative Example 1, so the thermal properties of the obtained product were poor, T g With T 5％ Lower (T g is 277.8℃, T 5％ In the comparative example 3, the amount of BPF used in the preparation process is the least, so the thermal properties of the obtained product are the worst, Tg With T 5％ Lower (T g is 273.6℃, ​​T 5％ is 453°C).

[0089] It can also be seen from Table 1 that the maximum peak wavelengths of ultraviolet absorption of all cases are similar, which indicates that due to the same molecular structure, the products can emit fluorescence better under the excitation of the same ultraviolet wavelength; in addition, the maximum wavelengths of fluorescence emission of all cases are also within the wavelength range of blue fluorescence, which again indicates that all products can emit blue fluorescence; according to the different block ratios of BPF and BPA, such as Example 3, its T g With T 5％ is the highest (T g 313.3℃, ​​T 5％ is 487°C), so when the raw material dosage is close to BPF, 30 parts; 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 used to explain the present invention and do not constitute any limitation to 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 words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention; although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A method for preparing a high temperature resistant polyarylate fluorescent film, characterized in that: The following steps are involved: S1. Add bisphenol fluorene and 18-crown ether-6 into a mixed solution of deionized water, stir at 120 rpm for 1 h under alkaline conditions to prepare a precursor solution. The reaction temperature is 20° C. During the reaction, nitrogen needs to be continuously introduced as a protective gas. S2, adding a portion of the dichloromethane solution containing a portion of terephthaloyl chloride to the precursor solution, and continuing the reaction for 3 hours; S3, adding the aqueous solution containing bisphenol A to the above solution, and continuously adding the remaining terephthaloyl chloride solution dropwise, and reacting for 5 hours; S4, adding hydrochloric acid (HCl) solution dropwise to the mixed solution until the pH value reaches 3, then standing and precipitating in an acetone solution, repeatedly washing with deionized water for 5 times, and finally crushing with a wall breaking machine at a speed of 25000 rpm, and drying in an oven for 12 hours to obtain a dry polyarylate fluorescent material; S5. Dissolve the above polyarylate fluorescent material in N-methylpyrrolidone (NMP) solution with a solid content of 20%, and apply the solution on a clean glass plate. Dry it in a vacuum oven at a vacuum degree of -0.1 MPa and a temperature of 120°C 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 obtained high temperature resistant polyarylate fluorescent film comprises the following components by weight: Bisphenol A: 30-95 parts; Bisphenol fluorene: 5-55 parts; Terephthaloyl chloride: 55 parts; 18-Crown ether-6: 0.5 parts.

3. The high temperature resistant polyarylate fluorescent film according to claim 2, characterized in that: The bisphenol A is referred to as BPA, has a purity of >99.8%, a melting point of 158° C., and a boiling point of 220° C. under a low pressure of 4 mm Hg.

4. The high temperature resistant polyarylate fluorescent film according to claim 2, characterized in that: The bisphenol fluorene is referred to as BPF, has a purity of 98%, a melting point of 225°C, and a boiling point of 503°C.

5. The high temperature resistant polyarylate fluorescent film according to claim 2, characterized in that: The terephthaloyl chloride is referred to as TPC, which has a purity of >97%, a melting point of 83° C., a boiling point of 259° C., a flash point of 180° C., and is dissolved in a dichloromethane solution with a purity of 99.5%.

6. The high temperature resistant polyarylate fluorescent film according to claim 2, 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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