Biphenylimine aryl polytriazoles, methods of making and using the same

Abstract

The application relates to a biphenylimine aryl polytriazole and a preparation method and application thereof. The biphenylimine aryl polytriazole has a structure as shown in formula (I): wherein R in the formula (I) is any one of R1-R10; and the number average molecular weight of the biphenylimine aryl polytriazole is 18000-22000. The biphenylimine aryl polytriazole not only has excellent heat resistance, but also can be dissolved in various different organic solvents to form a polymer solution, has excellent film forming property, and can be used for preparing a high-temperature-resistant thin film product or a high-temperature-resistant coating.

Description

Technical Field

[0001] This invention relates to the field of polymer compound technology, and more specifically, to a benzeneimine aryl polytriazole, its preparation method, and its application. Background Technology

[0002] Polytriazole resin is a polymer whose main chain structure contains 1,2,3-triazole rings, formed by the 1,3-dipolar cycloaddition reaction of a multi-azide compound and an alkynyl compound. Due to the presence of rigid aromatic heterocycles (triazole rings), this polymer has good heat resistance, heat oxidation resistance and chemical stability; however, the heat resistance of conventional polytriazole resins and their composites is still limited and cannot meet the requirements for use above 250°C.

[0003] To further improve the heat resistance of polytriazole resins, existing technologies generally introduce rigid groups such as benzene rings or biphenyls to increase the rigidity of the polymer molecular chains and the packing density between the chains, or introduce crosslinking groups to form a highly crosslinked structure after curing. However, in practical applications, it has been found that while the introduction of rigid groups or the formation of a highly crosslinked structure is beneficial to improving the heat resistance of polytriazole resins, it also deteriorates their melt processing and solubility, leading to difficulties in secondary processing and making them unsuitable for applications requiring casting or solution casting to prepare high-temperature resistant film products or high-temperature resistant coatings. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects or shortcomings of the poor secondary processing performance of existing aromatic polytriazole resins and to provide a biphenylimine aryl polytriazole.

[0005] Another object of the present invention is to provide a method for preparing benzeneimine aryl polytriazole.

[0006] Another object of the present invention is to provide an application of benzylimine aryl polytriazole in the preparation of high-temperature resistant thin film products or high-temperature resistant coatings.

[0007] Another object of the present invention is to provide a thin film.

[0008] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0009] This invention protects a benzeneimine aryl polytriazole, the structure of which is shown in formula (I):

[0010]

[0011] Where R is Any one of the following; the number-average molecular weight (Mn) of the biphenylimine aryl polytriazole is 18,000 to 22,000.

[0012] The molecular chain of the benzeneimine aryl polytriazole of the present invention contains a large number of rigid benzene rings and triazole rings, which can effectively restrict the movement of polymer chain segments, thereby improving the glass transition temperature and thermal stability of the polymer; moreover, the molecular chain contains flexible groups, making the molecular chain stacking relatively loose, allowing the solvent to effectively penetrate into the molecular chain to improve its solubility, thereby improving the secondary processing performance of benzeneimine aryl polytriazole.

[0013] In addition, the weight-average molecular weight (Mw) of the above-mentioned benzylimine aryl polytriazole is 22,000 to 26,000, and the molecular weight distribution coefficient (PDI) is 1.1 to 1.35.

[0014] Specifically, the number-average molecular weight of benzylimine aryl polytriazole can be 18300, 18595, 18970, 19500, 20000, 21394, 21639 or 21800, and the weight-average molecular weight can be 22500, 22798, 23000, 23500, 24000, 24500, 24861, 25006, 25433 or 25800.

[0015] Preferably, R in the biphenylimine aryl polytriazole is...

[0016] Optionally, the glass transition temperature (Tg) of the benzeneimine aryl polytriazole is ≥300℃, and can be 302~346℃, specifically 302.6℃, 310.5℃, 341.2℃ or 345.4℃.

[0017] This invention also protects a method for preparing the above-mentioned benzylimine aryl polytriazole, comprising the following steps:

[0018] The biphenyltetracarboxylic acid diimide yne monomer shown in formula (II), the biphenyltetracarboxylic acid diimide yne monomer shown in formula (III), and the polymerization catalyst are subjected to a click polymerization reaction to obtain biphenylimide aryl polytriazole.

[0019] N3-R-N3

[0020] Equation (II);

[0021]

[0022] Wherein, R in equation (II) above is Any one of them.

[0023] Optionally, the two -N3 groups in the above-mentioned diterminated azide monomer are respectively attached to any position on different benzene rings in R, preferably 4,4'-diterminated azide monomer (-N3 attached to the 4,4' para position of the benzene ring in R); the 4,4'-diterminated azide monomer is commercially available or prepared by the following method:

[0024] Sodium azide is reacted with any one of 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,4'-diaminobiphenyl, and 4,4'-diaminodiphenylmethane via a nucleophilic substitution reaction to obtain a 4,4'-diterminated azide monomer.

[0025] In the above preparation method, the molar ratio of 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,4'-diaminobiphenyl or 4,4'-diaminodiphenylmethane to sodium azide is 1:(1-1.4), the nucleophilic substitution reaction temperature is 0-5℃, and the time is 3-4h.

[0026] The specific reaction process is as follows: any one of 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,4'-diaminobiphenyl or 4,4'-diaminodiphenylmethane is dissolved in water and concentrated hydrochloric acid under a nitrogen atmosphere at room temperature. After the temperature of the reaction system is lowered to 0-5℃, an aqueous solution of sodium nitrite is added dropwise and stirred for 0.5-1.5 h. Then, an aqueous solution of sodium azide is added dropwise and stirred for 3-4 h. After standing overnight and filtration, the 4,4'-diterminated azide monomer is obtained.

[0027] Optionally, the biphenyltetracarboxylic acid diimide yne monomer is commercially available or prepared by the following methods:

[0028] 3,3',4,4'-Biphenyltetracarboxylic dianhydride and 3-aminophenylacetylene are mixed in a molar ratio of ≤1:2 and reacted in an inert atmosphere at 0-5°C for 4-5 hours. The mixture is then purified to obtain the biphenyltetracarboxylic diimide acetylene monomer.

[0029] Specifically, the process includes the following steps: 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3-aminophenylacetylene and anhydrous DMAC are mixed evenly and stirred at 0-5°C for 4-5 hours under a nitrogen atmosphere. Triethylamine and acetic anhydride are then slowly added dropwise through a constant pressure dropping funnel to allow the reaction to proceed overnight. The reaction solution is then poured into deionized water, filtered with ethanol, and dried to obtain the biphenyltetracarboxylic dianimide acetylene monomer.

[0030] Optionally, the reaction temperature of the click polymerization reaction is 50-60℃ and the reaction time is 6-10h. Specifically, the reaction temperature can be 50℃, 55℃ or 60℃, and the reaction time can be 6.5h, 7h, 7.5h, 8h, 8.5h, 9h or 9.5h. The molar ratio of the di-terminated azide monomer to the biphenyltetracarboxylic acid diimide yne monomer is 1:(0.8-1.2), specifically 1:1.

[0031] Specifically, the polymerization catalyst is a monovalent copper salt catalyst, and its molar ratio with the di-terminated azide monomer is (1-3):50.

[0032] The application of the above-mentioned benzylimine aryl polytriazole in the preparation of high-temperature resistant film products or high-temperature resistant coatings is also within the scope of protection of this invention.

[0033] This invention also protects a thin film prepared from the above-mentioned benzylimine aryl polytriazole.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The benzylimine aryl polytriazole of the present invention not only has excellent high temperature resistance, but also can be dissolved in a variety of different organic solvents to form polymer solutions, exhibiting excellent film-forming properties, and can be used to prepare high temperature resistant thin film products or high temperature resistant coatings. Attached Figure Description

[0036] Figure 1 4,4'-diazidodiphenyl sulfone monomer and its raw materials in CDCl3 1 H NMR comparison image.

[0037] Figure 2 4,4'-diazidodiphenyl ether monomer and its raw materials in CDCl3 1 H NMR comparison image.

[0038] Figure 3 4,4'-diazidobiphenyl monomer and its raw materials in CDCl3 1 H NMR comparison image.

[0039] Figure 4 4,4'-diazidodiphenylmethane monomer and its raw materials in DMSO 1 H NMR comparison image.

[0040] Figure 5 This is a FT-IR comparison image of biphenyltetracarboxylic diimide yne and its raw materials.

[0041] Figure 6 DSC curves for BPS-PTA, BPE-PTA, BPBP-PTA, and BPM-PTA.

[0042] Figure 7 TGA curves for BPS-PTA, BPE-PTA, BPBP-PTA, and BPM-PTA.

[0043] Figure 8 DTG curves for BPS-PTA, BPE-PTA, BPBP-PTA, and BPM-PTA. Detailed Implementation

[0044] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise stated, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0045] Example 1

[0046] A benzeneimine aryl polytriazole (denoted as BPS-PTA) can be obtained by the following preparation method:

[0047] Add 3 mmol of 4,4'-diphenyl sulfone azido, 3 mmol of biphenyltetracarboxylic acid diimide yne, and 0.3 mmol of CuI to a 50 mL flask. Add about 2 mL of acetone solvent to just completely dissolve the substances. Dissolve the substances by sonication. The system is light yellow. Then add about 0.5 mL of triethylamine and stir. Reflux at 55 °C for about 15 min. A yellow solid appears in the system, and the supernatant is basically colorless. Stop the reaction, discard the supernatant, filter with acetone, and then place the product in an oven for heating and polymerization. The heating program is 80 °C for 2 h → 130 °C for 2 h → 180 °C for 2 h → 230 °C to obtain BPS-PTA.

[0048] The above-mentioned 4,4'-diazidodiphenyl sulfone can be prepared by the following method:

[0049] In a flask containing 3 mmol of 4,4'-diaminodiphenyl sulfone, 20 mL of deionized water and 12 mL of concentrated hydrochloric acid (12 mol / L) were added and stirred until the solid completely dissolved. The system was colorless, clear, and transparent. The temperature of the mixture was maintained at 0–5 °C in an ice bath. 9 mL of a 1 mol / L sodium nitrite aqueous solution was added dropwise. The solution turned white to pale yellow. The reaction mixture was stirred until homogeneous. After stirring for 1 hour, the temperature was still maintained at 0–5 °C, and a 1 mol / L sodium azide aqueous solution was added dropwise. 9 mL was added, and the system gradually turned light yellow. A light yellow precipitate was formed and nitrogen gas was released. A layer of light yellow foam floated on the top of the system. After the addition was complete, the reaction continued at 0-5℃. The reaction process was tracked by spotting on a chromatographic plate. It was found that the reaction was almost complete after stirring for 4 hours, and the starting material spot basically disappeared. The reaction was stopped and allowed to stand for about 12 hours. The precipitate and solution were found to be clear. The mixture was filtered, and the filter cake was washed 2-3 times with deionized water and dried under vacuum at 50℃ for 12 hours to obtain a light yellow powder, which is 4,4'-diazidodiphenyl sulfone, with a yield of 88.2%.

[0050] The above-mentioned biphenyltetracarboxylic acid diimide yne monomer can be prepared by the following method:

[0051] 10 mmol of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 20 mmol of 3-aminophenylacetylene were dissolved in 50 mL of anhydrous DMAC and mixed thoroughly. The mixture was stirred for 4 h in a nitrogen atmosphere and an ice bath. Then, 3 mmol of triethylamine and 10 mmol of acetic anhydride were slowly added dropwise using a constant pressure dropping funnel to carry out the reaction overnight. The reaction solution was then poured into deionized water, filtered with ethanol, and dried to obtain the biphenyltetracarboxylic dianimide acetylene monomer.

[0052] Example 2

[0053] A benzeneimine aryl polytriazole (BPE-PTA) can be obtained by the following preparation method:

[0054] Add 3 mmol of 4,4'-diazidodiphenyl ether, 3 mmol of biphenyltetracarboxylic acid diimide yne, and 0.3 mmol of CuI to a 50 mL flask. Add about 2 mL of acetone solvent to just completely dissolve the substances. Dissolve the substances by sonication. The system is light yellow. Then add about 0.5 mL of triethylamine and stir. Reflux at 55 °C for about 15 min. A yellow solid appears in the system, and the supernatant is basically colorless. Stop the reaction, discard the supernatant, filter with acetone, and then place the product in an oven for heating and polymerization. The heating program is 80 °C for 2 h → 130 °C for 2 h → 180 °C for 2 h → 230 °C to obtain BPE-PTA.

[0055] The above-mentioned 4,4'-diazidodiphenyl ether can be prepared by the following method:

[0056] In a flask containing 3 mmol of 4,4'-diaminodiphenyl ether, 20 mL of deionized water and 12 mL of concentrated hydrochloric acid (12 mol / L) were added and stirred until the solid completely dissolved, resulting in a milky white system. The mixture was kept at 0–5 °C in an ice bath. 9 mL of a 1 mol / L sodium nitrite aqueous solution was added dropwise while stirring until the reaction mixture was homogeneous and the system turned pale yellow. After stirring for 1 hour, the temperature was still maintained at 0–5 °C, and 9 mL of a 1 mol / L sodium azide aqueous solution was added dropwise. The system gradually turned light yellow, with a pale yellow powder precipitating and nitrogen gas being released. After the addition of sodium azide, the system was transferred to room temperature for reaction. The reaction process was monitored by spotting on a chromatogram. It was found that the reaction was almost complete after stirring for 3 hours, and the starting material spot basically disappeared. The reaction was stopped and allowed to stand for about 12 hours. The precipitate and solution were found to be clear, with the solid located in the upper layer of the system. The mixture was filtered, and the filter cake was washed 2-3 times with deionized water and dried under vacuum at 50°C for 12 hours to obtain a pale yellow powder, which was 4,4'-diazidodiphenyl ether, with a yield of 66.5%.

[0057] The preparation method of the above-mentioned biphenyltetracarboxylic acid diimide yne monomer is the same as that in Example 1.

[0058] Example 3

[0059] A benzeneimine aryl polytriazole (BPBP-PTA) can be prepared by the following method:

[0060] Add 3 mmol of 4,4'-diazidobiphenyl, 3 mmol of biphenyltetracarboxylic acid diimide yne, and 0.3 mmol of CuI to a 50 mL flask. Add about 2 mL of acetone solvent to just completely dissolve the substances. Dissolve the substances by sonication. The system is light yellow. Then add about 0.5 mL of triethylamine and stir. Reflux at 55 °C for about 15 min. A yellow solid appears in the system, and the supernatant is basically colorless. Stop the reaction, discard the supernatant, filter with acetone, and then place the product in an oven for heating and polymerization. The heating program is 80 °C for 2 h → 130 °C for 2 h → 180 °C for 2 h → 230 °C to obtain BPBP-PTA.

[0061] The 4,4'-diazidobiphenyl mentioned above can be prepared by the following method:

[0062] In a flask containing 3 mmol of 4,4'-diaminobiphenyl, 20 mL of deionized water and 6 mL of 12 mol / L concentrated hydrochloric acid were added and stirred until the solid completely dissolved, resulting in a powdery white system. The mixture was kept at 0–5 °C in an ice bath, and 9 mL of 1 mol / L sodium nitrite aqueous solution was added dropwise while stirring until the reaction mixture was homogeneous and the system turned yellow. After stirring for 1 hour, while still maintaining the temperature at 0–5 °C, 9 mL of 1 mol / L sodium azide aqueous solution was added dropwise. The mixture gradually turned pale yellow, with a pale yellow powder precipitating and nitrogen gas being released. After the addition of sodium azide, the system was transferred to room temperature for reaction. The reaction process was monitored by spotting on a chromatogram. It was found that the reaction was almost complete after stirring for 3 hours, and the starting material spot had basically disappeared. The reaction was stopped, and the mixture was allowed to stand for about 12 hours. The precipitate and solution were found to be clear, with the solid located in the upper layer of the system. The mixture was filtered, and the filter cake was washed 2-3 times with deionized water and dried under vacuum at 50°C for 12 hours to obtain a pale yellow powder, which was 4,4'-diazidobiphenyl, with a yield of 81.9%.

[0063] The preparation method of the above-mentioned biphenyltetracarboxylic acid diimide yne monomer is the same as that in Example 1.

[0064] Example 4

[0065] A benzeneimine aryl polytriazole (BPM-PTA) can be prepared by the following method:

[0066] Add 3 mmol of 4,4'-diazidodiphenylmethane, 3 mmol of biphenyltetracarboxylic acid diimide yne, and 0.3 mmol of CuI to a 50 mL flask. Add about 2 mL of acetone solvent to just completely dissolve the substances. Dissolve the substances by sonication. The system is light yellow. Then add about 0.5 mL of triethylamine and stir. Reflux at 55 °C for about 15 min. A yellow solid appears in the system, and the supernatant is basically colorless. Stop the reaction, discard the supernatant, filter with acetone, and then place the product in an oven for heating and polymerization. The heating program is 80 °C for 2 h → 130 °C for 2 h → 180 °C for 2 h → 230 °C to obtain BPM-PTA.

[0067] The 4,4'-diazidodiphenylmethane mentioned above can be prepared by the following method:

[0068] In a flask containing 3 mmol of 4,4'-diaminodiphenylmethane, 20 mL of deionized water and 6 mL of 12 mol / L concentrated hydrochloric acid were added and stirred until the solid completely dissolved, resulting in a powdery white system. The mixture was kept at 0–5 °C in an ice bath. 9 mL of a 1 mol / L sodium nitrite aqueous solution was added dropwise while stirring until the reaction mixture was homogeneous and the system turned yellow. After stirring for 1 hour, while still maintaining the temperature at 0–5 °C, 9 mL of a 1 mol / L sodium azide aqueous solution was added dropwise. The mixture gradually turned pale yellow, with pale yellow powder precipitating and nitrogen gas being released. After the addition of sodium azide, the system was transferred to room temperature for reaction. The reaction process was monitored by spotting on a chromatographic plate. It was found that the reaction was almost complete after stirring for 3 hours, and the starting material spot basically disappeared. The reaction was stopped, and the mixture was allowed to stand for about 12 hours. The precipitate and solution were found to be clear, with the solid located in the upper layer of the system. The mixture was filtered, and the filter cake was washed 2-3 times with deionized water and dried under vacuum at 50°C for 12 hours to obtain a pale yellow powder, which is 4,4'-diazidodiphenylmethane, with a yield of 80.7%.

[0069] The preparation method of the above-mentioned biphenyltetracarboxylic acid diimide yne monomer is the same as that in Example 1.

[0070] Performance testing

[0071] 1. Nuclear magnetic resonance (NMR) test

[0072] Figure 1 It is the 4,4'-diazidodiphenyl sulfone monomer and its raw materials in CDCl3. 1 The ¹H NMR comparison revealed that the -NH₂ peak (corresponding to peak 3) at 3.72 ppm disappeared, while the peaks of H on the benzene ring of the 4,4'-diazidodiphenyl sulfone monomer that are close to the sulfone group and the peaks of H on the benzene ring that are close to the azido group shifted to the lower field. This is because the electron-donating ability of the azido group in the 4,4'-diazidodiphenyl sulfone monomer is less than that of the amino group in the reactant, which causes the chemical shift of H to shift to the lower field. This indicates that sodium azide and 4,4'-diaminodiphenyl sulfone underwent a nucleophilic substitution reaction, thus successfully synthesizing the 4,4'-diazidodiphenyl sulfone monomer.

[0073] Figure 2 It is the 4,4'-diazidodiphenyl ether monomer and its raw materials in CDCl3. 1 The ¹H NMR comparison shows that the -NH₂ peak of the raw material disappears at 6.63 ppm, while the peaks of H atoms near the oxygen atom on the benzene ring of the 4,4'-diazidodiphenyl ether monomer and the peaks of H atoms near the azido group on the benzene ring shift to a lower field. This is because the electron-donating ability of the azido group in the product is less than that of the amino group in the reactant, which causes the chemical shift of H atoms to shift to a lower field. This indicates that sodium azide and 4,4'-diaminodiphenyl ether underwent a nucleophilic substitution reaction, thus successfully preparing the 4,4'-diazidodiphenyl ether monomer.

[0074] Figure 3 It is the 4,4'-diazidobiphenyl monomer and its raw materials in CDCl3. 1 The ¹H NMR comparison diagram shows that the -NH₂ peak at 6.72 ppm disappears from the raw material, while the peaks of H on the benzene ring of the 4,4'-diazidobiphenyl monomer that are close to another benzene ring and the peaks of H on the benzene ring that are close to the azido group shift to a lower field. This is because the electron-donating ability of the azido group in the product is less than that of the amino group in the reactant, causing the chemical shift of H to shift to a lower field. This indicates that sodium azide and 4,4'-diaminobiphenyl underwent a nucleophilic substitution reaction, meaning that the 4,4'-diazidobiphenyl monomer was successfully prepared.

[0075] Figure 4 It is the 4,4'-diaminodiphenylmethane monomer and its raw materials in DMSO. 1 The HNMR comparison shows that the -NH2 peak of the raw material disappears at 4.76 ppm, while the H peaks on the benzene ring of the 4,4'-diaminodiphenylmethane monomer that are close to -CH2 and those that are close to the azido group shift to the lower field. This is because the electron-donating ability of the azido group in the product is less than that of the amino group in the reactant, causing the chemical shift of H to shift to the lower field. This indicates that sodium azide and 4,4'-diaminodiphenylmethane underwent a nucleophilic substitution reaction, thus successfully synthesizing the 4,4'-diazidodiphenylmethane monomer.

[0076] 2. Determination of molecular weight and distribution coefficient

[0077] The molecular weight and distribution coefficient of BPS-PTA, BPE-PTA, BPBP-PTA and BPM-PTA provided in Examples 1 to 4 were determined. The results are shown in Table 1. The number average molecular weight of the four benzylimine aryl polytriazoles is above 18,000, which is beneficial to the improvement of their film-forming processing performance.

[0078] Table 1. Molecular weight and distribution coefficient of BPS-PTA, BPE-PTA, BPBP-PTA and BPM-PTA

[0079] Polytriazoles Mn Mw PDI BPS-PTA 21394 25433 1.19 BPE-PTA 18595 24861 1.34 BPBP-PTA 21639 25006 1.16 BPM-PTA 18970 22798 1.20

[0080] 3. Infrared testing

[0081] Figure 5 These are infrared comparison images of biphenyltetracarboxylic acid diimide yne monomer and its raw materials, from... Figure 5 It can be known that the product is at 3274cm. -1 The appearance of an infrared peak at C≡CH indicates that the biphenyltetracarboxylic acid diimide yne monomer was successfully synthesized.

[0082] 4. Thermal performance test

[0083] The thermal properties of BPS-PTA, BPE-PTA, BPBP-PTA and BPM-PTA in Examples 1 to 4 were tested.

[0084] The differential scanning calorimetry (DSC) test procedure and conditions are as follows: Under a nitrogen atmosphere, the protective gas flow rate is 50 mL / min, the temperature is increased from 50℃ to 200℃ at a heating rate of 20℃ / min, then decreased from 400℃ to 50℃ at a heating rate of 20℃ / min, and finally increased from 50℃ to 400℃ at a heating rate of 10℃ / min. The third heating curve is selected to obtain the DSC spectrum of the sample.

[0085] The thermogravimetric analysis (TGA) test procedure and conditions were as follows: Under a nitrogen atmosphere, the protective gas flow rate was 30 mL / min, the purge gas flow rate was 30 mL / min, and the temperature was increased from 40℃ to 800℃ at a heating rate of 20℃ / min to obtain the thermogravimetric spectrum of the sample.

[0086] Figure 6 The DSC curves for BPS-PTA, BPE-PTA, BPBP-PTA, and BPM-PTA are shown. Figure 7 TGA curves for BPS-PTA, BPE-PTA, BPBP-PTA, and BPM-PTA. Figure 8 DTG curves for BPS-PTA, BPE-PTA, BPBP-PTA, and BPM-PTA.

[0087] according to Figure 6 It is known that the glass transition temperature (Tg) of BPS-PTA is 345.4℃, that of BPE-PTA is 310.5℃, that of BPBP-PTA is 341.2℃, and that of BPM-PTA is 302.6℃. All four biphenylimine aryl polytriazoles have relatively high glass transition temperatures, which means they have good thermal properties. This is due to the extremely rigid biphenyl groups in the dianhydride monomers. In particular, the molecular chain of BPS-PTA contains both rigid biphenyl groups and highly polar sulfone groups, which increases the rigidity of the molecular chain and further inhibits molecular chain movement, thus giving it excellent thermal properties.

[0088] according to Figure 7 It can be seen that all four types of biphenylimine aryl polytriazoles have high initial decomposition temperatures and consistent decomposition trends, with the temperature at which 5% mass decomposition occurs being the same (T). d5％ The temperature at which 10% of the mass decomposes above 480℃ (T) d10％ The residual mass at temperatures above 510°C and 800°C is greater than or equal to 58%, indicating that the benzylimine aryl polytriazole of the present invention has good stability. According to... Figure 8It can be observed that the molecular chains of the four types of benzylimine aryl polytriazole undergo extensive random decomposition at temperatures above 640°C, further demonstrating that the benzylimine aryl polytriazole of the present invention has excellent high-temperature resistance.

[0089] Table 2 Thermal performance test results of BPS-PTA, BPE-PTA, BBPBP-PTA and BPM-PTA

[0090] serial number <![CDATA[T g (℃)]]> <![CDATA[T d5％ (℃)]]> <![CDATA[T dmax (℃)]]> Residue rate at 800℃ (%) Example 1 345.4 534.7 665.1 63.01 Example 2 310.5 531.3 650.3 61.08 Example 3 341.2 480.4 640.1 62.15 Example 4 302.6 481.0 642.6 58.24

[0091] 5. Solubility test

[0092] The solubility of BPS-PTA, BPE-PTA, BPBP-PTA and BPM-PTA in Examples 1 to 4 was tested. The test procedure was as follows: 0.05 g of the test substance was accurately weighed using an electronic balance and added to 5 mL of solvent. The mixture was stirred continuously at room temperature. After a certain period of time, it was allowed to stand until the solid phase was completely precipitated. The upper layer solution was taken for analysis at certain intervals. The test was ended when the concentrations of the two samples were basically the same. The test results are shown in Table 3.

[0093] If there is no residue of the analyte, it is defined as completely dissolved and represented by "+";

[0094] If the residual amount of the analyte is 1% to 90%, it is defined as partially dissolved and represented by "~".

[0095] If the residual amount of the analyte is greater than 90%, it is defined as insoluble and represented by "-".

[0096] If the residual amount of the analyte is greater than 90%, and there is no analyte residue at 100℃, it is defined as completely dissolved upon heating, and is represented as "++".

[0097] As shown in Table 3, BPS-PTA, BPE-PTA, BPBP-PTA and BPM-PTA all exhibit good solubility in strongly polar aprotic solvents after heating.

[0098] Table 3 Solubility properties of BPS-PTA, BPE-PTA, BBP-PTA and BPM-PTA

[0099] solvent BPS-PTA BPE-PTA BPBP-PTA BPM-PTA THF ++ ++ ++ ++ DMSO ++ ++ ++ ++ DMF ～ ～ ～ ～ DMAc ～ ～ ～ ～ <![CDATA[CH2Cl2]]> - - - - Acetone ++ ++ ++ ++ Ethanol - - - -

[0100] 6. Film-forming property test

[0101] BPS-PTA, BPE-PTA, BPBP-PTA, and BPM-PTA from Examples 1-4 were respectively mixed with anhydrous DMAC at a solid content of 15% to form polymer solutions. The polymer solutions were then spread onto the surface of a clean glass plate using a casting method to form a film with a thickness of about 50 μm. The film was placed in a vacuum oven and heated according to the program of 80℃-2 hours → 120℃-2 hours → 160℃-2 hours → 200℃-2 hours. After the oven power was turned off, the oven temperature was allowed to drop to room temperature. The glass plate was then placed in hot water to remove the film, and the film was placed in a 100℃ ordinary oven to dry the moisture, thus obtaining BPS-PTA, BPE-PTA, BPBP-PTA, and BPM-PTA films. All four polymer films were intact and without cracks, which fully demonstrates that the biphenylimine aryl polytriazole of the present invention has good film-forming properties.

[0102] The above embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the implementation of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all possible implementations here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A biphenylimine aryl polytriazole, characterized by, It has the structure shown in equation (I): Wherein, R in equation (I) above is any one of them; The number-average molecular weight of the biphenylimine aryl polytriazole is 18,000 to 22,000.

2. The benzylimine aryl polytriazole according to claim 1, characterized in that, The R is 3. The benzylimine aryl polytriazole according to claim 1, characterized in that, The glass transition temperature of the biphenylimine aryl polytriazole is ≥300℃.

4. The benzylimine aryl polytriazole according to claim 3, characterized in that, The glass transition temperature of the biphenylimine aryl polytriazole is 302–346 °C.

5. A method for preparing the benzylimine aryl polytriazole according to any one of claims 1 to 4, characterized in that, Includes the following steps: The biphenyltetracarboxylic acid diimide yne monomer shown in formula (II), the biphenyltetracarboxylic acid diimide yne monomer shown in formula (III), and the polymerization catalyst are subjected to a click polymerization reaction to obtain biphenylimide aryl polytriazole. N3-R-N3 Equation (II); Wherein, R in equation (II) above is Any one of them.

6. The preparation method according to claim 5, characterized in that, The temperature of the click polymerization reaction is 50–60°C.

7. The preparation method according to claim 5, characterized in that, The molar ratio of the di-terminal azide monomer to the biphenyltetracarboxylic acid diimide yne monomer is 1:(0.8-1.2).

8. The preparation method according to claim 5, characterized in that, The polymerization catalyst is a monovalent copper salt catalyst, and its molar ratio with the di-terminated azide monomer is (1-3):

50.

9. The use of the biphenylimine aryl polytriazole according to any one of claims 1 to 4 in the preparation of high-temperature resistant thin film products or high-temperature resistant coatings.

10. A thin film, characterized in that, It is prepared from the biphenylimine aryl polytriazole according to any one of claims 1 to 4.

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