An aromatic ether imide polytriazole, and a preparation method and application thereof

Abstract

The present application relates to a kind of aryl ether imide polytriazole and its preparation method and application.The aryl ether imide polytriazole of the present application has the structure shown as follows:Wherein, R is any one in the, the weight average molecular weight of the aryl ether imide polytriazole is 20000-26000.The aryl ether imide polytriazole of the present application is not only with good heat resistance, but also can be dissolved in a variety of different organic solvents, significantly improve its processing performance.

Description

Technical Field

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

[0002] Polyimide is widely used in electronics, aerospace, automotive, and chemical machinery due to its good thermal stability, excellent mechanical properties, good dimensional stability, and high chemical stability. However, most polyimide resins have strong intramolecular and intermolecular interactions, making them difficult to melt or dissolve and thus difficult to meet the processing requirements of thin-walled products or films. To improve the processing and molding properties of polyimide, a polyetherimide and its preparation method are disclosed in the prior art. The method uses a mixture of three dihalogen monomers (dichloro-substituted naphthylimide monomer, difluorinated benzoimide monomer, and chloronaphthylfluorophenylimide monomer) as raw materials and reacts with a bisphenol monomer through a nucleophilic substitution method to prepare polyetherimide. The dichloro-substituted naphthylimide monomer and the difluorinated benzoimide monomer work together to improve the heat resistance of polyetherimide (glass transition temperature reaches 270-400℃), and the combination with the chloronaphthylfluorophenylimide monomer results in the simultaneous presence of three structural units in the molecule, thereby improving the melt processing properties of polyetherimide to a certain extent. However, its dissolution processing properties are not significantly improved, making it unsuitable for the preparation of high-temperature resistant films or high-temperature resistant coatings. Summary of the Invention

[0003] The purpose of this invention is to overcome the defects or deficiencies of existing polyetherimides with poor solubility and processing performance, and to provide an aryl etherimide polytriazole.

[0004] Another object of the present invention is to provide a method for preparing the above-mentioned aryl ether imide polytriazole.

[0005] Another object of the present invention is to provide an application of the above-mentioned aryl ether imide polytriazole in the preparation of high-temperature resistant films or high-temperature resistant coatings.

[0006] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0007] This invention protects an aryl ether imide polytriazole, the structure of which is shown in formula (I):

[0008]

[0009] Where R is Any one of the following; the weight-average molecular weight of the aryl ether imide polytriazole is 20,000 to 26,000; n is an integer from 26 to 34.

[0010] The aryl ether imide polytriazole of the present invention contains a large number of rigid benzene rings and triazole rings in its molecular chain, which can effectively restrict the movement of polymer chain segments, thereby improving the glass transition temperature and thermal stability of the polymer; while the flexible bonds connecting the benzene rings make the molecular chain stacking relatively loose, allowing the solvent to effectively penetrate into the molecular chain to improve the solubility of the polymer.

[0011] Optionally, the weight-average molecular weight (Mw) of the above-mentioned aryl ether imide polytriazole can be 20351, 20500, 20921, 21000, 21500, 22000, 22500, 23000, 23500, 23857, 24000, 24500, 25000 or 25345.

[0012] The glass transition temperature (Tg) of the aryl ether imide polytriazole of this invention is 305–325 °C. d5％ Reaching 542℃ or higher and T dmax It has a maximum thermal decomposition temperature of over 542°C in nitrogen and is soluble in common organic solvents (DMSO, DMF, DMAc or Acetone), thus possessing good heat resistance and excellent processability.

[0013] Compared to ether bonds or methylene bonds, sulfoxide bonds have a certain degree of rigidity, which can better improve the thermal stability of aryl etherimide polytriazole while maintaining its good solubility. Therefore, R is preferably...

[0014] Optionally, the number average molecular weight (Mn) of the aryl ether imide polytriazole is 15,000 to 21,000, specifically 15361, 15500, 16000, 16500, 17000, 17256, 17500, 18000, 18500, 19124, 19500, 20000 or 20236.

[0015] The weight-average molecular weight (Mw) or number-average molecular weight (Mn) of the above-mentioned aryl ether imide polytriazole can be determined by gel permeation chromatography (GPC).

[0016] Optionally, the molecular weight distribution coefficient (PDI) of the aryl ether imide polytriazole is 1.2 to 1.35; specifically, it can be 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, 1.31, 1.32, 1.33, or 1.34. The molecular weight distribution coefficient (mw / Mn) is usually expressed as Mw / Mn and is a parameter used to characterize the width of the polymer's molecular weight distribution. It reflects the uniformity of the polymer's molecular weight. When the molecular weight distribution coefficient is close to 1, it indicates a narrow molecular weight distribution, meaning the polymer's molecular weight is relatively uniform; while when the molecular weight distribution coefficient is far from 1, it indicates a wide molecular weight distribution, meaning the polymer's molecular weight is not uniform.

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

[0018] By clicking polymerization of the di-terminal azide monomer as shown in formula (II) and the bisphenol A type diether diimide yne monomer as shown in formula (III), aryl ether imide polytriazole is obtained.

[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 click polymerization reaction is carried out at a temperature of 100–110°C and for a time of 6–10 h; specifically, the reaction temperature can be 100°C, 105°C, or 110°C, and the reaction time can be 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, or 9.5 h. The catalyst for the click polymerization reaction is a monovalent copper salt catalyst, preferably cuprous chloride or cuprous iodide, with a molar ratio of (0.5–1.5):10 to the di-terminated azide monomer.

[0028] Optionally, the molar ratio of the di-terminal azide monomer to the bisphenol A type diether diimide yne monomer is 1:(0.8-1.2), specifically 1:0.9, 1:1 or 1:1.1.

[0029] Specifically, the bisphenol A type diether diimide yne monomer shown in formula (III) can be purchased or prepared by reacting bisphenol A type diether dianhydride with 3-aminophenylacetylene; wherein the reaction temperature is 0-5℃ and the time is 3-8h.

[0030] Optionally, the molar ratio of the bisphenol A type diether dianhydride to 3-aminophenylacetylene is 1:(1.5-2.5), specifically 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3 or 1:2.4.

[0031] The application of the above-mentioned aryl ether imide polytriazole in the preparation of high-temperature resistant films or high-temperature resistant coatings is also within the scope of protection of this invention.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The aryl ether imide polytriazole of the present invention has good heat resistance and can be dissolved in a variety of different organic solvents, which significantly improves its processing and molding performance. It can be used to prepare high-temperature resistant films or high-temperature resistant coatings. Attached Figure Description

[0034] Figure 1 It is a bisphenol A type diether diimide yne monomer and its raw materials in CDCl3. 1 H NMR comparison image.

[0035] Figure 2 This is an FT-IR comparison chart of BAS-PTA and its raw materials.

[0036] Figure 3 This is an FT-IR comparison chart of BAE-PTA and its raw materials.

[0037] Figure 4 This is an FT-IR comparison chart of BABP-PTA and its raw materials.

[0038] Figure 5 This is an FT-IR comparison chart of BAM-PTA and its raw materials.

[0039] Figure 6 These are the DSC curves for BAS-PTA, BAE-PTA, BABP-PTA, and BAM-PTA.

[0040] Figure 7 These are TGA diagrams for BAS-PTA, BAE-PTA, BABP-PTA, and BAM-PTA.

[0041] Figure 8 These are DTG diagrams for BAS-PTA, BAE-PTA, BABP-PTA, and BAM-PTA. Detailed Implementation

[0042] 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.

[0043] Example 1

[0044] An aryl ether imide polytriazole (denoted as BAS-PTA) can be prepared by the following process:

[0045] Add 3 mmol of 4,4'-diphenyl sulfone azido and 3 mmol of bisphenol A type diether diimide yne to a 50 mL flask, and add a DMF / toluene mixed solvent (v:v = 1:1) to make the solid content of the reaction system 70%. After dissolution, add 0.3 mmol of cuprous iodide and 3 mmol of triethylamine. Then, under a nitrogen atmosphere, reflux at 100 °C for 6 h. After the reaction is completed, remove the solvent by vacuum distillation, and dry the product under vacuum to obtain BAS-PTA.

[0046] The above-mentioned bisphenol A type diether diimide yne can be prepared by the following method:

[0047] Under a nitrogen atmosphere, 10 mmol of bisphenol A type diether dianhydride was dissolved in 32 mL of anhydrous DMAC. 20 mmol of 3-aminophenylacetylene was slowly injected into 2.25 mL of the solution using a syringe. After stirring at 0–5 °C for 4 h, triethylamine and acetic anhydride were slowly added dropwise using a constant pressure dropping funnel and the reaction was allowed to proceed overnight (12 h). The reaction solution was poured into deionized water to precipitate the precipitate, which was then filtered with ethanol and dried in a vacuum oven at 80 °C for 10 h to obtain the product, bisphenol A type diether diimide dianhydride monomer.

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

[0049] In a container containing 3 mmol In a flask containing 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 controlled at 0–5 °C under an ice bath. 9 mL of a 1 mol / L sodium nitrite aqueous solution was added dropwise. The solution turned from white to pale yellow. The reaction mixture was stirred until homogeneous. After stirring for 1 hour, the temperature was still controlled at 0–5 °C. 9 mL of a 1 mol / L sodium azide aqueous solution was added dropwise. The system gradually turned pale yellow, a pale yellow precipitate formed, and nitrogen gas was released. A layer of pale yellow foam floated on top of the system. After the addition was complete, the reaction continued at 0–5 °C. The reaction was tracked by spot chromatography. It was found that the reaction was almost complete after 4 hours of stirring, 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. 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'-diazidodiphenyl sulfone.

[0050] Example 2

[0051] An aryl ether imide polytriazole (denoted as BAE-PTA) can be prepared by the following process:

[0052] Add 3 mmol of 4,4'-diazidodiphenyl ether and 3 mmol of bisphenol A type diether diimide yne to a 50 mL flask, and add a DMF / toluene mixed solvent (v:v = 1:1) to make the solid content of the reaction system 70%. After dissolution, add 0.3 mmol of cuprous iodide and 3 mmol of triethylamine. Then, under a nitrogen atmosphere, reflux at 100 °C for 6 h. After the reaction is completed, remove the solvent by vacuum distillation, and dry the product under vacuum to obtain BAE-PTA.

[0053] The preparation method of the above-mentioned bisphenol A type diether diimide yne is the same as that in Example 1.

[0054] The above-mentioned 4,4'-diazidodiphenyl ether can be prepared by the following method:

[0055] In a container containing 3 mmol In a flask containing 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 was pale yellow. After stirring for 1 hour, the temperature was maintained at 0–5 °C, and 9 mL of a 1 mol / L sodium azide aqueous solution was added dropwise. The system gradually turned pale yellow, with a pale yellow powder precipitating and nitrogen gas being released. After the sodium azide addition was complete, the system was transferred to room temperature for further reaction. Chromatography was used to monitor the reaction process. After stirring for 3 hours, the reaction was almost complete, and the starting material spot essentially disappeared. The reaction was stopped, and the mixture was allowed to stand for approximately 12 hours. The precipitate was found to be clearly separated from the solution, with the solid at the top. 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'-diazidodiphenyl ether.

[0056] Example 3

[0057] An aryl ether imide polytriazole (denoted as BABP-PTA) can be prepared by the following process:

[0058] Add 3 mmol of 4,4'-diazidobiphenyl and 3 mmol of bisphenol A type diether diimide yne to a 50 mL flask, and add a DMF / toluene mixed solvent (v:v = 1:1) to make the solid content of the reaction system 70%. After dissolution, add 0.3 mmol of cuprous iodide and 3 mmol of triethylamine. Then, under a nitrogen atmosphere, reflux at 100 °C for 6 h. After the reaction is completed, remove the solvent by vacuum distillation, and dry the product under vacuum to obtain BABP-PTA.

[0059] The preparation method of the above-mentioned bisphenol A type diether diimide yne is the same as that in Example 1.

[0060] The above-mentioned 4,4'-diazidobiphenyl can be prepared by the following method:

[0061] 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. The reaction mixture remained homogeneous and the system turned yellow. After stirring for 1 hour, the temperature was maintained at 0–5 °C, and 9 mL of 1 mol / L sodium azide aqueous solution was added dropwise. The system gradually turned pale yellow, with a pale yellow powder precipitating and nitrogen gas being released. After the sodium azide addition was complete, the system was transferred to room temperature for further reaction. Chromatography was used to monitor the reaction process. After stirring for 3 hours, the reaction was almost complete, and the starting material spot essentially disappeared. The reaction was stopped, and the mixture was allowed to stand for approximately 12 hours. The precipitate was found to be clearly separated from the solution, with the solid in the upper layer. 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'-diaminobiphenyl.

[0062] Example 4

[0063] An aryl ether imide polytriazole (denoted as BAM-PTA) is prepared by the following process:

[0064] Add 3 mmol of 4,4'-diazidodiphenylmethane and 3 mmol of bisphenol A type diether diimide yne to a 50 mL flask, and add a DMF / toluene mixed solvent (v:v = 1:1) to make the solid content of the reaction system 70%. After dissolution, add 0.3 mmol of cuprous iodide and 3 mmol of triethylamine. Then, under a nitrogen atmosphere, reflux at 100 °C for 6 h. After the reaction is completed, remove the solvent by vacuum distillation, and dry the product under vacuum to obtain BAM-PTA.

[0065] The preparation method of the above-mentioned bisphenol A type diether diimide yne is the same as that in Example 1.

[0066] The above-mentioned 4,4'-diazidodiphenylmethane can be prepared by the following method:

[0067] In a container containing 3 mmol In a flask containing 4,4'-diaminodiphenylmethane, 20 mL of deionized water and 6 mL of concentrated hydrochloric acid (12 mol / L) 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, the temperature was maintained at 0–5 °C, and 9 mL of a 1 mol / L sodium azide aqueous solution was added dropwise. The system gradually turned pale yellow, with a pale yellow powder precipitating and nitrogen gas being released. After the sodium azide addition was complete, the system was transferred to room temperature for further reaction. Chromatography was used to monitor the reaction process. After stirring for 3 hours, the reaction was almost complete, and the starting material spot essentially disappeared. The reaction was stopped, and the mixture was allowed to stand for approximately 12 hours. The precipitate was found to be clearly separated from the solution, with the solid at the top. 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'-diazidodiphenylmethane.

[0068] Performance testing

[0069] (1) Nuclear magnetic resonance test

[0070] Examples 1-4 show the bisphenol A type diether diimide yne monomer and its raw materials in CDCl3. 1 H NMR comparison image as follows Figure 1 As shown. By Figure 1 It is known that the bisphenol A type diether diimide yne of the present invention exhibits a chemical shift of alkynyl hydrogen at 3.11 ppm and a chemical shift of methylene hydrogen on 3-aminophenylacetylene at 7.42 ppm (corresponding to peak 3). At the same time, it was found that the hydrogen at 3.71 ppm on 3-aminophenylacetylene-NH2 disappeared, indicating that the bisphenol A type diether dianhydride reacted with 3-aminophenylacetylene, and the bisphenol A type diether diimide yne monomer was successfully prepared.

[0071] (2) Infrared testing

[0072] The FT-IR comparison diagrams of BAS-PTA and its raw materials in Example 1 are as follows: Figure 2 As shown, where a is BADIA (bisphenol A type diether diimide yne), b is DAS (3-aminophenylacetylene), and c is BAS-PTA; Figure 2 It can be seen that the raw material contains 3274cm -1 and 2117cm -1 The absorption peaks of C≡CH and -N3 completely disappear in BAS-PTA; the polytriazole infrared spectrum is at 3070 cm⁻¹. -1 The presence of a characteristic absorption peak of CH on the triazole ring indicates that the addition cyclization of the alkynyl group and the azide group is complete, and the aryl ether imide polytriazole BAS-PTA is successfully prepared.

[0073] The FT-IR comparison diagrams of BAE-PTA and its raw materials in Example 2 are as follows: Figure 3 As shown, where a is BADIA (bisphenol A type diether diimide ykyne), b is DAE (4,4'-diazidodiphenyl ether), and c is BAE-PTA; Figure 3 It can be found that 3274cm in the raw material -1 and 2113cm -1 The absorption peaks of C≡CH and -N3 completely disappear in BAE-PTA; the polytriazole infrared spectrum is at 3064 cm⁻¹. -1 The presence of a characteristic absorption peak of CH on the triazole ring indicates that the addition cyclization of the alkynyl group and the azide group is complete, and the aryl ether imide polytriazole BAE-PTA is successfully prepared.

[0074] The FT-IR comparison diagrams of BABP-PTA and its raw materials in Example 3 are as follows: Figure 4 As shown, where a is BADIA (bisphenol A type diether diimide ykyne), b is DABP (4,4'-diazidobiphenyl), and c is BABP-PTA; Figure 4 It can be seen that 3271cm in the raw material -1 and 2088cm -1 The absorption peaks of C≡CH and -N3 completely disappear in BABP-PTA; the polytriazole infrared spectrum is at 3069 cm⁻¹. -1 The presence of a characteristic absorption peak of CH on the triazole ring indicates that the addition cyclization of the alkynyl group and the azide group is complete, and the aryl ether imide polytriazole BABP-PTA is successfully prepared.

[0075] The FT-IR comparison diagrams of BAM-PTA and its raw materials in Example 4 are as follows: Figure 5 As shown, b is BADIA (bisphenol A type diether diimide yne), a is DAM (4,4'-diazidodiphenylmethane), and c is BAM-PTA; Figure 5 It can be seen that the raw material contains 3274cm -1 and 2103cm -1 The absorption peaks of C≡CH and -N3 completely disappear in BAM-PTA; the polytriazole infrared spectrum is at 3068 cm⁻¹. -1 The presence of a characteristic absorption peak of CH on the triazole ring indicates that the addition cyclization of the alkynyl group and the azide group is complete, and the aryl ether imide polytriazole BAM-PTA is successfully prepared.

[0076] (3) Determination of molecular weight and distribution coefficient

[0077] The molecular weight and distribution coefficient of BAS-PTA, BAE-PTA, BABP-PTA and BAM-PTA provided in Examples 1 to 4 were determined, and the results are shown in Table 1.

[0078] Table 1. Molecular weight and distribution coefficient of BAS-PTA, BAE-PTA, BABP-PTA and BAM-PTA

[0079] Polytriazoles Mn Mw PDI BAS-PTA 15361 20351 1.32 BAE-PTA 19124 23857 1.25 BABP-PTA 17256 20921 1.21 BAM-PTA 20236 25348 1.25

[0080] (4) Thermal performance test

[0081] The thermal properties of BAS-PTA, BAE-PTA, BABP-PTA and BAM-PTA in Examples 1 to 4 were tested.

[0082] The differential scanning calorimetry (DSC) procedure and conditions are as follows: Under a nitrogen atmosphere, with a protective gas flow rate of 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 sample DSC spectrum. The thermogravimetric analysis (TGA) procedure and conditions are as follows: Under a nitrogen atmosphere, with a protective gas flow rate of 30 mL / min and a purge gas flow rate of 30 mL / min, the temperature is increased from 40℃ to 800℃ at a heating rate of 20℃ / min to obtain the sample thermogravimetric spectrum.

[0083] Figure 6 The DSC curves for BAS-PTA, BAE-PTA, BABP-PTA, and BAM-PTA are shown. Figure 7 TGA diagrams for BAS-PTA, BAE-PTA, BABP-PTA, and BAM-PTA. Figure 8 Table 2 shows the DTG diagrams for BAS-PTA, BAE-PTA, BABP-PTA, and BAM-PTA, and the thermal performance test results for BAS-PTA, BAE-PTA, BABP-PTA, and BAM-PTA.

[0084] according to Figure 6 It is known that the glass transition temperature (Tg) of BAS-PTA is 324℃, that of BAE-PTA is 307℃, that of BABP-PTA is 312℃, and that of BAM-PTA is 305℃. The difference in Tg is mainly influenced by the molecular chain structure. All four polymers exhibit good thermal stability, but BAS-PTA, due to its relatively rigid sulfoxide groups, has a higher Tg and the best thermal performance because its molecular chain segments are more difficult to move at high temperatures. Figure 7 It can be seen that the thermal decomposition curves of the four aryl ether imide polytriazoles are basically the same, and the temperature (T) corresponding to 5% decomposition by mass is also consistent. d5％ All are above 429℃, the temperature corresponding to 10% mass decomposition (T) d10％All values ​​were above 540℃, and the residual mass at 800℃ was greater than 48%, indicating that the aryl ether imide polytriazole of the present invention has good stability; according to Figure 8 It was found that the thermal weight loss rates of the four aryl ether imide polytriazoles all reached their maximum at around 550℃, indicating structural stability. In summary, the aryl ether imide polytriazoles of this invention exhibit excellent high-temperature resistance.

[0085] Table 2 Thermal performance test results of BAS-PTA, BAE-PTA, BABP-PTA and BAM-PTA

[0086] serial number <![CDATA[T g (℃)]]> <![CDATA[T d5％ (℃)]]> <![CDATA[T dmax (℃)]]> Residue rate at 800℃ (%) Example 1 324.0 447.1 550.1 51.27 Example 2 307.0 429.8 560.4 48.81 Example 3 312.0 438.5 542.5 51.25 Example 4 305.0 430.4 552.2 51.81

[0087] (5) Solubility test

[0088] The solubility of bisphenol A type diether diimide yne (BADIA) and BAS-PTA, BAE-PTA, BABP-PTA and BAM-PTA from Examples 1 to 4 were 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.

[0089] If there is no residue of the analyte, it is defined as completely dissolved and represented by "+";

[0090] If the residual amount of the analyte is 1% to 90%, it is defined as partially dissolved and represented by "~".

[0091] If the residual amount of the analyte is greater than 90%, it is defined as insoluble and represented by "-".

[0092] 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 "++".

[0093] According to the data in Table 3, it can be seen that the monomer BADIA has a certain rigidity and is soluble in most strongly polar solvents; BAS-PTA, BAE-PTA, BABP-PTA and BAM-PTA have good solubility in strongly polar aprotic solvents and have good processing performance.

[0094] Table 3. Solubility test results of BADIA, BAS-PTA, BAE-PTA, BABP-PTA and BAM-PTA

[0095] solvent BADIA BAS-PTA BAE-PTA BABP-PTA BAM-PTA THF - - - - - DMSO ++ + + + + DMF + + + + + DMAc + + + + + <![CDATA[CH2Cl2]]> - - - - - Acetone ++ ++ ++ ++ ++ Ethanol - - - - -

[0096] 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. An aryl ether imide polytriazole, characterized in that, It has the structure shown in equation (I): Wherein, R in equation (I) above is any one of them; The weight-average molecular weight of the aryl ether imide polytriazole is 20,000 to 26,000.

2. The aryl ether imide polytriazole according to claim 1, characterized in that, The R is 3. The aryl ether imide polytriazole according to claim 1, characterized in that, The molecular weight distribution coefficient of the aryl ether imide polytriazole is 1.2 to 1.

35.

4. A method for preparing the aryl ether imide polytriazole according to any one of claims 1 to 3, characterized in that, Includes the following steps: By clicking polymerization of the di-terminal azide monomer as shown in formula (II) and the bisphenol A type diether diimide yne monomer as shown in formula (III), aryl ether imide polytriazole is obtained. N3-R-N3 Equation (II); Wherein, R in equation (II) above is Any one of them.

5. The method for preparing aryl ether imide polytriazole according to claim 4, characterized in that, The temperature of the click polymerization reaction is 100–110°C.

6. The method for preparing aryl ether imide polytriazole according to claim 4, characterized in that, The molar ratio of the di-terminal azide monomer to the bisphenol A type diether diimide yne monomer is 1:(0.8-1.2).

7. The method for preparing aryl ether imide polytriazole according to claim 4, characterized in that, The bisphenol A type diether diimide yne monomer is prepared by reacting bisphenol A type diether dianhydride with 3-aminophenylacetylene.

8. The method for preparing aryl ether imide polytriazole according to claim 7, characterized in that, The reaction is carried out at a temperature of 0–5°C for 3–8 hours.

9. The method for preparing aryl ether imide polytriazole according to claim 7, characterized in that, The molar ratio of bisphenol A type diether dianhydride to 3-aminophenylacetylene is 1:(1.5-2.5).

10. The use of the aryl ether imide polytriazole according to any one of claims 1 to 3 in the preparation of high-temperature resistant films or high-temperature resistant coatings.

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