Perfluorocyclobutyl polyethersulfone polymer and preparation method thereof

Abstract

The invention discloses a perfluorocyclobutyl polyether sulfone polymer and a preparation method thereof. Specifically, the invention provides a copolymer A and a polymer B prepared by taking the copolymer A as an intermediate, and the copolymer A comprises a repeating unit I and a repeating unit II. The polymer disclosed by the invention has excellent solubility, optical performance, thermal stability or processability and the like.

Description

Technical Field

[0001] This invention belongs to the field of fluorine-containing polymer materials, specifically relating to a perfluorocyclobutyl polyethersulfone polymer and its preparation method. Background Technology

[0002] Polyethersulfone (PES) is a thermoplastic polymer material and one of the few special engineering plastics that are widely used. It has excellent properties: (1) Excellent heat resistance: the long-term operating temperature can reach 180℃, and it can withstand higher temperatures in the short term. It has a high heat distortion temperature and maintains stable performance in a wide temperature range (-100~200℃); (2) Excellent physical and mechanical properties: it has outstanding creep resistance and dimensional stability and can maintain high strength at high temperatures; (3) Excellent insulation properties: its dielectric properties are stable at high frequencies, making it suitable for the electronic and electrical fields; (4) Excellent chemical corrosion resistance: it has strong resistance to strong acids, strong alkalis, organic solvents (such as alcohols and aromatic hydrocarbons) and halogen compounds; (5) Good biocompatibility: it meets medical grade standards (ISO10993) and is suitable for medical devices such as hemodialysis membranes and artificial lungs. Due to these superior properties, polyethersulfone has been widely used in the medical, electronics, automotive and aerospace, water treatment, and food industries. However, while polyethersulfone boasts excellent performance and a wide range of applications, its limitations cannot be ignored: (1) Poor UV resistance: The performance of ether sulfone may be affected by long-term exposure to ultraviolet light, which limits its application in environments that require long-term exposure to the outdoors or strong ultraviolet light. (2) Limited resistance to organic solvents: Although polyethersulfone has good corrosion resistance to most inorganic substances such as acids, alkalis, and salts, it has poor resistance to highly polar organic solvents such as ketones, esters, halogenated hydrocarbons, and dimethyl sulfoxide. At high temperatures, these organic solvents may cause stress cracking in polyethersulfone, thus affecting its performance. (3) Relatively high water absorption: Polyethersulfone has a higher water absorption rate than some other polymer materials. This means that in a humid environment, polyethersulfone products may absorb a certain amount of moisture, which will affect their dimensional stability and mechanical properties. Therefore, polyethersulfone usually needs to be thoroughly dried before molding. (4) Notch sensitivity: Polyethersulfone has high impact strength when unnotched, but when notched, the notch radius has a significant impact on its impact strength. The smaller the notch radius, the lower the impact strength. This requires special attention to avoid sharp cuts or notches when designing polyethersulfone products; (5) High processing temperature: Polyethersulfone has a high melt processing temperature range. Due to the rigidity of the molecular chain, it requires high temperature (300-350℃) and high pressure molding, which requires the processing equipment to have high heating capacity and temperature control accuracy. At the same time, high-temperature processing also increases energy consumption and production costs; (6) High cost: As a special engineering plastic, polyethersulfone is relatively expensive, which may limit its application in some cost-sensitive fields.

[0003] Therefore, improving the properties of polyethersulfone polymers while reducing the difficulty of their synthesis, improving their processing conditions, and expanding their application areas are problems that need to be solved for this type of polymer. Summary of the Invention

[0004] The technical problem this invention aims to solve is that existing defective polyethersulfone polymers suffer from poor performance and high synthesis difficulty. This invention provides a perfluorocyclobutyl polyethersulfone polymer and its preparation method. This type of polymer exhibits excellent solubility, optical properties, thermal stability, and processability.

[0005] The present invention solves the above-mentioned technical problems through the following technical solution: This invention provides a copolymer A, which includes repeating unit I and repeating unit II. and , R 1 It is phenylene, naphthylene, , , or ;Y 1 It can be NH, O, or S; R a and R b Independently for H and C 1-4 Alkyl or C 1-4 Halogenated alkyl groups.

[0006] In one of the schemes, R a and R b It can be H, methyl, or CF3 independently.

[0007] In one of the schemes, R 1 for , , , , , , , or .

[0008] In one embodiment, the Tg of copolymer A is 100℃-170℃, preferably 110℃-160℃, and more preferably 128.57±2℃, 132.35±2℃, 140.51±2℃ or 142.63±2℃.

[0009] In one embodiment, copolymer A loses 1% of its weight at 410°C-435°C.

[0010] In one embodiment, copolymer A loses 5% of its weight at 465°C-485°C.

[0011] In one embodiment, copolymer A loses 10% of its weight at 486°C-505°C.

[0012] In one embodiment, copolymer A is a random copolymer.

[0013] In one embodiment, copolymer A is prepared by the following method, wherein the preparation method of copolymer A includes step III: Step III: Under solvent-free conditions, the compound shown in Formula M1 and the compound shown in Formula M2 undergo a cyclization polymerization reaction to obtain the copolymer A. , , R 1 The definition is as described in the previous scheme.

[0014] In the preparation method of copolymer A, the reaction conditions and reagent dosages are conventional conditions and dosages for this type of reaction in the art, and the present invention preferably includes the following.

[0015] In one embodiment, the cyclization polymerization reaction is carried out under an inert atmosphere, preferably a nitrogen atmosphere.

[0016] In one embodiment, the organic solvent is selected from phenyl ether organic solvents, preferably diphenyl ether.

[0017] In one embodiment, the ratio of the molar number of the compound represented by formula M1 to the volume of the organic solvent is (0.1-10) mmol:1mL, preferably (0.1-5) mmol:1mL, more preferably (0.7-0.9) mmol:1mL, (0.9-1.1) mmol:1mL, (1.1-1.3) mmol:1mL, (1.3-1.4) mmol:1mL, or (1.5-1.7) mmol:1mL, and even more preferably 0.8 mmol:1mL, 1 mmol:1mL, 1.2 mmol:1mL, 1.4 mmol:1mL, or 1.6 mmol:1mL.

[0018] In one embodiment, the molar ratio of the compound represented by formula M2 to the compound represented by formula M1 is (0.01-99):1, preferably (0.1-5):1, more preferably (0.1-2):1, and even more preferably (0.2-0.3):1, (0.3-0.5):1, (0.6-0.8):1, (0.9-1.1):1 or (1.4-1.6):1, for example 0.25:1, 0.4:1, 0.7:1, 1:1 or 1.5:1.

[0019] In one embodiment, the molar amount of the compound represented by formula M1 is 1-20 mmol, preferably 8 mmol, 10 mmol, 12 mmol, 14 mmol or 16 mmol.

[0020] In one embodiment, the temperature of the cyclization polymerization reaction is 100-300℃; preferably 150-250℃; more preferably 180-240℃, and even more preferably 190℃, 200℃, 210℃ or 220℃.

[0021] The cyclization polymerization reaction is monitored using conventional monitoring methods for such reactions in the art (e.g., TLC), with the reaction ending when the compound represented by Formula M1 disappears or ceases to decrease. In one embodiment, the polymerization reaction takes 5-30 hours, for example, 14, 15, 16, or 24 hours.

[0022] The cyclization polymerization reaction is followed by post-treatment conventional to such reactions in the art. In one embodiment, the post-treatment includes the following steps: removing the organic solvent (e.g., soaking in n-hexane to remove the phenyl ether organic solvent) and drying.

[0023] In one of the schemes, R 1 for .

[0024] In one embodiment, copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 128.57±2℃; (2) The copolymer A loses 1% of its weight at 423.2±2℃; 5% of its weight at 473.5±2℃; and 10% of its weight at 489.1±2℃. (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (0.9-1.1):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.9-1.1) mmol:1mL. Preferably, the number of moles of the compound shown in formula M1 is 10 mmol.

[0025] In one embodiment, copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 140.51±2℃; (2) The copolymer A loses 1% of its weight at 428.5±2℃, 5% of its weight at 478.9±2℃, and 10% of its weight at 494.6±2℃; (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (0.3-0.5):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (1.3-1.5) mmol:1mL. Preferably, the number of moles of the compound shown in formula M1 is 14 mmol.

[0026] In one embodiment, copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 142.63±2℃; (2) The copolymer A loses 1% of its weight at 414.2±2℃, 5% of its weight at 482.4±2℃, and 10% of its weight at 499.6±2℃; (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (0.2-0.3):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (1.5-1.7) mmol:1mL. Preferably, the number of moles of the compound shown in formula M1 is 16 mmol.

[0027] In one embodiment, copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 132.35±2℃; (2) The copolymer A loses 1% of its weight at 411.9±2℃, 5% of its weight at 477.5±2℃, and 10% of its weight at 493.6±2℃; (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (0.6-0.8):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (1.1-1.3) mmol:1mL. Preferably, the number of moles of the compound shown in formula M1 is 12mmol.

[0028] In one embodiment, copolymer A satisfies the following condition: The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (1.4-1.6):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.7-0.9) mmol:1mL. Preferably, the number of moles of the compound shown in formula M1 is 8 mmol.

[0029] Secondly, the present invention provides a method for preparing copolymer A according to any embodiment, comprising the following step III: Step III: Under solvent-free conditions, the compound shown in Formula M1 and the compound shown in Formula M2 undergo a cyclization polymerization reaction to obtain the copolymer A. , , R 1 The definition is as described in the previous scheme. The preparation method and conditions of the copolymer A can be as described in any embodiment of the present invention.

[0030] Thirdly, the present invention provides a polymer B, which is prepared by the following method, the preparation method comprising the following steps (IV): Step (IV): In an organic solvent or under solvent-free conditions, copolymer A (or copolymer described in the sixth aspect) and a compound as shown in formula III-A are subjected to a cyclization reaction to obtain polymer B; R 2 for , , , , or .

[0031] In one of the schemes, R 2 for .

[0032] In one embodiment, the T of polymer B g The temperature is 120-130℃, for example, 125.63±2℃.

[0033] In one embodiment, polymer B loses 1% of its weight in the range of 440°C to 450°C, for example, 445.1 ± 2°C.

[0034] In one embodiment, polymer B loses 5% of its weight in the range of 465°C to 485°C, for example, at 475.6 ± 2°C.

[0035] In one embodiment, polymer B loses 10% of its weight in the range of 480℃-500℃, for example, 489.2±2℃.

[0036] In the preparation method of polymer B, the reaction conditions and reagent dosages are conventional conditions and dosages for this type of reaction in the art, and the present invention preferably includes the following.

[0037] In one embodiment, in step (IV), the organic solvent is selected from one or two of amide organic solvents and phenyl ether organic solvents; preferably, the organic solvent is selected from N,N-dimethylacetamide or diphenyl ether.

[0038] In one embodiment, in step (IV), the mass ratio of the copolymer A to the volume of the organic solvent is (0.01-10) g:1 mL, preferably (0.05-5) g:1 mL; more preferably (0.05-3) g:1 mL, even more preferably (0.6-1) g:1 mL, for example 0.7 g:1 mL.

[0039] In one embodiment, in step (IV), the mass ratio of the compound as shown in Formula III-A to the copolymer A is (0.03-0.5):1, preferably (0.03-0.3):1, more preferably (0.1-0.2):1; for example, 0.17:1.

[0040] In one embodiment, in step (IV), the temperature of the cyclization reaction is 100-300°C; preferably 150-240°C; more preferably 200-240°C; and even more preferably 220°C.

[0041] In step (IV), the progress of the cyclization reaction is monitored using methods conventional for such reactions in the art (e.g., TLC), with the reaction ending when copolymer A disappears or ceases to decrease. In one embodiment, the reaction time is 1-10 hours, for example, 4 hours.

[0042] In one embodiment, the cyclization reaction is carried out under an inert atmosphere, preferably a nitrogen atmosphere.

[0043] In step (IV), after the cyclization reaction is completed, a post-treatment conventional to such reactions in the art is also included. In one embodiment, the post-treatment includes the following steps: removal of the organic solvent (e.g., immersion in n-hexane to remove the organic solvent) and drying.

[0044] In one embodiment, step (IV) is performed prior to step (III) as described in any previous embodiment.

[0045] In one embodiment, the preparation method of polymer B includes the following steps (III) and (IV): Step (III): In an organic solvent, the compound shown in Formula M1 and the compound shown in Formula M2 undergo a cyclization polymerization reaction to obtain a solution containing copolymer A; Step (IV): The solution containing copolymer A described in step (III) and the compound shown as formula III-A are mixed and cyclized to obtain polymer B.

[0046] Fourthly, the present invention provides a method for preparing polymer B, comprising the following steps (IV): Step (IV): In an organic solvent, copolymer A (or copolymer described in the sixth aspect) and a compound as shown in formula III-A undergo a cyclization reaction to obtain polymer B; R 2 for , , , , or ; The preparation method and conditions of polymer B can be as described in any embodiment of the present invention.

[0047] Fifthly, the present invention provides a method for preparing a copolymer, comprising the following step III: Step III: Under solvent-free conditions, the compound represented by formula M1 and the compound represented by formula M2 undergo a cyclization polymerization reaction to obtain the copolymer. , , R 1 The definition is as described in the previous scheme. The preparation method and conditions of the copolymer can be as described in any of the embodiments in the second aspect of the present invention.

[0048] In a sixth aspect, the present invention provides a copolymer prepared by the preparation method described in the fifth aspect.

[0049] In this invention, the repeating units of the polymer are read from left to right, with the left end being the head and the right end being the tail. Each repeating unit is connected in a head-to-tail manner, that is, the tail of the previous repeating unit is connected to the head of the next repeating unit.

[0050] The positive and progressive effects of this invention are as follows: (1) The polymer of the present invention is relatively simple to prepare, and polymerization can be achieved by simple heating; (2) It has very good solubility and can be dissolved in common solvents (such as THF, EA, DMF, DMAC, etc.). At room temperature, the maximum dissolved solid content of the polymer in this application can reach 30%. It can be easily prepared into a solution and used to prepare a film by casting method, or it can be prepared into a fiber. (3) The melting temperature is also relatively low compared to PSU, PPSU, PESU, etc. It can also be processed by melting and molding, which is simple, easy to process, and has low energy consumption. (4) Crosslinking agents can also be added during the processing and high-temperature curing can be carried out. After curing, the polymer has better thermal properties and is no longer soluble in common solvents. (5) It can be modified and polymerized with other polymers that have trifluorovinyl structures at the ends; (6) PSU, PPSU, PESU and other materials have relatively high water absorption. Therefore, they usually need to be fully dried before molding. However, the polymer of the present invention has significantly enhanced hydrophobic properties due to the introduction of a perfluorocyclobutyl structure. It does not need to be dried before processing and the processing is simple. (7) Although PSU, PPSU, PESU and other materials have good chemical stability, they will still be corroded to a certain extent in corrosive media such as strong acid and strong alkali. The polymer of the present invention contains a hexafluorocyclobutyl structure in the polymer main chain structure, which makes it relatively stable to both acids and alkalis and has good corrosion resistance. (8) Although PSU, PPSU, PESU and other materials have good chemical stability, their UV resistance is relatively weak, mainly because the bond energy of the ether bond (COC) is relatively low (about 485 kJ / mol), which makes it easy to break under UV irradiation, leading to molecular chain degradation. However, the polymer of the present invention contains a hexafluorocyclobutyl structure in its polymer main chain structure, which significantly enhances the stability of the ether bond and significantly improves its UV resistance. In summary, the method of this invention has the advantages of simple polymerization process, excellent performance or easy modification, and is suitable for large-scale batch preparation. The polymer of this invention not only possesses the excellent properties of perfluorocyclobutyl (PFCB) aryl ether polymers, such as excellent solubility, optical properties, thermal stability, and processability, but also serves as a low-dielectric insulating material in the electronics and electrical fields for 5G communication substrates, high-frequency circuit boards, and chip packaging, reducing signal transmission loss. In the aerospace field, it is suitable for use as a high-temperature resistant, wave-transparent material in radomes and satellite components, combining lightweight design and stability in extreme environments. In the new energy field, it is used as a proton exchange membrane material in batteries, utilizing its chemical stability and proton conductivity to improve battery life. In the field of optical devices, it is used as a transparent weather-resistant coating for camera lenses and laser protective windows, exhibiting outstanding resistance to ultraviolet aging. It can also be used as a special coating to achieve self-cleaning properties. It also possesses the excellent properties of polyethersulfone, such as excellent heat resistance, excellent physical and mechanical properties, chemical corrosion resistance, biocompatibility, and electrical insulation, making it suitable for applications in aerospace, medical, electronics and electrical, automotive, water treatment, and food industries. Therefore, the polymer invented by benzene not only improves the performance of perfluorocyclobutyl (PFCB) aryl ether polymers but also improves the preparation, processing, and molding conditions of polyethersulfone polymers, expanding the application scenarios of both types of polymers. Attached Figure Description

[0051] Figure 1 The image shows the DSC test results for polymer P1. Figure 2 The TGA test results for polymer P1 are shown below. Figure 3 The image shows the DSC test results for polymer P2. Figure 4 The TGA test results for polymer P2 are shown below. Figure 5 The image shows the DSC test result for polymer P3. Figure 6 The TGA test results for polymer P3 are shown below. Figure 7 The image shows the DSC test result for polymer P4. Figure 8 The TGA test results for polymer P4 are shown below. Figure 9 The image shows the DSC test results for polymer P5. Figure 10 The TGA test results for polymer P5 are shown below. Figure 11 The images show the morphological characteristics of polymers P1, P2, P3, P4, and P5. Detailed Implementation

[0052] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.

[0053] TGA testing method: Instrument: Thermal Analysis; Crucible: Ceramic crucible; Atmosphere: Nitrogen; Scan rate: 10℃ / min; Temperature range: room temperature - 800℃, linear heating.

[0054] DSC test: Instrument: Thermal Analysis; Atmosphere: Nitrogen; Scan rate: 20℃ / min; Temperature range: room temperature - 400℃, linear temperature rise.

[0055] Example 1: Copolymerization of 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M1) and 1,4-bis[4-(trifluorovinyl)oxy]benzene (monomer M2) in a molar ratio of 1:1:

[0056] The repeating unit of polymer P1 is and .

[0057] 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (4.1029 g, 10 mmol) and diphenyl ether (10 mL) were added to a 100 mL three-necked reaction flask. A reflux condenser was attached, and stirring was started. Nitrogen gas was purged three times using an oil pump. Then, 1,4-bis[4-(trifluorovinyl)oxy]benzene (2.7013 g, 10 mmol) was added. The mixture was heated to 190 °C and reacted for 24 hours. Heating was then stopped, and the mixture was cooled to room temperature. The diphenyl ether was removed by repeated soaking in n-hexane until no diphenyl ether remained in the leachate (TLC monitoring). The polymer was then dried in a vacuum oven at 180 °C for 10 hours to obtain a light-colored polymer P1 (6.4912 g), with a yield of 95.4%. DSC analysis showed that the polymer's T... g The temperature was 128.57℃. The DSC test result was as follows. Figure 1 TGA testing, such as Figure 2 .

[0058] like Figure 2 As shown, the polymer P1 loses 1% of its weight at 423.2℃; 5% at 473.5℃; 10% at 489.1℃; 50% at 534.7℃; 60% at 551.5℃; and 98.76% in the range of 383-667℃.

[0059] Example 2

[0060] Copolymerization of 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M1) and 1,4-bis[4-(trifluorovinyl)oxy]benzene (monomer M2) in a molar ratio of 7:3:

[0061] The repeating unit of polymer P2 is and .

[0062] 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (5.7440 g, 14 mmol) and diphenyl ether (10 mL) were added to a 100 mL three-necked reaction flask. A reflux condenser was attached, and stirring was started. Nitrogen gas was purged three times using an oil pump. Then, 1,4-bis[4-(trifluorovinyl)oxy]benzene (1.6208 g, 6 mmol) was added. The mixture was heated to 200 °C and reacted for 16 hours. Heating was then stopped, and the mixture was cooled to room temperature. The diphenyl ether was removed by repeated soaking in n-hexane until no diphenyl ether remained in the leachate (TLC monitoring). The polymer was then dried in a vacuum oven at 180 °C for 10 hours to obtain a light yellow polymer P2 (7.0849 g), with a yield of 96.2%. DSC analysis showed that the polymer's T... g The temperature was 140.51℃. The DSC test results were as follows. Figure 3 TGA testing, such as Figure 4 .

[0063] like Figure 4 As shown, the polymer P2 loses 1% of its weight at 428.5℃; 5% at 478.9℃; 10% at 494.6℃; 50% at 541.2℃; 60% at 559.7℃; and 98.04% in the range of 369-699.1℃.

[0064] Example 3

[0065] Copolymerization of 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M1) and 1,4-bis[4-(trifluorovinyl)oxy]benzene (monomer M2) in a molar ratio of 4:1:

[0066] The repeating unit of polymer P3 is and .

[0067] 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (6.5646 g, 16 mmol) and diphenyl ether (10 mL) were added to a 100 mL three-necked reaction flask. A reflux condenser was attached, and stirring was started. Nitrogen gas was purged three times using an oil pump. Then, 1,4-bis[4-(trifluorovinyl)oxy]benzene (1.0805 g, 4 mmol) was added. The mixture was heated to 220 °C and reacted for 14 hours. Heating was then stopped, and the mixture was cooled to room temperature. The diphenyl ether was removed by repeated soaking in n-hexane until no diphenyl ether remained in the leachate (TLC monitoring). The polymer was then dried in a vacuum oven at 180 °C for 10 hours to obtain a light yellow polymer P3 (7.4779 g), with a yield of 97.8%. DSC analysis showed that the polymer's T... g The temperature was 142.63℃. (DSC test results are as follows.) Figure 5 TGA testing, such as Figure 6 .

[0068] like Figure 6 As shown, the polymer P3 loses 1% of its weight at 414.2℃; 5% at 482.4℃; 10% at 499.6℃; 50% at 548.5℃; 60% at 563.6℃; and 98.28% in the range of 341.1-660.1℃.

[0069] Example 4

[0070] Copolymerization of 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M1) and 1,4-bis[4-(trifluorovinyl)oxy]benzene (monomer M2) in a molar ratio of 6:4:

[0071] The repeating unit of polymer P4 is and .

[0072] To a 100 mL three-necked reaction flask, add 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (4.9234 g, 12 mmol) and diphenyl ether (10 mL), attach a reflux condenser, start stirring, and purge with nitrogen three times using an oil pump. Then add 1,4-bis[4-(trifluorovinyl)oxy]benzene (2.1610 g, 8 mmol), heat to 210 °C, and react for 15 hours. Afterward, stop heating, cool to room temperature, and repeatedly soak in n-hexane to remove the diphenyl ether until no diphenyl ether remains in the leachate (TLC monitoring). Then dry the polymer in a vacuum oven at 180 °C for 10 hours to obtain a yellowish-brown polymer P4 (6.8152 g), with a yield of 96.2%. DSC analysis showed that the polymer's T... g The temperature was 132.35℃. The DSC test result was as follows. Figure 7 TGA testing, such as Figure 8 .

[0073] like Figure 8 As shown, the polymer P4 loses 1% of its weight at 411.9°C; 5% at 477.5°C; 10% at 493.6°C; 50% at 542.2°C; 60% at 559.8°C; and 97.4% in the range of 378-688.1°C.

[0074] Example 5

[0075] The copolymerization of 4,4'-bis(trifluorovinyloxy)benzophenone and 1,4-bis[4-(trifluorovinyl)oxy]benzene in a molar ratio of 4:6 was followed by crosslinking.

[0076]

[0077] 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (3.2823 g, 8 mmol) and diphenyl ether (10 mL) were added to a 100 mL three-necked reaction flask. A reflux condenser was attached, and the mixture was stirred. Nitrogen gas was pumped out three times. Then, 1,4-bis[4-(trifluorovinyloxy)oxy]benzene (3.2416 g, 12 mmol) was added, and the mixture was heated to 220 °C. After reacting for 12 hours, P5-1 was obtained. Crosslinking agent 1,1,1-tris[4-(trifluorovinyloxy)phenyl]ethane (1.0928 g, 2.0 mmol) was added, and the reaction was continued for 4 hours. Heating was then stopped, and the mixture was cooled to room temperature. The polymer was repeatedly soaked in n-hexane to remove the diphenyl ether until no diphenyl ether was found in the leachate (TLC monitoring). The polymer was then dried in a vacuum oven at 180 °C for 10 hours to obtain brown polymer P5 (7.2968 g), with a yield of 95.8%. DSC testing showed that the polymer's T g The temperature was 125.63℃. The DSC test results were as follows. Figure 9 TGA testing, such as Figure 10 .

[0078] like Figure 10 As shown, the polymer P5 loses 1% of its weight at 445.1°C; 5% at 475.6°C; 10% at 489.2°C; 50% at 543.5°C; 60% at 558.9°C; and 94.69% in the range of 423-627°C.

[0079] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of the present invention is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but all such changes and modifications fall within the scope of protection of the present invention.

Claims

1. A copolymer A, characterized in that, It includes repeating unit I and repeating unit II. and , R 1 It is phenylene, naphthylene, , , or ; Y 1 It can be NH, O, or S; R a and R b Independently for H and C 1-4 Alkyl or C 1-4 Halogenated alkyl groups.

2. The copolymer A according to claim 1, characterized in that, It meets one or more of the following conditions: (1) R a and R b Independently H, methyl, or CF3; Preferably, R 1 for , , , , , , , or ; (2) The Tg of the copolymer A is 100℃-170℃, preferably 110℃-160℃, more preferably 128.57±2℃, 132.35±2℃, 140.51±2℃ or 142.63±2℃; (3) The copolymer A loses 1% of its weight at 410℃-435℃; (4) The copolymer A loses 5% of its weight at 465℃-485℃; (5) The copolymer A loses 10% of its weight at 486℃-505℃; (6) The copolymer A is a random copolymer.

3. The copolymer A according to claim 1, characterized in that, The copolymer A is prepared by the following method, which includes step III: Step III: Under solvent-free conditions, the compound shown in Formula M1 and the compound shown in Formula M2 undergo a cyclization polymerization reaction to obtain the copolymer A. 、 ， R 1 The definition is as described in claim 1 or 2.

4. The copolymer A according to claim 3, characterized in that, The preparation method of copolymer A satisfies one or more of the following conditions: (1) The cyclization polymerization reaction is carried out under an inert atmosphere, preferably a nitrogen atmosphere; (2) The organic solvent is selected from phenyl ether organic solvents, preferably diphenyl ether; (3) The ratio of the number of moles of the compound as shown in formula M1 to the volume of the organic solvent is (0.1-10) mmol:1mL, preferably (0.1-5) mmol:1mL, more preferably (0.7-0.9) mmol:1mL, (0.9-1.1) mmol:1mL, (1.1-1.3) mmol:1mL, (1.3-1.4) mmol:1mL, or (1.5-1.7) mmol:1mL; (4) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (0.01-99):1, preferably (0.1-5):1, more preferably (0.1-2):1, and even more preferably (0.2-0.3):1, (0.3-0.5):1, (0.6-0.8):1, (0.9-1.1):1 or (1.4-1.6):1; (5) The temperature of the cyclization polymerization reaction is 100-300℃; preferably 150-250℃; preferably 180-240℃, more preferably 190℃, 200℃, 210℃ or 220℃; (6) After the cyclization polymerization reaction is completed, the post-treatment includes the following steps: removing the organic solvent and drying; for example, soaking in n-hexane to remove the phenyl ether organic solvent.

5. The copolymer A according to claim 1, characterized in that, R 1 for Preferably, the copolymer A is selected from any of the following: Option 1: The copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 128.57±2℃; (2) The copolymer A loses 1% of its weight at 423.2±2℃; 5% of its weight at 473.5±2℃; and 10% of its weight at 489.1±2℃. (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (0.9-1.1):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.9-1.1) mmol:1mL; Option 2: The copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 140.51±2℃; (2) The copolymer A loses 1% of its weight at 428.5±2℃, 5% of its weight at 478.9±2℃, and 10% of its weight at 494.6±2℃; (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (0.3-0.5):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (1.3-1.5) mmol:1mL; Option 3: The copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 142.63±2℃; (2) The copolymer A loses 1% of its weight at 414.2±2℃, 5% of its weight at 482.4±2℃, and 10% of its weight at 499.6±2℃; (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (0.2-0.3):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (1.5-1.7) mmol:1mL; Option 4: The copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 132.35±2℃; (2) The copolymer A loses 1% of its weight at 411.9±2℃, 5% of its weight at 477.5±2℃, and 10% of its weight at 493.6±2℃; (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (0.6-0.8):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (1.1-1.3) mmol:1mL; Option 5: The copolymer A satisfies the following conditions: The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (1.4-1.6):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.7-0.9) mmol:1mL.

6. A method for preparing copolymer A according to any one of claims 1-5, characterized in that, It includes the following step III: Step III: Under solvent-free conditions, the compound shown in Formula M1 and the compound shown in Formula M2 undergo a cyclization polymerization reaction to obtain the copolymer A. 、 ， R 1 The definition is as described in claim 1 or 2. The operation and conditions of the preparation method of copolymer A can be as described in claim 4 or 5.

7. A polymer B, characterized in that, The polymer B is prepared by the following method, which includes the following step (IV): Step (IV): In an organic solvent or under solvent-free conditions, copolymer A as described in any one of claims 1-5 and the compound shown in formula III-A are subjected to a cyclization reaction to obtain polymer B; R 2 for , , , , or .

8. The polymer B as claimed in claim 7, characterized in that, It meets one or more of the following conditions: (1) R 2 for ; (2) The T of the polymer B g The temperature is 120-130℃, for example, 125.63±2℃; (3) The polymer B loses 10% of its weight in the range of 480℃-500℃, for example, 489.2±2℃; (4) The polymer B loses 5% of its weight in the range of 465℃-485℃, for example, 475.6±2℃; (5) The polymer B loses 1% of its weight in the range of 440℃-450℃, for example, 445.1±2℃.

9. The polymer B as claimed in claim 7, characterized in that, It meets one or more of the following conditions: (1) The organic solvent is selected from one or two of amide organic solvents and phenyl ether organic solvents; preferably, the organic solvent is selected from N,N-dimethylacetamide or diphenyl ether; (2) The mass ratio of the copolymer A to the volume of the organic solvent is (0.01-10) g:1 mL, preferably (0.05-5) g:1 mL; more preferably (0.05-3) g:1 mL, and even more preferably (0.6-1) g:1 mL; (3) The mass ratio of the compound as shown in Formula III-A to the copolymer A is (0.03-0.5):1, preferably (0.03-0.3):1, and more preferably (0.1-0.2):1; (4) The temperature of the cyclization reaction is 100-300℃; preferably 150-240℃; more preferably 200-240℃; and even more preferably 220℃. (5) The cyclization reaction is completed and post-treatment is also included. The post-treatment includes the following steps: removing the organic solvent and drying, for example, soaking in n-hexane to remove the organic solvent; (6) The method further includes step (III) as described in claim 6 before step (IV); preferably, the preparation method of polymer B includes the following steps (III) and (IV): Step (III): In an organic solvent, the compound shown in Formula M1 and the compound shown in Formula M2 undergo a cyclization polymerization reaction to obtain a solution containing copolymer A; Step (IV): The solution containing copolymer A described in step (III) is mixed and cyclized with the compound shown as formula III-A to obtain polymer B.

10. A method for preparing polymer B, characterized in that, It includes the following steps (IV): Step (IV): In an organic solvent or under solvent-free conditions, copolymer A as described in any one of claims 1-5 and the compound shown in formula III-A are subjected to a cyclization reaction to obtain polymer B; R 2 for , , , , or ; The preparation method and conditions of polymer B are as described in claim 9.

Images