Perfluorocyclobutyl polyethersulfone ketone polymer and preparation method thereof

Abstract

The invention discloses a perfluorocyclobutyl polyethersulfone ketone 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 provided by the invention has the advantages of simple polymerization process, excellent performance or easy modification, and the method is suitable for large-scale batch preparation.

Description

Technical Field

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

[0002] Perfluorocyclobutyl (PFCB) aryl ether polymers are a new class of partially fluorinated polymers first reported by Dow in 1993. They are formed through a biradical thermocyclization dimerization of an aryl trifluorovinyl ether monomer, resulting in a polymer with covalently linked hexafluorocyclobutyl groups. As a novel type of fluorinated polymer, PFCB aryl ether polymers possess excellent optical transparency, as well as good processability and mechanical properties, low dielectric constant, low hygroscopicity, thermal stability, and chemical stability. They can be widely used as photoconductors, organic light-emitting diodes and optoelectronic materials, film materials, quantum dot encapsulation materials, and high-performance structural materials in the electronics industry, aerospace, fuel cells, coatings, and organic nanomaterials. Due to their unique properties, the structural design, synthesis, and applications of PFCB aryl ether polymers have attracted considerable attention from researchers.

[0003] Polyethersulfone ketone (PESK) is a high-performance specialty engineering plastic that has shown great application potential in aerospace, electronics, and medical devices in recent years. This material combines the high-temperature stability of PEEK with the processing ease of PSU, achieving a unique performance balance that makes it a rising star in the engineering plastics field. Structurally, the main chain of PESK consists of alternating ether bonds, sulfone groups, and ketone groups. This unique structure endows the material with excellent heat resistance, with a glass transition temperature exceeding 230°C and a long-term service temperature range between 180-200°C. Compared to traditional PEEK, PESK maintains a similar temperature resistance while improving melt flow by approximately 30%, making it easier to mold complex parts using processes such as injection molding and extrusion.

[0004] While PESK (polyethersulfone ketone) boasts excellent performance, its preparation is extremely difficult, primarily due to the stringent requirements for raw material purity, complex polymerization processes, poor batch stability, and challenging post-processing, resulting in high costs. Furthermore, its processing is challenging (melting temperature approximately 350℃, requiring specialized equipment and complex molding processes). Additionally, it exhibits some performance limitations, such as limited impact resistance (prone to brittleness under low-temperature or high-speed impact) and moderate weather resistance (long-term UV exposure may lead to performance degradation).

[0005] The presence of ketone, sulfone, and ether bonds in the PESK molecular structure endows it with excellent physicochemical properties. Similarly, perfluorocyclobutyl (PFCB) aryl ether polymers also possess ether bonds; therefore, introducing ketone and sulfone bonds into their structure could potentially lead to superior chemical properties. Furthermore, the preparation process for PFCB aryl ether polymers is very simple, allowing for rapid, large-scale production. Summary of the Invention

[0006] The technical problem this invention aims to solve is to overcome the shortcomings of existing polyether ether ketone (PEEK) materials, such as complex preparation processes, high melting temperatures, and difficulties in processing, molding, or modification. This invention provides a perfluorocyclobutyl aryl ether polymer containing a benzophenone structure and its preparation method. The polymer of this invention has the advantages of simple polymerization process, excellent performance, and ease of modification, and the method is suitable for large-scale batch production.

[0007] The present invention solves the above-mentioned technical problems through the following technical solution: In a first aspect, the present invention provides a copolymer A comprising repeating unit I and repeating unit II, and .

[0008] In one embodiment, the Tg of copolymer A is 100℃-220℃, preferably 110℃-160℃, and more preferably 119.68±2℃, 140.20±2℃, 143.88±2℃, 148.53±2℃ or 150.69±2℃.

[0009] In one embodiment, copolymer A loses 1% of its weight at 468°C-480°C or 1% of its weight at 390°C-425°C.

[0010] In one embodiment, copolymer A loses 1.84% of its weight in the range of 280°C to 465°C (e.g., 287.06°C to 461.09°C).

[0011] In one embodiment, copolymer A loses 5% of its weight at 482°C-507°C.

[0012] In one embodiment, copolymer A loses 10% of its weight at 500°C-510°C.

[0013] In one embodiment, copolymer A is a random copolymer.

[0014] In one embodiment, 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. , .

[0015] 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.

[0016] In one embodiment, the polymerization reaction is carried out under an inert atmosphere, preferably a nitrogen atmosphere.

[0017] In one embodiment, the organic solvent is selected from phenyl ether organic solvents, preferably diphenyl ether.

[0018] 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:1 mL, preferably (0.1-5) mmol:1 mL, more preferably (0.1-0.3) mmol:1 mL, (0.3-0.5) mmol:1 mL, (0.5-0.7) mmol:1 mL, (0.7-0.9) mmol:1 mL, (0.9-1.1) mmol:1 mL or (1.9-2.1) mmol:1 mL, and even more preferably 0.2 mmol:1 mL, 0.4 mmol:1 mL, 0.6 mmol:1 mL, 0.8 mmol:1 mL, 1 mmol:1 mL or 2 mmol:1 mL.

[0019] 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 (0.1-10.5):1, and even more preferably (0.2-0.3):1, (0.9-1.1):1, (1.4-1.6):1, (2.2-2.4):1, (3.9-4.1):1 or (10.9-10.1):1, for example 0.25:1, 1:1, 1.5:1, 2.3:1, 4:1, 10:1.

[0020] In one embodiment, the molar amount of the compound represented by formula M1 is 1-20 mmol, preferably 1-15 mmol, more preferably 1 mmol, 2 mmol, 3 mmol, 4 mmol, 5 mmol or 10 mmol.

[0021] In one embodiment, the temperature of the cyclization polymerization reaction is 100-300℃; preferably 150-250℃; more preferably 180-250℃, and even more preferably 190℃, 200℃, 210℃, 220℃ or 230℃.

[0022] 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 5-20 hours, for example, 12, 14, 16, 18, 20, or 24 hours.

[0023] 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: removal of the organic solvent (e.g., immersion in petroleum ether and ethyl acetate to remove the phenyl ether organic solvent) and drying.

[0024] In one embodiment, copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 143.88±2℃; (2) The copolymer A loses 1% of its weight at 445.8±2℃, 5% of its weight at 491.0±2℃, and 10% of its weight at 505.4±2℃; (3) The preparation method of 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 (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 5mmol.

[0025] In one embodiment, copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 150.69±2℃; (2) The copolymer A loses 1% of its weight at 477.7±2℃, 5% of its weight at 496.6±2℃, and 10% of its weight at 507.4±2℃; (3) The preparation method of 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 (9.9-10.1):1, the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.1-0.3) mmol:1mL, preferably, the number of moles of the compound shown in formula M1 is 1mmol.

[0026] In one embodiment, copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 148.53±2℃; (2) The copolymer A loses 1% of its weight at 413.9±2℃, 5% of its weight at 486.5±2℃, and 10% of its weight at 503.8±2℃; (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (3.9-4.1):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.3-0.5) mmol:1 mL. Preferably, the number of moles of the compound shown in formula M1 is 2 mmol.

[0027] In one embodiment, copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 119.68±2℃; (2) The copolymer A loses 1% of its weight at 471.7±2℃, 5% of its weight at 496.4±2℃, and 10% of its weight at 508.6±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 (1.9-2.1) mmol:1mL. Preferably, the number of moles of the compound shown in formula M1 is 10mmol.

[0028] In one embodiment, copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 140.20±2℃; (2) The copolymer A loses 1% of its weight at 398.2±2℃, 1.83% of its weight in the range of 287.1℃-461.1℃, 5% of its weight at 491.2±2℃, and 10% of its weight at 506.4±2℃; (3) 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 4 mmol.

[0029] In one embodiment, 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 (2.2-2.4):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.5-0.7) mmol:1mL. Preferably, the number of moles of the compound shown in formula M1 is 3 mmol.

[0030] Secondly, the present invention provides a method for preparing copolymer A, which includes the following step III: Step III: Under solvent or 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; , , The preparation method and conditions of the copolymer A can also be as described in any of the preceding schemes.

[0031] Thirdly, the present invention provides a polymer B, which is prepared by the following preparation method, the preparation method comprising the following steps (IV): Step (IV): In an organic solvent or under solvent-free conditions, copolymer A (or polymer as described in aspect VI) and compound as shown in formula III-A are subjected to a cyclization reaction to obtain polymer B; R 2 for , , , , or .

[0032] In one of the schemes, R 2 for .

[0033] In one embodiment, the T of polymer B g The temperature range is 110-122℃, for example, 117.54±2℃.

[0034] In one embodiment, polymer B loses 10% of its weight in the range of 495°C to 510°C, for example, at 503.0 ± 2°C.

[0035] In one embodiment, polymer B loses 5% of its weight in the range of 480°C to 500°C, for example, 484.2 ± 2°C.

[0036] In one embodiment, the random polymer loses 1% of its weight in the range of 420°C to 440°C, for example, 429±2°C.

[0037] 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.

[0038] 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.

[0039] 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 0.8 g:1 mL.

[0040] In one embodiment, in step (IV), the mass ratio of the compound as shown in Formula III-A to the copolymer A is (0.01-0.5):1, preferably (0.01-0.3):1, more preferably (0.01-0.1):1; for example, 0.07:1.

[0041] In one embodiment, in step (IV), the temperature of the cyclization reaction is 100-300°C; preferably 150-240°C; more preferably 180-220°C; and even more preferably 200°C.

[0042] 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 cyclization reaction takes 1-10 hours, for example, 2 hours.

[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 petroleum ether and ethyl acetate 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) is mixed and cyclized with the compound shown as formula III-A 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 or under solvent-free conditions, copolymer A (or polymer as described in aspect VI) and compound as 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 the polymer B can also be as described in any of the preceding schemes.

[0047] Fifthly, the present invention provides a method for preparing a copolymer, comprising the following step III: Step III: Under solvent or 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; , , The operation and conditions of the copolymer preparation method may also be as described in any of the schemes in the second aspect above.

[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: While commercially available materials such as polyetheretherketone (PEEK) exhibit excellent properties, their preparation processes are complex, and processing them presents numerous difficulties due to their extremely high melting temperatures. Furthermore, fabricating them into films or fibers is very challenging, limiting their application range. Modification of these materials is also quite difficult.

[0051] The polymer prepared by the method of the present invention has the following advantages: (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 much lower than that of PESK, and it can also be processed by melting. The conditions are simple, the processing is easy, and the energy consumption is low. (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) Although PESK materials have good chemical stability, they will still be corroded to a certain extent in corrosive media such as strong acids and strong alkalis. The polymer of the present invention contains a hexafluorocyclobutyl structure in its polymer main chain structure, which makes it relatively stable to acids and alkalis and has good corrosion resistance. (7) Although materials such as PESK 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.

[0052] In summary, the method of this invention features a simple polymerization process, excellent performance, and ease of modification, and is suitable for large-scale batch production. 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 processing performance, making it suitable for applications such as quantum dot encapsulation materials, fuel cell proton exchange membranes, liquid crystal materials, high-performance sealing materials, optical waveguide materials, antigenic oxygen coatings, organic light-emitting diodes, and photoelectric sensors; it also possesses the excellent properties of polyethersulfone ketone, such as excellent high-temperature resistance, chemical corrosion resistance, biocompatibility, and electrical insulation, making it suitable for use in highly corrosive environments such as strong acids and alkalis, strong ultraviolet environments, and high-temperature conditions. It is expected to replace currently available polymers on the market such as PESK, PSU, PSU, PPSU, PESU, and PAEK. Specifically, the polymers of this invention can be applied to the aerospace field (such as high-temperature resistant components and insulating materials), the medical field (such as surgical instruments, dialyzers, implants, etc.), the electronics and electrical field (circuit boards, connectors, insulating films), and the automotive industry (high-temperature resistant sensors and fuel system components). Therefore, the polymers invented by benzene not only improve the performance of perfluorocyclobutyl (PFCB) aryl ether polymers, but also improve the preparation, processing, and molding conditions of polyethersulfone ketone polymers, expanding the application scenarios of both types of polymers. Attached Figure Description

[0053] Figure 1 The image shows the DSC test result 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 image shows the DSC test result for polymer P6. Figure 12 The TGA test results for polymer P6 are shown below. Figure 13 The images show the morphological characteristics of polymers P1, P2, P3, P4, P5, and P6. Detailed Implementation

[0054] 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.

[0055] TGA testing method: Instrument: Thermal Analysis; Crucible: Ceramic crucible; Atmosphere: Nitrogen; Scan rate: 10℃ / min; Temperature range: room temperature - 800℃, linear heating.

[0056] DSC test: Instrument: Thermal Analysis; Atmosphere: Nitrogen; Scan rate: 20℃ / min; Temperature range: room temperature - 500℃ or room temperature - 400℃, linear temperature rise.

[0057] Example 1: Preparation of intermediates: Trifluorovinyl-substituted benzophenone monomer

[0058] Preparation of 4,4'-bis(2-bromo-1,1,2,2-tetrafluoroethoxy)benzophenone:

[0059] Under nitrogen protection, 4,4'-dihydroxybenzophenone (0.25 mol, 53.555 g), Cs₂CO₃ (0.75 mol, 244.365 g), and DMSO (600 mL) were added sequentially to a 1 L three-necked reaction flask. A reflux condenser was attached, and stirring was started. Then, 1,2-dibromotetrafluoroethane (0.66 mol, 171.484 g) was slowly added dropwise to the system at room temperature. After the addition was complete, the temperature was slowly raised to 80 °C. The reaction was monitored by TLC until the reactants were completely reacted, and by NMR fluorine spectroscopy until the monosubstituted product was completely converted to the disubstituted product. The reaction was then stopped, cooled to room temperature, and the reaction solution was poured into an ice-water bath. The solution was extracted three times with ethyl acetate, and the organic phase was collected. The organic phase was washed three times with saturated brine, dried with anhydrous sodium sulfate, filtered, concentrated, and column filtered (eluent volume ratio V(PE):V(EA) = 0.25 mol / L). (96:4) Vacuum drying yielded 100.1076 g of white solid, with a yield of 70%.

[0060] 1 H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 8.8 Hz, 4H), 7.36 (d, J = 8.7Hz, 4H);

[0061] 19 F NMR (376 MHz, CDCl3) δ -68.19 (t, J = 3.8 Hz, 4F), -85.93 (t, J =4.6 Hz, 4F);

[0062] 13 C NMR (101 MHz, CDCl3) δ 193.58 (s), 152.11 (s), 135.55 (s), 131.81(s), 121.17 (s), 115.85 (tt, J1 = 277.1 Hz, J2 =32.4 Hz), 113.36 (tt, J1 =312.6 Hz, J2 =44.3 Hz);

[0063] IR (film): 1649.14, 1600.92, 1502.55, 1411.89, 1328.95, 1307.14,1294.24, 1278.81, 1193.94, 1157.29, 1126.43, 1091.71, 1016.49, 925.83,869.90, 833.25, 817.82, 786.96, 750.31, 675.09, 648.08, 559.36 cm-1 ;

[0064] MS (FI, m / z): 572(M+); HRMS (FI): exact mass calcd for C 17 H8Br2F8O3:569.8707, found: 569.8713.

[0065] Preparation of 4,4'-bis(trifluorovinyloxy)benzophenone:

[0066] Under nitrogen protection, activated zinc powder (0.525 mol, 34.3245 g) was added to a 1 L three-necked reaction flask, followed by 400 mL of ultra-dry acetonitrile. A reflux condenser was attached, and the mixture was stirred and heated to 95 °C. Then, 4,4'-bis(2-bromo-1,1,2,2-tetrafluoroethoxy)benzophenone (0.175 mol, 100 g) was dissolved in 200 mL of ultra-dry acetonitrile to prepare a solution, which was slowly added dropwise to the reaction flask. After the addition was complete, the reaction continued at this temperature. Nuclear magnetic resonance (NMR) fluorine spectrometry was used to monitor the reaction until the starting materials and intermediates had completely reacted, at which point the reaction was stopped. The mixture was cooled to room temperature, filtered through diatomaceous earth, and washed with a small amount of acetonitrile. The filtrate was collected, concentrated, and subjected to column chromatography (eluent volume ratio V(PE):V(EA) = 95:5), followed by vacuum drying to obtain 52.3934 g of a white solid, with a yield of 80%.

[0067] 1 H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.9 Hz, 4H), 7.21 (d, J = 8.2Hz, 4H);

[0068] 19 F NMR (376 MHz, CDCl3) δ -118.50 (dd, J1 = 94.6, J2 = 58.5 Hz, 2F), -125.23 (dd, J1 = 110.4, J2 = 94.5 Hz, 2F), -134.60 (dd, J1 = 110.4, J2 = 58.3Hz, 2F).

[0069] 13C NMR (101 MHz, CDCl3) δ 193.29 (s), 157.96 (dd, J1 = 7.5 Hz, J2 =3.2 Hz), 146.94 (ddd, J1 = 280.1 Hz, J2 =274.2 Hz, J3 =60.4 Hz), 134.13 (s), 133.26 (ddd, J1 = 265.9 Hz, J2 = 48.3 Hz, J3 =42.3 Hz), 132.25 (s), 115.50(s).

[0070] IR (film): 1836.23, 1639.49, 1597.06, 1500.62, 1309.67, 1259.52,1203.58, 1130.29, 1116.78, 1012.63, 964.41, 929.69, 858.32, 840.96, 827.40,781.17, 759.95, 675.09, 648.08, 626.87, 596.00, 551.64, 524.64 cm -1 ;

[0071] MS (FI, m / z): 374(M+); HRMS (FI): exact mass calcd for C 17 H8F6O3:374.0372, found: 374.0378.

[0072] Example 1

[0073] Copolymerization of 4,4'-bis(trifluorovinyloxy)benzophenone (monomer M1) and 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M2) in a molar ratio of 1:1:

[0074] The repeating unit of polymer P1 is and .

[0075] To a 100 mL three-necked reaction flask, add 1.8712 g (5 mmol) of 4,4'-bis(trifluorovinyloxy)benzophenone, 2.052 g (5 mmol) of 4,4'-bis[(trifluorovinyl)]-1,1'-diphenyl sulfone, and 5 mL of diphenyl ether. Attach a reflux condenser, start stirring, and purge the nitrogen atmosphere three times with an oil pump. Then, heat to 210 °C and react for 18 hours. Afterward, stop heating and cool to room temperature. Soak the polymer repeatedly in a mixed solvent with a volume ratio of V(PE):V(EA) of 10:1 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 light brown polymer P1 (3.8604 g), with a yield of 98.4%. DSC analysis showed that the polymer's T... g The temperature was 143.88℃. The DSC test results were as follows. Figure 1 TGA testing, such as Figure 2 .

[0076] like Figure 2 As shown, polymer P1 loses 1% of its weight at 445.8℃, 5% at 491.0℃, 10% at 505.4℃, 50% at 558.4℃, 60% at 578.5℃, and 98.26% in the 409-700℃ range.

[0077] Example 2

[0078] Copolymerization of 4,4'-bis(trifluorovinyloxy)benzophenone (monomer M1) and 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M2) in a molar ratio of 1:10:

[0079] The repeating unit of polymer P2 is and .

[0080] To a 100 mL three-necked reaction flask, add 0.3742 g (1 mmol) of 4,4'-bis(trifluorovinyloxy)benzophenone, 4.1029 g (10 mmol) of 4,4'-bis[(trifluorovinyl)]-1,1'-diphenyl sulfone, and 5 mL of diphenyl ether. Attach a reflux condenser, start stirring, and purge the nitrogen atmosphere three times with an oil pump. Then, heat to 200 °C and react for 20 hours. Afterward, stop heating and cool to room temperature. Soak the polymer repeatedly in a mixed solvent with a volume ratio of V(PE):V(EA) of 10:1 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 light brown polymer P2 (4.3831 g), with a yield of 97.9%. DSC analysis showed that the polymer's T...g The temperature was 150.69℃. The DSC test result was as follows. Figure 3 TGA testing, such as Figure 4 .

[0081] like Figure 4 As shown, polymer P2 loses 1% of its weight at 477.7℃, 5% at 496.6℃, 10% at 507.4℃, 50% at 555℃, 60% at 571.9℃, and 93.85% in the 468-665℃ range.

[0082] Example 3

[0083] Copolymerization of 4,4'-bis(trifluorovinyloxy)benzophenone (monomer M1) and 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M2) in a molar ratio of 1:4:

[0084] The repeating unit of polymer P3 is and .

[0085] To a 100 mL three-necked reaction flask, add 0.7485 g (2 mmol) of 4,4'-bis(trifluorovinyloxy)benzophenone, 3.2823 g (8 mmol) of 4,4'-bis[(trifluorovinyl)]-1,1'-diphenyl sulfone, and 5 mL of diphenyl ether. Attach a reflux condenser, start stirring, and purge the nitrogen atmosphere three times with an oil pump. Then, heat to 220 °C and react for 16 hours. Afterward, stop heating and cool to room temperature. Repeatedly soak the polymer in a mixed solvent with a volume ratio of V(PE):V(EA) of 10:1 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 light brown polymer P3 (3.9663 g), with a yield of 98.4%. DSC analysis showed that the polymer's T... g The temperature was 148.53℃. (DSC test results are as follows.) Figure 5 TGA testing, such as Figure 6 .

[0086] like Figure 6 As shown, polymer P3 loses 1% of its weight at 413.9℃, 5% at 486.5℃, and 10% at 503.8℃; it loses 50% of its weight at 553.7℃; 60% at 574℃; and 98.05% of its weight in the range of 348.1-699.1℃.

[0087] Example 4

[0088] Copolymerization of 4,4'-bis(trifluorovinyloxy)benzophenone (monomer M1) and 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M2) in a molar ratio of 1:4:

[0089] The repeating unit of polymer P4 is and .

[0090] To a 100 mL three-necked reaction flask, add 3.7424 g (10 mmol) of 4,4'-bis(trifluorovinyloxy)benzophenone, 1.025 g (2.5 mmol) of 4,4'-bis[(trifluorovinyl)]-1,1'-diphenyl sulfone, and 5 mL of diphenyl ether. Attach a reflux condenser, start stirring, and purge with nitrogen three times using an oil pump. Then, heat to 190 °C and react for 24 hours. Afterward, stop heating and cool to room temperature. Soak repeatedly in a mixed solvent with a volume ratio of V(PE):V(EA) of 10:1 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 light brown polymer P4 (4.6577 g), with a yield of 97.7%. DSC analysis showed that the polymer's T... g The temperature was 119.68℃. The DSC test results were as follows. Figure 7 TGA testing, such as Figure 8 .

[0091] like Figure 8 As shown, polymer P4 loses 1% of its weight at 471.7℃, 5% at 496.4℃, and 10% at 508.6℃; it loses 50% of its weight at 565.4℃; 60% at 582.9℃; and 95.6% of its weight in the range of 452.1-672.1℃.

[0092] Example 5

[0093] Copolymerization of 4,4'-bis(trifluorovinyloxy)benzophenone (monomer M1) and 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M2) in a molar ratio of 2:3:

[0094] The repeating unit of polymer P5 is and .

[0095] To a 100 mL three-necked reaction flask, add 1.4968 g (4 mmol) of 4,4'-bis(trifluorovinyloxy)benzophenone, 2.4617 g (6 mmol) of 4,4'-bis[(trifluorovinyl)]-1,1'-diphenyl sulfone, and 5 mL of diphenyl ether. Attach a reflux condenser, start stirring, and purge the nitrogen atmosphere three times with an oil pump. Then, heat to 230 °C and react for 12 hours. Afterward, stop heating and cool to room temperature. Repeatedly soak the polymer in a mixed solvent with a volume ratio of V(PE):V(EA) of 10:1 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 light yellow polymer P5 (3.8754 g), with a yield of 97.9%. DSC analysis showed that the polymer's T... g The temperature was 140.20℃. The DSC test result was as follows. Figure 9 TGA testing, such as Figure 10 .

[0096] like Figure 10 As shown, polymer P5 loses 1% of its weight at 398.2℃, 1.83% of its weight in the range of 287.1℃-461.1℃, 5% of its weight at 491.2℃, 10% of its weight at 506.4℃, 50% of its weight at 556.2℃, 60% of its weight at 577.7℃, 96.92% of its weight in the range of 461.1-701℃, and 98.84% of its weight in the range of 213.1-729.1℃.

[0097] Example 6

[0098] The copolymerization of 4,4'-bis(trifluorovinyloxy)benzophenone (monomer M1) and 4,4'-bis(trifluorovinyloxy)diphenyl sulfone (monomer M2) in a molar ratio of 3:7, followed by crosslinking:

[0099] The repeating unit of polymer P6-1 is and .

[0100]

[0101] To a 100 mL three-necked reaction flask, add 1.123 g (3 mmol) of 4,4'-bis(trifluorovinyloxy)benzophenone, 2.8720 g (7 mmol) of 4,4'-bis[(trifluorovinyl)]-1,1'-diphenyl sulfone, and 5 mL of diphenyl ether. Attach a reflux condenser, start stirring, and purge the mixture with nitrogen three times using an oil pump. Then, heat to 200 °C and react for 14 hours to obtain polymer P6-1. Add 273.2 mg (1,1,1-tris[4-(trifluorovinyloxy)-phenyl]ethane) as a crosslinking agent. After reacting for 2 hours (0.5 mmol), heating was stopped, and the mixture was cooled to room temperature. It was then repeatedly soaked in a mixed solvent with a volume ratio of V(PE):V(EA) of 10:1 to remove diphenyl ether 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 brown polymer P6 (4.2000 g), with a yield of 98.4%. DSC analysis showed that the polymer's T... g The temperature was 117.54℃. The DSC test result was as follows. Figure 11 TGA testing, such as Figure 12 .

[0102] like Figure 12 As shown, polymer P6 loses 1% of its weight at 429℃, 5% at 484.2℃, and 10% at 503.0℃; it loses 50% of its weight at 557.9℃; 60% at 576.9℃; and 93.8% of its weight in the range of 373.1-685.1℃.

[0103] 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 .

2. The copolymer A according to claim 1, characterized in that, It meets one or more of the following conditions: (1) The Tg of the copolymer A is 100℃-220℃, preferably 110℃-160℃, preferably 119.68±2℃, 140.20±2℃, 143.88±2℃, 148.53±2℃ or 150.69±2℃; (2) The copolymer A loses 1% of its weight at 468℃-480℃ or 1% of its weight at 390℃-425℃; (3) The copolymer A loses 1.84% of its weight in the range of 280℃-465℃; for example, in the range of 287.06℃-461.09℃; (4) The copolymer A loses 5% of its weight at 482℃-507℃; (5) The copolymer A loses 10% of its weight at 500℃-510℃; (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. 、 。 4. The copolymer A according to claim 3, characterized in that, It meets 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 (0.1-0.3) mmol:1mL, (0.3-0.5) mmol:1mL, (0.5-0.7) mmol:1mL, (0.7-0.9) mmol:1mL, (0.9-1.1) mmol:1mL or (1.9-2.1) 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 (0.1-10.5):1, and even more preferably (0.2-0.3):1, (0.9-1.1):1, (1.4-1.6):1, (2.2-2.4):1, (3.9-4.1):1 or (10.9-10.1):1; (5) The temperature of the cyclization polymerization reaction is 100-300℃; preferably 150-250℃; even more preferably 180-250℃, and more preferably 190℃, 200℃, 210℃, 220℃ or 230℃; (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 petroleum ether and ethyl acetate to remove the phenyl ether organic solvent.

5. The copolymer A according to claim 3, characterized in that, 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 143.88±2℃; (2) The copolymer A loses 1% of its weight at 445.8±2℃, 5% of its weight at 491.0±2℃, and 10% of its weight at 505.4±2℃; (3) The preparation method of 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 (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 150.69±2℃; (2) The copolymer A loses 1% of its weight at 477.7±2℃, 5% of its weight at 496.6±2℃, and 10% of its weight at 507.4±2℃; (3) The preparation method of 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 (9.9-10.1):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.1-0.3) mmol:1mL; Option 3: The copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 148.53±2℃; (2) The copolymer A loses 1% of its weight at 413.9±2℃, 5% of its weight at 486.5±2℃, and 10% of its weight at 503.8±2℃; (3) The molar ratio of the compound shown in formula M2 to the compound shown in formula M1 is (3.9-4.1):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.3-0.5) mmol:1mL; Option 4: The copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 119.68±2℃; (2) The copolymer A loses 1% of its weight at 471.7±2℃, 5% of its weight at 496.4±2℃, and 10% of its weight at 508.6±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 (1.9-2.1) mmol:1mL; Option 5: The copolymer A satisfies one or more of the following conditions: (1) The Tg of copolymer A is 140.20±2℃; (2) The copolymer A loses 1% of its weight at 398.2±2℃, 1.83% of its weight in the range of 287.1℃-461.1℃, 5% of its weight at 491.2±2℃, and 10% of its weight at 506.4±2℃; (3) 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; Scheme 6: 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 (2.2-2.4):1, and the ratio of the number of moles of the compound shown in formula M1 to the volume of the organic solvent is (0.5-0.7) mmol:1m.

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: In an organic solvent or 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; 、 ， The preparation method and conditions of the copolymer A may also be as described in claim 4 or 5.

7. A polymer B, characterized in that, It is prepared by the following method, which 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 .

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 range is 110-122℃, for example, 117.54±2℃; (3) The polymer B loses 10% of its weight in the range of 495℃-510℃, for example, 503.0±2℃; (4) The polymer B loses 5% of its weight in the range of 480℃-500℃, for example, 484.2±2℃; (5) The polymer B loses 1% of its weight in the range of 420℃-440℃, for example, 429±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 (0.01-0.5):1, preferably (0.01-0.3):1, and more preferably (0.01-0.1):1; (4) The temperature of the cyclization reaction is 100-300℃; preferably 150-240℃; more preferably 180-220℃; and even more preferably 200℃. (5) The cyclization reaction is completed and post-treatment is also included, which includes the following steps: removing the organic solvent and drying, for example, soaking in petroleum ether and ethyl acetate to remove the organic solvent; (6) The procedure (IV) is preceded by step (III) as described in claim 6; Preferably, the method for preparing 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.

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 operation and conditions of the preparation method of polymer B may also be as described in claim 9.

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