A method for preparing a polyphenoxazine polymer membrane material

Abstract

A method for preparing a polyphenoxazine polymer membrane material is disclosed, which uses monomers containing phenolic hydroxyl and amino groups and fluorinated aromatic hydrocarbon monomers as raw materials, and synthesizes them under alkaline conditions through C-N and C-O coupling reactions. The alkaline is K2CO3 or Cs2CO3. This invention introduces nitrogen-containing groups, which facilitates subsequent functionalization modification. The raw materials are inexpensive (such as bisphenol A and potassium carbonate), and the process is simple. The product has excellent solubility in solvents such as tetrahydrofuran and good film-forming properties. It exhibits high selectivity and separation efficiency in gas separation and OSRO.

Description

Technical Field

[0001] This invention relates to the field of polymer material preparation, specifically a method for preparing a polyphenoxazine polymer membrane material. Background Technology

[0002] Intrinsically porous polymers (PIMs) exhibit immense application potential in fields such as environmental remediation, gas-liquid separation, sensors, and energy due to their interconnected microporous networks, high surface area, and structural diversity. Solution-processable PIMs can be transformed into various robust functional materials, including thin films, membranes, coatings, and fibers, to address diverse industrial challenges. However, despite numerous research findings on PIMs, with thousands of published papers and hundreds of patents, significant progress has been made in this area.

[0003] However, its industrial applications still require further development. Existing PIM material synthesis methods are relatively simple, mostly based on carbon-oxygen bonding to develop functional application materials. This not only limits its multifunctionality but also means that most PIM materials, due to their simple structure, can only be modified in a single way or are difficult to achieve multifunctional applications. Therefore, the development of new functional PIM materials is urgently needed. Summary of the Invention

[0004] In view of the above situation and to overcome the defects of the prior art, the present invention provides a method for preparing polyphenoxazine polymer membrane material, which effectively solves the problems mentioned in the background art.

[0005] To achieve the above objectives, the present invention provides the following technical solution: The present invention comprises the synthesis of a monomer containing phenolic hydroxyl and amino groups and a fluorinated aromatic hydrocarbon monomer as raw materials through a coupling reaction of CN and CO under alkaline conditions, wherein the alkaline is K2CO3 or Cs2CO3.

[0006] According to the above technical solution: the monomer containing phenolic hydroxyl and amino groups is selected from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-aminophenyl)propane or 3,3'-dihydroxybenzidine.

[0007] According to the above technical solution: the fluorinated aromatic monomer is tetrafluoroterephthalonitrile or decafluorobiphenyl.

[0008] According to the above technical solution: the reaction temperature is 0-80℃, and the reaction time is 4-72 hours.

[0009] According to the above technical solution: the solvent is anhydrous DMF or DMSO.

[0010] Application of a polyphenoxazine material prepared according to the above method in gas separation or organic liquid reverse osmosis membranes.

[0011] Beneficial effects: This invention introduces nitrogen-containing groups, which facilitates subsequent functionalization modification; the raw materials are inexpensive (such as bisphenol A and potassium carbonate), and the process is simple; the product has excellent solubility in solvents such as tetrahydrofuran and good film-forming properties; it exhibits high selectivity and separation efficiency in gas separation and OSRO. Attached Figure Description

[0012] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings:

[0013] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of monomer B of the present invention;

[0014] Figure 2 This is the carbon NMR spectrum of monomer B of this invention;

[0015] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of monomer C of this invention;

[0016] Figure 4 This is the carbon NMR spectrum of monomer C of this invention;

[0017] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of monomer D of the present invention;

[0018] Figure 6 This is the carbon NMR spectrum of monomer D of this invention;

[0019] Figure 7 This is the 1H NMR spectrum of the polymer MAPPOZ-1 of this invention;

[0020] Figure 8 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-1 of this invention;

[0021] Figure 9 This is the carbon NMR spectrum of the polymer MAPPOZ-1 of this invention;

[0022] Figure 10 This is the infrared spectrum of the polymer MAPPOZ-1 of this invention;

[0023] Figure 11 This is the GPC spectrum of the polymer MAPPOZ-1 of this invention;

[0024] Figure 12 This is the 1H NMR spectrum of the polymer MAPPOZ-2 of this invention;

[0025] Figure 13 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-2 of this invention;

[0026] Figure 14This is the carbon NMR spectrum of the polymer MAPPOZ-2 of this invention;

[0027] Figure 15 This is the infrared spectrum of the polymer MAPPOZ-2 of this invention;

[0028] Figure 16 This is the GPC spectrum of the polymer MAPPOZ-2 of this invention;

[0029] Figure 17 This is the 1H NMR spectrum of the polymer MAPPOZ-3 of this invention;

[0030] Figure 18 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-3 of this invention;

[0031] Figure 19 This is the carbon NMR spectrum of the polymer MAPPOZ-3 of this invention;

[0032] Figure 20 This is the infrared spectrum of the polymer MAPPOZ-3 of this invention;

[0033] Figure 21 This is the GPC spectrum of the polymer MAPPOZ-3 of this invention;

[0034] Figure 22 This is the proton NMR spectrum of the polymer MAPPOZ-4 of this invention;

[0035] Figure 23 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-4 of this invention;

[0036] Figure 24 This is the carbon NMR spectrum of the polymer MAPPOZ-4 of this invention;

[0037] Figure 25 This is the infrared spectrum of the polymer MAPPOZ-4 of this invention;

[0038] Figure 26 This is the GPC spectrum of the polymer MAPPOZ-4 of this invention;

[0039] Figure 27 This is the 1H NMR spectrum of the polymer MAPPOZ-5 of this invention;

[0040] Figure 28 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-5 of this invention;

[0041] Figure 29 This is the carbon NMR spectrum of the polymer MAPPOZ-5 of this invention;

[0042] Figure 30This is the infrared spectrum of the polymer MAPPOZ-5 of this invention;

[0043] Figure 31 This is the GPC spectrum of the polymer MAPPOZ-5 of this invention;

[0044] Figure 32 This is the 1H NMR spectrum of the polymer MAPPOZ-6 of this invention;

[0045] Figure 33 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-6 of this invention;

[0046] Figure 34 This is the carbon NMR spectrum of the polymer MAPPOZ-6 of this invention;

[0047] Figure 35 This is the infrared spectrum of the polymer MAPPOZ-6 of this invention;

[0048] Figure 36 This is the GPC spectrum of the polymer MAPPOZ-6 of this invention;

[0049] Figure 37 This is the 1H NMR spectrum of the polymer MAPPOZ-7 of this invention;

[0050] Figure 38 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-7 of this invention;

[0051] Figure 39 This is the carbon NMR spectrum of the polymer MAPPOZ-7 of this invention;

[0052] Figure 40 This is the infrared spectrum of the polymer MAPPOZ-7 of this invention;

[0053] Figure 41 This is the GPC spectrum of the polymer MAPPOZ-7 of this invention;

[0054] Figure 42 This is the 1H NMR spectrum of the polymer MAPPOZ-8 of this invention;

[0055] Figure 43 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-8 of this invention;

[0056] Figure 44 This is the carbon NMR spectrum of the polymer MAPPOZ-8 of this invention;

[0057] Figure 45 This is the infrared spectrum of the polymer MAPPOZ-8 of this invention;

[0058] Figure 46This is the GPC spectrum of the polymer MAPPOZ-8 of this invention;

[0059] Figure 47 This is the 1H NMR spectrum of the polymer MAPPOZ-9 of this invention;

[0060] Figure 48 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-9 of this invention;

[0061] Figure 49 This is the carbon NMR spectrum of the polymer MAPPOZ-9 of this invention;

[0062] Figure 50 This is the infrared spectrum of the polymer MAPPOZ-9 of this invention;

[0063] Figure 51 This is the GPC spectrum of the polymer MAPPOZ-9 of this invention;

[0064] Figure 52 This is the proton NMR spectrum of the polymer MAPPOZ-10 of this invention;

[0065] Figure 53 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-10 of this invention;

[0066] Figure 54 This is the carbon NMR spectrum of the polymer MAPPOZ-10 of this invention;

[0067] Figure 55 This is the infrared spectrum of the polymer MAPPOZ-10 of this invention;

[0068] Figure 56 This is the GPC spectrum of the polymer MAPPOZ-10 of this invention;

[0069] Figure 57 This is the 1H NMR spectrum of the polymer MAPPOZ-11 of this invention;

[0070] Figure 58 This is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-11 of this invention;

[0071] Figure 59 This is the carbon NMR spectrum of the polymer MAPPOZ-11 of this invention;

[0072] Figure 60 This is the infrared spectrum of the polymer MAPPOZ-11 of this invention;

[0073] Figure 61 This is the GPC spectrum of the polymer MAPPOZ-11 of this invention;

[0074] Figure 62These are the TGA spectra of the polymers of the present invention, MAPPOZ-1 to MAPPOZ-11;

[0075] Figure 63 This is a summary of PIMs publications and citations;

[0076] Figure 64 This is a summary of PIMs patent publications and citations. Detailed Implementation

[0077] The following is in conjunction with the appendix Figure 1-64 The specific embodiments of the present invention will be described in further detail below.

[0078] Example 1, by Figure 1-64 The present invention provides a method for preparing a polyphenoxazine polymer membrane material, the reaction formula of which is as follows:

[0079]

[0080] Monomer Synthesis

[0081]

[0082] Monomer B: Bisphenol A (20.0 g, 87.2 mmol, 1.0 equiv) and methanesulfonic acid (2 mL) were added to a 250 mL single-necked round-bottom flask. The mixture was reacted at 130 °C for 4 h, then cooled to room temperature. Excess water was added, and the mixture was stirred thoroughly until a large amount of solid precipitated. The reaction was quenched, and the mixture was heated to reflux. Ethanol was gradually added until the solid was just completely dissolved and the solution became clear and transparent. The solution was cooled to crystallize and dried in a vacuum oven at 80 °C to give approximately 18.0 g of white product B, with a yield of approximately 66%.

[0083] Monomer C: A solution of tetrabutylammonium nitrate (TBAB) (13.4 g, 44.0 mmol, 2.2 equiv) in dichloromethane (DCM) (60 mL) was added to a 250 mL double-necked flask. Trifluoromethanesulfonic anhydride (Tf₂O) (7.6 mL, 44.0 mmol, 2.2 equiv) was added dropwise to the above solution under nitrogen protection at room temperature. After reacting for 2 h, a solution of B (6.16 g, 20.0 mmol, 1.0 equiv) in DCM (40 mL) was added dropwise to the above mixture under nitrogen protection at -78 °C. The reaction was then allowed to proceed at room temperature, and the reaction was monitored by TLC. After the reaction was complete, a saturated sodium bicarbonate solution was slowly added directly to quench the reaction. The mixture was stirred thoroughly, and the aqueous phase was extracted with DCM. The combined organic phases were then used to remove the solvent using a rotary evaporator. Finally, the mixture was purified by column chromatography (pure PE to PE:EA = 5:1), and dried in a vacuum oven at 80 °C to remove residual solvent, yielding 5.5 g of yellow solid C, with a yield of 70%.

[0084] Monomer D: In a 200 mL double-necked flask, C (4.0 g, 10.0 mmol, 1.0 equiv) and Pd / C (10% wt, 0.7 g, 0.5 mmol, 0.05 equiv) were added. After 10 N2 displacements, ethanol (57 mL) was added, followed by the slow dropwise addition of hydrazine hydrate (50% inH2O, 10 mL, 100.0 mmol, 10.0 equiv). The mixture was refluxed overnight. After the reaction was complete, the mixture was directly filtered through diatomaceous earth, evaporated to dryness using a rotary evaporator, and dried under vacuum at 70 °C. 3.3 g of white product D was obtained, with a yield of 96%.

[0085] Synthetic steps of polyphenoxazine:

[0086] Synthesis of MAPPOZ-1:

[0087]

[0088] Solid reagents, including 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (168.1 mg, 0.5 mmol, 1.0 equiv), tetrafluoroterephthalonitrile (100.0 mg, 0.5 mmol, 1.0 equiv), and potassium carbonate (K2CO3, 138.2 mg, 1 mmol, 2.0 equiv), were added sequentially to a pressure-resistant reaction tube (Shinwell P260001 thick-walled tube with a side opening, 15 mL) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Then, anhydrous DMF (1 mL) was added, and the mixed reaction solution was stirred directly at 25 °C for 30 min. After the reaction was complete, THF (10 mL) and H₂O (2 mL) were added directly and stirred for 10 min to quench and dilute the reaction solution. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was added dropwise to 40 mL of n-hexane under stirring to precipitate and purify. The filtered solid was dried overnight in a vacuum oven at 60 °C to obtain a yellow powdery polymer solid MAPPOZ-1, 198 mg, with a yield of 87%. Fluorine spectrum calculation showed a ring closure degree of 76.5%.

[0089] Synthesis of MAPPOZ-2:

[0090]

[0091] Solid reagents, including 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (168.1 mg, 0.5 mmol, 1.0 equiv), decafluorobiphenyl (167.0 mg, 0.5 mmol, 1.0 equiv), and potassium carbonate (K2CO3, 138.2 mg, 1 mmol, 2.0 equiv), were added sequentially to a pressure-resistant reaction tube (Xinweier P260001 thick-walled tube with a side opening) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Then, anhydrous DMF (1 mL) was added. The mixed reaction solution was pre-stirred at room temperature for 15 min and then stirred at 80 °C for 4.5 h. After the reaction was complete, the mixture was cooled to room temperature, and THF (10 mL) and HCl (2 mL, 2 M) were added directly. The mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was adjusted to neutral with NaOH (1 M). The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was added dropwise to 40 mL of n-hexane under stirring for precipitation and purification, yielding a light green filamentous polymer, MAPPOZ-2, 251 mg, with a yield of 85%. Fluorine spectrum analysis showed a ring closure degree of 96%.

[0092] Synthesis of MAPPOZ-3:

[0093]

[0094] Solid reagents, including 2,2-bis(4-hydroxy-3-aminophenyl)propane (129.2 mg, 0.5 mmol, 1.0 equiv), tetrafluoroterephthalonitrile (100.0 mg, 0.5 mmol, 1.0 equiv), and cesium carbonate (Cs₂CO₃, 325.8 mg, 1 mmol, 2.0 equiv), were added sequentially to a pressure-resistant reaction tube (Sinwell P260001 thick-walled tube with a side opening, 15 mL) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Then, anhydrous DMF (1 mL) was added, and the mixed reaction solution was stirred overnight at 0 °C. After the reaction was complete, THF (10 mL) and HCl (2 mL, 2 M) were added directly, and the mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was then adjusted to neutral with NaOH (1 M). The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was then added dropwise to 40 mL of n-hexane under stirring for precipitation and purification, yielding 172 mg of red powdered polymer solid MAPPOZ-3, with a yield of 91%. Fluorine spectrum calculation showed a ring closure degree of 86%.

[0095] Synthesis of MAPPOZ-4:

[0096]

[0097] Solid reagents, including 2,2-bis(4-hydroxy-3-aminophenyl)propane (129.2 mg, 0.5 mmol, 1.0 equiv), decafluorobiphenyl (167.0 mg, 0.5 mmol, 1.0 equiv), and potassium carbonate (K2CO3, 138.2 mg, 1 mmol, 2.0 equiv), were added sequentially to a pressure-resistant reaction tube (Xinweier P260001 thick-walled tube with a side opening) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Then, anhydrous DMF (1 mL) was added. The mixed reaction solution was pre-stirred at room temperature for 15 min and then stirred at 80 °C for 3 h. After the reaction was complete, the mixture was cooled to room temperature, and THF (10 mL) and HCl (2 mL, 2 M) were added directly. The mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was adjusted to neutral with NaOH (1 M). The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was added dropwise to 40 mL of n-hexane under stirring for precipitation and purification. The grayish-white ribbon-like polymer MAPPOZ-4, 225 mg, yield was 88%. Fluorine spectrum analysis showed a ring-closing degree of 57%.

[0098] Synthesis of MAPPOZ-5:

[0099]

[0100] Solid reagents, including 3,3'-diamino-4,4'-biphenyl glycol (108.12 mg, 0.5 mmol, 1.0 equiv), tetrafluoroterephthalonitrile (100.0 mg, 0.5 mmol, 1.0 equiv), and potassium carbonate (K2CO3, 138.2 mg, 1 mmol, 2.0 equiv), were added sequentially to a pressure-resistant reaction tube (Shinwell P260001 thick-walled tube with a side opening, 15 mL) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Subsequently, anhydrous DMF (1 mL) was added, and the mixed reaction solution was stirred directly at 0 °C for 10 h. After the reaction was complete, THF (10 mL) and HCl (2 mL, 2 M) were added directly, and the mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was then adjusted to neutral with NaOH (1 M). The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was then added dropwise to 40 mL of n-hexane under stirring for precipitation and purification, yielding 144 mg of yellowish-brown flake-like polymer solid MAPPOZ-5, with a yield of 86%. Fluorine spectrum analysis showed a ring-closing degree of 72.5%.

[0101] Synthesis of MAPPOZ-6:

[0102]

[0103] Solid reagents, including 3,3'-diamino-4,4'-biphenyl glycol (108.12 mg, 0.5 mmol, 1.0 equiv), decafluorobiphenyl (167.0 mg, 0.5 mmol, 1.0 equiv), and potassium carbonate (K2CO3, 138.2 mg, 1 mmol, 2.0 equiv), were added sequentially to a pressure-resistant reaction tube (Xinweier P260001 thick-walled tube with a side opening) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Then, anhydrous DMF (1 mL) was added. The mixed reaction solution was pre-stirred at room temperature for 15 min and then stirred at 80 °C for 10 h. After the reaction was complete, the mixture was cooled to room temperature, and THF (10 mL) and HCl (2 mL, 2 M) were added directly. The mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was adjusted to neutral with NaOH (1 M). The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was added dropwise to 40 mL of n-hexane under stirring for precipitation and purification, yielding a grayish-white ribbon-like polymer, MAPPOZ-6, 209 mg, with a yield of 89%. Fluorine chromatography showed a ring-closing degree of 93.5%.

[0104] Synthesis of MAPPOZ-7:

[0105]

[0106] Solid reagents, including 3,3'-dihydroxybenzidine (108.12 mg, 0.5 mmol, 1.0 equiv), tetrafluoroterephthalonitrile (100.0 mg, 0.5 mmol, 1.0 equiv), and cesium carbonate (Cs₂CO₃, 325.8 mg, 1 mmol, 2.0 equiv), were added sequentially to a pressure-resistant reaction tube (Sinwell P260001 thick-walled tube with a side opening, 15 mL) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Subsequently, anhydrous DMF (1 mL) was added, and the mixed reaction solution was stirred directly at 25 °C for 4 days. After the reaction was complete, THF (10 mL) and HCl (2 mL, 2 M) were added directly, and the mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was then adjusted to neutral with NaOH (1 M). The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was then added dropwise to 40 mL of n-hexane under stirring for precipitation and purification, yielding a black solid powder, MAPPOZ-7, 90 mg, with a yield of 53%. Fluorine spectrum analysis showed a ring closure degree of 80.5%.

[0107] Synthesis of MAPPOZ-8:

[0108]

[0109] Solid reagents, including 3,3'-dihydroxybenzidine (108.12 mg, 0.5 mmol, 1.0 equiv), decafluorobiphenyl (167.0 mg, 0.5 mmol, 1.0 equiv), and potassium carbonate (K2CO3, 138.2 mg, 1 mmol, 2.0 equiv), were added sequentially to a pressure-resistant reaction tube (Shinwell P260001 thick-walled tube with a side opening) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Then, anhydrous DMF (1 mL) was added. The mixed reaction solution was pre-stirred at room temperature for 15 min and then stirred overnight at 80 °C. After the reaction was complete, the mixture was cooled to room temperature, and THF (10 mL) and HCl (2 mL, 2 M) were added directly. The mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was adjusted to neutral with NaOH (1 M). The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was added dropwise to 40 mL of n-hexane under stirring for precipitation and purification. The yield was 152 mg of a grayish-white powdery solid, MAPPOZ-8, with a yield of 65%. Fluorine spectrum analysis showed a ring closure degree of 87%.

[0110] Synthesis of MAPPOZ-9:

[0111]

[0112] Solid reagents, including product D (169.2 mg, 0.5 mmol, 1.0 equiv) and tetrafluoroterephthalonitrile (100.0 mg, 0.5 mmol, 1.0 equiv), were added sequentially to a pressure-resistant reaction tube (Shinwell P260001 thick-walled tube with a side opening, 15 mL) that had been dried in an oven. The pressure-resistant reaction tube was then purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Then, anhydrous DMSO (1 mL) was added. The mixed reaction solution was pre-stirred at room temperature for 15 min and then reacted at 120 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, and THF (10 mL) and HCl (2 mL, 2 M) were added directly. The mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was adjusted to neutral with NaOH (1 M). The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was added dropwise to 40 mL of n-hexane under stirring for precipitation and purification, yielding a reddish-brown solid powder, MAPPOZ-9, 98 mg, with a yield of 43%. Fluorine chromatography showed a ring-closing degree of 94.5%.

[0113] Synthesis of MAPPOZ-10:

[0114]

[0115] Solid reagents, including product D (169.2 mg, 0.5 mmol, 1.0 equiv), decafluorobiphenyl (167.0 mg, 0.5 mmol, 1.0 equiv), and potassium carbonate (K2CO3, 138.2 mg, 1 mmol, 2.0 equiv), were added sequentially to a pressure-resistant reaction tube (Shinwell P260001 thick-walled tube with a side opening) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Then, anhydrous DMF (1 mL) was added. The mixed reaction solution was pre-stirred at room temperature for 15 min and then stirred at 80 °C for 31 h. After the reaction was complete, the mixture was cooled to room temperature, and 10 mL of THF and 2 mL of HCl (2 M) were added directly. The mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was adjusted to neutral with 1 M NaOH. The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was added dropwise to 40 mL of n-hexane under stirring for precipitation and purification, yielding a grayish-white powdered polymer, MAPPOZ-10, 246 mg, with a yield of 83%. Fluorine spectroscopy showed a ring-closing degree of 88.5%.

[0116] Synthesis of MAPPOZ-11:

[0117]

[0118] Solid reagents including 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (190.2 mg, 0.5 mmol, 1.0 equiv), tetrafluoroterephthalonitrile (100.0 mg, 0.5 mmol, 1.0 equiv), and potassium carbonate (K2CO3, 138.2 mg, 1 mmol, 2.0 equiv) were added sequentially to a pressure-resistant reaction tube (Shinwell P260001 thick-walled tube with a side opening, 15 mL) that had been dried in an oven. Then, the pressure-resistant reaction tube was purged with gas (vacuumed and purged with nitrogen). The gas purging process was repeated 10 times. Then, anhydrous DMF (1 mL) was added, and the mixed reaction solution was stirred directly at 25 °C for 4 days. After the reaction was complete, THF (10 mL) and HCl (2 mL, 2 M) were added directly, and the mixture was stirred overnight until dissolved. After quenching, the diluted solution was transferred to a separatory funnel and washed thoroughly 2-3 times with 40 mL of saturated saline solution. The solution was then adjusted to neutral with NaOH (1 M). The organic phases were combined, and the solution containing the crude product was concentrated to 2-3 mL using a rotary evaporator. The polymer concentrate was then added dropwise to 40 mL of n-hexane under stirring for precipitation and purification, yielding a reddish-brown solid powder, MAPPOZ-11, 183 mg, with a yield of 73%. Fluorine spectrum analysis showed a ring closure degree of 85%.

[0119] The screening table refers to the reaction conditions screened under different solvents, bases, reaction times, and reaction temperatures. The bolded values ​​represent the best screening conditions. Unless otherwise specified, MAPPOZ polymers were not further screened, or their reaction results were poor. Unless otherwise specified, all monomers were added at 0.5 mmol, and the amount of base was 1 mmol.

[0120] Table 1. Conditional Filtering of MAPPOZ-1

[0121]

[0122] Table 2. Conditional Filtering of MAPPOZ-2

[0123]

[0124] Table 3. Conditional Filtering of MAPPOZ-3

[0125]

[0126] Table 4. Conditional Filtering of MAPPOZ-5

[0127]

[0128] Note: Monomer 3,3'-diamino-4,4'-biphenyl glycol (0.5 mmol), monomer tetrafluoroterephthalonitrile (0.52 mmol).

[0129] Table 5. Conditional Filtering of MAPPOZ-7

[0130]

[0131] Table 6. Conditional Filtering of MAPPOZ-9

[0132]

[0133] Table 7. Conditional Filtering of MAPPOZ-10

[0134]

[0135] The structural diagrams of the synthesized polymers MAPPOZ-1 to MAPPOZ-11 are as follows:

[0136]

[0137] Beneficial effects: Enhanced functionalization capability: By innovatively introducing nitrogen-containing groups (such as amino and hydroxyl groups) into the main chain, the post-modification capability of the polymer is significantly enhanced, overcoming the problem of limited introduction of functional groups in traditional inherent microporous polymers (PIMs), and providing a foundation for the multifunctional application of materials.

[0138] Low cost and simplified process: By using inexpensive and readily available raw materials (such as bisphenol A, potassium carbonate / cesium) and a simple CN / CO coupling reaction process, the use of expensive catalysts or complex synthesis steps is avoided, which greatly reduces the cost of industrial production.

[0139] Excellent solubility and processability: The resulting polymer is highly soluble in common solvents (such as tetrahydrofuran) and can be solution-processed into high-quality films, fibers or coatings to meet the needs of industrial-scale production.

[0140] Enhanced solvent resistance and stability: The material exhibits excellent swelling resistance and chemical stability in non-polar solvents, making it suitable for harsh separation environments (such as reverse osmosis of organic liquids).

[0141] High-efficiency separation performance:

[0142] Gas separation: The microporous structure is tunable, and it has high selective separation efficiency for gas pairs such as CO2 / CH4 and O2 / N2;

[0143] Organic liquid reverse osmosis (OSRO): Achieves high permeability and selectivity in the separation of organic solvent mixtures, suitable for the purification of high value-added chemicals.

[0144] Structural diversity: By adjusting the monomers and reaction conditions (such as temperature, time, and base type), a series of polyphenoxazine materials (MAPPOZ-1 to MAPPOZ-11) can be synthesized to meet the needs of different application scenarios.

[0145] Thermal stability: Thermogravimetric analysis (TGA) shows that the material remains stable at high temperatures (see example data for details), making it suitable for high-temperature separation or catalytic processes.

[0146] Supported data examples:

[0147] Yields are as high as 87%-96% (e.g., MAPPOZ-1, MAPPOZ-2);

[0148] With a wide molecular weight range (Mn=1.6-77.0kg / mol), it is suitable for different film thickness requirements;

[0149] The degree of ring closure reaches 57%-96%, and the porosity is adjusted to optimize the separation performance.

[0150] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a polyphenoxazine high molecular film material, characterized by: The monomer containing phenolic hydroxyl and amino and fluorinated aromatic monomer are used as raw materials, and are synthesized by C-N and C-O coupling reaction under alkaline condition, wherein the alkali is K2CO3 or Cs2CO3; The monomer containing phenolic hydroxyl and amino is selected from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-aminophenyl)propane or 3,3'-dihydroxybenzidine; The fluorinated aromatic monomer is tetrafluoro-p-phenylenedinitrile or decafluorobiphenyl.

2. The method of claim 1, wherein: The reaction temperature is 0-80 ℃, and the reaction time is 4-72 hours.

3. Application of the polyphenoxazine material prepared by the method in any one of claims 1-2 in gas separation or organic liquid reverse osmosis membrane.

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