Preparation method of polyphenoxazine polymeric membrane material

Abstract

The invention relates to a preparation method of a polyphenoxazine polymeric membrane material, the polyphenoxazine polymeric membrane material is synthesized through C-N and C-O coupling reaction by taking a monomer containing a phenolic hydroxyl group and an amino group and a fluorinated aromatic hydrocarbon monomer as raw materials under an alkaline condition, the alkali is K2CO3 or Cs2CO3, a nitrogen-containing group is introduced, and subsequent functional modification is facilitated; raw materials (such as bisphenol A and potassium carbonate) are cheap, and the process is simple; the product has excellent solubility in solvents such as tetrahydrofuran and the like and has good film-forming property; and high selectivity and separation efficiency are shown in gas separation and OSRO.

Description

Technical Field

[0001] The invention relates to the field of polymer material preparation, in particular to a method for preparing a polyphenoxazine polymer film material. Background Art

[0002] Intrinsically microporous polymers (PIMs) have great potential for application in environmental remediation, gas-liquid separation, sensors, and energy due to their interconnected microporous networks, high surface areas, and structural diversity. Solution-processable PIMs can be transformed into a variety of robust functional materials such as films, membranes, coatings, and fibers to meet different industrial challenges. However, despite the numerous research results related to PIMs, thousands of papers have been published, and hundreds of patents have been published.

[0003] However, its industrial application still needs further development. The existing PIM material synthesis pathway is relatively single, and most of them are based on carbon-oxygen connection to develop functional application materials, which not only limits their versatility, but also makes most PIM materials only able to be modified in a single way or difficult to achieve multifunctional applications due to their single structure. Therefore, the development of new PIM functional materials is imminent. Summary of the invention

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

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

[0006] According to the above technical solution: the monomer containing phenolic hydroxyl group and amino group 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 hydrocarbon monomer is tetrafluoroterephthalonitrile or decafluorobiphenyl.

[0008] According to the above technical solution: the reaction temperature is 0-80°C 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 the polyphenoxazine material prepared by the method in gas separation or organic liquid reverse osmosis membrane.

[0011] Beneficial effects: The present invention introduces nitrogen-containing groups, which is convenient for subsequent functional modification; the raw materials are cheap (such as bisphenol A, potassium carbonate), and the process is simple; the product has excellent solubility in solvents such as tetrahydrofuran and good film-forming performance; it exhibits high selectivity and separation efficiency in gas separation and OSRO. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings:

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

[0014] Figure 2 is the carbon nuclear magnetic resonance spectrum of monomer B of the present invention;

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

[0016] Figure 4 is the carbon nuclear magnetic resonance spectrum of monomer C of the present invention;

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

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

[0019] Figure 7 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-1 of the present invention;

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

[0021] Fig. 9 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-1 of the present invention;

[0022] Fig.10 is the infrared spectrum of the polymer MAPPOZ-1 of the present invention;

[0023] Fig.11 is the GPC spectrum of the polymer MAPPOZ-1 of the present invention;

[0024] Fig.12 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-2 of the present invention;

[0025] Fig.13 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-2 of the present invention;

[0026] Fig.14is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-2 of the present invention;

[0027] Fig.15 is the infrared spectrum of the polymer MAPPOZ-2 of the present invention;

[0028] Fig.16 is the GPC spectrum of the polymer MAPPOZ-2 of the present invention;

[0029] Fig.17 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-3 of the present invention;

[0030] Fig.18 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-3 of the present invention;

[0031] Fig.19 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-3 of the present invention;

[0032] Fig. 20 is the infrared spectrum of the polymer MAPPOZ-3 of the present invention;

[0033] Fig.21 is the GPC spectrum of the polymer MAPPOZ-3 of the present invention;

[0034] Fig. 22 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-4 of the present invention;

[0035] Fig.23 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-4 of the present invention;

[0036] Fig.24 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-4 of the present invention;

[0037] Fig.25 is the infrared spectrum of the polymer MAPPOZ-4 of the present invention;

[0038] Fig.26 is the GPC spectrum of the polymer MAPPOZ-4 of the present invention;

[0039] Fig. 27 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-5 of the present invention;

[0040] Fig.28 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-5 of the present invention;

[0041] Fig.29 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-5 of the present invention;

[0042] Fig.30is the infrared spectrum of the polymer MAPPOZ-5 of the present invention;

[0043] Fig.31 is the GPC spectrum of the polymer MAPPOZ-5 of the present invention;

[0044] Fig.32 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-6 of the present invention;

[0045] Fig.33 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-6 of the present invention;

[0046] Fig.34 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-6 of the present invention;

[0047] Fig.35 is the infrared spectrum of the polymer MAPPOZ-6 of the present invention;

[0048] Fig.36 is the GPC spectrum of the polymer MAPPOZ-6 of the present invention;

[0049] Fig.37 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-7 of the present invention;

[0050] Fig.38 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-7 of the present invention;

[0051] Fig.39 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-7 of the present invention;

[0052] Fig.40 is the infrared spectrum of the polymer MAPPOZ-7 of the present invention;

[0053] Fig.41 is the GPC spectrum of the polymer MAPPOZ-7 of the present invention;

[0054] Fig.42 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-8 of the present invention;

[0055] Fig.43 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-8 of the present invention;

[0056] Fig.44 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-8 of the present invention;

[0057] Fig.45 is the infrared spectrum of the polymer MAPPOZ-8 of the present invention;

[0058] Fig.46is the GPC spectrum of the polymer MAPPOZ-8 of the present invention;

[0059] Fig.47 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-9 of the present invention;

[0060] Fig.48 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-9 of the present invention;

[0061] Fig.49 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-9 of the present invention;

[0062] Fig.50 is the infrared spectrum of the polymer MAPPOZ-9 of the present invention;

[0063] Fig.51 is the GPC spectrum of the polymer MAPPOZ-9 of the present invention;

[0064] Fig.52 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-10 of the present invention;

[0065] Fig.53 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-10 of the present invention;

[0066] Fig.54 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-10 of the present invention;

[0067] Fig.55 is the infrared spectrum of the polymer MAPPOZ-10 of the present invention;

[0068] Fig.56 is the GPC spectrum of the polymer MAPPOZ-10 of the present invention;

[0069] Fig.57 is the hydrogen nuclear magnetic resonance spectrum of the polymer MAPPOZ-11 of the present invention;

[0070] Fig.58 is the nuclear magnetic resonance fluorine spectrum of the polymer MAPPOZ-11 of the present invention;

[0071] Fig.59 is the carbon nuclear magnetic resonance spectrum of the polymer MAPPOZ-11 of the present invention;

[0072] Fig.60 is the infrared spectrum of the polymer MAPPOZ-11 of the present invention;

[0073] Fig.61 is the GPC spectrum of the polymer MAPPOZ-11 of the present invention;

[0074] Fig.62are TGA spectra of MAPPOZ-1 to MAPPOZ-11 of the polymers of the present invention;

[0075] Fig.63 It is a summary of PIMs literature publication and citations;

[0076] Fig.64 It is a summary of PIMs patent publications and citations. DETAILED DESCRIPTION

[0077] The following is combined with Figure 1-64 The specific implementation modes of the present invention are described in further detail.

[0078] Embodiment 1, by Figure 1-64 The present invention provides a method for preparing a polyphenoxazine polymer film material, and the reaction formula is as follows:

[0079]

[0080] Monomer synthesis

[0081]

[0082] Monomer B: Add bisphenol A (20.0 g, 87.2 mmol, 1.0 equiv) and methanesulfonic acid (2 mL) to a 250 mL single-mouth round-bottom flask, react at 130°C for 4 h, and then cool to room temperature. Add excess water, stir thoroughly until a large amount of solid precipitates from the solution, quench the reaction, heat under reflux, gradually add ethanol until all of the solid is dissolved, until the solution is clear and transparent, cool and crystallize, and use a vacuum oven at 80°C to obtain about 18.0 g of white product B with a yield of about 66%.

[0083] Monomer C: Add tetrabutylammonium nitrate (TBAB) (13.4 g, 44.0 mmol, 2.2 equiv) in dichloromethane (DCM) (60 mL) to a 250 mL double-necked flask, and dropwise add trifluoromethanesulfonic anhydride (Tf2O) (7.6 mL, 44.0 mmol, 2.2 equiv) to the above solution under nitrogen at room temperature. After reacting for 2 h, add dropwise B (6.16 g, 20.0 mmol, 1.0 equiv) in DCM (40 mL) under nitrogen protection at -78 ° C to the above mixed system, react at room temperature, and monitor the reaction by TLC. After the reaction is completed, directly and slowly add saturated sodium bicarbonate solution to quench the reaction, stir well, extract the aqueous phase with DCM, combine the organic phases and remove the solvent using a rotary evaporator. Finally, column chromatography purification (pure PE to PE: EA = 5: 1) and dry in a vacuum oven at 80 ° C to remove the residual solvent to obtain 5.5 g of yellow solid C with a yield of 70%.

[0084] Monomer D: 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 to a 200 mL double-necked flask. After N2 replacement 10 times, ethanol (57 mL) was added, and hydrazine hydrate (50% inH2O, 10 ml, 100.0 mmol, 10.0 equiv) was slowly added dropwise to the reaction system, and refluxed overnight. After the reaction was completed, it was directly filtered with diatomaceous earth, dried by rotary evaporation, and dried in vacuo at 70°C. 3.3 g of white product D was obtained with a yield of 96%.

[0085] Synthesis 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 in sequence to a pressure reaction tube (Hinwell P260001 thick wall with side port, 15 mL) dried in an oven, and then the pressure reaction tube was gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times, and then anhydrous DMF (1 mL) was added, and the mixed reaction liquid was directly stirred at 25 °C for 30 min. After the reaction is completed, THF (10 mL) and H2O (2 mL) are directly added and stirred for 10 min to quench and dilute the reaction solution. After quenching, the diluted solution is transferred to a separatory funnel and washed 2-3 times with 40 mL of saturated brine. The organic phases are combined and the solution containing the crude product is concentrated to 2-3 mL by means of a rotary evaporator. The polymer concentrate is added dropwise to 40 mL of n-hexane under stirring to precipitate and purify. The filtered solid is dried in a vacuum oven at 60°C overnight to obtain a yellow powdery polymer solid MAPPOZ-1, 198 mg, with a yield of 87%. The degree of ring closure calculated by fluorine spectrum is 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 in sequence to a pressure reaction tube (Hinwell P260001 thick-walled, with side port, 15 mL) dried in an oven. The pressure reaction tube was then gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times. Subsequently, 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 is completed, cool to room temperature, directly add THF (10 mL) and HCl (2 mL, 2 M), stir overnight until dissolved, transfer the diluted solution to a separatory funnel after quenching, use 40 mL saturated brine to wash 2-3 times, adjust to neutral with NaOH (1 M), combine the organic phases, and use a rotary evaporator to concentrate the solution containing the crude product to 2-3 mL, and drop the polymer concentrate into 40 mL of n-hexane under stirring to precipitate and purify, and obtain a light green filamentous polymer MAPPOZ-2, 251 mg, with a yield of 85%. The degree of ring closure calculated by fluorine spectrum: 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 in sequence to a pressure reaction tube (Hinwell P260001 thick wall with side port, 15 mL) dried in an oven, and then the pressure reaction tube was gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times, and then anhydrous DMF (1 mL) was added, and the mixed reaction liquid was stirred directly at 0°C overnight. After the reaction is completed, THF (10 mL) and HCl (2 mL, 2 M) are directly added, and stirred overnight until dissolved. After quenching, the diluted solution is transferred to a separatory funnel, and washed 2-3 times with 40 mL of saturated brine, adjusted to neutral with NaOH (1 M), and the organic phases are combined. The solution containing the crude product is concentrated to 2-3 mL by means of a rotary evaporator, and the polymer concentrate is added dropwise to 40 mL of n-hexane under stirring to precipitate and purify, to obtain a red powdery polymer solid MAPPOZ-3, 172 mg, with a yield of 91%. The degree of ring closure calculated by fluorine spectrum: 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 in sequence to a pressure reaction tube (Hinwell P260001 thick-walled, with side port, 15 mL) dried in an oven. The pressure reaction tube was then gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times, and 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 is completed, cool to room temperature, directly add THF (10mL) and HCl (2mL, 2M), stir overnight until dissolved, transfer the diluted solution to a separatory funnel after quenching, use 40mL saturated brine to wash 2-3 times, adjust to neutral with NaOH (1M), combine the organic phases, use a rotary evaporator to concentrate the solution containing the crude product to 2-3mL, add the polymer concentrate dropwise to 40mL of n-hexane under stirring to precipitate and purify, off-white ribbon polymer MAPPOZ-4, 225mg, yield 88%. Fluorine spectrum calculation of ring closure degree: 57%.

[0098] Synthesis of MAPPOZ-5:

[0099]

[0100] Solid reagents including 3,3'-diamino-4,4'-biphenyl diol (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 in sequence to a pressure reaction tube (Hinwell P260001 thick wall with side port, 15 mL) dried in an oven. The pressure reaction tube was then gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times. Anhydrous DMF (1 mL) was then added and the mixed reaction liquid was stirred directly at 0°C for 10 h. After the reaction is completed, THF (10 mL) and HCl (2 mL, 2 M) are directly added, and stirred overnight until dissolved. After quenching, the diluted solution is transferred to a separatory funnel, and washed 2-3 times with 40 mL of saturated brine, and adjusted to neutral with NaOH (1 M), and the organic phases are combined. The solution containing the crude product is concentrated to 2-3 mL by means of a rotary evaporator, and the polymer concentrate is added dropwise to 40 mL of n-hexane under stirring to precipitate and purify, and a yellowish-brown flaky polymer solid MAPPOZ-5 is obtained, 144 mg, with a yield of 86%. The degree of ring closure calculated by fluorine spectrum is 72.5%.

[0101] Synthesis of MAPPOZ-6:

[0102]

[0103] Solid reagents including 3,3'-diamino-4,4'-biphenyldiol (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 in sequence to a pressure reaction tube (Hinwell P260001 thick-walled, with side port, 15 mL) dried in an oven. The pressure reaction tube was then gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times, and 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 is completed, cool to room temperature, directly add THF (10 mL) and HCl (2 mL, 2 M), stir overnight until dissolved, transfer the diluted solution to a separatory funnel after quenching, use 40 mL saturated brine to fully wash 2-3 times, adjust to neutral with NaOH (1 M), combine the organic phases, and use a rotary evaporator to concentrate the solution containing the crude product to 2-3 mL, and drop the polymer concentrate into 40 mL of n-hexane under stirring to precipitate and purify, to obtain an off-white ribbon polymer MAPPOZ-6, 209 mg, with a yield of 89%. The degree of ring closure calculated by fluorine spectrum: 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 in sequence to a pressure reaction tube (Hinwell P260001 thick wall with side port, 15 mL) dried in an oven. The pressure reaction tube was then gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times. Anhydrous DMF (1 mL) was then added and the mixed reaction solution was stirred directly at 25 °C for 4 d. After the reaction is completed, THF (10 mL) and HCl (2 mL, 2 M) are directly added, and stirred overnight until dissolved. After quenching, the diluted solution is transferred to a separatory funnel, and washed 2-3 times with 40 mL of saturated brine, adjusted to neutral with NaOH (1 M), and the organic phases are combined. The solution containing the crude product is concentrated to 2-3 mL by means of a rotary evaporator, and the polymer concentrate is added dropwise to 40 mL of n-hexane under stirring to precipitate and purify, to obtain a black solid powder MAPPOZ-7, 90 mg, with a yield of 53%. The degree of ring closure calculated by fluorine spectrum: 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 in sequence to a pressure reaction tube (Hinwell P260001 thick-walled, with side port, 15 mL) dried in an oven. The pressure reaction tube was then gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times. Subsequently, 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 is completed, cool to room temperature, directly add THF (10 mL) and HCl (2 mL, 2 M), stir overnight until dissolved, transfer the diluted solution to a separatory funnel after quenching, use 40 mL saturated brine to fully wash 2-3 times, adjust to neutral with NaOH (1 M), combine the organic phases, and use a rotary evaporator to concentrate the solution containing the crude product to 2-3 mL, and drop the polymer concentrate into 40 mL of n-hexane under stirring to precipitate and purify, off-white powder solid MAPPOZ-8, 152 mg, yield 65%. Fluorine spectrum calculation of ring closure degree: 87%.

[0110] Synthesis of MAPPOZ-9:

[0111]

[0112] To a pressure-resistant reaction tube (Hinwell P260001 thick-walled, with side port, 15 mL) dried in an oven, 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 in sequence, and then the pressure-resistant reaction tube was gas-substituted (vacuumed and flushed with nitrogen). The gas-substituted operation was repeated 10 times, and 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 is completed, cool to room temperature, directly add THF (10 mL) and HCl (2 mL, 2 M), stir overnight until dissolved, transfer the diluted solution to a separatory funnel after quenching, use 40 mL saturated brine to wash 2-3 times, adjust to neutral with NaOH (1 M), combine the organic phases, and use a rotary evaporator to concentrate the solution containing the crude product to 2-3 mL, and drop the polymer concentrate into 40 mL of n-hexane under stirring to precipitate and purify, to obtain a reddish brown solid powder MAPPOZ-9, 98 mg, yield 43%. Fluorine spectrum calculation of the degree of ring closure: 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 in sequence to a pressure reaction tube (Hinwell P260001 thick-walled, with side port, 15 mL) dried in an oven. The pressure reaction tube was then gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times, and 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 is completed, cool to room temperature, directly add THF (10mL) and HCl (2mL, 2M), stir overnight until dissolved, transfer the diluted solution to a separatory funnel after quenching, use 40mL saturated brine to wash 2-3 times, adjust to neutral with NaOH (1M), combine the organic phases, and use a rotary evaporator to concentrate the solution containing the crude product to 2-3mL, and drop the polymer concentrate into 40mL of n-hexane under stirring to precipitate and purify, and obtain an off-white powder polymer MAPPOZ-10, 246mg, with a yield of 83%. The degree of ring closure calculated by fluorine spectrum: 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 in sequence to a pressure reaction tube (Hinwell P260001 thick wall with side port, 15 mL) dried in an oven. The pressure reaction tube was then gas replaced (vacuumed and flushed with nitrogen). The gas replacement operation was repeated 10 times. Anhydrous DMF (1 mL) was then added and the mixed reaction solution was stirred directly at 25 °C for 4 d. After the reaction is completed, THF (10 mL) and HCl (2 mL, 2 M) are directly added, and stirred overnight until dissolved. After quenching, the diluted solution is transferred to a separatory funnel, and washed 2-3 times with 40 mL of saturated brine, adjusted to neutral with NaOH (1 M), and the organic phases are combined. The solution containing the crude product is concentrated to 2-3 mL by means of a rotary evaporator, and the polymer concentrate is added dropwise to 40 mL of n-hexane under stirring to precipitate and purify, to obtain a reddish brown solid powder MAPPOZ-11, 183 mg, with a yield of 73%. The degree of ring closure calculated by fluorine spectrum: 85%.

[0119] The condition screening table refers to the reaction conditions screened under different solvents, bases, reaction times and reaction temperatures. The best reaction conditions are marked. MAPPOZ polymers not specifically listed were not further screened or had poor reaction effects. Unless otherwise specified, all monomers were fed at 0.5 mmol and the amount of base was 1 mmol.

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

[0121]

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

[0123]

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

[0125]

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

[0127]

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

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

[0130]

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

[0132]

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

[0134]

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

[0136]

[0137] Beneficial effects: Improved functional modification capabilities: By innovatively introducing nitrogen-containing groups (such as amino and hydroxyl groups) into the main chain, the post-modification capabilities of the polymer are significantly enhanced, overcoming the problem of limited introduction of functional groups into traditional intrinsic microporous polymers (PIMs), providing a basis for the multifunctional application of materials.

[0138] Low cost and simplified process: Using cheap and readily available raw materials (such as bisphenol A, potassium carbonate / cesium) and a simple CN / CO coupling reaction process, avoiding the use of expensive catalysts or complex synthesis steps, greatly reducing the cost of industrial production.

[0139] Excellent solubility and processability: The obtained polymer has good solubility in conventional solvents (such as tetrahydrofuran) and can be processed into high-quality films, fibers or coatings in solution 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 and is suitable for harsh separation environments (such as reverse osmosis of organic liquids).

[0141] High efficiency separation performance:

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

[0143] Organic Liquid Reverse Osmosis (OSRO): Achieve high permeate flux 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), and is suitable for high-temperature separation or catalytic processes.

[0146] Supporting data examples:

[0147] The yield is as high as 87%-96% (such as MAPPOZ-1, MAPPOZ-2);

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

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

[0150] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a polyphenoxazine polymer film material, characterized in that: The method is synthesized by using a monomer containing a phenolic hydroxyl group and an amino group and a fluorinated aromatic hydrocarbon monomer as raw materials through a CN and CO coupling reaction under alkaline conditions, wherein the base is K2CO3 or Cs2CO3.

2. The method according to claim 1, characterized in that: The monomer containing phenolic hydroxyl group and amino group is selected from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-aminophenyl)propane or 3,3'-dihydroxybenzidine.

3. The method according to claim 2, characterized in that: The fluorinated aromatic hydrocarbon monomer is tetrafluoroterephthalonitrile or decafluorobiphenyl.

4. The method according to claim 3, characterized in that: The reaction temperature is 0-80°C, and the reaction time is 4-72 hours.

5. The method according to claim 4, characterized in that: The solvent is anhydrous DMF or DMSO.

6. Use of the polyphenoxazine material prepared by the method of any one of claims 1 to 5 in gas separation or organic liquid reverse osmosis membrane.

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