High-antifouling polyarylether separation membrane as well as preparation method and application thereof

Abstract

The invention discloses a high-antifouling polyarylether separation membrane and a preparation method and application thereof.The preparation method comprises the steps that polyarylether polymer powder is added into a solvent B, then a quaternization reagent is added, quaternization polyarylether polymer powder is obtained, the quaternization polyarylether polymer powder is added into a solvent C, and a membrane casting solution is prepared; and dropwise adding the membrane casting solution on a membrane casting glass plate to obtain the high-antifouling polyarylether separation membrane. According to the invention, the separation membrane applied to biomedical use and blood purification is prepared through condensation and quaternization reactions. The high-antifouling polyarylether separation membrane obtained by the invention has excellent separation efficiency, anti-pollution performance, good mechanical performance, thermal stability, blood compatibility and anticoagulation performance, and improves the circulating ultrafiltration stability and easy cleaning performance; the method has wide application prospects in the fields of biological clinical medical filter membranes, hemodialysis, water treatment, resource recovery, environmental protection and the like.

Description

Technical Field

[0001] The present invention belongs to the field of organic synthetic polymer materials, and in particular relates to a highly antifouling polyarylether separation membrane and a preparation method and application thereof. Background Art

[0002] With the continuous development of bioclinical medicine, the impact of protein and bacterial biofouling on biosensors, contact lenses, and medical devices has become increasingly significant. Preventing biofouling and creating new functional antifouling materials are crucial to the survival of life. Membrane separation technology has been applied in biomedicine to address global challenges in medical selective filtration and flux related to drug filtration and hemodialysis. Antifouling technologies based on separation membranes have attracted widespread attention due to their unique ability to remove large molecular proteins, low energy consumption, and acid and alkali resistance. Poly(arylene ether) separation membranes have excellent mechanical, thermal, and chemical durability and are widely used in antifouling, medical separation membranes, and medical coatings. Due to the inherent hydrophobicity of poly(arylene ether) separation membranes, membrane fouling (pore clogging, low water flux, protein adsorption, platelet adsorption, and bacterial adhesion) limits the effectiveness and service life of poly(arylene ether) separation membranes, which can rapidly lead to biofilm fouling. Therefore, improving membrane antifouling properties and developing new materials are crucial to maintaining the lifespan of antifouling and hemocompatible separation membranes. By producing hydrophilic modified antifouling membranes, permeability can be improved, membrane flow resistance can be reduced, and the adsorption and adhesion of pollutants on the membrane surface and within the membrane can be reduced. Zwitterionic polymers are the most common membrane materials for hydrophilic modification of separation membranes and enhancing membrane antifouling properties.

[0003] In recent years, zwitterionic inner salt polymers (including polyphosphorylcholine, polysulfonate, polyimidazole salt, polyzwitterionic acrylic acid and inner salt polysiloxane series) have shown significant application potential in many fields. The excellent antifouling performance and biocompatibility of this type of material are derived from its unique comprehensive properties: the highly hydrophilic surface can form a hydration layer barrier, effectively inhibiting the nonspecific adsorption of proteins; the charge shielding effect reduces interfacial interactions, and the anti-adhesion function is achieved through surface energy regulation; it has both self-assembly ability and long-term stability, and some systems also show broad-spectrum antibacterial activity. These characteristics enable inner salt polymers to not only block the adhesion of pollutants, but also show excellent adaptability in the biomedical field (such as drug carriers, implantable devices, tissue engineering materials, etc.).

[0004] As an important branch, phosphate functionalized polymers have unique mechanisms for improving antifouling and biocompatibility. The zwitterionic groups (carrying both positive and negative charges) in the molecular structure give the material cell membrane properties. The similarity between the phosphate group and the phospholipid structure of biological membranes produces a biomimetic effect: on the one hand, it enhances the affinity of the material-biological interface through intermolecular interactions, and on the other hand, it reduces immunogenicity and improves in vivo stability. Currently, the functionalization of phosphate polymers mostly adopts a structural model in which the phosphate group is directly grafted onto the main chain of the polymer, resulting in insufficient exposure of the choline group with key hydration function, which limits the full use of the material performance.

[0005] Existing polyarylether separation membranes suffer from membrane fouling problems due to their inherent hydrophobicity, specifically manifested as protein adsorption, platelet adhesion, flux attenuation, and insufficient blood compatibility, which seriously restricts their application in the biomedical field. Traditional zwitterion modification technology has defects such as insufficient exposure of functional groups and complex synthesis processes, making it difficult to achieve long-term antifouling while maintaining mechanical strength. The present invention anchors the choline group to the main side chain of the polymer through reverse functionalization, while releasing the surface modification ability of the phosphate group. This biomimetic structural reconstruction can greatly enhance the hydration effect and antifouling performance of the material, and the simplified synthesis path is more conducive to industrial implementation. Summary of the Invention

[0006] The present invention proposes a highly antifouling polyarylether separation membrane, its preparation method, and application. This design effectively improves the hydrophilicity and hydration effect of the material, breaking through the limitation of insufficient exposure of choline groups in the existing technology. At the same time, through a simplified synthesis path, stable control of functional groups is achieved, which significantly enhances the antifouling performance, anticoagulant properties and blood compatibility of the separation membrane, and solves the problems of short service life and poor biocompatibility caused by membrane fouling.

[0007] The technical solution adopted in the present invention is as follows:

[0008] In one aspect, the present invention provides a method for preparing a highly antifouling polyarylene ether separation membrane, comprising the following steps:

[0009] 1) adding polyarylene ether polymer powder to solvent B, then adding a quaternary ammonium reagent, reacting at a temperature of 80-100° C. for 48-72 hours, pouring the reaction solution into deionized water for precipitation, filtering to obtain a solid powder, washing with ethanol 3-5 times, and vacuum drying at 90° C. for 24 hours to obtain a quaternary polyarylene ether polymer powder;

[0010] 2) adding quaternized polyarylene ether polymer powder to solvent C and stirring at room temperature for 6 to 8 hours to prepare a casting solution; then dripping the casting solution onto a casting glass plate, scraping the asymmetric separation membrane using a 200 μm thick scraper at room temperature, and performing phase inversion exfoliation in deionized water, followed by washing to obtain a highly antifouling polyarylene ether separation membrane;

[0011] The molecule of the polyarylene ether polymer powder contains the structure shown in Formula 1:

[0012]

[0013] wherein n=0.01 to 0.99, R' is an oxygen element, and R' is any one of an oxygen atom, a bistrifluoromethyl group, a dimethyl group, a sulfone group, a biphenyl group, a carbonyl group, and a biphenyl group;

[0014] The molecular structural formula 2 of the quaternary ammonium reagent is as follows:

[0015]

[0016] wherein R is independently selected from a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsilyloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halophenyl group, a halobiphenyl group, a phenol group, a phenol group containing an alkyl group, a phenol group containing an alkenyl group, a phenol group containing an alkynyl group, a phenol group containing a nitrile group, a monohalogenated phenol group, and a polyhalogenated phenol group;

[0017] The molecule of the highly antifouling polyarylene ether separation membrane contains the structure shown in Formula 3:

[0018]

[0019] Wherein, R is independently selected from a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsilyloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenol group, an alkyl-containing phenol group, an alkenyl-containing phenol group, an alkynyl-containing phenol group, a nitrile-containing phenol group, a monohalogenated phenol group, and a polyhalogenated phenol group.

[0020] Preferably, the raw materials of the polyarylene ether polymer powder include, by mole fraction, 0.99 to 0.01 parts of sulfur- or oxygen-containing monomers, 0.01 to 0.99 parts of tertiary amine-containing bisphenol monomers, 1 part of dihalogenated aromatic compounds, 100 to 1000 parts of solvent A, 1 to 10 parts of base, and 30 to 60 parts of dehydrating agent.

[0021] Preferably, the tertiary amine-containing bisphenol monomer is any one or a combination of the compounds represented by the following structural formulas:

[0022]

[0023] The sulfur-containing or oxygen-containing monomer is any one or a combination of compounds represented by the following structural formulas:

[0024]

[0025] The structural formula of the dihalogenated aromatic compound is at least one or a combination of the following compounds:

[0026]

[0027] The solvent A is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane; the base is any one of potassium carbonate, cesium carbonate, sodium carbonate, and guanidine carbonate; and the dehydrating agent is any one of cyclohexane, toluene, xylene, and benzophenone.

[0028] Preferably, the synthesis steps of the tertiary amine-containing bisphenol monomer are as follows: A) dissolving bisphenol in ethanol to form a mixed solution, stirring at room temperature until the bisphenol is completely dissolved, and then sequentially adding formaldehyde aqueous solution and dimethylamine aqueous solution to the mixed solution to form a reaction solution; B) stirring the reaction solution in step A) at room temperature for 48 to 72 hours until a white solid appears in the reaction solution, filtering the reaction solution to obtain a solid crude product, then washing it with hot water 3 to 5 times, filtering to obtain a white product, and then recrystallizing it with ethanol at 80° C., cooling and filtering to obtain a white crystalline product, and vacuum drying it at 80° C. for 24 hours to obtain the tertiary amine-containing bisphenol monomer.

[0029] Preferably, the synthesis steps of the polyarylene ether polymer powder are as follows: under the protection of inert gas, a tertiary amine-containing bisphenol monomer, a sulfur-containing or oxygen-containing monomer, and a dihalogenated aromatic compound are dissolved in solvent A, and then a base and a dehydrating agent are added simultaneously, and the mixture is refluxed at 100-130° C. for 4-6 hours to remove water, and the dehydrating agent is completely evaporated at 135° C. within 1 hour, and the temperature is kept constant at 160-180° C. for reaction for 24-48 hours. Finally, the reaction is lowered to room temperature, and the reaction solution is poured into deionized water for precipitation, and the solid powder is filtered to obtain a solid powder, which is washed with ethanol 3-5 times and vacuum dried at 90° C. for 24 hours to obtain the polyarylene ether polymer powder.

[0030] Preferably, in the synthesis step of the polyarylene ether polymer powder, the molar ratio of tertiary amine-containing bisphenol monomer: sulfur-containing or oxygen-containing monomer: dihalogenated aromatic compound: base is (0.01-0.99): (0.99-0.01): 1: (1-10).

[0031] Preferably, in step 1), the molar ratio of polyarylene ether polymer powder to quaternizing agent is 1:(2-8); the solid content of the polyarylene ether polymer powder in solvent B in step 1) is 15-20 wt%; and solvent B in step 1) is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

[0032] Preferably, the solid content of the quaternized polyarylene ether polymer powder in the solvent C in step 2) is 15 to 20 wt %, and the solvent C in step 2) is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

[0033] Another aspect of the present invention provides a highly antifouling polyarylene ether separation membrane prepared by the above method.

[0034] Another aspect of the present invention provides the use of the highly antifouling polyarylene ether separation membrane prepared by the above method in biological clinical medicine and blood purification. The highly antifouling polyarylene ether separation membrane is used in biological clinical medicine and blood purification to achieve high antifouling performance and improve blood compatibility.

[0035] The present invention has the following advantages:

[0036] (1) The present invention synthesizes a tertiary amine-containing bisphenol monomer (DABPE) through the Mannich reaction. This monomer provides a modifiable tertiary amine site. DABPE is polycondensed with a sulfur / oxygen-containing monomer (such as 4,4'-dihydroxydiphenyl sulfone) and a dihalogenated aromatic compound (such as 4,4'-difluorodiphenyl sulfone) in a specific molar ratio to obtain a polyarylether polymer containing a modifiable tertiary amine in the main chain.

[0037] (2) The present invention innovatively uses a phosphate quaternization reagent to functionalize the polymer backbone to form a choline phosphate zwitterionic surface with a cell membrane-mimicking structure, successfully constructing a high-density zwitterionic functional layer.

[0038] (3) By optimizing and controlling the phase inversion process parameters (casting solution concentration 18 wt%, coagulation bath temperature 25°C), the phase inversion method was used to control the casting solution concentration to 15-20 wt%, the coagulation bath temperature to 25±2°C, and the scraping film thickness to 200 μm, thereby constructing an asymmetric pore structure and achieving a synergistic improvement in separation efficiency and flux. The highly antifouling polyarylether separation membrane prepared by this method exhibits excellent separation efficiency, antifouling performance, good mechanical properties, blood compatibility, anticoagulant properties, and improved cyclic ultrafiltration stability and easy cleaning. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1H NMR spectra of the examples, including: tertiary amine-containing bisphenol monomer DABPE (a), polymer PES-x (b), polymer PES-Zx (c), FTIR spectra of PES-50 and PES-Z-50 (d);

[0040] Figure 2 The ternary phase diagram (a) and phase transformation process (b) of the polymer PES-Zx casting solution prepared in the example;

[0041] Figure 3 DSC (a), TGA (b), stress-strain curve (c), and Zeta potential (d) of the polymer PES-Zx separation membrane prepared in the examples;

[0042] Figure 4 The water contact angle (a), static BSA adsorption degree (b), dynamic water flux and BSA retention rate (c), and cyclic ultrafiltration performance (d) of the polymer PES-Zx separation membrane prepared in the example;

[0043] Figure 5 The antibacterial coating (a) and bacterial adhesion rate (b) of the polymer PES-Zx separation membrane prepared in the example;

[0044] Figure 6 The hemolysis (a), blood coagulation index (b), plasma recalcification time (c), and complement activation concentration (d) of the polymer PES-Zx separation membrane prepared in the examples are shown. DETAILED DESCRIPTION

[0045] The highly antifouling polyarylene ether separation membrane of the present invention, its preparation method and application are further described below in conjunction with specific examples, but the present invention is not limited to the following examples.

[0046] Example 1

[0047] A method for preparing a highly antifouling polyarylene ether separation membrane comprises the following steps:

[0048] S1. Synthesis of a tertiary amine-containing bisphenol monomer: 4,4'-dihydroxydiphenyl ether (10.000 g, 0.0495 mol) was dissolved in ethanol, and then a solution containing dimethylamine (6.689 g, 0.1484 mol) and formaldehyde (5.945 g, 0.1980 mol) was added. The mixed solution was stirred at room temperature for 72 h, during which the solution was dark red. Subsequently, the reaction was terminated, the solution remained stationary, and a white solid precipitate was observed. Then, suction filtration was performed to obtain a crude product. The crude product was recrystallized from ethanol to obtain a white crystalline product. In this embodiment, the tertiary amine-containing bisphenol monomer is named DABPE;

[0049] S2. Preparation of a polyarylene ether polymer powder: DABPE (3.16 g, 0.01 mol), 4,4-dihydroxydiphenyl ether (8.09 g, 0.04 mmol), 4,4-difluorodiphenyl sulfone (12.71 g, 0.05 mol), K2CO3 (17.28 g, 0.125 mol), 80 mL of N,N-dimethylacetamide, and 20 mL of toluene were added to a 250 mL three-necked round-bottom flask equipped with a nitrogen inlet, a mechanical stirrer, and a condenser. The reaction mixture was refluxed at 130°C for 3 h to dehydrate the system. The temperature was then slowly raised to 180°C and polymerized for 8 h to obtain a viscous liquid. After the solution became very viscous, the reaction mixture was cooled to 80°C, diluted with 30 mL of N,N-dimethylacetamide, and poured into 500 mL of stirred deionized water. The precipitated product was filtered, washed several times with water, and dried under vacuum at 80°C for 24 h. A light brown product was obtained. In this example, the polyarylene ether polymer powder is named PES-20.

[0050] S3. Quaternization of a polyarylene ether polymer: Under a nitrogen atmosphere, PES-20 (10.00 g) was placed in a 250 mL three-necked round-bottom flask with a magnetic stirrer. Subsequently, N-methylpyrrolidone (50.00 mL) was added to the flask to fully dissolve the polymer, and 1.14 g of a quaternizing agent was slowly added to the polymer solution. The reaction mixture was heated at 80° C. for 48 h. The mixture was poured into deionized water (300 mL) to precipitate a light brown polymer. The resulting polymer was washed several times with deionized water and ethanol. The polymer was vacuum dried at 80° C. for 24 h to obtain a light brown polymer (quaternized polyarylene ether polymer powder). In this example, the quaternized polyarylene ether polymer powder was named PES-Z-20.

[0051] S4. Preparation of a highly antifouling polyarylene ether separation membrane: The polymer PES-Z-20 (18.0 wt%) was dissolved in N-methylpyrrolidone to obtain a casting solution. The casting solution was stirred at room temperature for 24 hours to achieve uniform mixing, and then the bubbles were released under vacuum. After 30 seconds in an air bath, the solution was cast on a glass plate with a knife gap of 200 μm, and then immersed in a deionized water coagulation bath at room temperature to obtain the prepared membrane. The prepared membrane was kept in deionized water for at least 24 hours to remove the residual solvent, and finally a highly antifouling polyarylene ether separation membrane was obtained, which was named polyarylene ether PES-Z-20 separation membrane.

[0052] The molecular structure of the highly antifouling polyarylether PES-Z-20 separation membrane prepared in this embodiment is as follows:

[0053]

[0054] The test results show that the T g is 190.7℃, T 5％ 213.1℃, T 10％ The porosity is 86.1%, the average pore size is 9.88 nm, the water absorption is 75.6%, the water contact angle is 68°, and the BSA adsorption degree is 9.52 μg / cm 2 , water flux is 254.6L / m 2 h, BSA retention rate was 94.3%, Staphylococcus aureus adhesion rate was 5.54%, Escherichia coli adhesion rate was 6.80%, hemolysis rate was 0.37%, blood coagulation index was 32.75%, plasma recalcification time was 27 min, C3a complement activation concentration was 40 ng / mL, and C5a complement activation concentration was 2.05 ng / mL.

[0055] Example 2

[0056] A method for preparing a highly antifouling polyarylene ether separation membrane comprises the following steps:

[0057] S1. Synthesis of a tertiary amine-containing bisphenol monomer: same as in Example 1;

[0058] S2. Preparation of a polyarylene ether polymer powder: DABPE (4.75 g, 0.015 mol), 4,4-dihydroxydiphenyl ether (7.08 g, 0.035 mmol), 4,4-difluorodiphenyl sulfone (12.71 g, 0.05 mol), K2CO3 (17.28 g, 0.125 mol), 80 mL of N,N-dimethylacetamide, and 20 mL of toluene were added to a 250 mL three-necked round-bottom flask equipped with a nitrogen inlet, a mechanical stirrer, and a condenser. The reaction mixture was refluxed at 130°C for 3 h to dehydrate the system. The temperature was then slowly raised to 180°C and polymerized for 8 h to obtain a viscous liquid. After the solution became very viscous, the reaction mixture was cooled to 80°C, diluted with 30 mL of N,N-dimethylacetamide, and poured into 500 mL of stirred deionized water. The precipitated product was filtered, washed several times with water, and dried under vacuum at 80°C for 24 h. A light brown product was obtained. In this example, the polyarylene ether polymer powder is named PES-30.

[0059] S3. Quaternization of a polyarylene ether polymer: Under a nitrogen atmosphere, PES-30 (10.00 g) was placed in a 250 mL three-necked round-bottom flask with a magnetic stirrer. Subsequently, N-methylpyrrolidone (50.00 mL) was added to the flask to fully dissolve the polymer, and 1.70 g of a quaternizing agent was slowly added to the polymer solution. The reaction mixture was heated at 80° C. for 48 h. The mixture was poured into deionized water (300 mL) to precipitate a light brown polymer. The resulting polymer was washed several times with deionized water and ethanol. The polymer was vacuum dried at 80° C. for 24 h to obtain a light brown polymer (quaternized polyarylene ether polymer powder). In this example, the quaternized polyarylene ether polymer powder was named PES-Z-30.

[0060] S4. Preparation of a highly antifouling polyarylene ether separation membrane: The polymer PES-Z-30 (18.0 wt%) was dissolved in N-methylpyrrolidone to obtain a casting solution. The casting solution was stirred at room temperature for 24 hours to achieve uniform mixing, and then the bubbles were released under vacuum. After 30 seconds in an air bath, the solution was cast on a glass plate with a knife gap of 200 μm, and then immersed in a deionized water coagulation bath at room temperature to obtain the prepared membrane. The prepared membrane was kept in deionized water for at least 24 hours to remove the residual solvent, and finally a highly antifouling polyarylene ether separation membrane was obtained, which was named polyarylene ether PES-Z-30 separation membrane.

[0061] The molecular structure of the highly antifouling polyarylether PES-Z-30 separation membrane prepared in this embodiment is as follows:

[0062]

[0063] The test results show that the T g is 192.0℃, T 5％ 301.4℃, T 10％ The porosity is 86.6%, the average pore size is 9.83 nm, the water absorption is 79.4%, the water contact angle is 60°, and the BSA adsorption degree is 7.77 μg / cm 2 , water flux is 271.62L / m 2 h, BSA retention rate was 95.14%, Staphylococcus aureus adhesion rate was 3.36%, Escherichia coli adhesion rate was 4.59%, hemolysis rate was 0.28%, blood coagulation index was 35.84%, plasma recalcification time was 29 min, C3a complement activation concentration was 37 ng / mL, and C5a complement activation concentration was 1.94 ng / mL.

[0064] Example 3

[0065] A method for preparing a highly antifouling polyarylene ether separation membrane comprises the following steps:

[0066] S1. Synthesis of a tertiary amine-containing bisphenol monomer: same as in Example 1;

[0067] S2. Preparation of a polyarylene ether polymer powder: DABPE (6.33 g, 0.02 mol), 4,4-dihydroxydiphenyl ether (6.07 g, 0.03 mmol), 4,4-difluorodiphenyl sulfone (12.71 g, 0.05 mol), K2CO3 (17.28 g, 0.125 mol), 80 mL of N,N-dimethylacetamide, and 20 mL of toluene were added to a 250 mL three-necked round-bottom flask equipped with a nitrogen inlet, a mechanical stirrer, and a condenser. The reaction mixture was refluxed at 130°C for 3 h to dehydrate the system. The temperature was then slowly raised to 180°C and polymerized for 8 h to obtain a viscous liquid. After the solution became very viscous, the reaction mixture was cooled to 80°C, diluted with 30 mL of N,N-dimethylacetamide, and poured into 500 mL of stirred deionized water. The precipitated product was filtered, washed several times with water, and dried in vacuo at 80°C for 24 h. A light brown product was obtained. In this example, the polyarylene ether polymer powder is named PES-40.

[0068] S3. Quaternization of a polyarylene ether polymer: Under a nitrogen atmosphere, PES-40 (10.00 g) was placed in a 250 mL three-necked round-bottom flask with a magnetic stirrer. Subsequently, N-methylpyrrolidone (50.00 mL) was added to the flask to fully dissolve the polymer, and 2.27 g of a quaternizing agent was slowly added to the polymer solution. The reaction mixture was heated at 80° C. for 48 h. The mixture was poured into deionized water (300 mL) to precipitate a light brown polymer. The resulting polymer was washed several times with deionized water and ethanol. The polymer was vacuum dried at 80° C. for 24 h to obtain a light brown polymer (quaternized polyarylene ether polymer powder). In this example, the quaternized polyarylene ether polymer powder was named PES-Z-40.

[0069] S4. Preparation of a highly antifouling polyarylene ether separation membrane: The polymer PES-Z-40 (18.0 wt%) was dissolved in N-methylpyrrolidone to obtain a casting solution. The casting solution was stirred at room temperature for 24 hours to achieve uniform mixing, and then the bubbles were released under vacuum. After 30 seconds in an air bath, the solution was cast on a glass plate with a knife gap of 200 μm, and then immersed in a deionized water coagulation bath at room temperature to obtain the prepared membrane. The prepared membrane was kept in deionized water for at least 24 hours to remove the residual solvent, and then a highly antifouling polyarylene ether separation membrane was obtained, which was named polyarylene ether PES-Z-40 separation membrane.

[0070] The molecular structure of the highly antifouling polyarylether PES-Z-40 separation membrane prepared in this embodiment is as follows:

[0071]

[0072] The test results show that the T g is 195.6℃, T 5％ is 303.9℃, T 10％ The porosity is 87.0%, the average pore size is 10.18 nm, the water absorption is 83.6%, the water contact angle is 53°, and the BSA adsorption degree is 5.84 μg / cm 2 , water flux is 305.57L / m 2 h, BSA retention rate was 96.46%, Staphylococcus aureus adhesion rate was 1.98%, Escherichia coli adhesion rate was 2.28%, hemolysis rate was 0.22%, blood coagulation index was 37.11%, plasma recalcification time was 31 min, C3a complement activation concentration was 35 ng / mL, and C5a complement activation concentration was 1.85 ng / mL.

[0073] Example 4

[0074] A method for preparing a highly antifouling polyarylene ether separation membrane comprises the following steps:

[0075] S1. Synthesis of a tertiary amine-containing bisphenol monomer: same as in Example 1;

[0076] S2. Preparation of a polyarylene ether polymer powder: DABPE (7.91 g, 0.025 mol), 4,4-dihydroxydiphenyl ether (5.06 g, 0.025 mmol), 4,4-difluorodiphenyl sulfone (12.71 g, 0.05 mol), K2CO3 (17.28 g, 0.125 mol), 80 mL of N,N-dimethylacetamide, and 20 mL of toluene were added to a 250 mL three-necked round-bottom flask equipped with a nitrogen inlet, a mechanical stirrer, and a condenser. The reaction mixture was refluxed at 130°C for 3 h to dehydrate the system. The temperature was then slowly raised to 180°C and polymerized for 8 h to obtain a viscous liquid. After the solution became very viscous, the reaction mixture was cooled to 80°C, diluted with 30 mL of N,N-dimethylacetamide, and poured into 500 mL of stirred deionized water. The precipitated product was filtered, washed several times with water, and dried in vacuo at 80°C for 24 h. A light brown product was obtained. In this example, the polyarylene ether polymer powder is named PES-50.

[0077] S3. Quaternization of a polyarylene ether polymer: Under a nitrogen atmosphere, PES-50 (10.00 g) was placed in a 250 mL three-necked round-bottom flask with a magnetic stirrer. Subsequently, N-methylpyrrolidone (50.00 mL) was added to the flask to fully dissolve the polymer, and 2.84 g of a quaternizing agent was slowly added to the polymer solution. The reaction mixture was heated at 80° C. for 48 hours. The mixture was poured into deionized water (300 mL) to precipitate a light brown polymer. The resulting polymer was washed several times with deionized water and ethanol. The polymer was vacuum dried at 80° C. for 24 hours to obtain a light brown polymer (quaternized polyarylene ether polymer powder). In this example, the quaternized polyarylene ether polymer powder was named PES-Z-50.

[0078] S4. Preparation of a highly antifouling polyarylene ether separation membrane: The polymer PES-Z-50 (18.0 wt%) was dissolved in NMP to obtain a casting solution. The casting solution was stirred at room temperature for 24 hours to achieve uniform mixing, and then the bubbles were released under vacuum. After 30 seconds in an air bath, the solution was cast on a glass plate with a knife gap of 200 μm, and then immersed in a deionized water coagulation bath at room temperature to obtain the prepared membrane. The prepared membrane was kept in deionized water for at least 24 hours to remove the residual solvent, and then a highly antifouling polyarylene ether separation membrane was obtained, which was named polyarylene ether PES-Z-50 separation membrane.

[0079] The molecular structure of the highly antifouling polyarylene ether separation membrane prepared in this embodiment is as follows:

[0080]

[0081] The test results show that the T g is 199.8℃, T 5％ is 288.8℃, T 10％ The porosity is 88.3%, the average pore size is 10.63 nm, the water absorption is 85.5%, the water contact angle is 45°, and the BSA adsorption degree is 4.58 μg / cm 2 , water flux is 288.6L / m 2 h, BSA retention rate was 95.9%, Staphylococcus aureus adhesion rate was 0.68%, Escherichia coli adhesion rate was 1.24%, hemolysis rate was 0.12%, blood coagulation index was 38.09%, plasma recalcification time was 33 min, C3a complement activation concentration was 33 ng / mL, and C5a complement activation concentration was 1.79 ng / mL.

[0082] In summary, the present invention successfully constructed a polyarylether separation membrane system with zwitterionic choline phosphate functionalization through molecular structure design and process innovation: (1) The tertiary amine group was precisely introduced into the bisphenol monomer structure through the Mannich reaction, and the polyarylether main chain containing the modifiable tertiary amine site was constructed through the condensation reaction, breaking the surface modification defects caused by the chemical inertness of traditional polyarylether; (2) The polymer main chain was innovatively functionalized by using a phosphate quaternization reagent to form a choline phosphate zwitterionic surface with a cell membrane-like structure, and a high-density zwitterionic functional layer was successfully constructed; (3) By optimizing and controlling the phase inversion process parameters (casting solution concentration 18wt%, coagulation bath temperature 25℃), an asymmetric membrane structure was prepared, achieving a synergistic improvement in separation efficiency and flux. The PES-Z-50 separation membrane has high hydrophilicity, and the BSA adsorption amount is only 4.58μg / cm 2 , dynamic flux reaches 288.6L / m 2 h while maintaining a BSA retention rate of 95.9%. The blood compatibility index is significantly better than that of clinical polysulfone dialysis membranes, and the hemolysis rate is only 0.12%. These performance indicators all meet the standards of the medical device industry. The highly anti-fouling polyarylether prepared by the present invention and the separation membrane made thereof have excellent separation efficiency, anti-fouling performance, good mechanical properties, thermal stability, blood compatibility, anti-coagulation performance, and improved cyclic ultrafiltration stability and easy cleaning. It has broad application prospects in multiple fields such as biological clinical medical filter membranes, hemodialysis, and water treatment.

[0083] The above detailed description is a specific description of one feasible embodiment of the present invention. This embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification that does not depart from the present invention should be included in the scope of the technical solution of the present invention.

Claims

1. A method for preparing a highly antifouling polyarylene ether separation membrane, characterized in that: The following steps are involved: 1) adding polyarylene ether polymer powder to solvent B, then adding a quaternary ammonium reagent, reacting at a temperature of 80-100° C. for 48-72 hours, pouring the reaction solution into deionized water for precipitation, filtering to obtain a solid powder, washing with ethanol 3-5 times, and vacuum drying at 90° C. for 24 hours to obtain a quaternary polyarylene ether polymer powder; 2) adding quaternized polyarylene ether polymer powder to solvent C and stirring at room temperature for 6 to 8 hours to prepare a casting solution; then dripping the casting solution onto a casting glass plate, scraping the plate with a 200 μm thick scraper to form an asymmetric separation membrane, and performing phase inversion exfoliation in deionized water, followed by washing to obtain a highly antifouling polyarylene ether separation membrane; The molecule of the polyarylene ether polymer powder contains the structure shown in Formula 1: wherein n=0.01 to 0.99, and R' is any one of an oxygen atom, a bistrifluoromethyl group, a dimethyl group, a sulfone group, a biphenyl group, a carbonyl group, and a biphenyl group; The molecular structural formula 2 of the quaternary ammonium reagent is as follows: wherein R is independently selected from a chain alkoxy group having 1 to 10 carbon atoms, a chain alkenyloxy group having 2 to 10 carbon atoms, a chain alkynyloxy group having 2 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a cyclic alkenyloxy group having 3 to 10 carbon atoms, a trimethylsilyl group, a trimethylsilyloxy group, a halogen-containing alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halophenyl group, a halobiphenyl group, a phenol group, a phenol group containing an alkyl group, a phenol group containing an alkenyl group, a phenol group containing an alkynyl group, a phenol group containing a nitrile group, a monohalogenated phenol group, and a polyhalogenated phenol group; The molecule of the highly antifouling polyarylene ether separation membrane contains the structure shown in Formula 3:

2. The method for preparing a highly antifouling polyarylene ether separation membrane according to claim 1, wherein: The raw materials of the polyarylene ether polymer powder include, by mole fraction, 0.99 to 0.01 parts of sulfur- or oxygen-containing monomers, 0.01 to 0.99 parts of tertiary amine-containing bisphenol monomers, 1 part of dihalogenated aromatic compound, 100 to 1000 parts of solvent A, 1 to 10 parts of base, and 30 to 60 parts of dehydrating agent.

3. The method for preparing a highly antifouling polyarylene ether separation membrane according to claim 2, wherein: The tertiary amine-containing bisphenol monomer is any one or a combination of the compounds shown in the following structural formulas: The sulfur-containing or oxygen-containing monomer is any one or a combination of compounds represented by the following structural formulas: The structural formula of the dihalogenated aromatic compound is at least one or a combination of the following compounds: The solvent A is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane; the base is any one of potassium carbonate, cesium carbonate, sodium carbonate, and guanidine carbonate; and the dehydrating agent is any one of cyclohexane, toluene, xylene, and benzophenone.

4. The method for preparing a highly antifouling polyarylene ether separation membrane according to claim 2 or 3, wherein: The synthesis steps of the tertiary amine-containing bisphenol monomer are as follows: A) dissolving bisphenol in ethanol to form a mixed solution, stirring at room temperature until the bisphenol is completely dissolved, and then sequentially adding a formaldehyde aqueous solution and a dimethylamine aqueous solution to the mixed solution to form a reaction solution; B) stirring the reaction solution in step A) at room temperature for reaction for 48 to 72 hours until a white solid appears in the reaction solution, filtering the reaction solution to obtain a solid crude product, then washing it with hot water 3 to 5 times, filtering to obtain a white product, then recrystallizing it with ethanol at 80° C., cooling and filtering to obtain a white crystalline product, and vacuum drying it at 80° C. for 24 hours to obtain the tertiary amine-containing bisphenol monomer.

5. The method for preparing a highly antifouling polyarylene ether separation membrane according to claim 1 or 2, characterized in that: The synthesis steps of the polyarylene ether polymer powder are as follows: under the protection of inert gas, dissolving a tertiary amine-containing bisphenol monomer, a sulfur-containing or oxygen-containing monomer, and a dihalogenated aromatic compound in solvent A, then simultaneously adding an alkali and a dehydrating agent, maintaining reflux at 100-130° C. for 4-6 hours to remove water, completely distilling off the dehydrating agent at 135° C. within 1 hour, maintaining a constant temperature at 160-180° C. for reaction for 24-48 hours, finally cooling the reaction to room temperature, pouring the reaction solution into deionized water for precipitation, filtering to obtain a solid powder, washing with ethanol 3-5 times, and vacuum drying at 90° C. for 24 hours to obtain the polyarylene ether polymer powder.

6. The method for preparing a highly antifouling polyarylene ether separation membrane according to claim 5, characterized in that: In the synthesis step of the polyarylene ether polymer powder, the molar ratio of tertiary amine-containing bisphenol monomer: sulfur-containing or oxygen-containing monomer: dihalogenated aromatic compound: base is (0.01-0.99): (0.99-0.01): 1: (1-10).

7. The method for preparing a highly antifouling polyarylene ether separation membrane according to claim 1, wherein: In the step 1), the molar ratio of the polyarylene ether polymer powder to the quaternizing agent is 1:(2-8); the solid content of the polyarylene ether polymer powder in the solvent B in the step 1) is 15-20 wt%; and the solvent B in the step 1) is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

8. The method for preparing a highly antifouling polyarylene ether separation membrane according to claim 1, wherein: The solid content of the quaternized polyarylene ether polymer powder in the solvent C in the step 2) is 15 to 20 wt %, and the solvent C in the step 2) is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

9. A highly antifouling polyarylene ether separation membrane prepared by the preparation method according to any one of claims 1 to 8.

10. Use of a highly antifouling polyarylene ether separation membrane prepared by the preparation method according to any one of claims 1 to 8 in biological clinical medicine and blood purification.

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