Random polyarylether nitrile sulfone membranes containing adamantane and methods of making the same

Abstract

The adamantane-containing random polyarylether nitrile sulfone film and the preparation method thereof, and the molecular structural formula of the adamantane-containing random polyarylether nitrile sulfone film segment is as follows: wherein: the content of the nitrile group segment x=0~1; the content of the sulfone group segment 1-x=0~1.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of ultrafiltration membrane in membrane separation technology, and particularly relates to a random polyarylether nitrile sulfone membrane containing adamantane and a preparation method thereof. BACKGROUND

[0002] Ultrafiltration (UF) is one of the membrane separation technologies driven by pressure, that is, under a certain pressure, small molecule solutes and solvents can pass through a specially designed membrane with a certain pore size, while large molecule solutes cannot pass through and are left on one side of the membrane, so that the large molecule substances are partially purified. Generally, the pore size of the ultrafiltration membrane is between 1-20 nm, and the operating pressure is 0.1-0.5 Mpa. Ultrafiltration is between microfiltration and nanofiltration, and there is no obvious dividing line between the three. Ultrafiltration can purify, separate or concentrate solutions, and is mainly used to remove large molecular substances such as suspended solids, colloids, particles, bacteria and viruses in water. As a kind of membrane separation technology, ultrafiltration has been widely used in various fields of national economy such as industrial production, medicine and health, environmental protection and people's life.

[0003] Polyaryl ether nitrile (PEN) refers to a kind of special polymer material containing a large number of benzene rings and ether bonds in the main chain, and containing cyano groups in the side chain. The large number of aromatic rings and ether bonds in the macromolecular main chain of polyaryl ether nitrile endow polyaryl ether nitrile with excellent heat resistance, mechanical strength and excellent toughness; at the same time, the existence of the strong polar group cyano in the side chain also endows polyaryl ether nitrile with excellent bonding properties. It is because polyaryl ether nitrile has such excellent comprehensive properties (high temperature resistance, chemical corrosion resistance, high flame resistance, high strength, creep resistance, high rigidity) that it is a revolutionary material essential in both military fields such as mechanical ships, aerospace, and civilian fields such as electronics, medical care and environmental protection. In 1973, the first patent on the synthesis and preparation process of polyaryl ether nitrile was published by D.R. Heath, but due to the complex reaction process at that time, the synthesis of polyaryl ether nitrile has been limited to laboratory preparation

[19] . Until 1986, Idemitsu Kosan Co., Ltd. of Japan realized the industrial production of polyaryl ether nitrile by nucleophilic substitution reaction of 2,6-difluorobenzonitrile and resorcinol in a protic solvent. The performance indicators of this product (glass transition temperature of 148℃, heat distortion temperature of 165℃ and tensile strength of more than 130 MPa) are comparable to those of the polyether ether ketone produced by ICI Company in the United Kingdom at that time.

[0004] Poly(aryl ether sulfone), PES) has a large number of benzene rings in the molecular chain, so that the polyether sulfone has a rigid structure, and a large number of ether bonds in the structure, which enhances the flexibility of the molecular chain. In addition, the structure unit of the sulfone group, ether bond and benzene ring forms a large conjugated system, and the conjugated structure makes the polyether sulfone show very stable chemical properties. The synthesis of polyether sulfone has a history of more than forty years, and it was first developed by the British Imperial Chemicals Company, and then more and more countries in the world developed and researched polyether sulfone materials. In China, in addition to a small amount of engineering plastics factories producing polyether sulfone, many universities synthesize polyether sulfone and explore its application. The special molecular structure of polyether sulfone makes it show good chemical and biological resistance, in addition, polyether sulfone also has good heat resistance, insulation and other physical properties. It has very high thermodynamic stability and mechanical strength, and the glass transition temperature (Tg) is as high as 230℃, the maximum use temperature can be 200℃, and it can be used at a temperature of 150-180℃ for a long time. Moreover, polyether sulfone is a self-extinguishing resin, which has low smoke diffusion (second only to polyether ether ketone, has a high limiting oxygen index, and can reach the American UL-94V-0 standard without adding inorganic flame retardant such as chlorine). Although polyether sulfone belongs to thermoplastic plastic, it still has excellent mechanical properties, and the tensile strain under the pressure of 150℃ and 20MPa is only 2.55%. Polyether sulfone has small dielectric loss and high dielectric strength, and good self-insulation. From low temperature to high temperature close to the glass transition point, the dielectric constant and dielectric loss factor of polyether sulfone remain basically unchanged. Compared with other polysulfone materials, the melt viscosity of PES is lower, so that its melt processing performance is good, the shrinkage rate is low (about 0.6%), and it has good dimensional stability. However, PES is more prone to water absorption than other polysulfone materials, so it needs to be dried before processing and forming, otherwise it will affect the product performance. At the same time, in the membrane separation technology, polyether sulfone is easy to dissolve in organic solvents, and the process of preparing film material from engineering plastic polyether sulfone by phase inversion method is very simple, and the structure and chemical properties of the film can be adjusted by physical blending or chemical modification method during the film forming process, which makes the separation film prepared from polyether sulfone have more applications in many fields.

[0005] In 2016, Dalian University of Technology published "Heteronaphthalene Polyphenyl Ether Nitrile Sulfone Series High Performance Resin and Its Application New Technology". Starting from the design of polymer molecular structure, through the corresponding polymerization process technology research, a number of key technologies are overcome, and a new type of polyarylether nitrile sulfone series high performance resin which is both heat resistant and soluble is successfully developed. The main invention points include: 1. The full aromatic ring, twisted non-planar naphthalene ketone biphenyl structure is successfully introduced into the polyarylether nitrile molecular main chain, and a new structure, excellent comprehensive performance, heat resistant and soluble heteronaphthalene polyphenyl ether nitrile sulfone (PPENS) is developed, which solves the technical problem that traditional polyarylether nitrile cannot have heat resistance and solubility; 2. A new polymerization process is developed, which is mainly characterized by composite catalyst system and mixed solvent system. The whole process is carried out at normal pressure, the highest temperature is <200℃, and the post-treatment only needs to be washed 3-5 times with water, which solves the technical problem that traditional polyarylether nitrile polymerization process cannot obtain high molecular weight and narrow distribution products, and realizes low-cost controllable preparation; 3. Through quaternary copolymerization, heat-resistant and soluble heteronaphthalene polyphenyl ether nitrile sulfone ketone (PPENSK) is developed. The introduction of carbonyl group makes PPENSK have high strength, high toughness and easy processing advantages on the premise of excellent heat resistance; 4. Through quaternary copolymerization, heteronaphthalene polyphenyl ether nitrile sulfone ketone ketone (PPENSKK) is developed. The introduction of diketone structure further enhances the toughness of PPENSKK, and has the comprehensive advantages of high strength and high toughness and cost reduction; 5. Heteronaphthalene polyphenyl ether nitrile sulfone ketone special functional film for aviation heat insulation, moisture and sound insulation, and seamless wrapping cable, and heteronaphthalene polyphenyl ether nitrile sulfone anion exchange membrane for new energy storage battery are developed.

[0006] Adamantane (tricyclo[3.3.1.13·7]decane, molecular formula C10H16) is a highly stable cage hydrocarbon with perfect symmetry, and its basic carbon skeleton is similar to a lattice unit of diamond, so it is called adamantane. The 1, 3, 5, 7 hydrogen atoms of adamantane are easy to undergo substitution, oxidation, alkylation and other reactions, and the potential derivative types and quantities far exceed benzene derivatives, so it is praised as the next generation of fine and special chemical raw materials. Introducing adamantane skeleton structure into the main chain or side chain of polymers such as polyester, polycarbonate, polyamide, polysulfone and polyimide can significantly improve the thermal oxygen stability, chemical stability, optical stability of the polymer, and improve its mechanical, dielectric and other properties, thereby obtaining a series of liquid crystal display materials, semiconductor photoresist materials, holographic photosensitive materials, membrane separation materials, intelligent plastics, contact lenses and drug carriers with special functions. Adamantane polymers have shown broad application prospects in microelectronics, communications, aviation, optical instruments, biomedicine and other high-tech fields. SUMMARY

[0007] The present application aims to provide a adamantane-containing random polyarylether nitrile sulfone film and a preparation method thereof. The main chain structure of the film is designed to be a random polymer containing nitrile groups and sulfone groups, and the adamantane groups are contained in the side chains of the polymer, so that the film has good heat resistance, anti-swelling performance and mechanical strength, while still maintaining good hot forming processing fluidity.

[0008] The present application is realized by the following technical solutions:

[0009] The adamantane-containing random polyarylether nitrile sulfone film (MAPENS-x) of the present application, the main chain of the polyarylether nitrile sulfone film is a random polymer containing nitrile groups and sulfone groups, wherein: one adamantane group is distributed on the side chain of each nitrile group and sulfone group, respectively, and the molecular structure formula of the adamantane-containing random polyarylether nitrile sulfone film segment is as follows:

[0010]

[0011] Wherein: the content of nitrile group segment x = 0-1; the content of sulfone group segment 1-x = 0-1.

[0012] The preparation method of the adamantane-containing random polyarylether nitrile sulfone film of the present application, wherein: it comprises:

[0013] (I) Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM)

[0014] 1 part of 2-adamantanone and at least 2 parts of 2,6-dimethylphenol are added in 2-5 parts of toluene as solvent, stirred at room temperature until completely dissolved, then 0.5-0.8 parts of 3-mercaptopropionic acid, 0.1-0.2 parts of fluorosulfonic acid and 0.1-0.2 parts of trifluoromethanesulfonic acid are added as catalyst, and the reaction is carried out at 60-100°C for 12-18 hours to obtain a solid product, then the solid product is washed with a 50% methanol aqueous solution at least three times until the washed solution is clear and the pH of the washed solution is 7-8, and then dried to obtain the MADM monomer compound;

[0015] (II) Synthesis of adamantane-containing polyarylether nitrile sulfone polymer (MAPENS-x)

[0016] The 1 part MADM monomer compound obtained in step (1) is fed into a solution containing 0.8-1 part anhydrous K2CO3, 2-5 parts toluene and 5-10 parts polar aprotic solvent in a molar ratio of 1:x:1-x, the MADM monomer compound, 2,6-difluorobenzonitrile (DFBN) and bis(4-fluorophenyl)sulfone (FPS) monomer are dissolved in the solution under the protection of nitrogen, the solution is heated to 140-145℃ and reacted for 3-4 hours, then heated to 160-165℃ and reacted for 12-24 hours, and then cooled to room temperature to obtain a solid product, which is precipitated, filtered and washed with a 50% methanol aqueous solution until the washing solution is clear and the pH is 7-8, and then subjected to Soxhlet purification with a 50% methanol aqueous solution, and dried to obtain a polymer;

[0017] (Three), preparation of the film

[0018] The 1 part polymer obtained in step (2) is dissolved in 10-50 parts N-methylpyrrolidone (NMP) to prepare a casting solution, the obtained casting solution is filtered through a 0.45 μm filter screen, coated on a glass plate, and then the glass plate is sent into a forced air drying oven and heated at 60-80℃ for 24-48 hours to volatilize the solvent and obtain a solid film.

[0019] The preparation method of the adamantane-containing random polyarylether nitrile sulfone film according to the application, wherein in step (1), the optimal amount of 2,6-dimethylphenol is 3 parts.

[0020] The preparation method of the adamantane-containing random polyarylether nitrile sulfone film according to the application, wherein in step (2), the value of x is in the range of 0

[0021] The preparation method of the adamantane-containing random polyarylether nitrile sulfone film according to the application, wherein in step (2), the polar aprotic solvent includes any one of dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide and N-methylpyrrolidone.

[0022] The preparation method of the adamantane-containing random polyarylether nitrile sulfone film according to the application, wherein the parts are parts by weight.

[0023] Compared with the background art, the adamantane-containing random polyarylether nitrile sulfone film and the preparation method thereof according to the application have the following advantages:

[0024] 1) By changing the feed ratio of 2,6-difluorobenzonitrile (DFBN) and bis(4-fluorophenyl)sulfone (FPS) monomers, adamantane-containing polyarylether nitrile sulfone polymers (MAPENS-x) containing different molar ratios of nitrile groups and sulfone groups are prepared, and then the corresponding polymer films are prepared, and the microstructure of the film is regulated by changing the polymer chemical structure.

[0025] 2) The adamantane group has a large steric hindrance, and its large volume prevents the close packing of the segments, thereby increasing the free volume fraction and improving the permeation performance of the film. At the same time, since the adamantane group is in the side group position of the molecular chain, the rotation and bending motion of the polymer chain is limited, thereby improving the mechanical properties of the film.

[0026] 3) The presence of nitrile groups in the polymer molecular chain makes the film have higher heat resistance, flame resistance, mechanical strength, etc. than ordinary polyarylether polymers. And it maintains good hot forming processing fluidity, making its application more extensive.

[0027] 4) By synthesizing adamantane monomers containing benzyl groups, and then introducing benzyl groups into the main chain structure, it is beneficial for further modification of the film material in the subsequent process.

[0028] 5) The prepared adamantane-containing random polyarylether nitrile sulfone film has good flexibility, high mechanical strength, good chemical stability and thermal stability, and exhibits excellent ultrafiltration membrane performance. The random structure of the polymer film is beneficial to industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the 2,2-bisadamantane (MADM) monomer prepared in Example 1.

[0030] Figure 2 The nuclear magnetic resonance hydrogen spectrum of the adamantane-containing random polyarylether nitrile sulfone polymer (MAPENS-0.2) prepared in Example 1. DETAILED DESCRIPTION

[0031] In order to more clearly illustrate the present application, the present application will be further described below in conjunction with examples and drawings.

[0032] Example 1

[0033] This example takes the preparation method of adamantane-containing random polyarylether nitrile sulfone film with x=0.2 as an example. The main chain of the polyarylether nitrile sulfone film is a random polymer containing nitrile groups and sulfone groups, wherein: one adamantane group is distributed on the side chain of each nitrile group and sulfone group. The molecular structure formula of the adamantane-containing random polyarylether nitrile sulfone film segment is as follows:

[0034]

[0035] wherein the nitrile group segment content x = 0.2; the sulfone group segment content 1-x = 0.8.

[0036] The method for preparing the adamantane-containing random polyarylether nitrile sulfone film of the present application comprises:

[0037] (I) Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM)

[0038] In a reaction flask, 12 g of 2-adamantanone (0.08 mol) and 25.495 mL of 2,6-dimethylphenol (0.24 mol) were added as a solvent in 50 mL of toluene (0.47 mol), stirred at room temperature until completely dissolved, and then 6 mL of 3-mercaptopropionic acid (0.069 mol), 1.2 mL of fluorosulfonic acid (0.021 mol), and 1.2 mL of trifluoromethanesulfonic acid (0.015 mol) were added as catalysts, and reacted at 60°C for 18 hours to obtain a solid product, which was washed three times with a 50% methanol aqueous solution, until the washed solution was clear and the pH of the washed solution was 7, and then dried to obtain the MADM monomer compound;

[0039] (II) Synthesis of adamantane-containing polyarylether nitrile sulfone polymer (MAPENS-x)

[0040] 3.752 g of the MADM monomer compound (10 mmol) obtained in step (I) was taken, and the 3.752 g of MADM monomer compound, 0.278 g of 2,6-difluorobenzonitrile (DFBN) (2 mmol), and 2.034 g of bis(4-fluorophenyl)sulfone (FPS) (8 mmol) were added to a three-necked flask, stirred and dissolved in 20 mL of N,N-dimethylacetamide, and then 10 mL of toluene (0.095 mol), 3.450 g of anhydrous K2CO3 (25 mmol) were added, and reacted at 145°C for 4 hours and then at 165°C for 24 hours under nitrogen protection, and then cooled to room temperature, precipitated with a 50% methanol aqueous solution, filtered and washed until the solution was clear and the pH was 7, and then Soxhlet purified with methanol, and dried to obtain the polymer;

[0041] (III) Preparation of the film

[0042] 1 part of the polymer obtained in step (II) was dissolved in 10-50 parts of N-methylpyrrolidone (NMP) to prepare a casting solution, which was filtered through a 0.45 μm filter and then coated on a glass plate, and then the glass plate was placed in a forced air drying oven and heated at 60°C for 48 hours to evaporate the solvent and obtain a solid film.

[0043] The obtained homogeneous film was tested and the results were obtained.

[0044] 1) Test: The structure of MADM monomer and adamantane-containing random polyarylether nitrile sulfone membrane was determined by nuclear magnetic resonance technology. According to GB / T 32360 2015, the ultrafiltration performance of the membrane was determined by permeation experiment and dextran method.

[0045] 2) The test results show that the adamantane-containing polyarylether nitrile sulfone polymer membrane with x = 0.2 is successfully synthesized. The 1H MMR spectrum of MADM monomer is shown in Figure 1 The peaks at chemical shifts 1.73-1.96 ppm and 3.181 ppm correspond to the methylene and tertiary carbon hydrogen on the adamantane group, respectively. The 1H MMR spectrum of MAPENS-0.2 is shown in Figure 2 The peak at 2.01-2.21 ppm corresponds to the benzyl proton hydrogen in the polymer; the proton peaks at 6.78 ppm and 7.81 ppm correspond to the hydrogen of the benzene ring in the sulfone group segment of the polymer; the proton peaks at 5.35 ppm and 6.05 ppm correspond to the hydrogen of the benzene ring on the benzonitrile group in the nitrile group segment. The chemical structure of the membrane is confirmed by nuclear magnetic resonance technology. Through the performance test of the membrane, it is shown that the pure water flux J of the MAPENS-0.2 membrane is 151±5 L / (m2·h), and the rejection rate R is 95.2±0.3%.

[0046] Example 2

[0047] This example takes the preparation method of adamantane-containing random polyarylether nitrile sulfone membrane with x = 0.4 as an example. The main chain of the polyarylether nitrile sulfone membrane is a random polymer containing nitrile groups and sulfone groups, wherein: one adamantane group is distributed on the side chain of each nitrile group and sulfone group. The molecular structure formula of the adamantane-containing random polyarylether nitrile sulfone membrane segment is as follows:

[0048]

[0049] Among them, the content of the nitrile group segment is x = 0.4; the content of the sulfone group segment is 1-x = 0.6.

[0050] The preparation method of the adamantane-containing random polyarylether nitrile sulfone membrane of the application comprises:

[0051] (I) Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM)

[0052] In a reaction flask, 12 g of 2-adamantanone (0.08 mol) and 25.495 mL of 2,6-dimethylphenol (0.24 mol) were added as solvents in 50 mL of toluene (0.47 mol), stirred at room temperature until completely dissolved, then 6 mL of 3-mercaptopropionic acid (0.069 mol), 1.2 mL of fluorosulfonic acid (0.021 mol) and 1.2 mL of trifluoromethanesulfonic acid (0.015 mol) were added as catalysts, and the reaction was carried out at 60°C for 18 hours to obtain a solid product, which was then washed with 50% methanol aqueous solution four times until the washed solution was clear and the pH of the washed solution was 7, and then dried to obtain the MADM monomer compound;

[0053] (II) Synthesis of adamantyl-containing poly(arylene ether nitrile sulfone) polymer (MAPENS-x)

[0054] The 3.752 g of MADM monomer compound (10 mmol) obtained in step (I) was taken, and the 3.752 g of MADM monomer compound, 0.556 g of 2,6-difluorobenzonitrile (DFBN) (4 mmol) and 1.526 g of bis(4-fluorophenyl)sulfone (FPS) (6 mmol) were added to a three-necked flask, stirred and dissolved in 20 mL of N,N-dimethylacetamide, then 10 mL of toluene (0.095 mol), 3.450 g of anhydrous K2CO3 (25 mmol) were added, and the reaction was carried out at 145°C for 4 hours and then at 165°C for 24 hours under nitrogen protection. After the reaction was stopped, the solution was cooled to room temperature, precipitated with 50% methanol aqueous solution, filtered and washed until the solution was clear and the pH was 7, then Soxhlet purified with methanol, and dried to obtain the polymer.

[0055] (III) Preparation of the membrane

[0056] The polymer obtained in step (II) was dissolved in 10-50 parts of N-methylpyrrolidone (NMP) to prepare a casting solution, which was filtered through a 0.45 μm filter and then coated on a glass plate, and then the glass plate was placed in a forced air drying oven and heated at 60°C for 48 hours to volatilize the solvent and obtain a solid membrane, which was demolded from the glass plate to obtain a homogeneous membrane formed by the casting solution.

[0057] The obtained homogeneous membrane was tested and the results were obtained.

[0058] 1) Test: The structure of the adamantyl-containing random poly(arylene ether nitrile sulfone) membrane was determined by nuclear magnetic resonance technology and infrared spectroscopy technology. The ultrafiltration performance of the membrane was determined by the transmission experiment and the dextran method according to GB / T 32360 2015.

[0059] 2) The test results show that adamantane-containing poly(arylene ether nitrile sulfone) polymer membranes with x = 0.4 are successfully synthesized. The chemical structure of the membranes is confirmed by nuclear magnetic resonance technology. Through the performance test of the membranes, it is shown that the pure water flux J of the MAPENS-0.4 membrane is 145±6 L / (m2·h), and the rejection rate R is 97.3±0.3%.

[0060] The above merely describes preferred embodiments of the present application, and therefore cannot limit the range of the present application. Equivalent changes and modifications made according to the scope of the present patent and the content of the specification should still be within the scope of the present application.

Claims

1. A random polyarylene ether sulfone membrane containing adamantane, characterized in that: The molecular structure of the random polyarylene ether sulfone membrane fragment containing adamantane is as follows: ； Wherein: nitrile group content x=0~1; sulfone group content 1-x=0~1.

2. The method for preparing adamantane-containing random polyarylene ether sulfone membrane according to claim 1, characterized in that: It includes: (I) Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM) Using 2-5 parts toluene as solvent, add 1 part 2-adamantanone and at least 2 parts 2,6-dimethylphenol, stir at room temperature until completely dissolved, then add 0.5-0.8 parts 3-mercaptopropionic acid, 0.1-0.2 parts fluorosulfonic acid and 0.1-0.2 parts trifluoromethanesulfonic acid as catalysts, react at 60-100 °C for 12-18 hours to obtain a solid product, then wash the solid product at least three times with an aqueous solution containing 50% methanol until the washing solution is clear and the pH of the washing solution is 7-8, and then dry to obtain the MADM monomer compound; (II) Synthesis of adamantyl-containing polyarylene ether nitrile sulfone polymer (MAPENS-x) Take 1 part of the MADM monomer compound obtained in step (I), and add the above 1 part of the MADM monomer compound, 2,6-difluorobenzyl nitrile (DFBN) and bis(4-fluorophenyl) sulfone (FPS) monomer in a molar ratio of 1:x:1-x to a solution containing 0.8-1 part of anhydrous K2CO3, 2-5 parts of toluene and 5-10 parts of polar aprotic solvent. Under the protection of nitrogen, the MADM monomer compound, 2,6-difluorobenzyl nitrile (DFBN) and bis(4-fluorophenyl) sulfone (FPS) monomer are dissolved in the above solution. React at 140-145 °C for 3-4 hours, then raise the temperature to 160-165 °C and react for 12-24 hours. After cooling to room temperature, a solid product is obtained. The above solid product is precipitated, filtered and washed with a 50% methanol aqueous solution until the washing solution is clear and pH=7. Then, Soxhlet purification is performed with a 50% methanol aqueous solution. After drying, the polymer is obtained. (III) Membrane Preparation Dissolve 1 part of the polymer obtained in step (II) in 10-50 parts of N-methylpyrrolidone (NMP) and stir until homogeneous to obtain a casting solution. Filter the obtained casting solution through a 0.45 μm filter screen and coat it onto a glass plate. Then, put the glass plate into a forced-air drying oven and heat it at 60-80℃ for 24-48 hours to evaporate the solvent and obtain a solid film.

3. The method for preparing adamantane-containing random polyarylene ether sulfone membrane according to claim 2, characterized in that: In step (a), the optimal amount of 2,6-dimethylphenol is 3 parts.

4. The method for preparing an adamantane-containing random polyarylene ether sulfone membrane according to claim 3, characterized in that: In step (ii), the range of x is 0. <x<1。 5. The method for preparing adamantane-containing random polyarylene ether sulfone membrane according to claim 4, characterized in that: In step (ii), the polar aprotic solvent includes any one of dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, and N-methylpyrrolidone.

6. The method for preparing adamantane-containing random polyarylene ether sulfone membrane according to claim 5, characterized in that: The number of portions refers to the number of weight portions.

Images