Adams polyarylether nitrile sulfone separation membrane and preparation method thereof

Abstract

The invention discloses a adamantane-containing polyarylether nitrile sulfone separation membrane (BrAPENS ‑m‑y ), a main chain of the polyarylether nitrile sulfone membrane is a random adamantane-containing polyarylether nitrile sulfone polymer, wherein: a nitrile group segment content is m, a sulfone group segment content is 1-m, hydrogen atoms of benzyl are partially replaced by bromine atoms, a fragment of a molecular structure formula of the adamantane-containing polyarylether nitrile sulfone separation membrane is as follows: wherein, a nitrile group / sulfone group segment molar ratio is 0-1; a bromination degree y=1-100; X=Br or H.

Description

Technical Field

[0001] This invention belongs to the field of nanofiltration in membrane separation technology, specifically relating to an adamantane-containing polyarylene ether nitrile sulfone separation membrane and its preparation method. Background Technology

[0002] Based on the applied operating pressure and the average pore size of the membrane used, filtration membranes can be divided into three types: microfiltration, ultrafiltration, and reverse osmosis.

[0003] The operating pressure used for microfiltration is typically less than 2 × 10⁻⁶. 5 Pa, the average pore size of the membrane is 500 angstroms to 14 micrometers, and it is used to separate larger particles, bacteria and pollutants.

[0004] The operating pressure used for ultrafiltration is 1×10 5 Pa~6×10 5 Pa, the average pore size of the membrane is 10-100 angstroms, used to separate macromolecular solutes.

[0005] The operating pressure used for reverse osmosis is much higher than that for ultrafiltration, often reaching 20 × 10⁻⁶. 5 Pa ~ 70 × 10 5 Pa, the average pore size of the membrane is the smallest, generally below 10 angstroms, and it is used to separate small molecule solutes, such as seawater desalination and the production of high-purity water.

[0006] Polyaryl ether nitrile (PEN) refers to a class of special polymer materials containing a large number of benzene rings and ether bonds in the main chain and cyano groups in the side chains. The large number of aromatic rings and ether bonds in the main chain endows PEN with excellent heat resistance, mechanical strength and excellent toughness; at the same time, the presence of the strongly polar cyano groups in the side chains also endows PEN with excellent adhesive properties.

[0007] It is precisely because of the excellent comprehensive properties of polyaryletheronitrile (high temperature resistance, chemical corrosion resistance, high flame retardancy, high strength, creep resistance, and high rigidity) that it is a crucial revolutionary material in both military fields such as machinery, ships, and aerospace, and civilian fields such as electronics, electrical engineering, medical care, and environmental protection.

[0008] In 1973, the first patent on the synthesis and preparation process of polyarylene ether nitrile was published by DR Heath, but due to the complex reaction process at that time, the synthesis of polyarylene ether nitrile was limited to laboratory preparation

[19] .

[0009] Until 1986, Idemitsu Kosan Co., Ltd. of Japan achieved the first industrial production of polyarylene ether nitrile through a nucleophilic substitution reaction of 2,6-difluorobenzonitrile with resorcinol in a protic solvent.

[0010] The product's performance indicators (glass transition temperature of 148°C, heat distortion temperature of 165°C, and tensile strength exceeding 130 MPa) were comparable to those of the polyetheretherketone (PEEK) produced by ICI in the UK at the time.

[0011] Poly(aryl ether sulfone) (PES) has a large number of benzene rings in its molecular chain, which gives it a rigid structure. The large number of ether bonds in its structure enhances the flexibility of the molecular chain.

[0012] Furthermore, the structural units composed of sulfone groups, ether bonds, and benzene rings in its structural units form a large conjugated system, and this conjugated structure makes polyethersulfone exhibit very stable chemical properties.

[0013] The synthesis of polyethersulfone has a history of more than 40 years. It was first developed by Imperial Chemical Industries in the UK, and subsequently, more and more countries around the world developed and researched polyethersulfone materials.

[0014] In China, in addition to a small number of engineering plastics plants producing polyethersulfone, many universities synthesize polyethersulfone and explore its applications.

[0015] The unique molecular structure of polyethersulfone gives it excellent chemical and biological resistance. In addition, polyethersulfone also has good heat resistance and high insulation properties.

[0016] It possesses extremely high thermodynamic stability and mechanical strength, with a glass transition temperature (Tg) as high as 230℃ and a maximum operating temperature of 200℃. It can be used for extended periods at temperatures of 150-180℃.

[0017] Moreover, polyethersulfone is a self-extinguishing resin with low smoke diffusion (second only to polyetheretherketone, and has a high limiting oxygen index, so it can meet the US UL-94V-0 standard without the need for inorganic flame retardants such as chlorine).

[0018] Although polyethersulfone is a thermoplastic, it still has excellent mechanical properties, with a tensile strain of only 2.55% at 150°C and 20 MPa pressure.

[0019] Polyethersulfone has low dielectric loss, high dielectric strength, and good self-insulation.

[0020] From low temperatures to high temperatures close to the glass transition point, the dielectric constant and dielectric loss factor of polyethersulfone remain essentially unchanged.

[0021] Compared with other polysulfone materials, PES has a lower melt viscosity, which makes it have good melt processing performance, low molding shrinkage (about 0.6%), and good dimensional stability.

[0022] However, PES is more prone to absorbing water than other polysulfone materials, so it needs to be dried before processing and molding, otherwise it will affect the product performance.

[0023] Meanwhile, in membrane separation technology, polyethersulfone is easily soluble in organic solvents, and the process of preparing engineering plastic polyethersulfone into membrane materials through phase inversion is very simple. Furthermore, the structure and chemical properties of the membrane can be controlled by physical blending or chemical modification during the membrane formation process, which makes separation membranes prepared with polyethersulfone widely used in many fields.

[0024] In 2016, Dalian University of Technology published "High-performance resins of heteronaphthalene-biphenyl polyether nitrile sulfone series and new application technologies".

[0025] Starting from polymer molecular structure design, and through breakthroughs in corresponding polymerization processes, several key technologies were overcome, resulting in the pioneering development of a novel series of high-performance polyarylene ether sulfone resins that are both high-temperature resistant and soluble. The main inventions include: 1. Successfully introducing a fully aromatic, twisted, non-coplanar diazanaphthyl ketone biphenyl structure into the main chain of polyarylene ether nitrile molecules, successfully developing a novel, high-performance, high-temperature resistant, and soluble polyarylene biphenyl sulfone (PPENS), solving the technical problem that traditional polyarylene ether nitriles cannot simultaneously possess high-temperature resistance and soluble properties; 2. Developing a new polymerization process characterized by a composite catalytic system and a mixed solvent system, the entire process is carried out under normal pressure, with a maximum temperature <200℃, and post-treatment requiring only 3-5 water washes, solving the technical problem that traditional polyarylene ether nitrile polymerization processes cannot obtain high molecular weight, narrow distribution products, and achieving low-cost, controllable preparation; 3. Developing a high-temperature resistant and soluble polyarylene biphenyl sulfone ketone (PPENSK) through quaternary copolymerization. The introduction of the carbonyl group makes PPENSK... While maintaining excellent heat resistance, it possesses the comprehensive advantages of high strength, high toughness, and easy processing; 4. Through quaternary copolymerization, PPENSKK (a poly(naphthalene biphenyl) ether sulfone ketone) was successfully developed. The introduction of the dual ketone structure further enhances the toughness of PPENSKK, taking into account the comprehensive advantages of high strength, high toughness, and reduced cost; 5. Multifunctional membranes for aerospace heat insulation, moisture insulation, and sound insulation, as well as special functional membranes for seamless cable wrapping, PPENSKK, and anion exchange membranes for new energy storage batteries were successfully developed.

[0026] Adamantane (tricyclic [3.3.1.1]) 3•7 Decane, molecular formula C 10 H 16 Adamantane is a well-formed, symmetrical, and highly stable cage-like hydrocarbon. Its basic carbon skeleton is similar to a lattice unit of diamond, hence it is called adamantane.

[0027] The hydrogen atoms at positions 1, 3, 5, and 7 of adamantane are prone to substitution, oxidation, and alkylation reactions, and its potential derivatives are far more numerous and varied than those of benzene derivatives. Therefore, it is hailed as a next-generation raw material for fine and specialty chemicals.

[0028] Introducing adamantane framework structures into the main chain or side chain of polymers such as polyester, polycarbonate, polyamide, polysulfone, and polyimide can significantly improve the thermo-oxidative stability, chemical stability, and optical stability of polymers, as well as improve their mechanical, dielectric, and other properties. This results in a series of liquid crystal display materials, semiconductor photoresist materials, holographic photosensitive materials, membrane separation materials, smart plastics, corneal contact lenses, and drug carriers with special functions.

[0029] Adamantane polymers have shown broad application prospects in high-tech fields such as microelectronics, communications, aerospace, optical instruments, and biomedicine.

[0030] Chinese patent CN116688778A discloses a random polyarylene ether nitrile sulfone membrane (MAPENS-x) containing adamantane. The main chain of the polyarylene ether nitrile sulfone membrane is a random polymer containing nitrile and sulfone groups. An adamantane group is distributed on the side chain of each nitrile and sulfone group. The content of nitrile group segment x = 0 to 1 and the content of sulfone group segment 1 to x are specified. Summary of the Invention

[0031] The purpose of this invention is to provide a separation membrane containing adamantane polyarylene ether sulfone and its preparation method.

[0032] The main chain structure of this membrane is designed to be a polyarylene ether sulfone polymer containing adamantyl groups. The hydrophobic portion of the polymer contains adamantyl groups, and the adamantyl groups and long, flat sulfone groups alternate, giving the membrane good heat resistance, flame retardancy and mechanical strength, while still maintaining good thermoforming process flowability.

[0033] To achieve the purpose of this invention, the following technical solution is adopted: The adamantane-containing polyarylene ether nitrile sulfone separation membrane (BrAPENS) of the present invention -m-y The main chain of the polyarylene ether nitrile sulfone membrane is a random polyarylene ether nitrile sulfone polymer containing adamantane, wherein: the nitrile segment content is m, the sulfone segment content is 1-m, and the hydrogen atom of the benzyl group is replaced by a bromine atom. A fragment of the molecular structure of the adamantane-containing polyarylene ether nitrile sulfone separation membrane is as follows: ;

[0034] The molar ratio of nitrile to sulfone groups is 0-1; the degree of bromination is y=1-100; and X = Br or H.

[0035] The method for preparing the adamantane-containing polyarylene ether nitrile sulfone separation membrane of the present invention comprises: Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM)

[0036] Dissolve 1 part of 2-adamantanone and at least 2 parts of 2,6-dimethylphenol completely in 1.5-3 parts of toluene. Stir until completely dissolved at room temperature. Then add 0.3-0.6 parts of methanesulfonic acid, 0.3-0.8 parts of trifluoromethanesulfonic acid, and 0.3-0.6 parts of 3-mercaptopropionic acid for catalysis. React at 50-90°C for 5-16 hours. After stopping the reaction, cool to room temperature. Precipitate the above reactants with 50% methanol aqueous solution. Dry the precipitate to remove toluene and volatile acids. Wash the precipitate several times with deionized water and then wash it with pure methanol until the polymer turns white. Dry the precipitate to obtain the MADM monomer compound. adamantyl-containing polyarylene ether sulfone polymer (MAPENS) -m Synthesis of )

[0037] Under nitrogen protection, 1 part of the MADM monomer compound obtained in step (I) and 0.678*(1-m) parts of bis(4-fluorophenyl) sulfone (FPS) were dissolved in 3-10 parts of N,N-dimethylacetamide. Then, 1-3 parts of toluene, 0.371*m parts of 2,6-difluorobenzyl nitrile (DFBN), and 0.8-1.5 parts of anhydrous K2CO3 were added as catalysts. The reaction was carried out at 140-145℃ for 3-5 hours, and then the temperature was raised to 160-165℃ for 24-30 hours. After stopping the reaction, the mixture was cooled to room temperature, and the reactants were precipitated with 50% methanol aqueous solution. After multiple filtrations and washings until the washing solution was clear, the mixture was purified by Soxhlet extraction with 50% methanol aqueous solution. After purification and drying, the polymer (MAPENS) was obtained. -m ); (III) Bromination modification of polymers and preparation of membranes Under nitrogen protection, dissolve 1 part of the dried polymer (MAPENS) from step (II) in 20-50 parts of 1,1,2,2-tetrachloroethane (TCE). -m In a light-protected environment, 0.2-2 parts of N-bromosuccinimide (NBS) and 0.008-0.05 parts of benzoyl peroxide (BPO) are added according to the degree of bromination γ. The reaction is carried out at 84-86℃ for 4-5 h. After the reaction is stopped, the mixture is cooled to room temperature, and then the polymer is precipitated with a 50% methanol aqueous solution, filtered, washed, and air-dried to obtain the brominated polymer (BrMAPENS). -m-y)One part of the brominated polymer was dissolved in 50-100 parts of N-methylpyrrolidone (NMP) and stirred until homogeneous to obtain a casting solution. The casting solution was filtered through a 0.45 μm filter membrane and then coated onto a glass plate or a support cloth. The solution was then placed in a drying oven and heated at 60-80℃ for 12-24 hours while the blower was turned on to evaporate the solvent, resulting in a solid membrane supported by a glass plate or support cloth.

[0038] The method for preparing the adamantane-containing polyarylene ether nitrile sulfone separation membrane of the present invention, wherein: in step (i), the optimal ratio of 2-adamantanone and 2,6-dimethylphenol is 1:2.5.

[0039] The method for preparing the adamantane-containing polyarylene ether nitrile sulfone separation membrane of the present invention, wherein: in step (I), the optimal ratio of the catalyst is methanesulfonic acid: trifluoromethanesulfonic acid: 3-mercaptopropionic acid = 1:1:1.

[0040] The method for preparing the adamantane-containing polyarylene ether nitrile sulfone separation membrane of the present invention, wherein: in step (ii), the optimal amount of anhydrous K2CO3 is 1 times the amount of MADM.

[0041] The method for preparing the adamantane-containing polyarylene ether nitrile sulfone separation membrane of the present invention, wherein: the number of parts is by mass.

[0042] Compared with the prior art, the adamantane-containing polyarylene ether nitrile sulfone separation membrane and its preparation method of the present invention have the following advantages: By varying the ratio of 2,6-difluorobenzyl nitrile (DFBN) and bis(4-fluorophenyl) sulfone (FPS) monomers, adamantane-containing polyarylene ether nitrile sulfone polymers (MAPENS) with different nitrile / sulfone molar ratios were synthesized. -m A series of adamantane-containing polyarylene ether nitrile sulfone separation membranes were prepared by adjusting the molecular chain spacing, thereby regulating the performance and realizing the controllable microstructure of the membrane.

[0043] The adamantyl group has significant steric hindrance, and its large volume prevents the chain segments from packing tightly, thus increasing the free volume fraction. At the same time, the alternation of adamantyl and long, flat sulfone groups leads to molecular asymmetry on the chain segment rotation axis, which restricts the rotation and bending motion of the polymer chain, thereby simultaneously improving the functionality of the membrane.

[0044] Because of the presence of highly polar cyano groups, the film exhibits significantly improved heat resistance, flame retardancy, and mechanical strength compared to cyano-free polyarylethers, while still maintaining good thermoforming process flowability. This makes it suitable for a wider range of applications and an indispensable type of polymer material for developing high technologies such as aerospace and nuclear energy, and enhancing national strength.

[0045] A benzyl group is introduced by synthesizing adamantane monomers containing benzyl groups.

[0046] This method improves upon previous methods of modifying membranes using chloromethylation, avoiding the highly polluting and carcinogenic chloromethylation reaction.

[0047] The prepared adamantane-containing polyarylene ether sulfone separation membrane has good flexibility, high mechanical strength, good chemical stability and thermal stability, and exhibits excellent ultrafiltration membrane performance.

[0048] The random structure of membranes facilitates synthesis and is beneficial for industrial production.

[0049] Compared with Chinese patent CN116688778A, this invention modifies and changes the structure of the membrane through bromination and thermal crosslinking modification processes, resulting in a smaller pore size in the prepared membrane, which is more suitable for material screening and is beneficial for improving the membrane's separation performance in the later stages. Attached Figure Description

[0050] Figure 1 For MADM 1 H NMR spectrum; Figure 2 For MAPENS -0.2 of 1 H NMR spectrum; Figure 3 For BrAPENS -0.2 -20 1 H NMR spectrum. Detailed Implementation

[0051] To illustrate the present invention more clearly, the present invention will be further described below in conjunction with embodiments and accompanying drawings.

[0052] Example 1

[0053] This embodiment uses a synthetic adamantane-containing polyarylene ether sulfone (BrAPENS) separation membrane with m=0.2 and y=20. -m-y Taking the preparation method of the adamantane-containing polyarylene ether sulfone separation membrane as an example, the main chain of the membrane is a random polyarylene ether sulfone polymer containing adamantane, wherein 20% of the hydrogen atoms in the benzyl group are replaced by bromine atoms. The molecular structure fragment of the adamantane-containing polyarylene ether sulfone separation membrane is as follows: ;

[0054] The nitrile group content is m=0.2; the sulfone group content is 1-m=0.8; and X=Br or H.

[0055] The adamantane-containing polyarylene ether nitrile sulfone separation membrane (BrAPENS) of the present invention -m-y The preparation methods of ) include: Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM)

[0056] 12 g of 2-adamantanone and 21.246 mL of 2,6-dimethylphenol were completely dissolved in 30 mL of toluene. Then, 3 mL of methanesulfonic acid, 4 mL of trifluoromethanesulfonic acid and 4 mL of 3-mercaptopropionic acid were added for catalysis. The reaction was carried out at 50 °C for 16 hours. After stopping the reaction and cooling to room temperature, the above reactants were precipitated with 50% methanol aqueous solution, dried to remove toluene and volatile acids, washed several times with deionized water, and then washed with pure methanol until the polymer turned white. After drying, the MADM monomer compound was obtained. (II) Polymers Containing Adamantyl Alkyl Polyarylene Ether Sulfonates (MAPENS) -m Synthesis of ) Under nitrogen protection, 3.752 g of the MADM monomer compound and 2.034 g of bis(4-fluorophenyl)sulfone (FPS) obtained in step (I) were dissolved in 16 mL of N,N-dimethylacetamide, followed by the addition of 4 mL of toluene and 0.278 g of 2,6-difluorobenzyl nitrile (DFBN), and then 3.450 g of anhydrous K₂CO₃. The reaction was first carried out at 145 °C for 4 hours, then the temperature was increased to 165 °C and the reaction was carried out for 24 hours. After the reaction was stopped, the mixture was cooled to room temperature, precipitated with 50% methanol aqueous solution, and washed repeatedly by filtration until the washing solution was clear. The mixture was then purified by Soxhlet extraction with 50% methanol aqueous solution, and dried to obtain the polymer (MAPENS). -m ); bromination modification of polymers and preparation of membranes

[0057] Under nitrogen protection, 1.000 g of the dried polymer obtained in step (II) was dissolved in 15 mL of 1,1,2,2-tetrachloroethane (TCE). 0.376 g of N-bromosuccinimide (NBS) and 0.010 g of benzoyl peroxide (BPO) were added under light-protected conditions. The reaction was carried out at 85 °C for 4.5 h. After stopping the reaction and cooling to room temperature, the polymer was precipitated with 50% methanol aqueous solution, filtered, washed, and air-dried to obtain the brominated polymer (BrAPENS-0.2-20). One part of the brominated polymer was dissolved in 60 parts of N-methylpyrrolidone (NMP) and stirred until homogeneous to prepare a casting solution. The casting solution was filtered through a 0.45 μm filter membrane and then coated onto a glass plate or a support cloth. The mixture was then placed in a drying oven and heated at 60 °C for 24 hours while the blower was turned on to evaporate the solvent, resulting in a solid membrane supported by a glass plate or support cloth.

[0058] The obtained homogeneous membrane was tested and the results were obtained.

[0059] Tests: The structure and actual degree of bromination of the adamantane-containing polyarylene ether sulfone separation membrane were determined using nuclear magnetic resonance (NMR) and infrared spectroscopy.

[0060] The ultrafiltration performance of the membrane was determined by permeation test and dextran method in accordance with GB / T 32360 2015.

[0061] Referencing HY / T 113-2008, the nanofiltration performance of the membrane was determined by calculating the desalination rate and permeate volume.

[0062] The test results show that Example 1 successfully synthesized polyarylene ether sulfone polymers containing adamantane in different proportions.

[0063] The chemical structure of the membrane was confirmed using nuclear magnetic resonance (NMR) and infrared spectroscopy.

[0064] The actual degree of bromination of the adamantane-containing polyarylene ether sulfone separation membrane is 20.1%, which means that each adamantane-containing repeating unit contains 0.804 benzyl bromide groups.

[0065] The pure water flux J of the adamantane-containing polyarylene ether nitrile sulfone separation membrane is 154 L / (m²). 2 h), the retention rate R is 93%.

[0066] The monovalent ion removal rate of the adamantane-containing polyarylene ether nitrile sulfone separation membrane is 31%, and the water production rate is 35 L / (m³). 2 h), the removal rate of divalent ions is 93%, and the water production rate is 26 L / (m³). 2 h).

[0067] Example 2

[0068] This embodiment uses a synthetic adamantane-containing polyarylene ether sulfone (BrAPENS) separation membrane with x=0.2 and y=60. -m-y Taking the preparation method of the adamantane-containing polyarylene ether sulfone separation membrane as an example, the main chain of the membrane is a random polyarylene ether sulfone polymer containing adamantane, wherein 60% of the hydrogen atoms in the benzyl group are replaced by bromine atoms. The molecular structure fragment of the adamantane-containing polyarylene ether sulfone separation membrane is as follows: ;

[0069] The nitrile group content is m=0.2; the sulfone group content is 1-m=0.8; and X=Br or H.

[0070] The adamantane-containing polyarylene ether nitrile sulfone separation membrane (BrAPENS) of the present invention -x The preparation methods of -y) include: (I) Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM) 12 g of 2-adamantanone and 21.246 mL of 2,6-dimethylphenol were completely dissolved in 25 mL of toluene. Then, 3.6 mL of methanesulfonic acid, 4 mL of trifluoromethanesulfonic acid and 4.5 mL of 3-mercaptopropionic acid were added for catalysis. The reaction was carried out at 50 °C for 16 hours. After stopping the reaction and cooling to room temperature, the above reactants were precipitated with 50% methanol aqueous solution, dried to remove toluene and volatile acids, washed several times with deionized water, and then washed with pure methanol until the polymer turned white. After drying, the MADM monomer compound was obtained. (II) Polymers Containing Adamantyl Alkyl Polyarylene Ether Sulfonates (MAPENS) -m Synthesis of ) Under nitrogen protection, 3.752 g of polymer obtained in step (I) and 2.034 g of bis(4-fluorophenyl) sulfone (FPS) were dissolved in 18 mL of N,N-dimethylacetamide, followed by the addition of 6 mL of toluene and 0.278 g of 2,6-difluorobenzyl nitrile (DFBN). Then, 3.450 g of anhydrous K2CO3 was added for catalysis. The reaction was first carried out at 145 °C for 4 hours, and then the temperature was increased to 165 °C for 24 hours. After the reaction was stopped, the mixture was cooled to room temperature, precipitated with 50% methanol aqueous solution, and washed repeatedly by filtration until the washing solution was clear. The mixture was then purified by Soxhlet extraction with 50% methanol aqueous solution and dried to obtain the polymer.

[0071] (III) Bromination modification of polymers and preparation of membranes Under nitrogen protection, 1.000 g of the dried polymer obtained in step (II) was dissolved in 18 mL of 1,1,2,2-tetrachloroethane (TCE). 1.129 g of N-bromosuccinimide (NBS) (6.3 mmol) and 0.031 g of benzoyl peroxide (BPO) were added under light-protected conditions. The reaction was carried out at 85 °C for 4.5 h. After stopping the reaction and cooling to room temperature, the reactants were precipitated with 50% methanol aqueous solution, filtered, washed, and air-dried to obtain the brominated polymer (BrMAPENS-0.2-60). One part of the obtained brominated polymer was dissolved in 65 parts of N-methylpyrrolidone (NMP) and stirred until homogeneous to prepare a casting solution. The obtained casting solution was filtered through a 0.45... The filter is filtered through a μm filter membrane, then coated onto a glass plate or a support cloth, and placed in a drying oven at 60°C for 24 hours while the blower is turned on to evaporate the solvent, resulting in a solid membrane supported by a glass plate or support cloth.

[0072] The obtained homogeneous membrane was tested and the results were obtained.

[0073] Tests: The structure and actual degree of bromination of the adamantane-containing polyarylene ether sulfone separation membrane were determined using nuclear magnetic resonance (NMR) and infrared spectroscopy.

[0074] The ultrafiltration performance of the membrane was determined by permeation test and dextran method in accordance with GB / T 32360 2015.

[0075] Referencing HY / T 113-2008, the nanofiltration performance of the membrane was determined by calculating the desalination rate and permeate flow rate.

[0076] The test results show that Example 2 successfully synthesized polyarylene ether sulfone polymers containing adamantane in different proportions.

[0077] The chemical structure of the membrane was confirmed using nuclear magnetic resonance (NMR) and infrared spectroscopy.

[0078] The actual degree of bromination of the adamantane-containing polyarylene ether sulfone separation membrane is 47.8%, which means that each adamantane-containing repeating unit contains 1.912 benzyl bromide groups.

[0079] The pure water flux J of the adamantane-containing polyarylene ether nitrile sulfone separation membrane is 152 L / (m²). 2 h), the retention rate R was 94%.

[0080] The monovalent ion removal rate of the adamantane-containing polyarylene ether nitrile sulfone separation membrane is 33%, and the water production rate is 33 L / (m³). 2 h), the removal rate of divalent ions is 95%, and the water production rate is 25 L / (m³). 2 h).

[0081] Example 3

[0082] This embodiment uses a synthetic adamantane-containing polyarylene ether sulfone (BrAPENS) separation membrane with m=0.6 and y=20. -m-y Taking the preparation method of adamantane-containing polyarylene ether sulfone separation membrane as an example, the main chain of the membrane is a random polyarylene ether sulfone polymer containing adamantane, wherein 20% of the hydrogen atoms at the benzyl position are replaced by bromine atoms. The molecular structure of the adamantane-containing polyarylene ether sulfone separation membrane is as follows: ;

[0083] The nitrile group content is m=0.6; the sulfone group content is 1-m=0.4; and X=Br or H.

[0084] The adamantane-containing polyarylene ether nitrile sulfone separation membrane (BrAPENS) of the present invention -m-y The preparation methods of ) include: (I) Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM) 12 g of 2-adamantanone and 21.246 mL of 2,6-dimethylphenol were completely dissolved in 28 mL of toluene. Then, 4 mL of methanesulfonic acid, 4.5 mL of trifluoromethanesulfonic acid, and 4.8 mL of 3-mercaptopropionic acid were added for catalysis. The reaction was carried out at 50 °C for 16 hours. After stopping the reaction and cooling to room temperature, the above reactants were precipitated with 50% methanol aqueous solution, dried to remove toluene and volatile acids, washed several times with deionized water, and then washed with pure methanol until the polymer turned white. After drying, the MADM monomer compound was obtained. (ii) Polymers containing adamantyl alkyl polyarylene ether nitrile sulfones (MAPENS) -m Synthesis of ) Under nitrogen protection, 3.752 g of MADM monomer compound (10 mmol) obtained in step (I) and 1.017 g of bis(4-fluorophenyl) sulfone (FPS) were dissolved in 20 mL of N,N-dimethylacetamide, followed by the addition of 8 mL of toluene and 0.835 g of 2,6-difluorobenzyl nitrile (DFBN), and then 3.450 g of anhydrous K2CO3. The reaction was first carried out at 145 °C for 4 hours, and then the temperature was raised to 165 °C for 24 hours. After the reaction was stopped, the mixture was cooled to room temperature, and the reactants were precipitated with 50% methanol aqueous solution. The mixture was filtered and washed multiple times until the washing solution was clear. The mixture was then purified by Soxhlet extraction with 50% methanol aqueous solution. After purification, the mixture was dried to obtain the polymer (MAPENS-x). (III) Bromination modification of polymers and preparation of membranes Under nitrogen protection, 1.000 g of the polymer obtained in step (II) was dissolved in 20 mL of 1,1,2,2-tetrachloroethane (TCE). 0.409 g of N-bromosuccinimide (NBS) (2.3 mmol) and 0.011 g of benzoyl peroxide (BPO) were added under light-protected conditions. The reaction was carried out at 85 °C for 4.5 h. After stopping the reaction and cooling to room temperature, the polymer was precipitated with 50% methanol aqueous solution, filtered, washed, and air-dried to obtain the brominated polymer (BrAPENS-0.6-20). One part of the obtained brominated polymer was dissolved in 70 parts of N-methylpyrrolidone (NMP) and stirred until homogeneous to prepare a casting solution. The casting solution was filtered through a 0.45 μm filter membrane and then coated onto a glass plate or a support cloth. The solution was then placed in a drying oven and heated at 60 °C for 24 h while a blower was turned on to evaporate the solvent, resulting in a solid membrane supported by a glass plate or support cloth.

[0085] The obtained homogeneous membrane was tested and the results were obtained.

[0086] Testing: The structure and actual degree of bromination of the polyarylene ether sulfone separation membrane containing adamantane were determined by nuclear magnetic resonance (NMR) and infrared spectroscopy.

[0087] The ultrafiltration performance of the membrane was determined by permeation test and dextran method in accordance with GB / T 32360 2015.

[0088] Referencing HY / T 113-2008, the nanofiltration performance of the membrane was determined by calculating the desalination rate and permeate flow rate.

[0089] The test results show that Example 3 successfully synthesized polyarylene ether sulfone polymers containing adamantane in different proportions.

[0090] The chemical structure of the membrane was confirmed using nuclear magnetic resonance (NMR) and infrared spectroscopy.

[0091] The actual degree of bromination of the adamantane-containing polyarylene ether sulfone separation membrane is 19.0%, which means that each adamantane-containing repeating unit contains 0.760 benzyl bromide groups.

[0092] The pure water flux J of the adamantane-containing polyarylene ether nitrile sulfone separation membrane is 153 L / (m²). 2 h), the retention rate R was 96%.

[0093] The monovalent ion removal rate of the adamantane-containing polyarylene ether nitrile sulfone separation membrane is 34%, and the water production rate is 32 L / (m³). 2 h), the removal rate of divalent ions is 93%, and the water production rate is 27 L / (m³). 2 h).

[0094] Example 4

[0095] This embodiment uses a synthetic adamantane-containing polyarylene ether sulfone (BrAPENS) separation membrane with m=0.6 and y=60. -m-y Taking the preparation method of the adamantane-containing polyarylene ether sulfone separation membrane as an example, the main chain of the membrane is a random polyarylene ether sulfone polymer containing adamantane, wherein 60% of the hydrogen atoms at the benzyl position are replaced by bromine atoms. The molecular structure fragment of the adamantane-containing polyarylene ether sulfone separation membrane is as follows: ;

[0096] The nitrile group content is m=0.6; the sulfone group content is 1-m=0.4; and X=Br or H.

[0097] The preparation method of the adamantane-containing polyarylene ether nitrile sulfone separation membrane (BrAPENS-xy) of the present invention includes: (I) Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM) 12 g of 2-adamantanone and 21.246 mL of 2,6-dimethylphenol were completely dissolved in 32 mL of toluene. Then, 4 mL of methanesulfonic acid, 5 mL of trifluoromethanesulfonic acid and 5 mL of 3-mercaptopropionic acid were added as catalysts. The reaction was carried out at 50 °C for 16 hours. After stopping the reaction and cooling to room temperature, the product was precipitated with 50% methanol aqueous solution, filtered and washed repeatedly until the solution was clear, and dried to obtain the MADM monomer compound.

[0098] (II) Synthesis of adamantyl-containing polyarylene ether nitrile sulfone polymer (MAPENS-x) Under nitrogen protection, 3.752 g of polymer and 1.017 g of bis(4-fluorophenyl) sulfone (FPS) obtained in step (I) were dissolved in 22 mL of N,N-dimethylacetamide, followed by the addition of 10 mL of toluene and 0.835 g of 2,6-difluorobenzyl nitrile (DFBN), and then 3.450 g of anhydrous K2CO3. The reaction was first carried out at 145 °C for 4 hours, and then the temperature was increased to 165 °C for 24 hours. After the reaction was stopped, the mixture was cooled to room temperature, precipitated with 50% methanol aqueous solution, dried to remove toluene and volatile acids, washed several times with deionized water, and then washed with pure methanol until the polymer turned white. The polymer was then dried to obtain the MADM monomer compound. (III) Bromination modification of polymers and preparation of membranes Under nitrogen protection, 1.000 g of the polymer obtained in step (II) was dissolved in 22 mL of 1,1,2,2-tetrachloroethane (TCE). 1.228 g of N-bromosuccinimide (NBS) and 0.033 g of benzoyl peroxide (BPO) were added under light-protected conditions. The reaction was carried out at 85 °C for 4.5 h. After stopping the reaction and cooling to room temperature, the above reactants were precipitated with 50% methanol aqueous solution, filtered, washed, and air-dried to obtain the brominated polymer (BrAPENS-0.6-60). One part of the obtained brominated polymer was dissolved in 75 parts of N-methylpyrrolidone (NMP) and stirred evenly to prepare a casting solution. The obtained casting solution was filtered through a 0.45 μm filter membrane and then coated onto a glass plate or a support cloth. The solution was placed in a drying oven and heated at 60 °C for 24 h while the blower was turned on to evaporate the solvent, resulting in a solid membrane supported by a glass plate or support cloth.

[0099] The obtained homogeneous membrane was tested and the results were obtained.

[0100] Tests: The structure and actual degree of bromination of the adamantane-containing polyarylene ether sulfone separation membrane were determined using nuclear magnetic resonance (NMR) and infrared spectroscopy.

[0101] The ultrafiltration performance of the membrane was determined by permeation test and dextran method in accordance with GB / T 32360 2015.

[0102] Referencing HY / T 113-2008, the nanofiltration performance of the membrane was determined by calculating the desalination rate and permeate flow rate.

[0103] The test results show that Example 4 successfully synthesized polyarylene ether sulfone polymers containing adamantane in different proportions.

[0104] The chemical structure of the membrane was confirmed using nuclear magnetic resonance (NMR) and infrared spectroscopy.

[0105] The actual degree of bromination of the adamantane-containing polyarylene ether sulfone separation membrane is 47.5%, which means that each adamantane-containing repeating unit contains 1,900 benzyl bromide groups.

[0106] The pure water flux J of the adamantane-containing polyarylene ether nitrile sulfone separation membrane is 151 L / (m²). 2 h), the retention rate R is 98%.

[0107] The monovalent ion removal rate of the adamantane-containing polyarylene ether nitrile sulfone separation membrane is 33%, and the water production rate is 32 L / (m³). 2 h), the removal rate of divalent ions is 95%, and the water production rate is 28 L / (m³). 2 h).

[0108] The above description only discloses specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or modifications that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A separation membrane containing adamantane polyarylene ether nitrile sulfone (BrMAPENS) -m-y The polyarylene ether sulfone separation membrane has a main chain of adamantane-containing random polyarylene ether sulfone polymer, characterized in that: The nitrile segment content is m, the sulfone segment content is 1-m, and the hydrogen atom of the benzyl group is replaced by a bromine atom. The molecular structural fragment of the adamantane polyarylene ether nitrile sulfone separation membrane is as follows: ； The content ratio of nitrile group to sulfone group is 0~1; the degree of bromination y=1~100; X = Br or H.

2. A method for preparing the adamantane-containing polyarylene ether nitrile sulfone separation membrane as described in claim 1, characterized in that: It includes: (I) Synthesis of monomer 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane (MADM) Dissolve 1 part of 2-adamantanone and at least 2 parts of 2,6-dimethylphenol completely in 1.5-3 parts of toluene. Stir until completely dissolved at room temperature. Then add 0.3-0.6 parts of methanesulfonic acid, 0.3-0.8 parts of trifluoromethanesulfonic acid, and 0.3-0.6 parts of 3-mercaptopropionic acid for catalysis. React at 50-90°C for 5-16 hours. After stopping the reaction, cool to room temperature. Precipitate the above reactants with 50% methanol aqueous solution. Dry the precipitate to remove toluene and volatile acids. Wash the precipitate several times with deionized water and then wash it with pure methanol until the polymer turns white. Dry the precipitate to obtain the MADM monomer compound. (II) Polymers Containing Adamantyl Alkyl Polyarylene Ether Sulfonates (MAPENS) -m Synthesis of Under nitrogen protection, 1 part of the MADM monomer compound obtained in step (I) and 0.678*(1-m) parts of bis(4-fluorophenyl) sulfone (FPS) were dissolved in 3-10 parts of N,N-dimethylacetamide. Then, 1-3 parts of toluene, 0.371*m parts of 2,6-difluorobenzyl nitrile (DFBN), and 0.8-1.5 parts of anhydrous K2CO3 were added as catalysts. The reaction was carried out at 140-145℃ for 3-5 hours, and then the temperature was raised to 160-165℃ for 24-30 hours. After stopping the reaction, the mixture was cooled to room temperature, and the reactants were precipitated with 50% methanol aqueous solution. After multiple filtrations and washings until the washing solution was clear, the mixture was purified by Soxhlet extraction with 50% methanol aqueous solution. After purification and drying, the polymer (MAPENS) was obtained. -m ); (III) Bromination modification of polymers and preparation of membranes Under nitrogen protection, dissolve 1 part of the dried polymer (MAPENS) from step (II) in 20-50 parts of 1,1,2,2-tetrachloroethane (TCE). -m In a light-protected environment, 0.2-2 parts of N-bromosuccinimide (NBS) and 0.008-0.05 parts of benzoyl peroxide (BPO) are added according to the degree of bromination γ. The reaction is carried out at 84-86℃ for 4-5 h. After the reaction is stopped, the mixture is cooled to room temperature, and then the polymer is precipitated with a 50% methanol aqueous solution, filtered, washed, and air-dried to obtain the brominated polymer (BrMAPENS). -m-y One part of the brominated polymer was dissolved in 50-100 parts of N-methylpyrrolidone (NMP), and stirred evenly to obtain a casting solution. The casting solution was filtered through a 0.45 μm filter membrane, then coated onto a glass plate or a support cloth, and placed in a drying oven at 60-80℃ for 12-24 h while the blower was turned on to evaporate the solvent, resulting in a solid membrane supported by a glass plate or support cloth. The above numbers refer to parts by weight.

3. The method for preparing the adamantane-containing polyarylene ether nitrile sulfone separation membrane according to claim 2, characterized in that: In step (a), the ratio of 2-adamantanone to 2,6-dimethylphenol is 1:2.

5.

4. The method for preparing the adamantane-containing polyarylene ether nitrile sulfone separation membrane according to claim 3, characterized in that: In step (i), the ratio of catalyst parts is methanesulfonic acid: trifluoromethanesulfonic acid: 3-mercaptopropionic acid = 1:1:

1.

5. The method for preparing the adamantane-containing polyarylene ether nitrile sulfone separation membrane according to claim 4, characterized in that: In step (ii), the amount of anhydrous K2CO3 is 1 times the amount of MADM.

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