Macrocycle-regulated interfacial polymerization composite nanofiltration membrane, preparation method and application thereof

Abstract

The present application relates to the field of membrane separation technology, and more particularly to a macrocyclic molecule regulated interface polymerization composite nanofiltration membrane and a preparation method and application thereof. A macrocyclic supramolecular host molecule is introduced into the preparation process of an interface polymerization polyamide composite membrane, and then a new type of macrocyclic molecule functionalized polyamide separation membrane is formed. The polyamide separation membrane has fine regulation and control of the nanochannel structure and surface chemical properties of the polyamide separation layer, and can realize high selective separation of the size, shape and polarity of dyes and salt ions in printing and dyeing wastewater, breaking through the traditional separation mode based on screening and electrostatic interaction. The macrocyclic molecule regulated interface polymerization composite nanofiltration membrane provided by the present application significantly improves the water flux and anti-fouling performance while maintaining high retention rate of dyes, and is expected to solve the problems of membrane fouling, high treatment cost and poor water quality adaptability of traditional polyamide membranes in printing and dyeing wastewater treatment.

Description

Technical Field

[0001] This invention relates to the field of membrane separation technology, and in particular to macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membranes, their preparation methods, and applications. Background Technology

[0002] The discharge of dyeing and printing wastewater is enormous and complex, containing high concentrations of dyes and salts. Traditional treatment technologies suffer from high energy consumption, low separation efficiency, and resource waste. Nanofiltration membrane technology has become the preferred technology for treating dyeing and printing wastewater due to its advantages such as high separation efficiency and environmental friendliness. However, its core challenge lies in achieving efficient separation of dyes and salts while ensuring high water flux and long-term stability.

[0003] Currently, the technology for preparing polyamide composite membranes through interfacial polymerization is relatively mature. Domestic and international researchers have achieved preliminary control over membrane structure and performance. The prepared loose nanofiltration membranes have demonstrated high rejection rates and a certain flux enhancement effect in dye separation. Some membrane materials exhibit good solvent resistance and stability, laying the foundation for industrial applications. Regarding macrocyclic molecule modification, the regulatory mechanism of traditional macrocyclic molecules (cyclodextrins, crown ethers) on the interfacial polymerization process has been basically clarified, and their role in improving membrane flux and optimizing separation selectivity has been experimentally verified.

[0004] Research on novel macrocyclic molecules such as pentacyclic aromatic hydrocarbons is in its early stages, currently showing potential only in the specific separation of certain pollutants (such as PFOA), but has not yet been applied to the treatment of dyeing and printing wastewater. Overall, existing research has established a basic theoretical framework for the preparation of interfacial polymerized membranes and the modification of macrocyclic molecules; however, for the precise requirements of dye-salt separation, there is a lack of systematic research combining novel macrocyclic molecules with classic polyamide composite membrane systems, and the separation performance and application stability of membrane materials still have considerable room for improvement. Summary of the Invention

[0005] This invention aims to at least solve one of the technical problems existing in related technologies. Therefore, the first objective of this invention is to provide a method for preparing a macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membrane; the second objective is to provide a macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membrane; and the third objective is to provide applications of the macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membrane.

[0006] To achieve the first objective, the technical solution adopted by this invention is as follows:

[0007] The preparation method of macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane includes the following steps:

[0008] S100. Lay the base film flat and fix it between the two plates to form a sandwich structure;

[0009] The base membrane is selected from polyacrylonitrile (PAN) membrane;

[0010] S200. Add an aqueous solution to the sandwich structure to wet the surface of the base membrane and form an aqueous adsorption layer on the surface of the base membrane to obtain a base membrane covered with an aqueous adsorption layer.

[0011] The aqueous solution is a mixed solution containing macrocyclic molecules and amine monomers;

[0012] The structural formula of the macrocyclic molecule is shown below:

[0013] n is selected from 3, 4, or 5;

[0014] The concentration of macrocyclic molecules in the mixed solution was 0.01 wt% to 0.02 wt%.

[0015] S300. An organic phase solution containing acyl chloride monomers is added to the base membrane covered with an aqueous adsorption layer. The aqueous phase and the organic phase undergo an interfacial polymerization reaction on the surface of the base membrane to obtain a macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membrane.

[0016] Interfacial polymerization involves dissolving two highly reactive monomers in two immiscible solvents. When these solutions come into contact, a rapid polymerization reaction occurs at the interface between the two phases. Amide monomers are strongly hydrophilic and soluble in the aqueous phase, while acyl chloride monomers are hydrophobic and soluble in an organic solvent phase that is immiscible with water. When an organic phase solution containing acyl chloride monomers is added to a base film covering an aqueous adsorption layer, acyl chloride molecules migrate from the organic phase to the surface of the base film. At the base film surface, amine monomers and amide monomers undergo interfacial polymerization (i.e., amidation condensation reaction at the interface between the aqueous and organic phases), thereby generating a high molecular weight polyamide polymer film.

[0017] The flux-rejection trade-off effect manifests as follows: In traditional nanofiltration membranes, decreasing the pore size increases the rejection rate of target substances, but increases the mass transfer resistance of water molecules, leading to a decrease in permeate flux. Conversely, increasing the pore size can improve flux, but the rejection rate will significantly decrease due to reduced sieving precision. This study added macrocyclic aromatic hydrocarbon molecules during interfacial polymerization to prepare a composite nanofiltration membrane that combines high selectivity and high flux, with a molecular weight cutoff as low as 407 Da and a water flux of 167 L·m⁻¹. -2 ·h -1 ·bar -1 This composite nanofiltration membrane can increase the membrane pore size while ensuring the retention rate, thus overcoming the flux-retention rate trade-off effect. Based on this performance, the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane provided by this invention is expected to be widely used in the treatment of dyeing and printing wastewater.

[0018] Preferably, in step S200, the macrocyclic molecule has the following structural formula:

[0019] The synthesis process includes the following steps:

[0020] S210, Utilization and The reaction synthesizes compound I. ;

[0021] S220, using compound I and The reaction synthesized compound II. ;

[0022] S230, using P[5]-OTf Reaction with compound II to synthesize macrocyclic molecules .

[0023] Preferably, the synthesis of P[5]-OTf includes the following steps:

[0024] S231, utilizing With paraformaldehyde, DMP[5] columnar aromatic hydrocarbons were synthesized, the structural formula of which is shown below: ;

[0025] S232. DMP4A1Q was synthesized by reacting DMP[5] columnar aromatics with an oxidant. Its structural formula is shown below: ;

[0026] S233. 4DM1HQP[5] was synthesized by reacting DMP4A1Q with a reducing agent, and its structural formula is shown below: ;

[0027] S234. P[5]-OTf was synthesized by reacting 4DM1HQP[5] with trifluoromethanesulfonic anhydride.

[0028] Preferably, in step S232, the oxidant is selected from (NH4)2Ce(NO3)6.

[0029] Preferably, in step S233, the reducing agent is selected from Na2S2O4.

[0030] Preferably, in step S200, the amine monomer is selected from m-phenylenediamine and has a concentration of 0.01wt% to 0.04wt%.

[0031] Preferably, in step S200, the solvent for the mixed solution of macrocyclic molecules and amine monomers is selected from n-hexane.

[0032] Preferably, in step S300, the acyl chloride monomer is selected from trimesoyl chloride and has a concentration of 0.1wt% to 0.3wt%.

[0033] To achieve the second objective, the technical solution adopted by this invention is as follows:

[0034] The macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membrane is prepared using any of the above-described methods for preparing macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membranes.

[0035] To achieve the third objective, the technical solution adopted by this invention is as follows:

[0036] The application of macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membranes involves treating dyes in wastewater using the aforementioned macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membranes.

[0037] The above-described one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:

[0038] The macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membrane and its preparation method provided by this invention are the first to introduce macrocyclic supramolecular host molecules into the preparation process of polyamide composite membranes via interfacial polymerization, thus forming a novel macrocyclic molecule-functionalized polyamide separation membrane. Its innovation is mainly reflected in the following aspects:

[0039] Firstly, by utilizing the interfacial polymerization reaction, the polymerization process occurs only at the interface of two immiscible phases, enabling the functionalized columnar aromatic molecules to possess the nanochannel structure and surface chemical properties of the polyamide separation layer with fine control.

[0040] Secondly, the polyamide membrane modified with columnar aromatic hydrocarbon molecules can achieve highly selective separation of dyes and salt ions in dyeing and printing wastewater based on the recognition ability of host-guest interaction, breaking through the traditional separation mode based on sieving and electrostatic interaction.

[0041] Thirdly, the test results on different dye rejection conditions show that the macromolecular-controlled interfacial polymerization composite nanofiltration membrane provided by this invention significantly improves water flux and antifouling performance while maintaining a high dye rejection rate. It is expected to solve the problems of membrane fouling, high treatment cost and poor adaptability to water quality in the treatment of dyeing and printing wastewater by traditional polyamide membranes.

[0042] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0043] Figure 1 The hydrogen nuclear magnetic resonance spectrum of P[5]-OTf provided in Embodiment 1 of the present invention is shown.

[0044] Figure 2The above is the hydrogen nuclear magnetic resonance spectrum of P[5] columnar aromatic hydrocarbons provided in Example 2 of this invention.

[0045] Figure 3 This is a scanning electron microscope (SEM) image of the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane provided in Embodiment 3 of the present invention.

[0046] Figure 4 This is the Fourier Transform Infrared Spectroscopy (FITR) of the macrocyclic molecular-regulated interfacial polymerization composite nanofiltration membrane and PAN membrane provided in Embodiment 3 of the present invention.

[0047] Figure 5 This is a graph showing the relationship between the zeta potential and pH of the macrocyclic molecular-regulated interfacial polymerization composite nanofiltration membrane and the PAN membrane provided in Embodiment 3 of the present invention.

[0048] Figure 6 This is an X-ray photoelectron spectroscopy (XPS) spectrum of the macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membrane and PAN membrane provided in Example 3 of the present invention.

[0049] Figure 7 This is a graph showing the water flux measurement results of the macrocyclic molecular-regulated interfacial polymerization composite nanofiltration membrane and the MP-0 membrane provided in the test examples of this invention.

[0050] Figure 8 This is an example of the macrocyclic molecular-regulated interfacial polymerization composite nanofiltration membrane provided in this invention, which shows the retention of different dyes.

[0051] Figure 9 This is a scatter plot of the retention rate-molecular weight relationship of the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane provided in the test examples of this invention. Detailed Implementation

[0052] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. The following embodiments are used to illustrate this invention, but cannot be used to limit the scope of this invention.

[0053] In the following embodiments, unless otherwise specified, the experimental methods used are conventional methods, and the materials and reagents used are commercially available, unless otherwise specified, and are carried out in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions.

[0054] Example 1

[0055] The structure of P[5]-OTf is as follows:

[0056] ;

[0057] Its synthesis process is as follows:

[0058] I. Synthesis of DMP[5] columnar aromatics by Friedel-Crafts alkylation condensation reaction .

[0059] Using 1,4-dimethoxybenzene (10 mmol) and 1,2-dichloroethane (20 mL) as the reaction solution, paraformaldehyde (10 mmol) and boron trifluoride diethyl ether (10 mmol) were added sequentially under a nitrogen atmosphere. After stirring for 3 h at room temperature, methanol was added to the reaction solution to precipitate the product. The precipitate was collected by filtration, and the obtained solid was recrystallized using acetonitrile to obtain DMP[5] column aromatic solid (0.33 g).

[0060] II. Synthesis of DMP4A1Q using selective oxidation reaction .

[0061] Add 20 mL of (NH4)2Ce(NO3)6 (4 mmol) aqueous solution to a 100 mL dichloromethane solution of DMP[5] column aromatics (2 mmol). Stir the reaction at room temperature for 10 min, wash with water (100 mL × 3), concentrate under reduced pressure, and purify the residue by silica gel chromatography (mobile phase: ethyl acetate / n-hexane = 1:9, v / v) to obtain red DMP4A1Q solid (812 mg).

[0062] III. Synthesis of 4DM1HQP by reduction reaction[5] .

[0063] DMP4A1Q (0.278 mmol) was added to dichloromethane (10 mL), stirred in a 50 mL round-bottom flask, and Na2S2O4 (5.56 mmol) aqueous solution (2 mL) was added at the same time. After stirring at room temperature for 12 h, the aqueous layer was extracted with dichloromethane (50 mL × 3). The combined organic phase was then washed with water (100 mL) and saturated NaCl solution (100 mL). After drying on anhydrous Na2SO4, the white 4DM1HQP[5] solid was obtained after filtration and evaporation.

[0064] IV. Synthesis of P[5]-OTf by trifluoromethanesulfonation reaction .

[0065] Add 0.69 mmol of 4DM1HQP[5], 1 mL of dry C5H5N, and 20 mL of dry dichloromethane to a dry flask in sequence. Stir until 4DM1HQP[5] is completely dissolved. Cool the reaction system to 0 °C and then add 2 mL of trifluoromethanesulfonic anhydride dropwise. After the addition is complete, continue stirring for 30 min. Then raise the temperature to room temperature and stir for 12 h. After vacuum concentration of the reaction mixture, purify it by silica gel column chromatography (mobile phase: hexane / dichloromethane = 1:1, v / v) to obtain white P[5]-OTf powder (520 mg). Its proton nuclear magnetic resonance spectrum is as follows. Figure 1 As shown.

[0066] Example 2

[0067] Synthesize P[5] columnar aromatics, the structural formula of which is shown below:

[0068]

[0069] The synthesis process is as follows:

[0070] I. Synthesis of Compound I using the selective acylation reaction of chiral alcohols. .

[0071] Under nitrogen protection, 4-iodobenzoyl chloride (3.75 mmol) was dissolved in a solution prepared by dichloromethane (10 mL). This solution was then added dropwise to a solution of (S)-2-pyrrolidinemethanol (4.9 mmol) and triethylamine (1.65 mL) in dichloromethane (20 mL). After the addition was complete, the mixture was stirred at 0 °C for 30 min. Then, the temperature was slowly raised to room temperature and stirred for 16 h. The mixture was then concentrated under reduced pressure and purified by silica gel column chromatography (mobile phase: dichloromethane / methanol = 97:3, V / V) to obtain compound I (1.04).

[0072] II. Synthesis of Compound II using Palladium-Catalyzed Iodoaromatic Borylation Reaction .

[0073] In a dry three-necked flask, compound I (0.60 mmol) prepared above was added sequentially. Add 1.8 mmol of potassium acetate (1.8 mmol), then add 50 mL of dried and degassed dimethyl sulfoxide. Stir until the solid is completely dissolved. Under nitrogen protection, add 50 mg of 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride. Stir to disperse evenly, then heat to 70 °C and maintain this temperature for 16 h. Cool the reaction solution to room temperature, then extract with 100 mL of dichloromethane and wash with 200 mL of water. Combine the organic phases and wash with water. After washing, dry with Na2SO4. After drying, concentrate under reduced pressure and purify by silica gel column chromatography (mobile phase CH2Cl2 / MeOH=98:2, V / V) to obtain compound II.

[0074] III. Synthesis using cross-coupling reactions .

[0075] Add P[5]-OTf (1.01 mmol), compound II (3.05 mmol), and dried and degassed tetrahydrofuran (100 mL) to a dry three-necked flask in sequence. Stir until the solid dissolves. Then slowly add 25 mL of sodium carbonate aqueous solution with a concentration of 26 mg / mL. Stir until homogeneous. Then add tetratriphenylphosphine palladium (300 mg) under a nitrogen atmosphere. After stirring at 80 °C for 24 h, cool the reaction solution to room temperature. Then add dichloromethane (300 mL) to the reaction solution to extract the product. Collect the organic phase. Wash the organic phase with deionized water (100 mL × 2) and saturated sodium chloride solution (100 mL) in sequence. After drying the washed organic phase with sodium sulfate, concentrate under reduced pressure. Analyze the concentrate by silica gel column chromatography (mobile phase: dichloromethane / methanol = 95:5, V / V) to obtain P[5] column aromatics. Its nuclear magnetic resonance spectrum is as follows: Figure 2 As shown.

[0076] Example 3

[0077] The preparation process of macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane is as follows:

[0078] 1. Prepare the aqueous solution.

[0079] Trifluoroethanol (TFE) and deionized water were mixed at a volume ratio of 1:1 and stirred until homogeneous to obtain a mixed solvent. Then, P[5] columnar aromatic hydrocarbons and m-phenylenediamine (MPD) were added to the mixed solvent, and their concentrations were adjusted to 0.014wt% and 0.02wt% respectively. The prepared mixed solution was placed in an ultrasonic instrument and ultrasonically dispersed for 30 minutes to ensure that P[5] columnar aromatic hydrocarbons and MPD were completely dissolved to form a homogeneous and stable aqueous solution.

[0080] II. Preparation of organic phase solution.

[0081] Take an appropriate amount of trimesoyl chloride (TMC) and add it to n-hexane solvent. Adjust the TMC concentration to 0.1 wt%. Place the solution in an ultrasonic instrument and sonicate for 30 min to allow the TMC to dissolve uniformly in n-hexane, thus obtaining a homogeneous organic phase solution.

[0082] III. Pretreatment of polyacrylonitrile (PAN) base film.

[0083] The PAN film was placed in a constant temperature environment of 4℃ and pretreated by soaking in deionized water for 24 hours (the deionized water was replaced every 2 hours during the soaking process) to obtain a clean PAN film.

[0084] IV. Preparation of macrocyclic molecular-regulated interfacial polymerization composite nanofiltration membranes.

[0085] The clean PAN membrane obtained above was smoothly sandwiched between a polytetrafluoroethylene plate and a glass plate, ensuring that the base film was free of wrinkles and bubbles. Then, the prepared aqueous solution was added, ensuring the solution completely submerged the PAN membrane. The mixture was allowed to stand at room temperature for 3 minutes. After standing, excess aqueous solution was slowly poured out along the edge of the apparatus to avoid rapid erosion of the base film surface. Immediately after pouring, the prepared organic solution was added, ensuring the organic solution completely submerged the base film. Interfacial polymerization was carried out at room temperature for 6 minutes. After the reaction, the organic solution was slowly poured out. Then, n-hexane was added. Gently rinse the surface of the base membrane 2-3 times to remove unreacted monomers and reaction byproducts. Then, pour out the hexane. Use clean filter paper to gently absorb excess hexane and residual solution from the edges of the PTFE plate. Next, place the PTFE plate and glass plate holding the nanofiltration membrane into a 60°C constant temperature oven for 8 minutes. Remove from the oven and allow to cool naturally to room temperature. Disassemble the clamping device, peel off the prepared macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membrane, and completely immerse it in a deionized water solution. Store at 4°C, denoted as MP. Its SEM image is shown below. Figure 3 As shown in the figure, the MP nanofiltration membrane is very flat and uniform, with no obvious particles or pores.

[0086] FITR spectra of MP and PAN films, as follows Figure 4 As shown;

[0087] The relationship between zeta potential and pH for MP membrane and PAN membrane is shown in the figure. Figure 5 As shown;

[0088] XPS spectra of MP and PAN membranes, such as Figure 6 As shown.

[0089] Comparative Example

[0090] Except that the aqueous solution does not contain P[5] columnar aromatics, the rest of the process is the same as in Example 3. The nanofiltration membrane prepared is denoted as MP-0.

[0091] Detection example

[0092] I. The process for determining water flux is as follows:

[0093] Using a cross-flow apparatus, the membrane was first pre-pressurized with pure water at 4 bar for 30 minutes. Then, under the same pressure of 4 bar, the water flux was tested. The volume of pure water collected within a certain time period was recorded. The water flux was calculated based on the volume, test area, and time. The results are as follows: Figure 7 As shown in the figure, it can be seen that the MP-0 nanofiltration membrane without P[5] column aromatics has a low water flux, almost zero; while the MP nanofiltration membrane with P[5]A column pentaaromatics added to the aqueous phase can significantly increase the water flux to 167 L·m -2 ·h -1 ·bar -1 .

[0094] II. The process for determining the retention rate of different printing and dyeing materials is as follows:

[0095] Using a cross-flow apparatus, the system was first pre-pressurized with pure water at 4 bar for 30 minutes. Then, the feed solution was replaced with a dye solution at a concentration of 20 ppm. Under a pressure of 4 bar, the solution after membrane separation was collected. The absorbance of the feed solution and the absorbance of the filtered solution were measured using UV light. The absorbance was converted to concentration, and the membrane's dye rejection rate was calculated. After the test, the system was circulated with deionized water under low pressure for 15–20 minutes to remove residual dye. After cleaning, the next dye was used for testing. The test results are as follows: Figure 8 As shown in the figure, it can be seen that MP nanofiltration membrane has a good effect on the treatment of dyeing and printing wastewater, and the rejection rate of dyes (AB, CBB, CR and CV) in the wastewater can reach more than 90%.

[0096] Figure 8 In the text, AB stands for Alcian Blue, with a molecular weight of approximately 1299.

[0097] CBB is Coomassie Brilliant Blue, with a molecular weight of approximately 854.

[0098] CR is Congo Red, with a molecular weight of approximately 697;

[0099] CV is crystal violet, with a molecular weight of approximately 407;

[0100] MO stands for methyl orange, with a molecular weight of approximately 327.

[0101] A graph was plotted based on the molecular weight and corresponding rejection rate of each dye, and the results are as follows: Figure 9As shown in the figure, the MP membrane can retain dye molecules with a molecular weight of 407 Da (crystal violet) or higher, and can effectively clean dyeing wastewater.

[0102] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membranes, characterized in that, Includes the following steps: S100. Lay the base film flat and fix it between the two plates to form a sandwich structure; The base film is selected from polyacrylonitrile film; S200. Add an aqueous solution to the sandwich structure to wet the surface of the base membrane and form an aqueous adsorption layer on the surface of the base membrane to obtain a base membrane covered with an aqueous adsorption layer. The aqueous solution is a mixed solution containing macrocyclic molecules and amine monomers; The structural formula of the macrocyclic molecule is shown below: n is selected from 3, 4, or 5; The concentration of macrocyclic molecules in the mixed solution was 0.01 wt% to 0.02 wt%. S300. An organic phase solution containing acyl chloride monomers is added to the base membrane covered with an aqueous adsorption layer. The aqueous phase and the organic phase undergo an interfacial polymerization reaction on the surface of the base membrane to obtain a macrocyclic molecule-controlled interfacial polymerization composite nanofiltration membrane.

2. The method for preparing the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane as described in claim 1, characterized in that, In step S200, the structural formula of the macrocyclic molecule is as follows: The synthesis process includes the following steps: S210, Utilization and The reaction synthesizes compound I. ; S220, using compound I and The reaction synthesized compound II. ; S230, using P[5]-OTf Reaction with compound II to synthesize macrocyclic molecules .

3. The method for preparing the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane as described in claim 2, characterized in that, The synthesis of P[5]-OTf includes the following steps: S231, utilizing With paraformaldehyde, DMP[5] columnar aromatic hydrocarbons were synthesized, the structural formula of which is shown below: ; S232. DMP4A1Q was synthesized by reacting DMP[5] columnar aromatics with an oxidant. Its structural formula is shown below: ; S233. 4DM1HQP[5] was synthesized by reacting DMP4A1Q with a reducing agent, and its structural formula is shown below: ; S234. P[5]-OTf was synthesized by reacting 4DM1HQP[5] with trifluoromethanesulfonic anhydride.

4. The method for preparing the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane as described in claim 3, characterized in that, In step S232, the oxidant is selected from (NH4)2Ce(NO3)6.

5. The method for preparing the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane as described in claim 3, characterized in that, In step S233, the reducing agent is selected from Na2S2O4.

6. The method for preparing the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane as described in claim 1, characterized in that, In step S200, the amine monomer is selected from m-phenylenediamine and has a concentration of 0.01wt% to 0.04wt%.

7. The method for preparing the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane as described in claim 1, characterized in that, In step S200, the solvent for the mixed solution of macrocyclic molecules and amine monomers is selected from n-hexane.

8. The method for preparing the macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane as described in claim 1, characterized in that, In step S300, the acyl chloride monomer is selected from trimesoyl chloride and has a concentration of 0.1wt% to 0.3wt%.

9. A macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membrane, characterized in that, It is prepared using the method for preparing macrocyclic molecular-regulated interfacial polymerization composite nanofiltration membrane as described in any one of claims 1 to 8.

10. The application of macrocyclic molecule-regulated interfacial polymerization composite nanofiltration membranes, characterized in that, The macrocyclic molecular-regulated interfacial polymerization composite nanofiltration membrane as described in claim 9 is used to treat dyes in wastewater.

Images