High-selectivity polyamide acid-resistant nanofiltration membrane containing telomer base and preparation method thereof

Abstract

This invention discloses a highly selective polyamide acid-resistant nanofiltration membrane containing telrogalg bases and its preparation method, comprising: firstly, using haloaniline monomers and aldehyde monomers as raw materials, synthesizing a telrogalg-based halobenzene intermediate under acidic conditions; then reducing the intermediate to prepare a telrogalg-based phenylenediamine (PDA-TB) functional monomer; subsequently, dissolving it together with polyethersulfone in a polar solvent to prepare a casting solution, which is then coated onto a nonwoven fabric. A polyethersulfone-supported substrate membrane rich in PDA-TB is prepared through a non-solvent-induced phase inversion. Next, a polyacrylamide organic phase solution is brought into single-sided contact with the substrate membrane surface, and a PDA-TB and polyacrylamide interfacial polymerization reaction is performed to prepare a highly selective polyamide acid-resistant nanofiltration membrane containing telrogalg bases. Compared with conventional piperazine amide nanofiltration membranes, the nanofiltration membrane prepared by this invention exhibits significantly improved acid resistance, narrower pore size distribution, and higher separation selectivity, and has broad application prospects.

Description

Technical Field

[0001] This invention relates to the field of polymer separation membrane technology for water treatment, specifically to a highly selective polyamide acid-resistant nanofiltration membrane containing telrog bases and its preparation method. Background Technology

[0002] Over the past few decades, global industrial production has expanded rapidly. Processes in industries such as chemical and pharmaceutical manufacturing, metallurgy, textiles, electroplating, and papermaking consume large amounts of water and generate significant quantities of acidic wastewater. Direct discharge of this wastewater pollutes water sources, damages the ecological environment, and endangers human health. While traditional methods such as adsorption, precipitation, and extraction can recover some acids and heavy metals from wastewater, these processes are complex, inefficient, costly, and pose a risk of secondary pollution. Nanofiltration (NF), as a novel, highly efficient, and environmentally friendly separation technology, can effectively separate monovalent and polyvalent salts and retain organic matter with molecular weights ranging from 200 to 1000 Da. The process is simple to operate, energy-saving, highly efficient, and offers high separation precision, and has been widely used in wastewater treatment, drinking water purification, and product separation and purification.

[0003] The core of nanofiltration technology is the nanofiltration membrane. Currently, commercially available polypiperazine amide composite nanofiltration membranes are prepared by interfacial polymerization of piperazine and trimesoyl chloride on a polysulfone-supported substrate. Because the polypiperazine amide bonds are easily attacked by protons under strong acid conditions, leading to bond breakage, the separation performance of the polypiperazine amide nanofiltration membrane drops sharply, severely affecting its lifespan and significantly hindering the application of nanofiltration technology under acidic conditions. Therefore, there is an urgent need to develop high-performance, acid-resistant nanofiltration membranes from the source. Due to the stability of sulfonyl and amine bonds and the hyperconjugation effect of the triazine ring, which can withstand strong acid attacks, materials containing these structures, such as polysulfonamides and polyamines, have been reported in recent years for the development of acid-resistant nanofiltration membranes. For example, Yu Sanchuan et al. (J.Membr.Sci.,2012,415:122–131; Desalination,2013,315:164-172) prepared a series of acid-resistant polysulfonamide nanofiltration membranes by interfacial polymerization of naphthalenesulfonyl chloride monomers (such as NTSC) and polyamine monomers (such as piperazine PIP); patents US2016 / 0051944A1, CN107349804A, CN109999666A, etc. A series of acid-resistant polyamine nanofiltration membranes were prepared by polymerization of polyamine compounds (such as PEI, diethylenetriamine, or triethylenetetramine) with crosslinking agents such as cyanuric chloride or benzyl chloride. Zhang et al. (J.Membr.Sci.,2018,546:225-233) synthesized a poly(triazine)amine (TPT) precursor by pre-reacting cyanuric chloride (CC) and piperazine, and then successfully prepared an acid-resistant high-flux poly(triazine-amide) nanofiltration membrane by interfacial polymerization with trimesoyl chloride (TMC). Although these membranes exhibited good stability under strongly acidic conditions of pH=0-1, the introduction of acid-resistant groups can reduce the reactivity of the monomers to some extent, thereby affecting the interfacial polymerization reaction and the separation performance of the membrane, such as selectivity and water flux. When improvements are made by adding additives, catalysts, or performing multiple interfacial polymerizations, the membrane preparation process becomes cumbersome, inefficient, and costly. Patent CN2022102595270 describes a modified polypiperazine amide nanofiltration membrane prepared by mixing a diamine monomer TBDA containing a tellegatin base with piperazine. Although the water flux of the membrane is significantly increased, its acid resistance is only slightly improved, and it is difficult to withstand high concentrations of strong acids. Therefore, this invention uses a tellegatin-based phenylenediamine monomer to prepare a highly selective polyamide acid-resistant nanofiltration membrane containing a tellegatin base. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing technologies, particularly the insufficient acid resistance of traditional commercial polypiperazine amide nanofiltration membranes and those previously prepared by the inventor using TBDA doping modification. This invention provides a highly selective polyamide acid-resistant nanofiltration membrane containing telrogalg bases and its preparation method. The nanofiltration membrane is prepared by casting a liquid solution of a single telrogalg-based phenylenediamine monomer (PDA-TB) with polyethersulfone, which is then coated onto a nonwoven fabric to form a liquid membrane. This liquid membrane is then placed in a coagulation bath aqueous solution for a solvent-induced phase transformation, resulting in a porous polyethersulfone substrate membrane rich in PDA-TB. After surface cleaning with deionized water, the membrane undergoes interfacial polymerization through one-sided contact with an organic phase solution containing acyl chloride monomers, followed by heat treatment. Because the PDA-TB molecule contains telrogalg bases with a unique rigid twisted structure, it imparts excellent acid resistance to the membrane, resulting in a narrower pore size distribution and simultaneously improving the membrane's separation selectivity.

[0005] This invention proposes to synthesize a telrogal base phenylenediamine monomer and introduce it onto the surface of a polyethersulfone support layer via a non-solvent-induced phase inversion method, and then prepare a highly selective polyamide acid-resistant nanofiltration membrane containing telrogal bases through interfacial polymerization.

[0006] A highly selective polyamide acid-resistant nanofiltration membrane containing telage bases is prepared by the following method:

[0007] (1) Dissolve 2-12 parts by mass of haloaniline monomer molecules in 100 parts by mass of acidic solvent, then add 2-6 parts by mass of aldehyde monomer to the above acidic solvent, mix well, and react at -10 to 40°C for 12-96 hours to obtain a telrogallobenzene intermediate; finally, disperse 1-10 parts by mass of the telrogallobenzene intermediate into 20 parts by mass of aromatic hydrocarbon monomer, and under inert gas conditions, add 0.03-0.06 parts by mass of catalyst. 0.04–0.08 parts by weight of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.8–1.2 parts by weight of sodium tert-butoxide, and 0.8–1.6 parts by weight of benzophenone imine were added to the above aromatic hydrocarbon monomers, mixed evenly, and reacted at 80–120°C for 12–48 hours. Then, the mixture was reacted for 1–6 hours in a mixed solvent of tetrahydrofuran and 10–40 parts by weight of 2M inorganic acid to obtain telroglycan phenylenediamine monomer (PDA-TB).

[0008] Wherein, the aniline monomer molecule is one of 4-fluoroaniline, 4-bromoaniline, 4-iodoaniline or 4-chloroaniline; the aldehyde monomer is one of formaldehyde, paraformaldehyde, benzaldehyde, phenylacetaldehyde, phenylpropionaldehyde or octanal; the aromatic hydrocarbon monomer is one of benzene, toluene, xylene or ethylbenzene; the inert gas is one of nitrogen or argon; and the inorganic acid solvent is one of hydrochloric acid, sulfuric acid or nitric acid.

[0009] (2) Add a certain amount of PDA-TB, polyethersulfone and polar solvent to a round bottom flask, stir evenly under a certain temperature condition for a period of time, and let stand to remove bubbles to obtain a uniform casting solution without bubbles.

[0010] (3) The casting solution from step (2) is scraped onto a nonwoven fabric and placed in a coagulation bath aqueous solution for non-solvent-induced phase transformation for 30-120 seconds. After that, the membrane surface is washed with deionized water and air-dried for later use.

[0011] (4) Pour the polyacrylamide chloride monomer solution onto the PDA-TB-rich polyethersulfone support substrate membrane that was air-dried in step (3). After reacting for 30 to 300 seconds, remove the remaining organic phase solution. Then, heat-treat the membrane at 25 to 40°C for 20 to 60 minutes. After immersing and washing the membrane in deionized water, a highly selective polyamide acid-resistant nanofiltration membrane containing telage bases is obtained.

[0012] Wherein, the polar solvent in step (2) is one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone; the polyacrylamide monomer in step (4) is one of isophthaloyl chloride, biphenyltetracarboxylic acid chloride, 1,3,5-triazine-2,4,6-triacryl chloride, adipyl chloride, pyromellitic acid chloride or phthaloyl chloride;

[0013] Furthermore, in step (2), the stirring temperature is 20-60°C, the stirring time is 12 hours, and the standing degassing time is 12-24 hours.

[0014] Further, in step (2), the total content of PDA-TB monomer is 0-3 wt%. Further, calculated as 100% by weight, the weight percentages of the telrogallic base phenylenediamine monomer, polyethersulfone, and polar solvent are:

[0015] 1-3 wt% of telrogallodiamine monomer;

[0016] Polyethersulfone 10-20 wt%;

[0017] Balance of polar solvent.

[0018] Further, in step (2), the polar solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

[0019] Furthermore, in step (3), the volume of the coagulation bath aqueous solution is 2-4 L, and the time for non-solvent-induced phase transition is 30-120 seconds.

[0020] Preferably, in step (3), the air-drying time is 10-30 minutes.

[0021] Preferably, in step (4), the concentration of the polyacrylamide chloride monomer is 0.01–0.2 wt%.

[0022] Preferably, in step (4), the organic solvent for dissolving the polyacrylamide monomer is one of Isopar G, cyclohexane, n-decane, n-hexane, or n-heptane.

[0023] Furthermore, in step (4), the reaction time in the polyacrylamide chloride monomer solution is 30 to 300 seconds.

[0024] Furthermore, the post-processing temperature described in this invention is 25–40°C, and the time is 20–60 minutes.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] This invention involves adding synthesized telroglycan-based phenylenediamine to a casting solution and preparing a highly selective, acid-resistant polyamide nanofiltration membrane containing telroglycan bases via a coupled solvent-inducible phase transformation and in-situ interfacial polymerization method. Compared to conventional piperazine amide nanofiltration membranes, the fully telroglycan-based polyamide segments in this membrane result in a more uniform pore size and narrower pore distribution in the separation layer. Furthermore, the membrane surface exhibits electropositivity under strongly acidic conditions, significantly enhancing the membrane's receptivity to heavy metal ions or cationic dyes and H+. + The selective separation of ions imparts excellent acid resistance to the membrane, making it promising for a wide range of applications. Furthermore, directly enriching the telroglycan base phenylenediamine monomer onto the surface of the supporting membrane via a solvent-free induced phase inversion method simplifies the nanofiltration membrane preparation process, improves membrane fabrication efficiency, reduces wastewater generation, lowers membrane fabrication costs, and facilitates industrialization. Attached Figure Description

[0027] Figure 1 This is a structural diagram of the functional monomer of the telroglycan base phenylenediamine (PDA-TB) described in this invention.

[0028] Figure 2 The Fourier attenuated total reflectance infrared (ATR-FTIR) spectra of the acid-resistant nanofiltration membrane with high selectivity polyamide containing Teleg bases (M1), the conventional polypiperazine amide nanofiltration membrane (M2), and the blank PES porous support substrate membrane described in this invention.

[0029] Figure 3 The images are SEM images of the high-selectivity polyamide acid-resistant nanofiltration membrane (a) containing telage bases described in this invention before and after long-term immersion in 20wt% H2SO4 solution for 30 days, and SEM images of a conventional commercial polyamide nanofiltration membrane (b) prepared from piperazine before and after long-term immersion in 20wt% H2SO4 solution for 12 days. Detailed Implementation

[0030] The following detailed description, in conjunction with specific embodiments, further clarifies the invention. However, the scope and content of this patent are not limited to the following embodiments. Any variations or implementations that do not depart from the scope and content of this invention should be included within the technical scope of this invention.

[0031] Example 1:

[0032] ① Synthesis of the telroglycan base phenylenediamine monomer

[0033] At -15°C, 17.5 g of 2-methyl-4-nitroaniline, 6.2 g of paraformaldehyde, and 200 mL of trifluoroacetic acid were added to a three-necked flask. The mixture was stirred until room temperature and continued stirring for 48 h. Excess ice and NH3 (25%) were slowly added to the mixture, and the mixture was stirred thoroughly. The mixture was extracted three times with CH2Cl2, dried over anhydrous MgSO4, and concentrated under vacuum using silica gel. The residue was purified by alkaline alumina column chromatography (eluent: petroleum ether: ethyl acetate = 10:1) to obtain the intermediate (2,8-dibromo-6H,12H-5,11-methylenedibenzo[b,f][1,5]diazopyrimidine). Under nitrogen protection, 9.45 g of the obtained intermediate was dispersed in 200 mL of toluene, and 0.6 g of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 7.2 g of sodium tert-butoxide, and 10 mL of benzophenone imine were added. Then, 0.3 g of tris(di-methylenebenzylacetone)dipalladium was added as a catalyst, and the mixture was refluxed for 24 hours. The reaction solution was concentrated under vacuum. The residue was added to a mixture of 100 mL of tetrahydrofuran and 200 mL of hydrochloric acid (2M) and reacted for three hours. The reaction solution was poured into ice water and neutralized to alkalinity with NH3 (25%). The mixture was extracted three times with CH2Cl2, washed with brine, dried over anhydrous MgSO4, and concentrated under vacuum with silica gel. The residue was subjected to alkaline alumina column chromatography (eluent: dichloromethane:methanol = 20:1) to obtain the telroglycan base phenylenediamine monomer (PDA-TB), which was dried in an oven at 60 °C for 36 hours and then sealed for storage.

[0034] ② Preparation of casting solution

[0035] 1 wt% PDA-TB, 16.2 wt% polyethersulfone E6020P and dimethyl sulfoxide were added to a round-bottom flask, stirred at 25°C for 12 hours and allowed to stand for 12 hours to remove bubbles, resulting in a uniform, bubble-free casting solution.

[0036] ③ Non-solvent-induced phase transformation

[0037] The casting solution was poured evenly onto the nonwoven fabric S53, and then scraped into a uniform liquid film with a 200-micron doctor blade. The nonwoven fabric coated with the liquid film was then immersed in a 2L coagulation bath aqueous solution for a non-solvent-induced phase transformation for 60 seconds to obtain a PES porous support substrate film with PDA-TB monomers on its surface.

[0038] ④ In-situ interface aggregation

[0039] A 0.075 w / v% hexane solution of 1,3,5-benzenetricarboxyl chloride was poured onto the surface of an air-dried PES porous support membrane rich in PDA-TB monomers for interfacial polymerization for 60 seconds. After removing excess organic phase solution from the membrane surface, the membrane was heat-treated at 30°C for 30 minutes to finally obtain a highly selective polyamide acid-resistant nanofiltration membrane containing telage bases.

[0040] Example 2:

[0041] The PDA-TB concentration in step ② was changed from 1.0 wt% to 0.5 wt%, and other operations were the same as in Example 1. The membrane performance data are listed in Table 1.

[0042] Example 3:

[0043] The PDA-TB concentration in step ② was changed from 1.0 wt% to 1.5 wt%, and other operations were the same as in Example 1. The membrane performance data are listed in Table 1.

[0044] Example 4:

[0045] The PDA-TB concentration in step ② was changed from 1.0 wt% to 2.0 wt%, and other operations were the same as in Example 1. The membrane performance data are listed in Table 1.

[0046] Example 5:

[0047] The concentration of 1,3,5-benzenetricarboxylic acid chloride in step ④ was changed from 0.075 wt% to 0.025 wt%, and other operations were the same as in Example 1. The membrane performance data are listed in Table 1.

[0048] Example 6:

[0049] In step ④, the concentration of 1,3,5-benzenetricarboxylic acid chloride was changed from 0.075 w / v% to 0.05 w / v%. Other operations were the same as in Example 1. The membrane performance data are listed in Table 1.

[0050] Example 7:

[0051] The concentration of 1,3,5-benzenetricarboxylic acid chloride in step ④ was changed from 0.075 w / v% to 0.1 w / v%. Other operations were the same as in Example 1. The membrane performance data are listed in Table 1.

[0052] Example 8:

[0053] The concentration of 1,3,5-benzenetricarboxylic acid chloride in step ④ was changed from 0.075 w / v% to 0.125 w / v%. Other operations were the same as in Example 1. The membrane performance data are listed in Table 1.

[0054] Comparative Example 1:

[0055] In step ②, the telegated phenylenediamine monomer PDA-TB was replaced with piperazine, and other operations were the same as in Example 1. The resulting membrane was used for comparative testing, and the performance data are listed in Tables 1-2.

[0056] Table 1: Performance comparison of nanofiltration membranes prepared in Examples 1-4

[0057] 1 36.89 98.47 2 90.20 93.75 3 19.64 96.16 4 30.09 94.69

[0058] Table 2: Performance comparison of nanofiltration membranes prepared in Examples 5-8

[0059] 5 23.27 94.38 6 29.49 97.86 7 26.36 97.12 8 26.94 95.01

[0060] Example 1 and Comparative Group 1 were selected as examples to test the selective separation performance of iron ions and hydrogen ions. The separation test results of ferric chloride solution with pH=1 and 2000ppm at 25℃ and 0.6MPa are shown in Table 3.

[0061] Table 3: Comparison of iron ion and hydrogen ion separation performance of nanofiltration membranes prepared in Example 1 and Comparative Example 1

[0062]

[0063] The separation test results of ferric sulfate at pH=1 and 2000ppm under 25℃ and 0.6MPa pressure are shown in Table 4.

[0064] Table 4: Comparison of iron ion and hydrogen ion separation performance of nanofiltration membranes prepared in Example 1 and Comparative Example 1

[0065]

[0066] Example 1 and Comparative Group 1 were selected as examples to test the selective separation performance of iron ions and hydrogen ions. The separation test results of a crystal violet dye solution with pH=1 and 50ppm at 25℃ and 0.6MPa are shown in Table 5.

[0067] Table 5: Comparison of the separation performance of crystal violet dye and hydrogen ions in nanofiltration membranes prepared in Example 1 and Comparative Example 1

[0068]

[0069] Example 1 and Comparative Group 1 were selected as examples to test the selective separation performance of iron ions and hydrogen ions. The separation test results of a Rhodamine B dye solution with pH=1 and 50ppm at 25℃ and 0.6MPa are shown in Table 6.

[0070] Table 6: Comparison of Rhodamine B dye separation performance of nanofiltration membranes prepared in Example 1 and Comparative Example 1.

[0071]

[0072] Example 1 and Comparative Group 1 were selected as examples to test the selective separation performance of iron ions and hydrogen ions. The separation test results of Congo red dye solution with pH=1 and 50ppm at 25℃ and 0.6MPa pressure are shown in Table 7.

[0073] Table 7: Comparison of Congo red dye and hydrogen ion separation performance of nanofiltration membranes prepared in Example 1 and Comparative Example 1

[0074]

[0075] Example 1 and Comparative Group 1 were selected as examples for acid resistance testing. The membranes prepared in Example 1 and Comparative Group 1 were immersed in a 20 wt% sulfuric acid solution. The separation test results for 2000 ppm sodium sulfate at 25°C and 0.6 MPa are shown in Tables 8-9.

[0076] Table 8: Changes in salt rejection rate of nanofiltration membranes prepared in Example 1 and Comparative Group 1 after immersion in strong acid.

[0077] 0 97.68％ 93.75％ 3 97.15％ 60.88％ 6 95.65％ 65.84％ 9 95.25％ 25.01％ 12 94.10％ 18.01％ 15 93.14％ 18 92.96％ 24 92.60％ 30 88.90％

[0078] Table 9: Flux changes of nanofiltration membranes prepared in Example 1 and Comparative Group 1 after strong acid immersion.

[0079] 0 35.81 55.45 3 35.33 68.28 6 33.54 73.32 9 32.09 217.09 12 38.06 242.65 15 37.55 18 39.08 24 41.58 30 46.46

[0080] Based on the above results, it can be seen that the acid-resistant polyamide nanofiltration membrane containing telrog bases prepared in this invention exhibits superior acid resistance and separation selectivity compared to the traditional piperazine amide nanofiltration membrane. The retention capacity of the piperazine amide nanofiltration membrane decreased from 93.75% to 18.01% after 12 days, indicating that the polyamide separation layer was damaged by hydrogen ions, leading to the destruction of the entire membrane structure. In contrast, the polyamide nanofiltration membrane prepared based on telrog base PDA-TB showed a decrease in retention capacity from 97.86% to 88.90% after 30 days of 20wt% sulfuric acid immersion, a smaller decrease compared to the traditional piperazine amide, while maintaining the integrity of the membrane structure. This demonstrates the great potential of this telrog base-containing polyamide nanofiltration membrane in the treatment of acidic wastewater. Under strongly acidic conditions (pH=1), the acid-resistant polyamide nanofiltration membrane containing telrog bases showed excellent performance in treating Fe... 3+ / H + The selective separation factor exceeds 29, which is much higher than that of conventional piperazine amide for Fe. 3+ / H +The separation selectivity was approximately 17. Under strongly acidic conditions at pH 1, the highly selective polyamide acid-resistant nanofiltration membrane containing the Teleg base exhibited good separation selectivity for two cationic dyes: crystal violet (408 Da) and rhodamine B (479 Da) / H. + The selective separation factors reached 100.57 and 193.04, respectively, far exceeding the selective separation factors of conventional polypiperazine amide (46.13 and 130.92). Simultaneously, the highly selective acid-resistant polyamide nanofiltration membrane containing the telage base exhibited better performance against the anionic dye Congo Red / H + The selective separation factor of (696Da) exceeds 131.58, which is higher than the selective separation performance of conventional polypiperazine amide (approximately 61.85), demonstrating the excellent performance and great industrial application potential of polyamide nanofiltration membranes containing telage bases in treating acidic wastewater containing heavy metals or dyes.

Claims

1. A method for preparing a highly selective polyamide acid-resistant nanofiltration membrane containing telrog bases, characterized in that, Includes the following steps: (1) Preparation of telroglycan base phenylenediamine monomer; (2) Disperse the telrogalpine diamine monomer and polyethersulfone obtained in step (1) into a polar solvent, stir evenly, and let stand to remove bubbles to obtain a casting solution. In step (2), the weight percentages of the telrogallic base phenylenediamine monomer, polyethersulfone, and polar solvent, calculated at 100% by weight, are as follows: 1-3 wt% of telrogallodiamine monomer; Polyethersulfone 10~20wt% Balance of polar solvent; (3) The casting solution from step (2) is scraped onto a nonwoven fabric and placed in a coagulation bath aqueous solution for non-solvent-induced phase transformation. The non-solvent-induced phase transformation time is 30~120 seconds. After that, the membrane surface is rinsed clean with deionized water and then air-dried to obtain a polyethersulfone support substrate membrane with a surface rich in telogen phenylenediamine monomer. (4) Pour the organic phase solution containing polyacrylamide chloride monomer onto the polyethersulfone support substrate membrane with surface rich in telrogal base phenylenediamine monomer obtained in step (3). After reacting for 30 to 300 seconds, remove the remaining organic phase solution. Then, heat-treat at 25 to 40°C for 20 to 60 minutes. Finally, soak and wash the obtained membrane in deionized water to obtain a highly selective polyamide acid-resistant nanofiltration membrane containing telrogal base.

2. The method for preparing a highly selective polyamide acid-resistant nanofiltration membrane containing telrogal bases as described in claim 1, characterized in that: In step (1), the preparation of the telroglycan base phenylenediamine monomer specifically includes: (1.1) Dissolve 2-12 parts by mass of haloaniline monomer molecules in 100 parts by mass of acidic solvent, then add 2-6 parts by mass of aldehyde monomer, mix evenly, and react at -10 to 40°C for 12 to 96 hours to obtain a halobenzene intermediate containing telrog bases. (1.2) Disperse 1-10 parts by mass of the telrogallo-based halobenzene intermediate into 20 parts by mass of aromatic hydrocarbon monomer. Under inert gas conditions, add 0.03-0.06 parts by mass of catalyst, 0.04-0.08 parts by mass of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), 0.8-1.2 parts by mass of sodium tert-butoxide, and 0.8-1.6 parts by mass of benzophenone imine. Mix well and react at 80-120°C for 12-48 hours. Then react for 1-6 hours under the action of 4-16 parts by mass of tetrahydrofuran and 10-40 parts by mass of a 1-3 mol / L inorganic acid mixed solvent to obtain the telrogallo-based phenylenediamine monomer.

3. The method for preparing a highly selective polyamide acid-resistant nanofiltration membrane containing telrogal bases as described in claim 2, characterized in that: In step (1.1), the halogenated aniline monomer molecule is one of 4-fluoroaniline, 4-bromoaniline, 4-iodoaniline, and 4-chloroaniline; the aldehyde monomer is one of formaldehyde, paraformaldehyde, benzaldehyde, phenylacetaldehyde, phenylpropionaldehyde, and octanal.

4. The method for preparing a highly selective polyamide acid-resistant nanofiltration membrane containing telrogal bases as described in claim 2, characterized in that: In step (1.2), the aromatic hydrocarbon monomer is one of benzene, toluene, xylene or ethylbenzene; the inert gas is one of nitrogen or argon; and the inorganic acid is one of hydrochloric acid, sulfuric acid or nitric acid.

5. The method for preparing a highly selective polyamide acid-resistant nanofiltration membrane containing telrogal bases as described in claim 1, characterized in that: In step (2), stir at 20~60℃ for 16~30 hours and let stand for 12~24 hours to remove bubbles.

6. The method for preparing a highly selective polyamide acid-resistant nanofiltration membrane containing telrogal bases as described in claim 1, characterized in that: In step (2), the polar solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, or N-methylpyrrolidone.

7. The method for preparing a highly selective polyamide acid-resistant nanofiltration membrane containing telrogal bases as described in claim 1, characterized in that: In step (3), the air-drying time is 10 to 30 minutes.

8. The method for preparing a highly selective polyamide acid-resistant nanofiltration membrane containing telrogal bases as described in claim 1, characterized in that: In step (4), the polyacrylamide chloride monomer is isophthaloyl chloride, 1,3,5-triazine-2,4,6-triacryl chloride, adipic acid chloride, biphenyltetracarboxylic acid chloride, pyromellitic tricarboxylic acid chloride, or phthaloyl chloride, and the concentration of the polyacrylamide chloride monomer in the organic phase solution containing the polyacrylamide chloride monomer is 0.01~0.2wt%; The organic solvent in the organic phase solution containing polyacrylamide chloride monomers is one or more of Isopar G, cyclohexane, n-decane, n-hexane, and n-heptane.

9. A highly selective polyamide acid-resistant nanofiltration membrane containing telage bases prepared by the preparation method according to any one of claims 1 to 8.

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