CN-120393778-B - Binaphthyl amine chiral inherent microporous polymer composite membrane, preparation and application thereof

Abstract

The invention relates to the technical field of separation membranes, in particular to a binaphthyl amine chiral inherent microporous polymer composite membrane, and preparation and application thereof, wherein a DMAc-H 2 O mixed solvent system is used as a dissolution medium of binaphthyl amine, n-hexane is used as a solvent of trimesic acid chloride, interfacial polymerization reaction is carried out on a polyacrylonitrile-based membrane, and the S-BINAM/PAN chiral inherent microporous polymer composite membrane is self-assembled. The mixed solvent of DMAc-H 2 O is adopted to replace the traditional aqueous phase solvent, so that the problem of low reaction activity of the inherent microporous polymer monomer due to hydrophobicity is solved, the polar aprotic property of DMAc enhances the solubility of benzidine, meanwhile, the introduction of H 2 O optimizes the interfacial polymerization kinetics, the solvent system breaks through the dependence of the traditional interfacial polymerization on hydrophilic monomers, a new path is provided for the efficient reaction of the hydrophobic chiral monomers, and the chemical stability and separation efficiency of the membrane are remarkably improved.

Inventors

• SUN YUE
• LIU ZHENG
• LI ZICHEN
• FAN YANGYANG
• Wang Mintian
• NIE MINGXIN
• MA XIAO

Assignees

• 天津工业大学

Dates

Publication Date

20260508

Application Date

20250311

Claims (8)

1. 1. The preparation method of the binaphthyl amine-based chiral intrinsic microporous polymer composite membrane is characterized by comprising the following steps of: s1, preparing a reaction solution: Fully dissolving water phase monomer in mixed solution of N, N-dimethylacetamide and H 2 O to prepare aqueous phase solution, The aqueous phase monomer comprises S-binaphthyl amine and NaOH, Dissolving an oil phase monomer in normal hexane to prepare an oil phase solution, The oil phase monomer is trimesic acid chloride; S2, pretreatment of a base material: Fixing the polyacrylonitrile membrane by using a mould, limiting the polymerization reaction range on the polyacrylonitrile membrane, fixing and maintaining the polyacrylonitrile membrane in the mould, After the polyacrylonitrile membrane is soaked by aqueous solution, removing residual liquid on the surface; s3, chiral polymerization: Dripping the oil phase solution on the surface of the polyacrylonitrile membrane soaked in the water phase solution obtained in the step S2, performing interfacial polymerization on the surface of the polyacrylonitrile membrane, removing the reaction solution after the polymerization time is reached, The n-hexane solution is removed after the polyacrylonitrile membrane is covered with n-hexane for a second time, And (3) carrying out thermal crosslinking treatment, and removing the die after the thermal crosslinking is finished to obtain the binaphthyl amine chiral inherent microporous polymer composite film.
2. 2. The method for preparing a binaphthyl amine based chiral inherent microporous polymer composite membrane according to claim 1, wherein, In S1, the volume ratio of N, N-dimethylacetamide to H 2 O used in the mixed solution of N, N-dimethylacetamide and H 2 O is 7:3.
3. 3. The method for preparing a binaphthyl amine based chiral inherent microporous polymer composite membrane according to claim 1, wherein, In S2, the polyacrylonitrile membrane is pretreated before being fixed by using a die, The polyacrylonitrile membrane is pretreated by immersing the polyacrylonitrile membrane in deionized water, and after the immersing is finished, the moisture on the surface of the polyacrylonitrile membrane is absorbed by absorbent paper.
4. 4. The method for preparing a binaphthyl amine based chiral inherent microporous polymer composite membrane according to claim 1, wherein, In S3, the polymerization reaction time is 1.5-3min, The thermal crosslinking treatment mode is that after the polyacrylonitrile film surface reagent is completely volatilized, the die is put into a blast drying box for thermal crosslinking treatment, the thermal crosslinking temperature is 55-65 ℃, and the thermal crosslinking time is 5-8min.
5. 5. The method for preparing a binaphthyl amine based chiral inherent microporous polymer composite membrane according to claim 1, wherein, The binaphthyl amine chiral inherent microporous polymer composite membrane is soaked in deionized water, and is preserved in a refrigerated environment for standby, wherein the temperature of the deionized water is 2-8 ℃.
6. 6. A binaphthyl amine-based chiral microporous polymer composite membrane prepared by the preparation method of any one of claims 1 to 5.
7. 7. The binaphthyl amine based chiral microporous polymer composite membrane according to claim 6, The separating layer has sub-nanometer pore size of 0.8-1.4 nm and specific surface area greater than 50 。
8. 8. Use of the binaphthyl amine based chiral inherently microporous polymer composite membrane of claim 6 for chiral compound separation.

Description

Binaphthyl amine chiral inherent microporous polymer composite membrane, preparation and application thereof Technical Field The invention relates to the technical field of separation membranes, in particular to a binaphthyl amine chiral inherent microporous polymer composite membrane and preparation and application thereof. Background The traditional interfacial polymerization method generally adopts a hydrophilic amine monomer (such as m-phenylenediamine, piperazine or phenol compounds) and an acyl chloride compound to react at a water/n-hexane two-phase interface, and the technology severely restricts the development of a high-performance separation membrane due to the singleness of a film structure caused by limited monomer selection. Based on the deep understanding of polymerization kinetics, researchers have proposed multidimensional performance regulation strategies including thin film thinning, microporous structure regulation, functional additive introduction, surface engineering modification, and precise control of stoichiometry. Notably, in recent years, inherently microporous Polymer (PIMs) monomers of non-planar topology exhibit unique advantages-their rigid backbone can build high free volume channels, theoretically enabling ultra-fast solvent transport and accurate sieving. But are limited by their inherent hydrophobicity, such monomers have significantly reduced reactivity in conventional water/oil interfacial polymerization systems. To address this bottleneck, research has turned to the development of new solvent systems. Polar aprotic solvents such as Tetrahydrofuran (THF), N-Dimethylformamide (DMF) are of great interest for their excellent solubility (especially for aromatic compounds), cost effectiveness and volatility. Experiments show that the solvent is adopted to replace the traditional aqueous phase for interfacial polymerization, the obtained polyamide membrane not only maintains excellent chemical stability, but also greatly improves the separation selectivity. However, the problem that the phase interface of the organic solvent cannot stably form a polyamide membrane in the synthesis process often occurs, and the problem that the existing separation membrane has poor separation effect on chiral chemical substances is solved. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a binaphthyl amine chiral inherent microporous polymer composite membrane and preparation and application thereof, and solves the technical problems of low reactivity and poor separation effect of a separation membrane on chiral chemical substances in a conventional water/oil interfacial polymerization system in the prior art. According to an embodiment of the present invention, there is provided a first aspect of: A preparation method of a binaphthyl amine-based chiral intrinsic microporous polymer composite membrane comprises the following steps: s1, preparing a reaction solution: Fully dissolving water phase monomer in mixed solution of N, N-dimethylacetamide and H 2 O to prepare aqueous phase solution, The aqueous phase monomer comprises S-binaphthyl amine and NaOH, Dissolving an oil phase monomer in normal hexane to prepare an oil phase solution, The oil phase monomer is trimesic acid chloride; S2, pretreatment of a base material: Fixing the polyacrylonitrile membrane by using a mould, limiting the polymerization reaction range on the polyacrylonitrile membrane, fixing and maintaining the polyacrylonitrile membrane in the mould, After the polyacrylonitrile membrane is soaked by aqueous solution, removing residual liquid on the surface; s3, chiral polymerization: Dripping the oil phase solution on the surface of the polyacrylonitrile membrane soaked in the water phase solution obtained in the step S2, performing interfacial polymerization on the surface of the polyacrylonitrile membrane, removing the reaction solution after the polymerization time is reached, The n-hexane solution is removed after the polyacrylonitrile membrane is covered with n-hexane for a second time, And (3) carrying out thermal crosslinking treatment, and removing the die after the thermal crosslinking is finished to obtain the binaphthyl amine chiral inherent microporous polymer composite film. Further, in S1, the volume ratio of N, N-dimethylacetamide to H 2 O used in the mixed solution of N, N-dimethylacetamide and H 2 O is 7:3. Further, in the step S2, the polyacrylonitrile membrane is pretreated before being fixed by using a die; the polyacrylonitrile membrane is pretreated by immersing the polyacrylonitrile membrane in deionized water, and after the immersing is finished, the moisture on the surface of the polyacrylonitrile membrane is absorbed by absorbent paper. Further, in S3, the polymerization reaction time is 1.5-3min; the thermal crosslinking treatment mode is that after the polyacrylonitrile film surface reagent is completely volatilized, the die is put into a blast drying box