Binaphthylamine chiral intrinsic microporous polymer composite membrane as well as preparation and application thereof

Abstract

The invention relates to the technical field of separation membranes, in particular to a binaphthylamine chiral intrinsic microporous polymer composite membrane and preparation and application thereof, a DMAc-H2O mixed solvent system is used as a dissolving medium of binaphthylamine, n-hexane is used as a solvent of trimesoyl chloride, an interfacial polymerization reaction is carried out on a polyacrylonitrile-based membrane, and the binaphthylamine chiral intrinsic microporous polymer composite membrane is prepared. And the S-BINAM / PAN chiral intrinsic microporous polymer composite membrane is obtained through self-assembly. A DMAc-H2O mixed solvent is adopted to replace a traditional water-phase solvent, so that the problem of low reaction activity caused by hydrophobicity of an inherent microporous polymer monomer is solved; the polarity aprotic characteristic of DMAc enhances the dissolvability of benzidine, and meanwhile, the introduction of H2O optimizes interfacial polymerization kinetics; the solvent system breaks through the dependence of traditional interfacial polymerization on hydrophilic monomers, provides a new path for efficient reaction of hydrophobic chiral monomers, and significantly improves the chemical stability and separation efficiency of the membrane.

Description

Technical Field

[0001] The present invention relates to the technical field of separation membranes, and in particular, to a binaphthylamine-based chiral intrinsically microporous polymer composite membrane and its preparation and application. Background Art

[0002] Traditional interfacial polymerization usually uses hydrophilic amine monomers (such as m-phenylenediamine, piperazine or phenolic compounds) to react with acyl chloride compounds at the water / n-hexane two-phase interface. This technology is limited by the monomer selection, resulting in the singularity of the film structure, which severely restricts the development of high-performance separation membranes. Based on the in-depth understanding of the polymerization reaction kinetics, researchers have proposed multi-dimensional performance regulation strategies, including: film thinning, microporous structure regulation, introduction of functional additives, surface engineering modification, and precise control of stoichiometry. It is worth noting that in recent years, intrinsically microporous polymer (PIMs) monomers with non-planar topological structures have shown unique advantages - their rigid skeletons can construct high-free-volume channels, and theoretically, ultrafast solvent transport and precise sieving can be achieved. However, due to their inherent hydrophobicity, the reactivity of such monomers is significantly reduced in conventional water / oil interfacial polymerization systems. To solve this bottleneck, the research has turned to the development of new solvent systems. Polar aprotic solvents such as tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) have attracted much attention due to their excellent solubility (especially for aromatic compounds), cost-effectiveness, and volatility. Experiments have shown that by using such solvents to replace the traditional aqueous phase for interfacial polymerization, the resulting polyamide membranes not only maintain excellent chemical stability, but also have greatly improved separation selectivity.

[0003] However, in the synthesis process, there are often problems that the polyamide membrane cannot be stably formed at the organic solvent phase interface, and the existing separation membranes have poor separation effects on chiral chemical substances. In view of the above technical problems, the inventor has proposed a new synthesis scheme for polyamide composite membranes to improve the separation effect on chiral chemical substances. Summary of the Invention

[0004] Aiming at the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide a binaphthylamine-based chiral intrinsically microporous polymer composite membrane and its preparation and application; it solves the technical problems of low reactivity in the conventional water / oil interfacial polymerization system and poor separation effects of the separation membrane on chiral chemical substances existing in the prior art.

[0005] According to an embodiment of the present invention, the first solution is provided as follows: A preparation method of a binaphthylamine-based chiral intrinsically microporous polymer composite membrane, comprising the following steps: S1. Prepare a reaction solution: Fully dissolve the aqueous-phase monomer in a mixed solution of N,N-dimethylacetamide and H2O to prepare an aqueous-phase solution. The aqueous-phase monomer includes S-binaphthylamine and NaOH. Dissolve the oil-phase monomer in n-hexane to prepare an oil-phase solution. The oil-phase monomer is trimesoyl chloride. S2. Substrate pretreatment: Fix the polyacrylonitrile membrane using a mold to define the polymerization reaction range on the polyacrylonitrile membrane. The polyacrylonitrile membrane is fixed in the mold and kept horizontal. After soaking the polyacrylonitrile membrane with the aqueous solution, remove the residual liquid on the surface. S3. Chiral polymerization step: Drop the oil-phase solution onto the surface of the polyacrylonitrile membrane soaked with the aqueous solution obtained in step S2, and an interfacial polymerization reaction occurs on the surface of the polyacrylonitrile membrane. After reaching the polymerization reaction time, remove the reaction solution. Cover the polyacrylonitrile membrane with n-hexane, soak for a second time, and then remove the n-hexane solution. Perform thermal crosslinking treatment. After the thermal crosslinking is completed, remove the mold to obtain a binaphthylamine-based chiral intrinsically microporous polymer composite membrane.

[0006] Further, in S1, the volume ratio of N,N-dimethylacetamide to H2O in the N,N-dimethylacetamide and H2O mixture is 7:3.

[0007] Further, in step S2, the polyacrylonitrile membrane is pretreated before being fixed using a mold. The pretreatment step of the polyacrylonitrile membrane is to soak the polyacrylonitrile membrane in deionized water. After the soaking is completed, blot the water on the surface of the polyacrylonitrile membrane with absorbent paper.

[0008] Further, in S3, the polymerization reaction time is 1.5 - 3 min. The thermal crosslinking treatment method is as follows: After the reagents on the surface of the polyacrylonitrile membrane are completely volatilized, put the mold into a forced-air drying oven for thermal crosslinking treatment. The thermal crosslinking temperature is 55 - 65 °C, and the thermal crosslinking time is 5 - 8 min.

[0009] Further, the binaphthylamine-based chiral intrinsically microporous polymer composite membrane is soaked in deionized water and stored for standby in a refrigerated environment. The temperature of the deionized water is 2 - 8 °C.

[0010] According to the embodiments of the present invention, using the preparation method of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane in the first scheme provided by the present invention, the second scheme is as follows: A binaphthylamine-based chiral intrinsically microporous polymer composite membrane prepared by the preparation method of the foregoing binaphthylamine-based chiral intrinsically microporous polymer composite membrane.

[0011] Further, the pore size of the separation layer is sub-nanometer pore size, and the pore size is 0.8 - 1.4 nm; the specific surface area is greater than 50 .

[0012] According to the embodiment of the present invention, using the binaphthylamine-based chiral intrinsically microporous polymer composite membrane in the second solution provided by the present invention, the third solution is provided as follows: Application of binaphthylamine-based chiral intrinsically microporous polymer composite membrane in the separation of chiral compounds.

[0013] Compared with the prior art, the beneficial effects of the technical solution provided by this application.

[0014] Using the DMAc-H2O mixed solvent to replace the traditional aqueous solvent, this solvent system breaks through the dependence on hydrophilic monomers in traditional interfacial polymerization, provides a new path for the efficient reaction of hydrophobic chiral monomers, and significantly improves the chemical stability and separation efficiency of the membrane.

[0015] The three-dimensional structure of the synthesized polymer composite membrane provides high free volume channels, high permeation flux and mechanical stability, and solves the "trade-off" effect that it is difficult to balance the permeability and selectivity of traditional membrane materials.

[0016] It provides an efficient and low-energy consumption solution for the continuous separation of chiral compounds in the pharmaceutical industry and has the potential for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required to be used in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0018] Among them: Figure 1 Is a flowchart of the preparation method of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane in one embodiment; Figure 2 Is a film-forming mechanism diagram of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane in one embodiment; Figure 3 Is a SEM comparison diagram of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane in one embodiment; Figure 4 Is an XPS and XRD diagram of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane in one embodiment; Figure 5 Is an AFM three-dimensional topography diagram of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane in one embodiment; Figure 6 It is a comparison chart of the chiral recognition ability effect of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane in one embodiment; Figure 7 It is a comparison chart of the circular dichroism spectra of S-BINAM monomer and S-BINAM-CPIM3 membrane in one embodiment; Figure 8 It is the wide-angle X-ray scattering curve and BET test chart of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane in one embodiment. Detailed implementation manners

[0019] In order to enable those skilled in the art to better understand the technical solutions in this application, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of this application. Obviously, the described embodiments are only a part of the embodiments of this application, rather than all the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of this application.

[0020] A binaphthylamine-based chiral intrinsically microporous polymer composite membrane was prepared according to the technical solution of this application, including; A polyacrylonitrile-based (PAN) membrane substrate and a polymer separation layer on the polyacrylonitrile-based (PAN) membrane substrate, and the separation layer covers the surface and the interior of the pores of the polyacrylonitrile-based (PAN) membrane substrate. The separation layer is polymerized from S-binaphthylamine and trimesoyl chloride.

[0021] Furthermore, the preparation method of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane was described by way of examples.

[0022] Figure 2 It shows the selection basis of reactants and solvents, and at the same time shows the synthesis mechanism of this synthesis scheme.

[0023] As Figure 2 shown in (b) therein, since the two reactants use organic solvents, trimesoyl chloride (TMC) can directly enter the N,N-dimethylacetamide (DMAc) solvent, resulting in the inability to form a stable S-binaphthylamine (S-BINAM)-trimesoyl chloride (TMC) polymer membrane; As Figure 2 shown in (c) therein, in this scheme, by adding a certain amount of deionized water to the N,N-dimethylacetamide (DMAc) solvent, the entry of trimesoyl chloride (TMC) is inhibited, enabling the formation of a stable S-binaphthylamine (S-BINAM)-trimesoyl chloride (TMC) polymer membrane at the interface between the N,N-dimethylacetamide (DMAc) and H2O mixture and n-hexane.

[0024] Figure 1 Show the preparation process of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane, and the specific steps include: S1. Prepare the reaction solution; Prepare the aqueous solution; Dissolve the aqueous monomers: S-binaphthylamine (S-BINAM) and NaOH in a mixed solution of N,N-dimethylacetamide (DMAc) and H2O to prepare an aqueous solution. The volume ratio of N,N-dimethylacetamide (DMAc) to H2O is 7:3.

[0025] Prepare the organic solution; Dissolve the organic monomer: trimesoyl chloride (TMC) in n-hexane.

[0026] S2. Pretreat the substrate; Soak the polyacrylonitrile (PAN) membrane in deionized water. After soaking, blot the surface moisture of the polyacrylonitrile membrane with absorbent paper and set it aside.

[0027] Lay the polyacrylonitrile membrane flat on a clean plate, use a mold to fix the polyacrylonitrile membrane, limit the range of the polymerization reaction, and ensure that the membrane is fixed in the mold and remains horizontal.

[0028] After soaking the polyacrylonitrile membrane with the aqueous solution, remove the residual liquid on the surface; S3. Chiral polymerization; Drop the organic solution onto the surface of the polyacrylonitrile membrane soaked with the aqueous solution obtained in step S2, and an interfacial polymerization reaction occurs on the surface of the polyacrylonitrile membrane. After reaching the polymerization reaction time, remove the reaction solution; Cover the polyacrylonitrile membrane with n-hexane and soak it for a second time, then remove the n-hexane solution; After the reagents on the surface of the polyacrylonitrile membrane are completely volatilized, put the mold into a blast drying oven for thermal cross-linking treatment; After the thermal cross-linking is completed, remove the mold to obtain the composite membrane, take out the composite membrane and soak it in deionized water.

[0029] Example 1 1. Preparation of the aqueous solution: Add S-BINAM (1 wt%) and sodium hydroxide (0.2 wt%) to a mixed solution of N,N-dimethylacetamide / deionized water (7:3, v:v), and ultrasonicate for 5 min to completely dissolve it; Preparation of the organic solution: Dissolve trimesoyl chloride (TMC) (0.1 wt%) in n-hexane.

[0030] 2. Immerse the purchased polyacrylonitrile (PAN) membrane in deionized water for 24 h. After the immersion, wipe it clean with absorbent paper and set it aside. Cut the PAN membrane into appropriate sizes as needed, lay it flat on a clean glass plate, install the rubber gasket and polytetrafluoroethylene mold in sequence, and clamp it with a fixed clamp to ensure that the membrane is fixed and kept horizontal in the mold.

[0031] Next, use a plastic pipette to add 5 mL of DMAc / H2O mixed solution along the edge of the mold. After soaking the PAN membrane for 5 min, pour the solution into the waste liquid bottle. Then, remove the mold in sequence and use a rubber roller to roll off the residual solvent on the membrane surface. Reassemble each mold in the original order.

[0032] 3. After ensuring that the mold is placed horizontally, add 5 mL of n-hexane solution along the edge of the mold to cause an interfacial polymerization reaction on the surface of the PAN membrane. The reaction time is 3 min. After that, pour the solution into the waste liquid bottle, and then add an appropriate amount of n-hexane solution along the edge to stop the reaction. Let it stand for 1 min and then pour out the solution and wait for the surface reagent to completely volatilize. Then, put the mold into a forced-air drying oven for thermal cross-linking treatment. The thermal cross-linking temperature is 60 °C and it lasts for 7 min. After the thermal cross-linking is completed, remove the mold in sequence, take out the prepared composite membrane and soak it in deionized water, and finally store it in a refrigerator at 2 °C for later use.

[0033] Example 2 The PAN membrane, aqueous solution and oil phase solution used are the same as those in Example 1. The difference in the control parameters lies in that the polymerization reaction time in the chiral polymerization step of step S3 is 1.5 min, the thermal cross-linking temperature is 65 °C, the thermal cross-linking time is 5 min, take out the membrane and soak it in deionized water, and store it in a refrigerator at 6 °C for later use.

[0034] We also characterized the synthesized polymer separator.

[0035] As Figure 3 shown, the SEM images of S-BINAM / PAN chiral intrinsically microporous polymer (CPIM) composite membranes with different polymerization reaction times are presented. The polymerization time for figures c and e is 1.5 min; the polymerization time for figures d and f is 3 min. It can be seen from figures c and d that the synthesized composite membrane is continuous and defect-free, and it can be seen from figures e and f that a stable pore structure is formed.

[0036] Figure 4 The XPS and XRD diagrams of the prepared composite membrane are shown. It can be seen from the diagrams that the PAN membrane is not damaged, and at the same time, the S-BINAM chiral intrinsically microporous polymer component has stably existed in the composite membrane, proving the successful preparation of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane.

[0037] Figure 5 The AFM three-dimensional topography of self-supporting S-BINAM-CPIM3 membranes prepared with different polymerization reaction times is shown in the figure.

[0038] It can be seen from the height distribution curves at different polymerization times that when the polymerization time is 1.5 min, the average thickness of the separation layer is about 15 nm; when the polymerization time is 3 min, the thickness of the separation layer increases significantly to 30 nm, with an increase rate of 100%. Extending the reaction time before the reactants are completely reacted can effectively increase the thickness of the separation layer. Composite membranes with different separation layer thicknesses can be prepared by controlling the reaction time according to actual needs to meet different separation effect requirements.

[0039] Application Example The application of the synthesized S-BINAM / PAN chiral intrinsically microporous polymer (CPIM) composite membrane in the continuous separation of chiral compounds was verified.

[0040] Figure 6 The separation effects of S-BINAM / PAN chiral intrinsically microporous polymer (CPIM) composite membranes with polymerization times of 1.5 min and 3 min are shown using an ethanol solution of ibuprofen / phenethyl alcohol racemate as the model system.

[0041] Under the action of a concentration gradient without external pressure driving, a permeation experiment was carried out. The S-BINAM / PAN composite membrane exhibited excellent chiral recognition ability, and high-performance liquid chromatography (HPLC) detection showed that the enantiomeric excess value (ee) of racemic ibuprofen could reach the theoretical extreme value of 100%.

[0042] It is worth noting that the composite membrane also exhibited excellent cyclic stability and could maintain extremely high selectivity after 5 consecutive separation cycles. These characteristics provide important technical support for its application in the continuous separation of chiral compounds in the pharmaceutical industry.

[0043] In this scheme, a DMAc-H2O mixed solvent system is used as the dissolution medium for binaphthylamine (S-BINAM), and n-hexane is used as the solvent for trimesoyl chloride (TMC). An interfacial polymerization reaction is carried out on a polyacrylonitrile-based (PAN) membrane. Subsequently, a S-BINAM / PAN chiral intrinsically microporous polymer (CPIM) composite membrane is self-assembled. By optimizing the interfacial polymerization process parameters, a chiral intrinsically microporous polyamide thin film material with a three-dimensional rigid twisted topological structure is constructed. The use of a DMAc-H2O mixed solvent to replace the traditional aqueous solvent solves the problem of low reaction activity of intrinsically microporous polymer (PIMs) monomers due to their hydrophobicity. The polar aprotic property of DMAc enhances the solubility of benzidine, while the introduction of H2O optimizes the interfacial polymerization kinetics. This solvent system breaks through the dependence of traditional interfacial polymerization on hydrophilic monomers, provides a new path for the efficient reaction of hydrophobic chiral monomers, and significantly improves the chemical stability and separation efficiency of the membrane.

[0044] As Figure 7 shown, through experimental verification, the axial chiral center of binaphthylamine is successfully introduced. The Cotton effect shows a significant signal at λ = 350 nm as confirmed by CD spectroscopy, endowing the membrane material with excellent chiral recognition ability.

[0045] The composite membrane also exhibits characteristic chiral signal peaks similar to those of the monomer. In-depth analysis shows that this is due to the effective chiral transfer from the chiral spiro monomer to the polymer matrix. The research results reveal the structure-property relationship of chiral functional materials at the molecular level, providing an important theoretical basis for the rational design of novel chiral separation membranes.

[0046] Figure 8 In figures a and b, the wide-angle X-ray scattering curves of the self-supporting membranes of S-BINAM and S-BINAM-CPIM3 are shown respectively. Figure c is the CO2 adsorption isotherm of the self-supporting membrane of S-BINAM-CPIM3; Figure d is the pore size distribution fitted by non-local density functional theory (NLDFT) of the self-supporting membrane of S-BINAM-CPIM3.

[0047] From the comparison of figures a and b, it can be seen that obvious Bragg diffraction peaks appear at 2θ = 15.6° and 22.5° for the S-BINAM monomer, indicating its typical crystal structure; while only broad hump peaks (the sharp peak at 33° is the glass characteristic peak of the test sample stage) appear in the range of 2θ = 5° - 50° for the S-BINAM-CPIM3 thin film, confirming that the material has successfully constructed an amorphous network structure. The d-spacing value calculated based on the Bragg equation is 0.347 nm. This parameter not only reflects the tightness of molecular chain stacking but also intuitively reveals the existence of sub-nanometer microporous channels inside the material.

[0048] As can be seen from Figures c and d, the CO2 adsorption curve (77 K) shows a steep upward trend in the low-pressure range, which is highly consistent with the type I adsorption isotherm, confirming that the material has a well-developed microporous structure. The BET specific surface area obtained by calculation using the Langmuir model reaches 57.12 , which is about 3-5 times higher than that of traditional polyamide membranes. This breakthrough value provides an important structural basis for efficient mass transfer. Further analysis of the adsorption isotherm using non-local density functional theory (NLDFT) shows that the thin film exhibits a porous size distribution characteristic, with pore sizes in the sub-nanometer range, and the distribution range is 0.8-1.4 nm.

[0049] This unique microporous structure results from the synergistic effect of the steric hindrance effect of the binaphthyl structure in the S-BINAM molecule and the rigid aromatic ring structure of the TMC crosslinker: ① The V-shaped configuration of binaphthyl diamine hinders the regular packing of molecular chains, promoting the formation of an amorphous structure; ② The controllable crosslinking of acyl chloride groups constructs molecular sieve pores with relatively uniform sizes at the sub-nanometer scale. This sub-nanometer pore system forms a functional synergistic effect with the surface charge characteristics and hydrophilic gradient characterized previously, providing a theoretical support for the preparation of a new type of separation membrane with high selectivity (pore size screening) and high flux (short microporous path).

[0050] At the same time, through the continuous separation experiment of chiral compounds, it can be seen from the experimental results that the S-BINAM / PAN chiral intrinsically microporous polymer (CPIM) composite membrane prepared by this scheme exhibits excellent chiral screening performance and long-term stability.

[0051] The technical features of the above embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0052] The above-described embodiments only represent several implementation manners of the present application. Their descriptions are relatively specific and detailed, but they should not be construed as limiting the patent scope of the present application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can still be made, and these all belong to the protection scope of the present application.

Claims

1. A preparation method of a binaphthylamine-based chiral intrinsically microporous polymer composite membrane, characterized in that, It includes the following steps: S1. Prepare the reaction solution: Fully dissolve the aqueous monomer in a mixed solution of N,N-dimethylacetamide and H2O to prepare an aqueous solution, wherein the aqueous monomer includes S-binaphthylamine and NaOH, dissolve the oil-phase monomer in n-hexane to prepare an oil-phase solution, and the oil-phase monomer is trimesoyl chloride; S2. Pretreat the substrate: Fix the polyacrylonitrile membrane using a mold to define the polymerization reaction range on the polyacrylonitrile membrane. The polyacrylonitrile membrane is fixed in the mold and kept horizontal, after soaking the polyacrylonitrile membrane with the aqueous solution, remove the residual liquid on the surface; S3. Chiral polymerization step: Drop the oil-phase solution onto the surface of the polyacrylonitrile membrane soaked with the aqueous solution obtained in step S2, and an interfacial polymerization reaction occurs on the surface of the polyacrylonitrile membrane. After reaching the polymerization reaction time, remove the reaction solution, cover the polyacrylonitrile membrane with n-hexane and soak for a second time, then remove the n-hexane solution, perform thermal cross-linking treatment. After the thermal cross-linking is completed, remove the mold to obtain a binaphthylamine-based chiral intrinsically microporous polymer composite membrane.

2. The method for preparing a binaphthylamine-based chiral intrinsically microporous polymer composite membrane according to claim 1, wherein in S1, the volume ratio of N,N-dimethylacetamide to H2O in the mixed solution of N,N-dimethylacetamide and H2O is 7:

3.

3. The method for preparing a binaphthylamine-based chiral intrinsically microporous polymer composite membrane according to claim 1, wherein in S2, before fixing the polyacrylonitrile membrane using a mold, pre-treat the polyacrylonitrile membrane, and the pre-treatment steps of the polyacrylonitrile membrane are to soak the polyacrylonitrile membrane in deionized water. After soaking, blot the water on the surface of the polyacrylonitrile membrane with absorbent paper.

4. The method for preparing a binaphthylamine-based chiral intrinsically microporous polymer composite membrane according to claim 1, wherein in S3, the polymerization reaction time is 1.5 - 3 min, and the thermal cross-linking treatment method is that after the reagents on the surface of the polyacrylonitrile membrane are completely volatilized, put the mold into a forced air drying oven for thermal cross-linking treatment. The thermal cross-linking temperature is 55 - 65 °C, and the thermal cross-linking time is 5 - 8 min.

5. The method for preparing a binaphthylamine-based chiral intrinsically microporous polymer composite membrane according to claim 1, wherein the binaphthylamine-based chiral intrinsically microporous polymer composite membrane is soaked in deionized water and stored for standby in a refrigerated environment, and the temperature of the deionized water is 2 - 8 °C.

6. A binaphthylamine-based chiral intrinsically microporous polymer composite membrane, characterized in that, It is prepared by the preparation method according to any one of claims 1 - 5.

7. The binaphthylamine-based chiral intrinsically microporous polymer composite membrane according to claim 6, wherein The pore size of the separation layer is sub-nanometer level pore size, and the pore size is 0.8 - 1.4 nm; the specific surface area is greater than 50 .

8. An application of the binaphthylamine-based chiral intrinsically microporous polymer composite membrane according to claim 6 in the separation of chiral compounds.

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