CN-121972024-A - Chiral separation composite membrane and preparation method and application thereof

CN121972024ACN 121972024 ACN121972024 ACN 121972024ACN-121972024-A

Abstract

The invention discloses a chiral separation composite membrane, a preparation method and application thereof, and belongs to the technical field of membrane separation. The invention provides a composite membrane prepared by surfactant-assisted interfacial polymerization technology, which aims to solve the technical problems of low enantioselectivity and poor stability of the existing chiral membrane. The membrane comprises a porous support substrate and a chiral polyamide separation layer disposed thereon. The key to the preparation process is that an aqueous solution comprising a short chain chiral amine monomer and a surfactant is subjected to interfacial polymerization with an organic phase solution comprising a polyfunctional acyl halide. The introduction of the surfactant reduces interfacial tension and regulates and controls the diffusion kinetics of chiral monomers, so that a sub-nanometer separation channel which has more uniform structure, higher chiral site density and highly matched aperture with the size of a target molecule is formed. The composite membrane prepared by the invention shows up to 99% of enantioselectivity to chiral enantiomers such as D/L-tryptophan and the like, and has high flux and excellent cycling stability.

Inventors

LIU JIAYI
WANG YUE
YU HAIPING
YANG PENG

Assignees

山东师范大学

Dates

Publication Date: 20260505
Application Date: 20260127

Claims (10)

1. A chiral separation composite membrane comprising: the porous support substrate comprises a porous support substrate and a chiral polyamide separation layer arranged on the porous support substrate, wherein the chiral polyamide separation layer is formed by performing interfacial polymerization reaction on an aqueous phase solution containing chiral amine monomers and surfactants and an organic phase solution containing polyfunctional acyl halide on the surface of the porous support substrate.
2. The chiral separation composite membrane of claim 1, wherein the chiral amine monomer is a C2-C6 chiral diamine and the polyfunctional acyl halide is an aromatic or aliphatic acyl halide having at least two acyl halide groups.
3. The chiral separation composite membrane of claim 1 or 2, wherein the surfactant is at least one of a cationic surfactant, an anionic surfactant, or a nonionic surfactant.
4. The chiral separation composite membrane of claim 3, wherein the surfactant is a cationic surfactant, and wherein the cationic surfactant is a quaternary ammonium surfactant.
5. The chiral separation composite membrane according to any one of claims 1-4, wherein the thickness of the chiral polyamide separation layer is 40-150nm, the average effective pore radius of the composite membrane is 0.3-0.8nm, the thickness of the chiral polyamide separation layer is 50-100nm, and the average effective pore radius of the composite membrane is 0.3-0.5nm.
6. A method of preparing a chiral separation composite membrane according to claim 1, comprising the steps of: (a) Providing an aqueous solution comprising a chiral amine monomer and a surfactant; (b) Providing an organic phase solution comprising a polyfunctional acyl halide; (c) Contacting a porous support substrate with the aqueous solution; (d) The porous support substrate after being contacted with the aqueous phase solution is contacted with the organic phase solution to form a chiral polyamide separation layer by interfacial polymerization.
7. The method according to claim 6, wherein the concentration of the chiral amine monomer is 0.5 to 5.0wt%, the concentration of the surfactant is 0.05 to 5.0wt%, the concentration of the polyfunctional acyl halide is 0.01 to 1.0wt%, the concentration of the chiral amine monomer is 1.0 to 3.0wt%, the concentration of the surfactant is 0.5 to 3.0wt%, and the concentration of the polyfunctional acyl halide is 0.05 to 0.2wt%, respectively, in the aqueous phase solution.
8. The process according to claim 6, wherein in step (a) the aqueous phase solution has a pH of 7 to 10, in step (c) the contacting is carried out for a period of 0.5 to 5 minutes, and/or in step (d) the contacting is carried out for a period of 1 to 10 minutes, and in step (b) the organic phase solution is formulated with a water-insoluble organic solvent, preferably an aliphatic hydrocarbon solvent, more preferably n-hexane.
9. Use of a chiral separation composite membrane according to any one of claims 1-4 for separating enantiomers.
10. The use according to claim 9, wherein the enantiomer is a chiral amino acid.

Description

Chiral separation composite membrane and preparation method and application thereof Technical Field The invention relates to a chiral separation composite membrane, a preparation method and application thereof, and belongs to the technical field of membrane separation. Background The chiral drug accounts for over 60% of the drugs currently sold in the top 200 of the global sales rank. Enantiomers of chiral drugs often have significant differences in pharmacological activity, metabolic processes and toxicity, which continues to expand the market share of single isomer drugs. Chiral separation is therefore a key element of the modern pharmaceutical industry. However, the traditional chiral separation technologies such as preparative chromatography and crystallization separation have the defects of small processing capacity, high energy consumption, large solvent consumption and the like, and severely restrict the industrial production of chiral medicaments. The membrane separation technology has the remarkable advantages of continuous operation, low energy consumption, scalability and the like, becomes a very promising candidate scheme in the chiral separation field, and provides a very promising solution for chiral drug separation. Although membrane technology has been widely used in many fields, traditional membrane separation techniques based on size exclusion and the donnan effect are not suitable for chiral separations, as they require the construction of a chiral environment to provide selective affinity. Nojavan and the like to develop a novel maltodextrin-starch chiral membrane for separating chiral amino acid and medicine, wherein the enantiomer purity of the novel maltodextrin-starch chiral membrane reaches 98.2 percent. Peng et al embedded beta-cyclodextrin into piperazine polyamide membrane to prepare chiral membrane for amino acid separation, and the ee value is increased from nearly 0 to 25.6%. In addition, nanochannel membrane size has a significant impact on chiral selectivity. The membrane aperture and chiral drug size can be matched to greatly improve the membrane separation performance. Conventional chiral membranes often face challenges of lower flux and lack of enantioselectivity due to the difficulty in controlling membrane structure. In recent years, a variety of nanochannel membranes for chiral drug separation have been reported by growing chiral porous materials such as Metal Organic Frameworks (MOFs), covalent Organic Frameworks (COFs), and Graphene Oxide (GO) on the membrane surface. However, the poor film forming capability and nanoscale pore size often lead to low chiral small molecule separation precision, and it is difficult to combine high selectivity and high flux, thus preventing the wide application of the chiral small molecule. Chiral polymer films have the advantage of low cost and high processing capacity, which enable enantioselectivity through chiral selectors on the films, and have been used for enantioselective recognition. Interfacial Polymerization (IP) is one of the most promising methods for preparing membranes, incorporating chiral selectors by reacting amine monomers with acid chlorides at the water-oil interface to form Polyamide (PA) nanofilms. Functionalized cyclodextrins and a series of amino acids have been applied to membrane preparation and chiral separation. However, limited chiral recognition sites in PA networks can bind only a few enantiomers, limiting the separation accuracy and lifetime of the membrane. In addition, polyamide nanofilms often have a broad pore size distribution due to uncontrollable polymerization reactions, resulting in non-selective pore channels and reduced separation accuracy. Therefore, constructing uniform membrane nanochannels and increasing chiral site density within the channels is a key factor in improving enantioselectivity. Disclosure of Invention The technical problem to be solved by the patent is that the chiral separation membrane prepared by the interfacial polymerization method is difficult to consider high enantioselectivity, high flux and long-term operation stability when separating enantiomers due to the fact that chiral recognition site density of a separation layer is limited, pore channel structures are uneven and nonselective pores exist. The invention provides a novel Surfactant Assisted Interfacial Polymerization (SAIP) technology, which improves chiral site density and high matching nano channels through (2 s) -1,2- (s-PD) and acyl chloride synchronously, thereby improving enantioselectivity. The polymer chains obtained by polymerization of the short-chain chiral amine monomer are closely packed, and the chiral site density can be remarkably improved. The surfactant reduces the interfacial tension of two phases and regulates and controls the monomer diffusion process, and a uniform nano channel which is highly matched with chiral drug molecules is constructed by regulating the monomer diffusion and reactio