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CN-122006525-A - Network structured molecular cage film with regular structure, and preparation method and application thereof

CN122006525ACN 122006525 ACN122006525 ACN 122006525ACN-122006525-A

Abstract

The invention discloses a network structured molecular cage membrane with a regular structure, a preparation method and application thereof, belonging to the technical field of membrane separation, wherein the preparation method comprises the following steps of S1, dissolving a cyanuric chloride molecular cage in an organic solvent to obtain an organic phase solution, and dissolving a polyamine monomer in water to obtain an aqueous phase solution; S2, removing excessive aqueous phase solution on the surface of the porous support membrane after the porous support membrane is soaked by the aqueous phase solution, adding organic phase solution on the surface of the membrane after the aqueous phase solution treatment to enable melamine chloride molecular cages and polyamine monomers to undergo nucleophilic substitution reaction at a water-oil interface to form a porous organic molecular cage selection layer, and drying and cleaning the membrane obtained in the S2 to obtain the network structured molecular cage membrane with a regular structure.

Inventors

  • LIU MING
  • YU SAISAI

Assignees

  • 浙江大学

Dates

Publication Date
20260512
Application Date
20251229

Claims (9)

  1. 1. The preparation method of the network structured molecular cage film with the regular structure is characterized by comprising the following steps of: s1, dissolving a cyanuric chloride molecular cage in an organic solvent to obtain an organic phase solution, and dissolving polyamine monomers in water to obtain an aqueous phase solution; S2, removing redundant aqueous phase solution on the surface of the porous support membrane after the porous support membrane is soaked by the aqueous phase solution, and then adding organic phase solution on the surface of the membrane treated by the aqueous phase solution to enable melamine-based molecular cages and polyamine monomers to undergo nucleophilic substitution reaction at a water-oil interface to form a porous organic molecular cage selection layer; s3, drying and cleaning the film obtained in the step S2 to obtain the network structured molecular cage film with the regular structure; the structural formula of the cyanuric chloride molecular cage is shown as follows: 。
  2. 2. The method for preparing the network structured molecular cage film with the regular structure according to claim 1, wherein the organic solvent is n-hexane, ethyl acetate, petroleum ether, butyl acetate, toluene, xylene or methylene dichloride, and the concentration of the cyanuric chloride-based molecular cage in the organic phase solution is 0.35 mg/mL-1.4 mg/mL.
  3. 3. The method for preparing a structured molecular cage film according to claim 1, wherein the polyamine monomer is selected from piperazine, 1,4, 7-triazacyclononane or 1,4,7, 10-tetraazacyclotetradecane, and the concentration of the polyamine monomer in the aqueous solution is 0.25 mg/mL-1 mg/mL.
  4. 4. The method for preparing the structured molecular cage membrane according to claim 1, wherein the porous support membrane is a polymer porous membrane with a molecular weight cut-off of 10kDa-100kDa, and the polymer porous membrane is one or more of polyethylene, polypropylene, polytetrafluoroethylene, polysulfone, polyethersulfone, polyamide, polyimide and polypropylene nitrile.
  5. 5. The method for preparing a structured network structured molecular cage membrane according to claim 1, wherein the nucleophilic substitution reaction is performed at a temperature of 20 ℃ to 60 ℃ and a reaction time of 1 min to 120 min.
  6. 6. A network structured molecule of any one of claims 1-5 having a structured structure the network structured molecular cage film with the regular structure is prepared by the preparation method of the cage film.
  7. 7. Use of a network structured molecular cage membrane with a structured structure according to claim 6 for drug purification, organic solvent recovery or dye removal.
  8. 8. A method for purifying a drug, which is characterized in that a material liquid containing the drug is filtered by using the network structured molecular cage membrane with a regular structure according to claim 6, so that the drug is trapped and purified, wherein the molecular weight of the drug is more than or equal to 300 Da, and the drug comprises vitamin B12, rifampicin, tetracycline or curcumin.
  9. 9. A method for removing dye molecules, which is characterized in that a solution containing the dye is filtered by using the network structured molecular cage film with a regular structure as claimed in claim 6, so that the dye is trapped and removed, wherein the molecular weight of the dye molecules is more than or equal to 300 Da, and the dye molecules comprise methyl orange, acid fuchsin or congo red.

Description

Network structured molecular cage film with regular structure, and preparation method and application thereof Technical Field The invention belongs to the technical field of membrane separation, and particularly relates to a network structured molecular cage membrane with a regular structure, and a preparation method and application thereof. Background In the course of drug synthesis, highly active agents employed may introduce genotoxic impurities (GTIs, molecular weight range typically 55-225 Da) in the final product, which impurities are often electrophilic and can covalently bind to DNA, potentially inducing genetic mutations or chromosomal damage and possibly carry the risk of carcinogenesis. In addition, organic solvents are also of concern as an indispensable reaction medium in the synthesis of Active Pharmaceutical Ingredients (APIs). Because of the strong physical interactions that may exist between the solvent and the active pharmaceutical ingredient, or limited by the economics and feasibility of the process, achieving complete removal thereof is often difficult. Even a trace amount of solvent remains can significantly increase the difficulty of subsequent treatment of the wastewater from pharmaceutical production due to the inherent toxicity thereof. The membrane separation is an efficient and environment-friendly separation process, and has the advantages of high efficiency, energy conservation, strong adaptability, flexible process, high treatment efficiency and the like. However, the conventional polymer separation membrane has certain limitation in practical application, namely, on one hand, the conventional polymer separation membrane has dynamic change of pore channel structure due to the relaxation of molecular chain conformation, so that performance attenuation in long-term operation is caused, and on the other hand, the polymer separation membrane with accurate pore diameter and stable structure is lacking in the prior art. The technical bottleneck severely restricts the application of the polymer separation membrane in drug purification. To accurately separate target products and impurities from a complex raw material flow, the key point is to develop a separation membrane with uniform pore canal, accurate aperture and through mass transfer path. Chinese patent publication No. CN111318187a discloses a chiral separation membrane based on a covalent organic framework material, which is a membrane material with crystallinity formed by a condensation reaction of monomer m-hydrazide groups and aldehyde groups through schiff base, and connected by hydrazone bonds. The chiral membrane obtained by the method has a uniform and regular pore structure, excellent integrity and machinability, and meanwhile, chiral recognition units which are uniformly distributed in the material are beneficial to fully contacting with a substrate in the separation process, so that good chiral separation performance is exerted, and the chiral membrane has a good application prospect in chiral medicine separation. The Chinese patent publication No. CN103408783A discloses a preparation method of a porous membrane with regular vertical pore channels, which comprises the steps of firstly annealing a segmented copolymer film by using a solvent to induce phase separation of the segmented copolymer to form a microphase structure with vertical orientation, then selectively swelling a disperse phase of the segmented copolymer by using a swelling agent to convert the dispersibility into the pore channel structure, thereby forming the porous membrane with highly ordered vertical pore channel structure. The film prepared by the invention has a vertically oriented cylindrical pore structure, the pore size is uniform, the distribution height is regular, and the pore diameter is adjustable. Although the separation membranes with uniform and regular pore structures can be prepared by the method, the problems of limited structure regulation, insufficient processing compatibility and the like exist. Therefore, there is a need to develop an advanced separation membrane material with adjustable pores, which has good processing compatibility and a regular pore structure, and meets the requirements of active pharmaceutical ingredient purification and efficient recovery of organic solvents. Disclosure of Invention Aiming at the defects in the prior art, the invention provides a preparation method of a network structured molecular cage membrane with a regular structure, the process is simple and efficient, and the prepared membrane material has obvious advantages in the aspects of purification of active drugs, recovery of organic solvents, dye removal and the like. The technical scheme adopted is as follows: The preparation method of the network structured molecular cage film with the regular structure comprises the following steps: s1, dissolving a cyanuric chloride molecular cage in an organic solvent to obtain an organic phase solution,