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CN-121975159-A - Composite membrane loaded with metal organic framework material and preparation method and application thereof

CN121975159ACN 121975159 ACN121975159 ACN 121975159ACN-121975159-A

Abstract

The invention relates to the technical field of membrane material preparation, and particularly discloses a composite membrane loaded with a metal organic framework material, and a preparation method and application thereof, wherein Co 2+ doping is carried out on a ZIF-8 framework, and the introduction of Co 2+ changes the electronic structure of the ZIF-8 framework and reduces the overall polarity, so that the interaction force between the ZIF-8 framework and eugenol molecules is enhanced, the adsorption capacity of the ZIF-8 material on butyl essential oil is improved, and the antibacterial performance and the oxidation resistance of the composite membrane material are further improved; and then, a layer of functional polymer is grafted on the surface of the double bond modified MOF through a free radical initiated copolymerization reaction, so that the surface of the MOF subjected to organic modification has stronger affinity to eugenol molecules, the diffusion and adsorption processes of the eugenol molecules to the inner pore canal of the MOF are promoted, the loading capacity of the eugenol is improved, and the antibacterial performance and the oxidation resistance of the composite membrane material are further improved.

Inventors

  • LIU YIKE
  • SHAN ZHONGGUO
  • WANG HAIHUA
  • LI SIHANG
  • XIAO FAN

Assignees

  • 西北农林科技大学

Dates

Publication Date
20260505
Application Date
20260202

Claims (9)

  1. 1. The preparation method of the composite film loaded with the metal-organic framework material is characterized by comprising the following steps of: S1, adding a zinc salt solution and a cobalt salt solution into a 2-methylimidazole solution, stirring for reaction, and centrifuging, washing and drying a product after the reaction is finished to obtain an MOF material; s2, dispersing the MOF material in an ethanol water solution, then adding a vinyl silane coupling agent into the MOF material, stirring, and then centrifuging, washing and drying to obtain a double bond modified MOF material; S3, dispersing the double bond modified MOF material in deionized water, adding sodium styrene sulfonate and 4-vinyl phenol into the deionized water, uniformly stirring, then adding an initiator persulfate, heating and stirring for reaction, and centrifuging, washing and drying after the reaction is finished to obtain the organic modified MOF material; S4, adding the organic modified MOF material and the butane essential oil into absolute ethyl alcohol, stirring, centrifuging, washing and drying to obtain the MOF material loaded with the butane essential oil; S5, dissolving chitosan quaternary ammonium salt, gelatin, soluble starch and glycerol in deionized water, then adding MOF material loaded with butyl essential oil, uniformly dispersing, and then casting to form a film, thus obtaining the composite film loaded with the metal organic framework material.
  2. 2. The method according to claim 1, wherein in step S1, the molar ratio of zinc salt, cobalt salt and 2-methylimidazole is 0.02-0.04:0.01-0.02:0.1-0.2.
  3. 3. The method according to claim 1, wherein in step S2, the mass ratio of the MOF material to the vinyl silane coupling agent is 10-15:0.1-0.3.
  4. 4. The preparation method according to claim 1, wherein in the step S3, the mass ratio of the double bond modified MOF material, sodium styrenesulfonate, 4-vinylphenol, and persulfate is 10-15:2-4:2-4:0.05-0.1.
  5. 5. The method according to claim 1, wherein in step S3, the temperature of the heating and stirring reaction is 70-80 ℃ and the time of the heating and stirring reaction is 3-5 hours.
  6. 6. The preparation method according to claim 1, wherein in step S4, the mass ratio of the organically modified MOF material to the clove essential oil is 1:2-4.
  7. 7. The preparation method according to claim 1, wherein in step S5, the mass ratio of chitosan quaternary ammonium salt, gelatin, soluble starch, glycerin, deionized water and MOF material loaded with butane essence oil is 4-6:4-6:1-2:4-8:100:0.2-0.5.
  8. 8. A composite membrane loaded with a metal-organic framework material prepared by the preparation method according to any one of claims 1 to 7.
  9. 9. Use of a composite film loaded with a metal-organic framework material according to claim 8 in packaging film materials.

Description

Composite membrane loaded with metal organic framework material and preparation method and application thereof Technical Field The invention relates to the technical field of membrane material preparation, in particular to a composite membrane loaded with a metal organic framework material, and a preparation method and application thereof. Background The oleum Caryophylli is a volatile oily liquid with strong fragrance extracted from dry bud of flos Caryophylli of plant, and its main active ingredient is eugenol. The essential oil has great application potential in the fields of food preservation, medical preparation, personal care products and the like because of broad-spectrum and strong antibacterial, antioxidant and anti-inflammatory activities. However, the clove essential oil contains unstable chemical properties of active ingredients, is sensitive to light, heat and oxygen, is easy to degrade or oxidize to reduce efficacy, and meanwhile, the high volatility of the clove essential oil also causes the problems of extremely easy loss of the active ingredients in the production, storage and use processes, low utilization rate and the like, and the factors severely restrict the further development and application of the clove essential oil in industry. The porous Metal Organic Framework (MOF) material is a porous material composed of organic and inorganic components, has the advantages of uniform pore structure, large internal specific surface area, adjustable porosity, network topology, geometric structure, dimension, chemical function flexibility and the like, and has great application potential in the biomedical field. In theory, the MOF material can hold clove essential oil molecules in the nanoscale cavities of the MOF material through physical adsorption, so that adverse effects of external environment are shielded to a certain extent, and a slow release effect is realized, however, the MOF material has a very high theoretical specific surface area, but the inherent pore channel structure and the clove essential oil molecules (especially the main active ingredient eugenol) are possibly poor in matching degree in spatial scale and physicochemical properties, so that the effective loading space is not fully utilized, the cladding amount of the clove essential oil is limited, and the effect of a final product is further influenced. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a composite membrane loaded with a metal organic framework material, and a preparation method and application thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme: In a first aspect, the present invention provides a method for preparing a composite membrane loaded with a metal-organic framework material, comprising the steps of: S1, adding a zinc salt solution and a cobalt salt solution into a 2-methylimidazole solution, stirring for reaction, and centrifuging, washing and drying a product after the reaction is finished to obtain an MOF material; s2, dispersing the MOF material in an ethanol water solution, then adding a vinyl silane coupling agent into the MOF material, stirring, and then centrifuging, washing and drying to obtain a double bond modified MOF material; S3, dispersing the double bond modified MOF material in deionized water, adding sodium styrene sulfonate and 4-vinyl phenol into the deionized water, uniformly stirring, then adding an initiator persulfate, heating and stirring for reaction, and centrifuging, washing and drying after the reaction is finished to obtain the organic modified MOF material; S4, adding the organic modified MOF material and the butane essential oil into absolute ethyl alcohol, stirring, centrifuging, washing and drying to obtain the MOF material loaded with the butane essential oil; S5, dissolving chitosan quaternary ammonium salt, gelatin, soluble starch and glycerol in deionized water, then adding MOF material loaded with butyl essential oil, uniformly dispersing, and then casting to form a film, thus obtaining the composite film loaded with the metal organic framework material. In the technical scheme disclosed by the invention, in the step S1, the molar ratio of zinc salt to cobalt salt to 2-methylimidazole is 0.02-0.04:0.01-0.02:0.1-0.2. In the technical scheme disclosed by the invention, in the step S1, the solvent in the zinc salt solution, the cobalt salt solution and the 2-methylimidazole solution is preferably methanol, the zinc salt is selected from zinc salts which are soluble in methanol, for example, zinc nitrate can be selected, and the cobalt salt is selected from cobalt salts which are soluble in methanol, for example, cobalt nitrate can be selected. In the technical scheme disclosed by the invention, in the step S1, the stirring reaction time is 4-8h, for example, 4h, 5h, 6h, 7h and 8h can be selected, but the stirring reaction time is not limited to the listed values, a