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CN-121991280-A - Amidoxime macroporous resin and preparation method and application thereof

CN121991280ACN 121991280 ACN121991280 ACN 121991280ACN-121991280-A

Abstract

The invention discloses amidoxime macroporous resin and a preparation method and application thereof, and belongs to the technical field of preparation of functional polymer materials. The preparation method comprises the steps of introducing an organic phase containing an organic monomer mixture, an initiator, a photo-curing agent and a pore-forming agent into a microfluidic chip through water containing a stabilizing agent to generate monodisperse liquid drops, initiating polymerization and curing through illumination to obtain precursor resin microspheres with uniform size and adjustable pore structure, and finally introducing functional groups through amidoxime reaction. The method utilizes a microfluidic technology to realize accurate control of liquid drops, combines photopolymerization to realize rapid solidification, and can cooperatively regulate and control the size, morphology, aperture and functional group distribution of the resin from the source. The prepared resin has high monodispersity, a through macroporous structure and uniformly distributed amidoxime groups, and has high adsorption capacity, rapid adsorption kinetics and good cycle stability for uranyl ions.

Inventors

  • QIN ZHIFENG
  • YANG ZHEN
  • JIANG YANG
  • LIU JUAN

Assignees

  • 成都先进金属材料产业技术研究院股份有限公司

Dates

Publication Date
20260508
Application Date
20260226

Claims (10)

  1. 1. The preparation method of the amidoxime group macroporous resin is characterized by comprising the following steps: S1, preparing an organic phase: mixing acrylonitrile, divinylbenzene and styrene to obtain an organic monomer mixture; adding an initiator, a photo-curing agent and a pore-foaming agent into the organic monomer mixture, and uniformly mixing to obtain an organic phase; s2, preparing a water phase, namely preparing a polyvinyl alcohol water solution as the water phase; s3, preparing monodisperse liquid drops, namely introducing the organic phase obtained in the step S1 and the water phase obtained in the step S2 into a microfluidic chip to generate the monodisperse liquid drops; S4, photopolymerization curing, namely initiating monomer polymerization in the monodisperse liquid drops obtained in the step S3 under the condition of illumination, and performing primary washing, soxhlet extraction, secondary washing and drying after curing to obtain macroporous resin precursor microspheres; S5, amidoxime reaction, namely fully reacting the macroporous resin precursor microsphere obtained in the step S4 with hydroxylamine reagent, and washing and drying after the reaction is finished to obtain amidoxime macroporous resin.
  2. 2. The method according to claim 1, wherein in step S1, at least one of the following is satisfied: the mass ratio of the acrylonitrile to the divinylbenzene to the styrene in the organic monomer mixture is 5-7:2-3:1-2; the addition amount of the initiator is 0.5-2% of the total mass of the organic monomer mixture; the initiator is azodiisobutyronitrile; the addition amount of the photo-curing agent is 0.1-1% of the total mass of the organic monomer mixture; the photocuring agent is any one of benzoin dimethyl ether, acetophenone derivatives, acyl phosphine oxides, thioxanthones and 4-isobutylphenyl-4' -methylphenyl iodonium hexafluorophosphate; The mass ratio of the organic monomer mixture to the pore-foaming agent is 2-5:1; the pore-forming agent is at least one of kerosene, liquid paraffin, dimethylbenzene, cyclohexanone, polyvinylpyrrolidone and gasoline.
  3. 3. The method according to claim 1, wherein in the step S2, the mass concentration of the aqueous solution of polyvinyl alcohol is 2-10%.
  4. 4. The method according to claim 1, wherein in step S3, at least one of the following is satisfied: The liquid drop generating unit of the microfluidic chip is of a flow focusing structure or a T-shaped structure; The diameter of the monodisperse liquid drops is 50-500 mu m; the organic phase is introduced at a rate of 5-100 mu L/min, the aqueous phase is introduced at a rate of 10-200 mu L/min, and the aqueous phase is introduced at a rate always greater than that of the organic phase.
  5. 5. The method according to claim 1, wherein in the step S4, the irradiation condition is irradiation with ultraviolet light having a wavelength of 365 nm.
  6. 6. The preparation method of claim 1, wherein in the step S5, the mass-volume ratio of the macroporous resin precursor microsphere to the hydroxylamine reagent is 1 g:10-50 mL.
  7. 7. The method according to claim 1, wherein in step S5, the hydroxylamine reagent is a hydroxylamine hydrochloride solution prepared from hydroxylamine hydrochloride and sodium hydroxide; wherein the concentration of hydroxylamine hydrochloride is 1-5 mol/L, and the molar ratio of sodium hydroxide to hydroxylamine hydrochloride is 1-1.5:1.
  8. 8. The method according to claim 1, wherein in the step S5, the reaction temperature of the amidoximation reaction is 60-90 ℃ and the reaction time is 4-12 hours.
  9. 9. An amidoxime-based macroporous resin produced by the production process according to any one of claims 1 to 8.
  10. 10. Use of the amidoxime-based macroporous resin according to claim 9 for adsorbing uranium, gallium and vanadium metal ions in an aqueous solution.

Description

Amidoxime macroporous resin and preparation method and application thereof Technical Field The invention belongs to the technical field of preparation of functional polymer materials, relates to macroporous adsorption resin with uniform size and amidoxime functional groups, and in particular relates to amidoxime macroporous resin and a preparation method and application thereof. Background The amidoxime group resin has important application value in the fields of hydrometallurgy, nuclear fuel circulation, wastewater treatment and the like because of the special strong coordination capability of the amidoxime group resin to metal ions such as uranium, vanadium, gallium and the like. The properties of the resin depend to a large extent on the physical structure (such as particle morphology, size distribution, pore size and specific surface area) and chemical structure (functional group type, density and distribution uniformity) of the resin. Currently, the conventional process for preparing amidoxime-based resins is mainly divided into two steps, namely, first obtaining a precursor resin (usually a polyacrylonitrile-based resin) by suspension polymerization or dispersion polymerization, and then introducing amidoxime groups by chemical modification. However, such conventional polymerization methods rely on mechanical agitation to disperse monomer droplets, the droplet size being controlled by the agitation shear force, resulting in a broad size distribution and irregular morphology of the final resin particles. This can easily cause problems such as uneven fluid distribution, increased pressure drop, and reduced mass transfer efficiency in practical applications (e.g., packed columns). In addition, the traditional method has limited fine regulation capability on the porous structure inside the resin, and is difficult to realize uniform design of pore diameter and uniform loading of functional groups while maintaining high specific surface area. CN118930688a discloses a method for preparing amidoxime material by microfluidic, which is to drop polyacrylonitrile solution into coagulation bath by microfluidic pump to realize physical molding. Although the method can obtain particles with uniform size, the essence is that the existing polymer is reprocessed and formed, and polymerization reaction and structure construction are not carried out from monomers. Therefore, the method has inherent limitations in synchronously and precisely regulating and controlling the crosslinked network structure, the pore size distribution and the chemical environment of the functional groups of the resin. Therefore, a new method capable of integrating precise control and controllable polymerization chemical reaction of fluid to prepare functional resin with designable structure and excellent performance is developed, and important research value and application requirements are provided. Disclosure of Invention The invention aims to solve the technical problems of accurately and controllably constructing the size and the morphology of the resin microsphere from a monomer source, so as to solve the problems that the traditional suspension polymerization product is not uniform, and the existing microfluidic technology can only carry out physical molding on the existing polymer and cannot synchronously control the chemical structure. In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows. In a first aspect, the present invention provides a method for preparing an amidoxime-based macroporous resin, comprising the steps of: S1, preparing an organic phase: Mixing acrylonitrile, divinylbenzene and styrene as an organic monomer mixture; adding an initiator, a photo-curing agent and a pore-foaming agent into the organic monomer mixture, and uniformly mixing to obtain an organic phase; s2, preparing a water phase, namely preparing a polyvinyl alcohol water solution as the water phase; s3, preparing monodisperse liquid drops, namely introducing the organic phase obtained in the step S1 and the water phase obtained in the step S2 into a microfluidic chip to generate the monodisperse liquid drops; S4, photopolymerization curing, namely initiating monomer polymerization in the monodisperse liquid drops obtained in the step S3 under the condition of illumination, and performing primary washing, soxhlet extraction, secondary washing and drying after curing to obtain macroporous resin precursor microspheres; S5, amidoxime reaction, namely fully reacting the macroporous resin precursor microsphere obtained in the step S4 with hydroxylamine reagent, and washing and drying after the reaction is finished to obtain amidoxime macroporous resin. In the step S1, the mass ratio of acrylonitrile, divinylbenzene to styrene in the organic monomer mixture is 5-7:2-3:1-2. In the step S1, the addition amount of the initiator is 0.5-2% of the total mass of the organic monomer mixture. In the step S1, the