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CN-121991281-A - Gallium ion imprinting amidoxime macroporous resin and preparation method and application thereof

CN121991281ACN 121991281 ACN121991281 ACN 121991281ACN-121991281-A

Abstract

The invention discloses gallium ion imprinting amidoxime macroporous resin and a preparation method and application thereof, and belongs to the technical field of functional polymer materials and separation. The method comprises the steps of pre-assembling a gallium trichloride template and monomers such as acrylonitrile, generating monodisperse liquid drops by utilizing a microfluidic technology, combining ultraviolet polymerization, and carrying out amidoxime modification by using a hydrochloric acid eluting template and a hydroxylamine hydrochloride alkaline solution to prepare the resin. The resin is a monodisperse spherical microsphere, has a macroporous structure, has high selective recognition capability and high adsorption capacity for gallium ions, has fast adsorption kinetics and good regeneration performance, and is suitable for selectively separating or enriching gallium ions from a complex solution system.

Inventors

  • QIN ZHIFENG
  • JIANG YANG
  • YANG ZHEN
  • 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 gallium ion imprinting amidoxime group macroporous resin is characterized by comprising the following steps of: S1, preparing an organic continuous phase: s1-1, mixing acrylonitrile, divinylbenzene and styrene to obtain an organic monomer mixture; S1-2, adding a gallium trichloride solution, an organic solvent and a pore-forming agent into an organic monomer mixture for pre-assembly; S1-3, adding an initiator and a photo-curing agent into the system after the preassembly in the step S1-2, and uniformly mixing to obtain an organic continuous phase; S2, preparing a water phase dispersion solution, namely uniformly mixing sodium dodecyl sulfate, polyvinyl alcohol and water to obtain the water phase dispersion solution; s3, preparing monodisperse liquid drops, namely introducing the organic continuous phase obtained in the step S1 and the aqueous phase dispersion solution obtained in the step S2 into a microfluidic chip to generate the monodisperse liquid drops; s4, photopolymerization curing and template eluting, namely initiating monomer polymerization in the monodisperse liquid drops obtained in the step S3 under ultraviolet irradiation, washing with pure water, soxhlet extraction with ethanol, eluting, and drying after curing to obtain molecular imprinting precursor resin microspheres; s5, amidoxime reaction, namely fully reacting the molecular imprinting precursor resin microspheres obtained in the step S4 with hydroxylamine hydrochloride alkaline solution, and washing and drying after the reaction is finished to obtain the gallium ion imprinting amidoxime macroporous resin.
  2. 2. The method of claim 1, wherein in step S1-1, the mass ratio of acrylonitrile, divinylbenzene to styrene in the organic monomer mixture is 6-8:1-3:1-2.
  3. 3. The method of claim 1, wherein in step S1-2, at least one of the following is satisfied: The concentration of the gallium trichloride solution is 20-200 mg/L; the molar ratio of gallium ions in the gallium trichloride solution to cyano groups in acrylonitrile is 1:2-10; The volume ratio of the gallium trichloride solution to the organic solvent is 1:50-500; the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; The mass ratio of the organic monomer mixture to the pore-foaming agent is 1.5-3.0:1; The pore-forming agent is at least one of kerosene, liquid paraffin, dimethylbenzene, cyclohexanone, polyvinylpyrrolidone and gasoline; the preassembly time is 1-6 hours.
  4. 4. The method according to claim 1, wherein at least one of the following is satisfied in step S1-3: the addition amount of the initiator is 0.05-0.20% of the total mass of the organic monomer mixture; the initiator is any one of azodiisobutyronitrile and dibenzoyl peroxide; The addition amount of the photo-curing agent is 0.05-0.10% of the total mass of the organic monomer mixture; the photocuring agent is any one of 2-hydroxy-2-methyl propiophenone, acetophenone derivatives, acyl phosphine oxide, thioxanthone and 4-isobutylphenyl-4' -methylphenyl iodonium hexafluorophosphate.
  5. 5. The method according to claim 1, wherein in step S2, the aqueous dispersion solution contains 0.1 to 1.0% of sodium dodecyl sulfate and 1 to 10% of polyvinyl alcohol.
  6. 6. The method according to claim 1, wherein in step S3, at least one of the following is satisfied: The organic continuous phase is introduced at a rate of 5-100 mu L/min, the aqueous dispersion solution is introduced at a rate of 50-200 mu L/min, and the aqueous dispersion solution is introduced at a rate always greater than that of the organic continuous phase; The liquid drop generating unit of the microfluidic chip is of a flow focusing structure or a T-shaped structure; the width of the oil channel of the microfluidic chip is 100 mu m, and the width of the water channel is 150 mu m; The diameter of the monodisperse liquid drops is 50-300 mu m.
  7. 7. The method according to claim 1, wherein in step S4, at least one of the following is satisfied: the ultraviolet irradiation condition is that the wavelength is 365nm, the intensity is 10-100 mW/cm 2 , and the time is 30-120 minutes; The elution treatment is carried out by adopting hydrochloric acid solution with the concentration of 0.1-1.0 mol/L.
  8. 8. The method according to claim 1, wherein in step S5, at least one of the following is satisfied: The concentration of hydroxylamine hydrochloride in the hydroxylamine hydrochloride alkaline solution is 2-6 mol/L, and the molar ratio of sodium hydroxide to the hydroxylamine hydrochloride is 1-1.3:1; the reaction temperature of the amidoxime reaction is 70-95 ℃ and the reaction time is 6-15 hours.
  9. 9. A gallium ion imprinting amidoxime-based macroporous resin prepared by the preparation method according to any one of claims 1-8, which is characterized in that the resin is monodisperse spherical microspheres, the variation coefficient of particle size is less than 5%, the specific surface area is more than 200m 2 /g, and the average pore diameter is 50-150 nm.
  10. 10. Use of the gallium ion-imprinted amidoxime-based macroporous resin according to claim 9 for selective separation or enrichment of gallium ions.

Description

Gallium ion imprinting amidoxime macroporous resin and preparation method and application thereof Technical Field The invention belongs to the technical field of functional polymer materials and separation, relates to a molecular imprinting material with specific recognition capability on gallium ions, and in particular relates to gallium ion imprinting amidoxime macroporous resin and a preparation method and application thereof. Background Gallium is an important strategic metal and is widely used in the fields of semiconductors, photoelectricity, alloys, medicines and the like. The resources are often dispersed in bauxite, lead zinc ore or exist as associated elements, and the content of the resources in modern electronic wastes is increasing. Efficient and selective separation and recovery of gallium from complex solution systems (e.g., ore leaches, industrial effluents, electronic waste leaches) is of great economic and environmental significance. Amidoxime groups have good coordination ability to a variety of metal ions and are often used to prepare adsorbent materials. For example, the functionalization of gallium-adsorbing special chelate resins (e.g., CN101875004A, CN104292383 a) prepared by conventional suspension polymerization and amidoxime in the prior art is mainly focused on the introduction of amidoxime groups. However, such materials are often not sufficiently selective for gallium ions and it is difficult to achieve efficient separation from complex systems rich in competing ions such as aluminum, iron, copper, etc. The traditional method for preparing the metal ion imprinted polymer adopts bulk polymerization or suspension polymerization. The former needs to be crushed and screened to cause destruction of imprinting sites and irregular morphology, while the latter can directly obtain particles, but has limited control accuracy on particle size and pore structure, and imprinting process is carried out in heterogeneous water phase, and pre-combination of monomer and template ions can be interfered by water. These factors all affect the blotting efficiency, adsorption capacity and kinetic properties of the final blotting material. The molecular imprinting technique is an effective means of improving the selectivity of materials, and the principle is that functional monomers are polymerized after being preassembled with template ions, and then the template is eluted, so that imprinting holes matched with target ions in space and chemical action sites are left in a polymer network. However, conventional methods for preparing metal ion imprinted polymers mostly employ bulk polymerization or suspension polymerization. The suspension polymerization can directly obtain particles, but the control precision of particle size and pore structure is limited, the imprinting process is usually carried out in heterogeneous water phase, and the pre-combination of monomers and template ions can be interfered by water. These factors all affect the morphology uniformity, blotting efficiency and adsorption performance of the final blotting material. The microfluidic technology can generate highly monodisperse emulsion droplets, and provides an ideal platform for preparing microsphere materials with regular morphology and uniform size. Recent prior art research has explored the use of microfluidics for material preparation, for example CN118930688a discloses a method for preparing amidoxime material by using microfluidics, which uses microfluidic technology to drop-shape polyacrylonitrile solution, and then performs amidoxime modification. However, the core of the method is to realize physical forming by utilizing micro-flow control, the functionalization is the post-modification of formed particles, and a molecular imprinting technology is not introduced to create specific recognition sites, so that the difficulty of selective recognition of gallium ions by materials cannot be fundamentally solved. In summary, the traditional polymerization-based molecularly imprinted material is difficult to realize precise control of morphology, and the microfluidic-based precisely formed material lacks high-selectivity recognition capability for specific ions. Therefore, how to prepare a gallium ion adsorption material with high selective recognition capability and regular, uniform and ideal morphology is a technical problem to be solved in the field. Disclosure of Invention The invention aims to solve the technical problem that the selectivity of the traditional amidoxime group adsorption material to gallium ions is insufficient. In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows. In a first aspect, the invention provides a preparation method of gallium ion imprinting amidoxime macroporous resin, which comprises the following steps: S1, preparing an organic continuous phase: s1-1, mixing acrylonitrile, divinylbenzene and styrene to obtain an organic monomer mixt