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CN-121972006-A - In-situ polymerization modified polyethersulfone ultrafiltration membrane and preparation method and application thereof

CN121972006ACN 121972006 ACN121972006 ACN 121972006ACN-121972006-A

Abstract

The invention provides an in-situ polymerization modified polyethersulfone ultrafiltration membrane, a preparation method and application thereof, wherein the preparation raw materials of the in-situ polymerization modified polyethersulfone ultrafiltration membrane comprise, by weight, 15-26 parts of membrane skeleton material PES, 30-80 parts of organic solvent, 1-5 parts of hydrophilic monomer, 0.1-0.5 part of initiator, 0.5-3.5 parts of cross-linking agent, 0.1-3 parts of pore-forming agent and 5-35 parts of non-solvent. The in-situ polymerization modified polyethersulfone ultrafiltration membrane provided by the invention utilizes the hydrophilic monomer to carry out in-situ polymerization modification by a crosslinking reaction, solves the problems of easy loss, weak combination, complex process and poor anti-pollution effect of the conventional ultrafiltration membrane modification technology, realizes low protein adsorption, high hydrophilicity, high flux, long-acting stability, and simple preparation process, and can be industrially produced in a large scale.

Inventors

  • LV PENGPENG
  • ZHU DI
  • SUN WEI

Assignees

  • 睿纯(苏州)科技有限公司

Dates

Publication Date
20260505
Application Date
20260326

Claims (10)

  1. 1. The in-situ polymerization modified polyethersulfone ultrafiltration membrane is characterized in that the preparation raw materials of the in-situ polymerization modified polyethersulfone ultrafiltration membrane comprise, by weight, 15-26 parts of membrane skeleton material PES, 30-80 parts of organic solvent, 1-5 parts of hydrophilic monomer, 0.1-0.5 part of initiator, 0.5-3.5 parts of cross-linking agent, 0.1-3 parts of pore-forming agent and 5-35 parts of non-solvent.
  2. 2. The in situ polymerization modified polyethersulfone ultrafiltration membrane of claim 1, wherein the organic solvent comprises any one or a combination of at least two of N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone, preferably N-methylpyrrolidone.
  3. 3. The in situ polymerization modified polyethersulfone ultrafiltration membrane of claim 1 or 2, wherein said hydrophilic monomer comprises N-vinylpyrrolidone; Preferably, the initiator comprises any one or a combination of at least two of azobisisobutyronitrile, azobisisoheptonitrile or dibenzoyl peroxide, preferably azobisisobutyronitrile.
  4. 4. The in situ polymerization modified polyethersulfone ultrafiltration membrane of any of claims 1-3, wherein said cross-linking agent comprises a primary cross-linking agent and a secondary cross-linking agent; Preferably, the main crosslinking agent comprises any one or a combination of at least two of sodium divinylbenzene sulfonate, sodium methacryloyloxyethyl sulfonate, sulfobutyl diacrylate or carboxyl diacrylate, preferably sodium methacryloyloxyethyl sulfonate; Preferably, the secondary crosslinking agent comprises any one or a combination of at least two of divinylbenzene, N-methylenebisacrylamide or ethylene glycol dimethacrylate, preferably N, N-methylenebisacrylamide.
  5. 5. The in situ polymerization modified polyethersulfone ultrafiltration membrane of claim 4, wherein the mass ratio of the primary crosslinking agent to the secondary crosslinking agent is (4-6): 1.
  6. 6. The in situ polymerization modified polyethersulfone ultrafiltration membrane of any one of claims 1 to 5, wherein said pore-forming agent comprises any one or a combination of at least two of PVP K17, PVP K30, PVP K90 or LiCl, preferably PVP K90; preferably, the non-solvent comprises any one or a combination of at least two of glycerol, DEG, TEG, PEG or water, preferably PEG.
  7. 7. A method of preparing an in situ polymerization modified polyethersulfone ultrafiltration membrane according to any one of claims 1 to 6, comprising the steps of: mixing a membrane framework material with an organic solvent, and then mixing the mixture with a hydrophilic monomer, an initiator and a cross-linking agent for reaction to obtain a modified PES solution; Mixing a pore-forming agent, a non-solvent and a modified PES solution, and standing to obtain PES casting solution; Coating PES (polyether sulfone) casting film liquid on a substrate, and standing at constant temperature and constant humidity to obtain pre-phasing coating liquid; And sequentially standing the pre-phasing coating liquid in a coagulating bath and water to obtain the in-situ polymerization modified polyethersulfone ultrafiltration membrane.
  8. 8. The method according to claim 7, wherein the mixing reaction is performed under a nitrogen atmosphere.
  9. 9. The method according to claim 7 or 8, wherein the temperature of the mixing reaction is 50-70 ℃ and the time is 2-4 h.
  10. 10. Use of an in situ polymerization modified polyethersulfone ultrafiltration membrane according to any one of claims 1-6 in the preparation of a separation membrane.

Description

In-situ polymerization modified polyethersulfone ultrafiltration membrane and preparation method and application thereof Technical Field The invention belongs to the technical field of polymer separation membrane materials, and particularly relates to an in-situ polymerization modified polyethersulfone ultrafiltration membrane, and a preparation method and application thereof. Background Polyether sulfone (PES) has excellent chemical stability, thermal stability, mechanical strength and film forming property, is one of the most common materials in the field of ultrafiltration films, and is widely applied to industries such as biological medicine, food fermentation, industrial water treatment and the like. The conventional PES film has strong surface hydrophobicity, is easy to generate protein nonspecific adsorption when a protein-containing system is processed, causes film hole blockage, quick flux attenuation, frequent cleaning and shortened service life, and severely limits the application of the PES film in the fields of biological medicine, protein separation and the like. At present, the main method for improving the anti-fouling performance of the PES film comprises the steps of blending and adding hydrophilic polymers such as PVP, wherein PVP is easy to dissolve and run off, the hydrophilicity cannot be durable, the surface is coated with a hydrophilic layer, the binding force is weak, the scouring resistance and the chemical cleaning resistance are poor, the surface graft polymerization is complex, the equipment requirement is high, and the large-scale production is difficult. CN107081079A discloses a preparation method and application of an efficient hydrophilization modified anti-pollution polyether sulfone membrane, the preparation method comprises two parts of physical blending hydrophilization modification and chemical grafting hydrophilization modification of a pure polyether sulfone membrane, synthesizing a hydrophilic block polymer through a reversible addition fragmentation chain transfer polymerization (RAFT) method initiated by a surface, then physically blending the hydrophilic block polymer with polyether sulfone to prepare a PES/PAA-F127-PAA membrane, synthesizing a strong hydrophilic substance NH2-PDMAPS through an electron transfer activation regeneration catalyst-atom transfer free radical polymerization method (ARGET ATRP), and preparing the efficient hydrophilization modified anti-pollution polyether sulfone membrane by a chemical grafting method on the basis of blending modification. The invention designs molecules by using two polymerization methods of efficient green RAFT and ARGET ATRP, has novel structure, mild reaction condition and more obvious effect of the hydrophilization modification method, and has wide application prospect in the field of oil-water separation. But the grafting process employed causes production difficulties. CN101259387a discloses a controllable flux protein pollution resistant polyether sulfone ultrafiltration membrane and a preparation method thereof. The preparation method comprises the steps of taking polyethersulfone and Pluronic F127 as raw materials, adding Pluronic F127 into a polyethersulfone solution of N, N-dimethylformamide, stirring and fully mixing to prepare casting solution, standing for defoaming, cooling, pouring the casting solution on a glass plate for scraping a film, standing, solidifying in a water bath for film formation, and soaking in water. The preparation method is simple and convenient, the anti-pollution performance is greatly improved, and the invention has good interception characteristic for protein. The maximum flux of the polyether sulfone ultrafiltration membrane with controllable flux and protein pollution resistance prepared by the invention can reach more than 200L/(m 2 h). CN108479432A discloses a preparation method of a hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane, which comprises the steps of dissolving phenolphthalein polyether sulfone PES-C in an organic solvent to obtain a spinning solution, spraying the spinning solution, drying to obtain a PES-C nanofiber membrane, spraying a crosslinked polyvinylpyrrolidone PVPP solution on the surface of the PES-C nanofiber membrane, and carrying out hot pressing treatment. Compared with the current widely-used electrostatic spinning technology, the method for preparing the composite nanofiber ultrafiltration membrane by using the solution jet spinning method has the advantages of high production efficiency, low energy consumption, wide application object range, suitability for industrial production and the like, and the prepared phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane has higher hydrophilicity, thermal stability, acid and alkali corrosion resistance, higher pollution resistance, durability of hydrophilicity, contribution to realizing industrial production, and wide application prospect