Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (12): 1-10.doi: 10.13475/j.fzxb.20250401001

• Academic Salon Column for New Insight of Textile Science and Technology: Fiber-based Functional Filtration Materials •     Next Articles

Preparation of porous sulfonated hydrogenated styrene-butadiene block copolymer fiber membrane and its adsorption performance for lysozyme

LIU Ke1,2, WANG Yuxi1,2, CHENG Pan1,2, ZHU Liping3, XIA Ming1,2, MEI Tao4, XIANG Yang5, ZHOU Feng1,2,5, GAO Fei5, WANG Dong1,2()   

  1. 1. Key Laboratory of Textile Fibers and Products, Ministry of Education, Wuhan Textile University, Wuhan, Hubei 430200, China
    2. Key Laboratory of Nonwoven Filtration and Separation Materials for Textile Industry, Wuhan Textile University, Wuhan, Hubei 430200, China
    3. State Key Laboratory of Advanced Fiber Materials, Donghua University, Shanghai 201620, China
    4. Wuhan We-Change Technology Co., Ltd., Wuhan, Hubei 430106, China
    5. Wuhan Branch of Anheisi-Busch Enterprise Management (Shanghai) Co., Ltd., Wuhan, Hubei 430051, China
  • Received:2025-04-07 Revised:2025-09-10 Online:2025-12-15 Published:2026-02-06
  • Contact: WANG Dong E-mail:wangdon08@126.com

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Abstract:

Objective To address the issues of insufficient mass transfer kinetics and adsorption capacity of functional materials in the development of bioseparation media, this study employed electrospinning technology combined with a chemical modification strategy to construct porous sulfonated hydrogenated styrene-butadiene block copolymer fiber membrane materials with a hierarchical meso-microporous structure and cation exchange properties.

Method Pristine Hydrogenated Styrene-Butadiene Block Copolymer (SEBS) fiber membrane materials were prepared using electrospinning technology. On this basis, sulfonated porous SEBS cation exchange fiber mem-branes (designated as S2-PFM-1) were successfully synthesized via two sequential chemical modifications. The first was the employment of Friedel-Crafts alkylation reaction to directionally modify chloroethyl and carbonyl polar groups on the benzene rings of SEBS, and the reaction kinetics was regulated to achieve controllable construction of the membrane’s pore structure. The second modification sulfonation treatment to introduce high-density sulfonic acid groups on the fiber surface, endowing the material with surface negative charge characteristics and enhanced hydrophilicity.

Results The porous SEBS block copolymer cation exchange fiber membrane was prepared successfully, and its performance as a protein adsorptive separation material was systematically studied. By scanning electron microscopy analysis, it was found that sulfonation had no significant effect on the morphology of SEBS fiber membrane, indicating that sulfonation mainly occurred at the molecular level and did not significantly change the macroscopic structure of the fiber. FT-IR analysis confirmed that sulfonic acid base group was successfully grafted to the surface of the fiber membrane. The hydrophilicity of the sulfonated porous SEBS fiber membrane was significantly superior to that of the sulfonated SEBS fiber membrane, attributing to the enhanced surface polarity of the material by the introduction of sulfonic acid groups. The cell activity of the porous SEBS fiber membrane remained above 80% after sulfonation using cck-8 method, indicating that sulfonic acid groups introduced into the SEBS molecular chain had good biocompatibility and no toxic byproducts were introduced. Due to the negative charge of sulfonic acid group, the fiber membrane exhibited strong electrostatic adsorption to the positively charged lysozyme. The experimental results showed that the adsorption equilibrium of S2-PFM-1 was reached within 120 min under the condition of lysozyme concentration of 2 g/L, and the maximum adsorption capacity was 226 mg/g, which was significantly higher than that of the sulfonated flat membrane.

Conclusion Based on electrospinning and multistage chemical modification strategy, sulfonic acid-based functional porous SEBS fiber membrane material was successfully constructed. Friedel-Crafts alkylation reaction accurately regulated the meso-microporous structure of the fiber network. Combined with surface sulfonation modification, high-density sulfonic acid group was introduced into the molecular chain, endowing the material with strong cation exchange ability and significantly enhanced hydrophilicity. The experimental results showed that the sulfonation modification did not change the macroscopic morphology of the fibers, but effectively regulated the surface charge distribution. The separation mechanism led by electrostatic adsorption showed excellent selectivity to lysozyme. At the optimal pH of 5, the material exhibited rapid adsorption kinetics, and the adsorption capacity was significantly better than that of traditional sulfonated membrane systems, which was attributed to the synergistic effect of multi-stage pore path reduction and high surface density of active sites. In addition, the sulfonation process did not affect the biocompatibility of the material, and the cell activity viability retention rate was more than 80%, indicating the sulfonated porous SEBS fiber membrane having excellent hydrophilicity, lysozyme adsorption performance, and cycling stability, which make it suitable for efficient protein separation and endowing it with potential application prospects in the biomedical field. This study also reveals the structure-activity relationship and action mechanism of the membrane as a protein adsorption material, providing valuable reference for the design and development of high-performance bioseparation media.

Key words: functional polymer material, block copolymer, porous fiber, electrospinning, sulfonic acid group, adsorption-elution, bioseparation, lysozyme

CLC Number: 

  • TS174

Fig.1

Preparation process of porous sulfonated SEBS fiber membrane"

Fig.2

Schematic diagram of chemical reaction process of porous sulfonated SEBS fiber membrane. (a) Hydrolyzation of FDA to form a methylene carbocation; (b) Formation of a methylene bridge bond by aromatic ring with carbocation via Friedel-Crafts alkylation; (c) Chloroethyl cation reacts with benzene rings of SFBS to introduce chloroethyl group;(d) Introduction of sulfonic acid group via an electrophilic substitution reaction"

Fig.3

Morphology images of SEBS fiber membranes with pre-crosslinking at different time"

Fig.4

Morphology images of FM-1, FM-3,and FM-5 after hypercrosslinking for 1 h"

Fig.5

Morphology images of FM-1 at different hypercrosslinking times"

Fig.6

Surface morphology of PFM-series fibrous membranes after sulfonation"

Tab.1

Specific surface area and porosity of various specimens"

试样编号 比表面积/(m2·g-1) 孔隙率/%
FM 1.987 2 49.27 ± 0.85
FM-1 3.542 3 51.23 ± 1.54
FM-3 3.997 8 51.98 ± 0.98
FM-5 4.092 5 50.25 ± 1.65
PFM-1 5.171 2 57.32 ± 2.72
PFM-3 8.225 2 60.74 ± 1.65
PFM-5 19.649 8 78.76 ± 1.27
PFM-9 18.663 0 73.64 ± 1.89
S2-PFM-1 6.171 0 65.18 ± 2.16

Fig.7

FT-IR spectra of fiber membranes before and after sulfonation"

Fig.8

Water contact angle of fiber membranes before and after sulfonation"

Fig.9

Effects of sulfonation modification on mechanical properties of FM and PFM-1.(a)Stress-strain curves of FM and S2-FM; (b) Stress-strain curves of PFM-1 and S2-PFM-1"

Fig.10

Cell viability rate of samples with different extract concentrations"

Fig.11

Factors influencing adsorption capacity of SEBS-based fiber membrane materials for lysozyme and their static cyclic adsorption-desorption performance. (a) Variation of adsorption capacity of S2-PFM-1 with lysozyme concentration; (b) Adsorption capacity of PFM-1 fiber membranes at different sulfonation time; (c) Adsorption capacity of fiber membranes with different crosslinking time after 2-hour sulfonation; (d) Static adsorption-desorption diagram of S2-PFM-1 over 5 cycles"

Fig.12

Comparison of surface morphologies of M,FM, S2-M, S2-PM-1, S2-FM, and S2-PFM-1"

Fig.13

Comparison of lysozyme adsorption performance between flat membrane and fiber membrane materials. (a) Static adsorption capacity of sulfonated flat film/fiber film; (b) Static adsorption capacity of sulfonated flat film/fiber film over time; (c) Eluted agarose gel electrophoresis electropherogram"

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