纺织学报 ›› 2025, Vol. 46 ›› Issue (12): 1-10.doi: 10.13475/j.fzxb.20250401001

• 纺织科技新见解学术沙龙专栏：纤维基功能过滤材料 •    下一篇

多孔磺化氢化苯乙烯-丁二烯嵌段共聚物纤维膜制备及其吸附性能

刘轲1,2, 王雨曦1,2, 程盼1,2, 朱丽萍3, 夏明1,2, 梅涛4, 向阳5, 周丰1,2,5, 高飞5, 王栋1,2()   

  1. 1.武汉纺织大学 纺织纤维及制品教育部重点实验室, 湖北 武汉 430200
    2.武汉纺织大学 纺织行业非织造过滤与分离材料重点实验室, 湖北 武汉 430200
    3.东华大学 先进纤维材料全国重点实验室, 上海 201620
    4.武汉维晨科技有限公司, 湖北 武汉 430106
    5.安海斯布希企业管理(上海)有限公司武汉分公司, 湖北 武汉 430051
  • 收稿日期:2025-04-07 修回日期:2025-09-10 出版日期:2025-12-15 发布日期:2026-02-06
  • 通讯作者: 王栋(1979—),男,教授,博士。主要研究方向为聚合物及功能纤维材料。E-mail:wangdon08@126.com。
  • 作者简介:刘轲(1984—),男,教授,博士。主要研究方向为纤维基过滤分离材料。
  • 基金资助:
    国家自然科学基金项目(U23A20585);国家自然科学基金项目(52273061);国家自然科学基金项目(52373098);湖北省自然科学基金杰出青年项目(2023AFA086);湖北省技术创新计划项目(2024BAB119);武汉市科技计划项目(2023030103010633)

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 Published:2025-12-15 Online:2026-02-06

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摘要： 为解决生物分离介质开发中功能化材料传质动力学与吸附容量不足的问题,采用静电纺丝技术结合化学改性策略,构建了具有介-微孔分级结构和阳离子交换特性的多孔磺化氢化苯乙烯-丁二烯嵌段共聚物纤维膜材料。基于Friedel-Crafts烷基化反应,在苯环上定向修饰氯乙基及羰基极性基团,通过调控反应动力学实现孔结构的可控构筑;进一步通过磺化处理在纤维表面引入高密度磺酸基团,赋予材料表面负电荷特性并增强其亲水性。结果表明:磺化反应在分子层面精准接枝功能基团,未显著改变纤维形貌,且材料生物相容性良好(细胞存活率大于80%);磺化多孔纤维膜的吸附效果优于磺化平板膜和磺化纤维膜,其静态吸附容量可达226 mg/g。上述结果证实,多级孔道结构协同表面电荷分布特性可显著提升传质动力学与吸附容量,为开发高效生物分离介质提供了新型功能化材料设计思路。

关键词: 功能高分子材料, 嵌段共聚物, 多孔纤维, 静电纺丝, 磺酸基, 吸附洗脱, 生物分离, 溶菌酶

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

中图分类号: 

  • TS174

图1

多孔磺化SEBS纤维膜制备流程"

图2

多孔磺化SEBS纤维膜的化学反应过程示意图"

图3

SEBS纤维膜预交联不同时间的形貌照片"

图4

FM-1、FM-3、FM-5超交联1 h的形貌照片"

图5

FM-1超交联不同时间的形貌照片"

图6

PFM系列纤维膜磺化后的表面形貌照片"

表1

不同试样的比表面积和孔隙率"

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

图7

磺化前后纤维膜的FT-IR谱图"

图8

磺化前后纤维膜水接触角"

图9

磺化改性对 FM与 PFM-1力学性能的影响"

图10

不同体积分数浸取液试样的细胞存活率"

图11

SEBS纤维膜对溶菌酶吸附容量影响因素及静态循环性能"

图12

M、FM、S2-M、S2-PM-1、S2-FM、S2-PFM-1表面形貌对比图"

图13

平板膜与纤维膜材料溶菌酶吸附性能对比"

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