高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (2): 358-364.doi: 10.7503/cjcu20190374

• 高分子化学 • 上一篇    下一篇

超亲水聚偏氟乙烯中空纤维膜的制备及性能

程继锋1,蒋团辉2,詹晓梅1,祁娅婷1,杨园园2,康逊2,秦舒浩1,2,*()   

  1. 1. 贵州大学材料与冶金学院, 贵阳 550025
    2. 国家复合改性聚合物材料工程技术研究中心, 贵阳 550014
  • 收稿日期:2019-07-03 出版日期:2020-02-10 发布日期:2019-12-23
  • 通讯作者: 秦舒浩 E-mail:qinshgz@163.com
  • 基金资助:
    贵州省高层次人才项目([2015]4014);贵州省高层次人才项目([2019]5633);贵州省科技计划项目([2019]1422);国家自然科学基金资助(51763003);国家自然科学基金资助(21604016)

Preparation and Properties of Superhydrophilic Polyvinylidene Fluoride Hollow Fiber Membrane

CHENG Jifeng1,JIANG Tuanhui2,ZHAN Xiaomei1,QI Yating1,YANG Yuanyuan2,KANG Xun2,QIN Shuhao1,2,*()   

  1. 1. College of Materials Science and Metallurgy of Guizhou University, Guiyang 550025,China
    2. National Engineering Research Center for Compounding and Modification of Polymer Materials, Guiyang 550014, China
  • Received:2019-07-03 Online:2020-02-10 Published:2019-12-23
  • Contact: Shuhao QIN E-mail:qinshgz@163.com
  • Supported by:
    ? Supported by the Guizhou High-level Talent Project([2015]4014);Supported by the Guizhou High-level Talent Project([2019]5633);the Science and Technology Planning Project of Guizhou Province, China(Nos.[2019]1422)([2019]1422);the National Natural Science Foundation of China(51763003);the National Natural Science Foundation of China(21604016)

摘要:

采用超声辅助接枝聚合技术, 将甲基丙烯酸缩水甘油酯(GMA)接枝到聚偏氟乙烯(PVDF)膜表面, 制备PVDF-g-GMA膜; 再利用氨基诱导环氧基团发生开环反应, 将苏氨酸(Thr)接枝到PVDF-g-GMA膜表面, 制备了具有两性离子结构表面的PVDF-g-GMA-Thr膜. 通过衰减全反射傅里叶变换红外光谱(ATR-FTIR)、 X射线光电子能谱(XPS)、 接触角测试仪、 场发射扫描电子显微镜(FESEM)和牛血清白蛋白(BSA)过滤实验等系统研究了改性前后PVDF膜表面的化学组成、 润湿性能、 表面形貌和抗污染性能. 研究结果表明, 随着PVDF-g-GMA接枝Thr反应时间的增加, PVDF-g-GMA-Thr膜的亲水性能明显提高, 接触角从90°降为0°, 呈现出超亲水性能. 同时PVDF-g-GMA-Thr膜的水通量明显提高, 当Thr诱导开环反应时间为12 h时, PVDF-g-GMA-Thr膜的水通量高达686 L/(m 2·h), 与PVDF原膜相比, 水通量提高了204.5%. 在BSA的过滤测试中, 与PVDF膜相比, PVDF-g-GMA-Thr膜呈现出良好的截留性能和抗污染性能, BSA截留率从42%提高到84%,水通量恢复率从53%提高到87%, 不可逆污染率从47%降到12%, 表明通过接枝Thr构筑两性离子结构表面可以有效减小膜污染.

关键词: 聚偏氟乙烯膜, 超亲水, 苏氨酸, 抗污染性能

Abstract:

PVDF-g-GMA membrane was prepared by grafting glycidyl methacrylate(GMA) onto the surface of polyvinylidene fluoride(PVDF) membrane by ultrasonic assisted graft polymerization. A modified membrane with zwitterionic structure surface(PVDF-g-GMA-Thr) was prepared by grafting threonine(Thr) onto the surface of the PVDF membrane through the ring opening reaction of epoxy groups induced by amino group. The chemical composition, wettability, surface morphology and antifouling performance of PVDF membrane before and after modification were systematically studied by Attenuated total reflection Fourier infrared spectroscopy(ATR-FTIR), X-ray photoelectron spectroscopy(XPS), contact angle analyzer, scanning electron microscopy(SEM) and bovine serum albumin(BSA) filtration experiments. The results show that with the increase of PVDF-g-GMA grafted threonine reaction time, the hydrophilicity of the prepared modified membrane with zwitterionic structure surface is obviously improved, and the contact angle is reduced from 90° to 0°, showing the superhydrophilicity. At the same time, the water flux of the modified membrane is obviously improved, when the threonine induces the ring opening reaction for 12 h, the modified membrane has the highest water flux as high as 686 L/(m 2·h), it increased by 204.5%. In addition, in the filtration test of BSA, the modified membrane exhibited good anti-fouling performance and retention performance. BSA rejection ratio is increased from 42% to 84% for the modified membranes. Moreover, compared with PVDF original membrane, the water flux recovery rate of the modified membrane increased from 53% to 87% and the irreversible fouling decreased from 47% to 12%, which indicated that the membrane fouling can be effectively reduced by grafting threonine to construct zwitterionic structure surface on the PVDF membrane.

Key words: Polyvinylidene fluoride membrane, Superhydrophilic, Threonine, Anti-fouling performance

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