Zhu Li-Jing, Zhu Li-Ping, Zhang Pei-Bin, Zhu Bao-Ku, Xu You-Yi
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, Zhejiang Province 310027, PR China; Polymer and Composite Division, Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, PR China.
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, Zhejiang Province 310027, PR China.
J Colloid Interface Sci. 2016 Apr 15;468:110-119. doi: 10.1016/j.jcis.2016.01.043. Epub 2016 Jan 21.
We demonstrate the preparation and properties of poly(vinylidene fluoride) (PVDF) filtration membranes modified via surface zwitterionicalization mediated by reactive core-shell silica nanoparticles (SiO2 NPs). The organic/inorganic hybrid SiO2 NPs grafted with poly(methyl meth acrylate)-block-poly(2-dimethylaminoethyl methacrylate) copolymer (PMMA-b-PDMAEMA) shell were prepared by surface-initiated reversible addition fragmentation chain transfer (SI-RAFT) polymerization and then used as a membrane-making additive of PVDF membranes. The PDMAEMA exposed on membrane surface and pore walls were quaternized into zwitterionic poly(sulfobetaine methacrylate) (PSBMA) using 1,3-propane sultone (1,3-PS) as the quaternization agent. The membrane surface chemistry and morphology were analyzed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), respectively. The hydrophilicity, permeability and antifouling ability of the investigated membranes were evaluated in detail. It was found that the PSBMA chains brought highly-hydrophilic and strong fouling resistant characteristics to PVDF membranes due to the powerful hydration of zwitterionic surface. The SiO2 cores and PMMA chains in the hybrid NPs play a role of anchors for the linking of PSBMA chains to membrane surface. Compared to the traditional strategies for membrane hydrophilic modification, the developed method in this work combined the advantages of both blending and surface reaction.
我们展示了通过由反应性核壳二氧化硅纳米颗粒（SiO₂ NPs）介导的表面两性离子化改性的聚偏氟乙烯（PVDF）过滤膜的制备及其性能。通过表面引发的可逆加成-断裂链转移（SI-RAFT）聚合制备了接枝有聚（甲基丙烯酸甲酯）-嵌段-聚（甲基丙烯酸2-二甲基氨基乙酯）共聚物（PMMA-b-PDMAEMA）壳的有机/无机杂化SiO₂ NPs，然后将其用作PVDF膜的制膜添加剂。使用1,3-丙烷磺内酯（1,3-PS）作为季铵化剂，将暴露在膜表面和孔壁上的PDMAEMA季铵化为两性离子聚（甲基丙烯酸磺基甜菜碱）（PSBMA）。分别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）和扫描电子显微镜（SEM）分析膜的表面化学和形态。详细评估了所研究膜的亲水性、渗透性和抗污染能力。结果发现，由于两性离子表面的强水合作用，PSBMA链赋予PVDF膜高亲水性和强抗污染特性。杂化纳米颗粒中的SiO₂核和PMMA链起到将PSBMA链连接到膜表面的锚定作用。与传统的膜亲水性改性策略相比，本工作中开发的方法结合了共混和表面反应的优点。
