Zhang Bo, Wang Panpan, Yu Jianxin, Jiang Haicheng, Gao Po, Ma Jun
School of Chemistry and Material Sciences, Heilongjiang University, Harbin, 150080, China E-mail:
State Key Laboratory of Urban Water Resource and Environment, School of Environments, Harbin Institute of Technology, Harbin 150090, China.
Water Sci Technol. 2019 Jun;79(11):2068-2078. doi: 10.2166/wst.2019.203.
A simple and efficient route was used to prepare an amphiphilic copolymer (poly(propylene glycol)-co-poly(ethylene glycol)-co-poly(propylene glycol)) (PPG-co-PEG-co-PPG) by one-pot polymerization reaction. This copolymer was used as the hydrophilic additive in preparation of poly(vinylidene fluoride) (PVDF) ultrafiltration membranes via immersion-precipitation process. Surface characteristics of the membranes were confirmed by contact angle measurements, zeta potential, attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy. During filtration experiments, the modified membranes showed better permeation and antifouling performances compared to PVDF membranes with bovine serum albumin, sodium alginate and yeast. After hydraulic stirring cleaning with deionized water, water flux recovery and rejection ratio of the modified membranes were higher than those of pristine PVDF membrane, and the flux recovery ratio was maximized at 94.29%. It was suggested that PPG-co-PEG-co-PPG copolymer was anchored in the PVDF membrane through the two hydrophobic ends of PPG blocks, while the hydrophilic intermediate of the PEG block segregated onto the membrane or pore surface during the membrane preparation process. The synthesized method of amphiphilic PPG-co-PEG-co-PPG copolymer paved a novel way to solve the problems of less compatibility between the copolymer and membrane matrix and instability with water molecules in the ultrafiltration process.
通过一锅法聚合反应,采用一种简单有效的路线制备了两亲共聚物(聚丙二醇 - 共聚乙二醇 - 共聚丙二醇)(PPG - co - PEG - co - PPG)。该共聚物用作亲水性添加剂,通过浸没沉淀法制备聚偏氟乙烯(PVDF)超滤膜。通过接触角测量、zeta电位、衰减全反射傅里叶变换红外光谱、X射线光电子能谱、扫描电子显微镜和原子力显微镜对膜的表面特性进行了确认。在过滤实验中,与含有牛血清白蛋白、海藻酸钠和酵母的PVDF膜相比,改性膜表现出更好的渗透性能和抗污染性能。用去离子水进行水力搅拌清洗后,改性膜的水通量回收率和截留率高于原始PVDF膜,通量回收率最高可达94.29%。研究表明,PPG - co - PEG - co - PPG共聚物通过PPG嵌段的两个疏水端锚定在PVDF膜中,而PEG嵌段的亲水性中间段在膜制备过程中分离到膜表面或孔表面。两亲性PPG - co - PEG - co - PPG共聚物的合成方法为解决共聚物与膜基质之间相容性差以及超滤过程中与水分子不稳定的问题开辟了一条新途径。