抗污染、高通量多孔膜的制备及膜过程强化
研究
Preparation of Antifouling, High Flux Porous Membranes and Membrane Process
Intensification
一级学科：化学工程与技术
学科专业：化学工艺
研究生：彭金明红绿灯的图片
芭学园指导教师：姜忠义教授
天津大学化工学院
二零一二年十二月北京温泉度假村
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摘要
膜污染和渗透通量低是制约聚合物多孔膜广泛应用的瓶颈，制备抗污染、高通量膜是膜分离领域的关键科学问题之一。本论文以解决膜分离过程中的膜污染和提高膜通量为主要目标，合理设计成膜材料（两亲性刷状聚合物）、优化成膜工艺（调控凝胶浴温度、构建界面共价键）和创新制膜方法（受限空间聚合），实现抗污染、高通量多孔膜的制备及过程强化。
复印机的使用方法从非溶剂诱导相转化成膜机理和分子设计出发，制备抗污染、高通量非对称膜。研究了不同凝胶浴温度下亲水性聚乙二醇（PEG）和两亲性改性剂Pluronic F127的表面偏析行为，并系统考察了凝胶浴温度对聚醚砜（PES）非对称膜断面结构、皮层孔径范围、表面亲水性、分离性能和抗污染性能的影响。设计制备了以疏水聚醚砜（PES）为主链、聚甲基丙烯酸聚乙二醇酯（polyPEGMA）为支链的刷状聚合物PES-g-PEGMA，并以其为成膜主体材料，考察了PEGMA接枝率、PEG链段长度等因素对PES-g-PEGMA非对称膜的成膜性能、表面化学组成、表面亲水性和蛋白吸附的影响。PES-g-PEGMA膜在保持PES优异的成膜性能和良好物化稳定性的同时，具有良好的亲水性和低蛋白吸附，分离性能和抗蛋白质污染性能同时提升。
基于界面聚合反应机理，采用1-乙基-(3-二甲基氨基丙基)碳二亚胺（EDC）/N-羟基琥珀酰亚胺（NHS）活化水解聚丙烯腈（HPAN）基膜表面的羧基，通过活性层与基膜间的界面共价酰胺键干预哌嗪（PIP）与均苯三甲酰氯（TMC）的界面聚合反应，优化聚酰胺活性层结构和电荷特性，实现了高通量聚酰胺（PA）复合纳滤膜的制备。通过共混亲水单体聚乙烯醇（PV A）赋予活性层亲水性，赋
予聚酰胺复合膜优异的抗蛋白污染性能。
创新了受限空间聚合的自支撑膜制备方法，研究成膜过程热力学和动力学因素对膜结构调控、表面性质的影响规律，系统考察了致孔剂对自支撑膜孔径、孔隙率的影响，实现了自支撑膜厚度的调控，制备了亲水性抗污染、高通量聚甲基丙烯酸羟基乙酯（polyHEMA）自支撑膜。通过成膜单体HEMA与含氟单体甲基丙烯酸十二氟庚酯（DFHM）共混，构建了含亲水区和低表面能区的两亲性自支撑膜表面，实现了两亲性抗污染、高通量自支撑膜的制备。通过成膜单体与弱酸性单体甲基丙烯酸（MAA）和温敏性单体N-异丙基丙烯酰胺（NIPAAm）共混，实现抗污染、刺激响应自支撑膜的制备。
关键词：抗污染高通量非对称膜复合膜自支撑膜受限空间聚合
ABSTRACT
Membrane fouling and low permeation flux constitute the bottleneck limiting the wide application of polymeric membranes. Preparation of antifouling and high flux membranes has become one of the most important rearch issues in membrane paration area. The target of the thesis is to prepare antifouling asymmetric, composite and free-standing membranes. We design the membrane matrix material (amphiphilic brush-like polymer), optimize the membrane formation conditions (adjusting coagulation temperature, generating covalent bonds between active layer and support), invent a new
fabrication approach of free-standing membrane (space-confined polymerization) and achieve the preparation and process intensification of the antifouling, high flux membranes.为自己读书
Starting from the mechanism of nonsolvent induced pha inversion and molecular design protocol, we investigate the surface gregation behavior of hydrophilic pore-forming agent polyethylene glycol (PEG) and amphiphilic Pluronic F127 under various coagulation bath temperatures. The influence of coagulation bath temperature on the cross ctional morphology, pore size, surface hydrophilicity, paration and antifouling properties of the poly(ethylene sulfone) (PES) asymmetric membranes is systematically studied. We design and synthesize the brush-like amphiphilic copolymer PES-g-poly(ethylene oxide) dimethacrylate (PEGMA) with the PES as main chain and the polyPEGMA as side chains. The asymmetric PES-g-PEGMA membranes are prepared using PES-g-PEGMA as the membrane matrix material. The impacts of graft yield of PEGMA and the length of PEG gment on the membrane-formation properties, surface composition, surface hydrophilicity and protein adsorption are investigated. The PES-g-PEGMA membranes maintain the excellent membrane-formation property of the PES membranes. Compared to the PES control membrane, the PES-g-PEGMA membranes are endowed with surface hydrophilicity and lower protein adsorption. Beside, the paration properties and antifouling properties of the PES-g-PEGMA membrane were enhanced.
Bad on the mechanism of interfacial polymerization, the carboxyl groups on the hydrolyzed polyacrylonitrile (HPAN) membrane surface are activated by N-(3-Dimethylaminopropyl)-N’-ethylcarbodiimide hydrochloride (EDC) / N-Hydroxysuccinimide (NHS), the interfacial polymerization between piperazidine (PIP) and trimesoyl chloride (TMC) is mediated by the generating amide bonds
between the active layer and the support. The morphology and zeta potential of active layer is optimized. The flux of the PA-EDC-HPAN composite membrane is of a high level. The PA-EDC-HPAN composite membrane is endowed with anti-protein-fouling properties via blending hydrophilic polyvinyl alcohol (PV A) with PIP.
We invent a space-confined approach to the poly(2-hydroxyethyl methacrylate) (polyHEMA) free-standing membranes. The influence of membrane formation thermodynamics and dynamics on membrane morphologies and surface properties is studied. The impacts of pore-forming agent on the membrane pore size and porosity is investigated. The polyHEMA free-standing membrane thickness can be easily adjusted. The polyHEMA membranes possd the superhydrophilicity, high flux and strong antifouling properties. Through blending the fluorine-containing monomer dodecafluoroheptyl methacrylate (DFHM) with the hydrophilic monomer HEMA, the membrane with amphiphilic surface bearing hydrophilic domains and low surface energy domains is constructed. Th
小学一年级班主任工作计划e membranes show high flux and strong antifouling properties. Through blending with the weak acid monomer methylacrylic acid (MAA) or the temperature-nsitive monomer N-isopropylacrylamide (NIPAAm), the free-standing membranes with antifouling, pH/temperature stimuli responsive properties are prepared.
Keywords:Antifouling, high flux, asymmetric membrane, composite membrane, free-standing membrane, space-confined polymerization
