【作者】 彭金明；

【导师】 姜忠义；

【作者基本信息】 天津大学 ， 化学工艺， 2012， 博士

【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。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PluronicF127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（PVA）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。更多还原

【Abstract】 Membrane fouling and low permeation flux constitute the bottleneck limiting thewide application of polymeric membranes. Preparation of antifouling and high fluxmembranes has become one of the most important research issues in membraneseparation 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 layerand support), invent a new fabrication approach of free-standing membrane(space-confined polymerization) and achieve the preparation and processintensification of the antifouling, high flux membranes.Starting from the mechanism of nonsolvent induced phase inversion and moleculardesign protocol, we investigate the surface segregation behavior of hydrophilicpore-forming agent polyethylene glycol (PEG) and amphiphilic Pluronic F127undervarious coagulation bath temperatures. The influence of coagulation bath temperatureon the cross sectional morphology, pore size, surface hydrophilicity, separation andantifouling properties of the poly(ethylene sulfone)(PES) asymmetric membranes issystematically studied. We design and synthesize the brush-like amphiphiliccopolymer PES-g-poly(ethylene oxide) dimethacrylate (PEGMA) with the PES asmain chain and the polyPEGMA as side chains. The asymmetric PES-g-PEGMAmembranes are prepared using PES-g-PEGMA as the membrane matrix material. Theimpacts of graft yield of PEGMA and the length of PEG segment on themembrane-formation properties, surface composition, surface hydrophilicity andprotein adsorption are investigated. The PES-g-PEGMA membranes maintain theexcellent membrane-formation property of the PES membranes. Compared to the PEScontrol membrane, the PES-g-PEGMA membranes are endowed with surfacehydrophilicity and lower protein adsorption. Beside, the separation properties andantifouling properties of the PES-g-PEGMA membrane were enhanced.Based on the mechanism of interfacial polymerization, the carboxyl groups onthe hydrolyzed polyacrylonitrile (HPAN) membrane surface are activated byN-(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 activelayer is optimized. The flux of the PA-EDC-HPAN composite membrane is of a highlevel. The PA-EDC-HPAN composite membrane is endowed with anti-protein-foulingproperties via blending hydrophilic polyvinyl alcohol (PVA) with PIP.We invent a space-confined approach to the poly(2-hydroxyethyl methacrylate)(polyHEMA) free-standing membranes. The influence of membrane formationthermodynamics and dynamics on membrane morphologies and surface properties isstudied. The impacts of pore-forming agent on the membrane pore size and porosity isinvestigated. The polyHEMA free-standing membrane thickness can be easilyadjusted. The polyHEMA membranes possessed the superhydrophilicity, high fluxand strong antifouling properties. Through blending the fluorine-containing monomerdodecafluoroheptyl methacrylate (DFHM) with the hydrophilic monomer HEMA, themembrane with amphiphilic surface bearing hydrophilic domains and low surfaceenergy domains is constructed. The membranes show high flux and strong antifoulingproperties. Through blending with the weak acid monomer methylacrylic acid (MAA)or the temperature-sensitive monomer N-isopropylacrylamide (NIPAAm), thefree-standing membranes with antifouling, pH/temperature stimuli responsiveproperties are prepared.更多还原