抗污染、高通量多孔膜的制备及膜过程强化研究

抗污染、高通量多孔膜的制备及膜过程强化研究PreparationofAntifouling,HighFluxPorousMembranesandMembraneProcessIntensification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独创性声明本人声明所呈交的学位论文是本人在导师指导下进行的研究工作和取得的研究成果，除了文中特别加以标注和致谢之处外，论文中不包含其他人已发表或撰写过的研究成果，也不包含为获得天津大学或其他教育机构的学位或证书而使用过的材料。与我一同工作的同志对本研究所做的任何贡献均已在论文中作了明确的说明并表示了谢意。学位论文作者签名：签字日期：年月日学位论文版权使用授权书本学位论文作者完全了解天津大学有关保留、使用学位论文的规定。特授权天津大学可将学位论文的全部或部分内容编入有关数据库进行检索，并采用影印、缩印或扫描等复制手段保存、汇编以供查阅和借阅。同意学校向国家有关部门或机构送交论文的复印件和磁盘。（保密的学位论文在解密后适用本授权说明）学位论文作者签名：导师签名：签字日期：年月日签字日期：年月日1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。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2ABSTRACTMembranefoulingandlowpermeationfluxconstitutethebottlenecklimitingthewideapplicationofpolymericmembranes.Preparationofantifoulingandhighfluxmembraneshasbecomeoneofthemostimportantresearchissuesinmembraneseparationarea.Thetargetofthethesisistoprepareantifoulingasymmetric,compositeandfree-standingmembranes.Wedesignthemembranematrixmaterial(amphiphilicbrush-likepolymer),optimizethemembraneformationconditions(adjustingcoagulationtemperature,generatingcovalentbondsbetweenactivelayerandsupport),inventanewfabricationapproachoffree-standingmembrane(space-confinedpolymerization)andachievethepreparationandprocessintensificationoftheantifouling,highfluxmembranes.Startingfromthemechanismofnonsolventinducedphaseinversionandmoleculardesignprotocol,weinvestigatethesurfacesegregationbehaviorofhydrophilicpore-formingagentpolyethyleneglycol(PEG)andamphiphilicPluronicF127undervariouscoagulationbathtemperatures.Theinfluenceofcoagulationbathtemperatureonthecrosssectionalmorphology,poresize,surfacehydrophilicity,separationandantifoulingpropertiesofthepoly(ethylenesulfone)(PES)asymmetricmembranesissystematicallystudied.Wedesignandsynthesizethebrush-likeamphiphiliccopolymerPES-g-poly(ethyleneoxide)dimethacrylate(PEGMA)withthePESasmainchainandthepolyPEGMAassidechains.TheasymmetricPES-g-PEGMAmembranesarepreparedusingPES-g-PEGMAasthemembranematrixmaterial.TheimpactsofgraftyieldofPEGMAandthelengthofPEGsegmentonthemembrane-formationproperties,surfacecomposition,surfacehydrophilicityandproteinadsorptionareinvestigated.ThePES-g-PEGMAmembranesmaintaintheexcellentmembrane-formationpropertyofthePESmembranes.ComparedtothePEScontrolmembrane,thePES-g-PEGMAmembranesareendowedwithsurfacehydrophilicityandlowerproteinadsorption.Beside,theseparationpropertiesandantifoulingpropertiesofthePES-g-PEGMAmembranewereenhanced.Basedonthemechanismofinterfacialpolymerization,thecarboxylgroupsonthehydrolyzedpolyacrylonitrile(HPAN)membranesurfaceareactivatedbyN-(3-Dimethylaminopropyl)-N’-ethylcarbodiimidehydrochloride(EDC)/N-Hydroxysuccinimide(NHS),theinterfacialpolymerizationbetweenpiperazidine(PIP)andtrimesoylchloride(TMC)ismediatedbythegeneratingamidebonds3betweentheactivelayerandthesupport.Themorphologyandzetapotentialofactivelayerisoptimized.ThefluxofthePA-EDC-HPANcompositemembraneisofahighlevel.ThePA-EDC-HPANcompositemembraneisendowedwithanti-protein-foulingpropertiesviablendinghydrophilicpolyvinylalcohol(PVA)withPIP.Weinventaspace-confinedapproachtothepoly(2-hydroxyethylmethacrylate)(polyHEMA)free-standingmembranes.Theinfluenceofmembraneformationthermodynamicsanddynamicsonmembranemorphologiesandsurfacepropertiesisstudied.Theimpactsofpore-formingagentonthemembraneporesizeandporosityisinvestigated.ThepolyHEMAfree-standingmembranethicknesscanbeeasilyadjusted.ThepolyHEMAmembranespossessedthesuperhydrophilicity,highfluxandstrongantifoulingproperties.Throughblendingthefluorine-containingmonomerdodecafluoroheptylmethacrylate(DFHM)withthehydrophilicmonomerHEMA,themembranewithamphiphilicsurfacebearinghydrophilicdomainsandlowsurfaceenergydomainsisconstructed.Themembranesshowhighfluxandstrongantifoulingproperties.Throughblendingwiththeweakacidmonomermethylacrylicacid(MAA)orthetemperature-sensitivemonomerN-isopropylacrylamide(NIPAAm),thefree-standingmembraneswithantifouling,pH/temperaturestimuliresponsivepropertiesareprepared.Keywords:Antifouling,highflux,asymmetricmembrane,compositemembrane,free-standingmembrane,space-confinedpolymerization1目录第一章文献综述..................