亲水型聚砜膜的制备及应用

发布时间：2018-04-30 16:39

本文选题：聚砜膜材料 + 亲水性改性　；参考：《济南大学》2015年硕士论文

【摘要】：聚砜分离膜由于其综合性能优异,越来越受到广大群众的青睐。但是,由于聚砜膜材料亲水性差,使用过程中易造成膜污染,使得分离效率降低,膜使用寿命缩短。近年来,亲水性聚砜成为当今国内外研究的热点,是高效聚砜膜材料的核心所在,也是提高分离膜性能的重要手段之一。目前,对聚砜亲水性改性主要为整体磺化法,此方法在反应过程中不可操控,会附带发生一系列的副反应,如分子链的降解、交联,且磺化度不易控制。本文通过两条路线,以分子设计角度,制备了结构明确,亲水性可控的聚砜膜材料。以酚酞原料,经过系列反应,合成酚酞啉亲水单体,以FT-IR、1H NMR为手段表征了其结构。以酚酞啉(PP)、联苯二酚(BP)和4,4’-二氯二苯砜(DCDPS)为反应单体,控制它们的摩尔变化,制备不同亲水性的聚砜膜材料。通过1H NMR对聚合物进行结构表征。研究了聚合反应中反应物的配比对聚合反应时间及反应产物比浓黏度、热性能和溶解性的影响。研究发现,随着酚酞啉单体含量增加,聚合反应时间延长,聚合物比浓黏度增大,耐热性能略有降低,聚合物在N,N-二甲基-甲酰胺等溶剂中的溶解度降低。利用浸没沉淀相转化法,将不同组分的聚砜树脂制备成分离膜。研究了酚酞啉含量与分离膜的水接触角、吸水率、尺寸变化率、拉伸断裂强度、纯水通量、微观形貌的关系。研究发现,随着酚酞啉含量的增加,分离膜水接触角降低,纯水通量先升高后降低,在酚酞啉含量为75%时最大,达到260 L·m-2·h-1,吸水率升高,尺寸变化率略有增加。酚酞啉含量对分离膜的拉伸断裂强度和微观形貌几乎没有影响。以DCDPS为原料,P2O5和浓硫酸为磺化剂,制备了带有磺酸根基团的3,3’-二磺酸钠-4,4’-二氯二苯砜(SDCDPS)单体,并通过FT-IR、1H NMR表征确定了其结构。以SDCDPS、六氟双酚A(BPAF)和4,4’-二氯二苯砜(DCDPS)为反应单体,控制它们的摩尔变化,制备不同磺化度的六氟双酚A型聚砜膜材料。通过1H NMR对聚合物进行结构表征。研究了聚合反应中反应物的配比对反应产物比浓黏度、热性能和溶解性的影响。研究发现,随着聚合物磺化度的增加,聚合物比浓黏度增大,耐热性能略有降低,聚合物在氯仿、1,2-二氯乙烷等溶剂中的溶解度降低。利用浸没沉淀相转化法,将不同磺化度的六氟双酚A型聚砜树脂制备成分离膜。研究了磺化度与分离膜的水接触角、吸水率、尺寸变化率、拉伸断裂强度、纯水通量、微观形貌的关系。研究发现,随着磺化度的增加,分离膜水接触角降低,纯水通量先升高后降低,在磺化度为5时最大,达到170 L·m-2·h-1,吸水率升高,尺寸变化率略有增加。聚合物的磺化度对分离膜的拉伸断裂强度和微观形貌几乎没有影响。
[Abstract]:Polysulfone separation membrane is more and more popular because of its excellent comprehensive performance. However, because of the poor hydrophilicity of polysulfone membrane materials, membrane fouling is easy to be caused in the process of use, which results in the reduction of separation efficiency and the shortening of membrane service life. In recent years, hydrophilic polysulfone has become a hot topic at home and abroad, which is the core of high efficiency polysulfone membrane material and one of the important means to improve the performance of separation membrane. At present, the hydrophilic modification of polysulfone is mainly a whole sulfonation method, which can not be manipulated in the reaction process, and a series of side reactions will occur, such as the degradation of molecular chains, crosslinking, and the degree of sulfonation is not easy to control. In this paper, polysulfone membrane materials with clear structure and controllable hydrophilicity were prepared by two routes. Phenolphthalein hydrophilic monomer was synthesized from phenolphthalein by a series of reactions. Its structure was characterized by FT-IRN 1H NMR. Poly (sulfone) membranes with different hydrophilic properties were prepared by using phenolphthaloline (PPN), diphenyl sulfone (DCDPS) and diphenyldiphenylsulfone (DCDPSs) as reactive monomers. The structure of the polymer was characterized by 1H NMR. The effects of the ratio of reactants on the polymerization time, the specific viscosity, thermal properties and solubility of the products were studied. It was found that with the increase of phenolphthaloline monomer content, the polymerization time was prolonged, the specific viscosity of the polymer was increased, the heat resistance was slightly decreased, and the solubility of the polymer in N- (N-dimethyl-formamide) and other solvents was decreased. The polysulfone resin with different components was prepared into a separation membrane by immersion precipitation phase inversion method. The relationships between phenolphthaloline content and water contact angle, water absorption, size change, tensile fracture strength, pure water flux and micromorphology of the membrane were studied. It was found that with the increase of phenolphthaloline content, the water contact angle of the membrane decreased, and the pure water flux first increased and then decreased. When the phenolphthaloline content was 75, the maximum value was 260 L m-2 h-1, the water absorption increased, and the size change rate increased slightly. The content of phenolphthalein had little effect on the tensile strength and microstructure of the membrane. Using DCDPS as raw material P2O5 and concentrated sulfuric acid as sulfonating agent, the monomer of 3 ~ (3 +) -sodium dichlorobenzene disulfonate (SDCDPSs) with sulfonic group was prepared, and its structure was characterized by FT-IR ~ (1H) NMR. Hexafluorobisphenol A polysulfone membrane materials with different sulfonation degree were prepared by using SDCDPS (hexafluorobisphenol A BPAF) and DCDPS4 (4) 4-dichlorobenzene sulfone (DCDPS) as reactive monomers. The structure of the polymer was characterized by 1H NMR. The effects of the ratio of reactants on the specific viscosity, thermal properties and solubility of the products were studied. It is found that with the increase of sulfonation degree, the specific viscosity of the polymer increases, the heat resistance decreases slightly, and the solubility of the polymer in chloroform 1, 2-dichloroethane and other solvents decreases. Hexafluorobisphenol A polysulfone resin with different sulfonation degree was prepared by immersion precipitation phase inversion method. The relationship between sulfonation degree and water contact angle, water absorption, size change, tensile fracture strength, pure water flux and micromorphology of the membrane was studied. It was found that with the increase of sulfonation degree, the water contact angle of the membrane decreased, and the pure water flux first increased and then decreased, and the maximum sulfonation degree was 5, reaching 170 L m-2 h-1, the water absorption increased and the size change rate slightly increased. The degree of sulfonation of the polymer has little effect on the tensile fracture strength and micromorphology of the membrane.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ051.893

【共引文献】