【作者】 朱月群；

【导师】 蓝立文； 宁荣昌；

【作者基本信息】 西北工业大学 ， 材料学， 2002， 博士

【摘要】 本文对国内外在含金属离子丙烯酸聚合物方面的研究进行了详细的评述，并就其中具有特殊性质的两种含金属离子丙烯酸聚合物：含钠离子丙烯酸聚合物和含锌离子丙烯酸聚合物展开了深入的研究，探讨了这两种含金属离子聚合物的合成、结构和性质。 含钠离子丙烯酸聚合物经轻度交联后是一种性能优异的高吸水性材料，在很多领域拥有广泛的应用背景，本文针对目前含钠离子丙烯酸聚合物合成方法中存在的缺陷，首次将紫外光照射法运用到该体系的合成，并深入研究了合成条件：光强、光引发剂种类及用量、交联剂种类及用量、中和度(钠离子用量)、反应体系单体浓度对聚合物高吸水性的影响。 为了提高该种聚合物的吸水性，我们将水溶性聚合物：聚乙烯醇(PVA)、聚氧乙烯(PEO)、以及自制线性聚丙烯酸钠(LPSA)引入反应体系，发现水溶性聚合物的加入可以大幅提高含钠离子丙烯酸聚合物的吸水率和吸水速度。并首次采用正交实验的方法研究了引发剂用量、交联剂用量、钠离子用量、单体浓度、PVA用量对聚合物性能的影响主次及其交互作用。 对含钠离子丙烯酸聚合物的吸水性，以及树脂粒径、酸、碱、盐离子、水温对吸水性的影响进行了探讨。并首次深入研究了该种聚合物的吸湿保水性，发现其吸湿性随环境湿度变化而变化，对环境具有很好的响应性；在加热蒸发过程中，具有比自由态的水慢的蒸发速率。 本文采用水溶液聚合方法合成了含锌离子丙烯酸聚合物，运用络合滴定的方法确定了其中锌离子和羧基的配位数，采用IR、DSC等手段对聚合物的结构进行了表征，DSC结果显示，当锌离子用量较少时，聚合物的Tg明显比不含锌离子时提高。对其溶解性进行研究发现，其具有既可溶于水性体系，而成膜后又具有优异耐水性的特殊性质，但膜的粘结性稍差，采用SEM对其膜形貌进行了观察。 将锌离子化丙烯酸和丙烯酸丁酯进行共聚，我们得到了同时具有优异耐水性和粘结性的含锌离子共聚物。因为高聚物分子量对于水溶性聚合物是一个非常重要的指标，我们通过测定重均分子量和特性粘数标定了该共聚物的K、α， 西北工业大学博士论文得到了该体系的分子量－特性粘数表达式，从而研究了引发剂、链转移剂、扩链剂、溶剂对聚合产物分子量的影响。通过 IR、DSC、‘HNMR、络合滴定等方法对共聚物的结构进行了表征。 对丙烯酸锌．丙烯酸丁酯共聚物的溶解性研究发现，其不溶于水，可以溶于氨／水混合溶剂，当丙烯酸丁酯含量超过40mol％时，可以溶于DMi、DMSO；对其成膜性研究表明，在保持优异耐水性的同时，共聚物的粘结性改善。SEM e照片显示，其膜的致密性也得到提高。更多还原

【Abstract】 In this paper, the studies on metallic ion containing polyacrylate at home and abroad was reviewed detailedly, and the synthesis, structure and properties of two kinds of polyacrylate: sodium ion containing polyacrylate and zinc ion containing polyacrylate which both have special properties were researched in detail.If slightly crosslinked, sodium ion containing polyacrylate(SCPSA) was one kind of superabsorbent polymer which showed excellent absorbing property to water and could be used in widely fields. In order to solve the limitation of present synthesis methods of SCPSA, the UV-curing method was firstly used in preparing slightly crosslinked sodium ion containing polyacrylate in this paper. The influences of preparation conditions: UV radiation intensity, photo-initiator’s kinds and contents, crosslinker’s kinds and contents, sodium content, monomer concentration on the properties of polymer were investigated.Water soluble polymers such as poly(vinyl alcohol)(PVA), polyoxyethylen e(PEO), and linear poly(sodium acrylate)(PSA) made in our lab were firstly i ntroduced into the reaction system to improve the absorbing rate and capacity of SCPSA, and orthogonal experiment was designed to evaluate the influenc es of five synthesis conditions and their reciprocity.Zinc ion containing polyacrylate(PZA) was synthesized by solution polym erization and its structure was determined with complexometric titration, IR, DSC,SEM, etc. The results showed that zinc ion in the polymer formed ionic bond and coordinative bond with carboxylic group. The studies on the film propertyof PZA indicated that the film highly tolerate water but its adherence was a little weak.The copolymer of zinc ionized acrylic acid and butyl acrylate was preparedwith by heterogeneous polymerization with redox system as initiator. The constants of K, a was determined by testing the intrinsic viscosity and weight average molecular weight. And so the equation of [ a ] -Mw was obtained: [ n]=0.5339M0.46, M=([ n ]/0.5339)1/0.46 . Thereby the influences of synthesis conditions on the molecular weights of the copolymers were investigated. The structure of the copolymer was studied with complexometric titration, IR, DSC, SEM, etc.The studies on solubility of the copolymer showed that they could be dissolved in water and the solution was easy to form film which revealed excellent water tolerance and strong adherence.更多还原