【作者】 陈健；

【导师】 曲荣君； 姜华；

【作者基本信息】 鲁东大学 ， 高分子化学与物理， 2007， 硕士

【摘要】 螯合树脂是一类能与金属离子形成多配位络合物的交联功能高分子材料。广泛应用于无机、冶金、分析、放射、药物、催化、海洋化学等领域。交联聚苯乙烯类是市场上应用最为广泛的螯合树脂吸附剂母体之一,具有制备工艺成熟、易功能化、机械强度高、化学稳定性好的特点,缺点是其亲水性能却很差;含硫螯合树脂对重金属及贵金属离子都有很好的吸附性能,但是大部分含硫基团都具有一定的疏水性;氨基吡啶基团中的两个N原子都有很强的配位能力,且最重要的是利用氨基吡啶中的氨基的反应活性可以很容易的将其键合到不同的高分子载体上。基于以上原因,本文以氯甲基化聚苯乙烯微球（氯球）为原料,分别设计、合成了三种以含硫醚、亚砜、砜基的分子链为悬臂,以氨基吡啶为功能基的螯合树脂PVBS-AP,PVBSO-AP,PVBSO₂-AP。采用红外光谱,元素分析,扫描电镜,孔径分析以及光电子能谱等手段对所合成的大孔树脂的结构进行了表征。研究了其对Hg²⁺、Ni²⁺、Pb²⁺、Fe³⁺、Au³⁺、Cu²⁺、Pd²⁺、Cd²⁺、Pt4+、Zn²⁺、Ag+等常见重金属以及贵金属离子的饱和吸附量,吸附选择性以及吸附机理。研究表明,PVBS-AP大孔树脂对Hg²⁺、Pd²⁺、Au³⁺、Pt4+、Ni²⁺的吸附量较高,PVBSO-AP大孔树脂对Hg²⁺、Ni²⁺、Pb²⁺、Au³⁺、Cu²⁺、Pd²⁺、Cd²⁺、Pt4+的吸附量较高,PVBSO2-AP大孔树脂对Ni²⁺、Cd²⁺、Pb²⁺、Cu²⁺等金属离子的吸附量较高;三种树脂均可用于Hg²⁺-Ni²⁺,Hg²⁺-Zn²⁺,Hg²⁺-Pb²⁺体系中的Hg²⁺离子,Au³⁺-Ni²⁺,Au³⁺-Pb²⁺,Au³⁺-Cu²⁺体系中的Au³⁺离子,Ag+-Pb²⁺,Ag+-Ni²⁺体系中的Ag+离子的分离、回收;酸度对PVBS-AP,PVBSO-AP树脂吸附金属离子的影响不大,而PVBSO2-AP树脂却随着酸度的升高吸附量呈下降趋势;三种树脂对Hg²⁺的吸附动力学研究表明,树脂PVBS-AP,PVBSO2-AP对Hg²⁺吸附平衡较快,PVBSO-AP树脂平衡较慢。且三种树脂都具有较好的重复使用性能。PVBS-AP,PVBSO-AP,PVBSO₂-AP树脂对Hg²⁺和Ag⁺的吸附机理研究表明,三种树脂中的2-氨基吡啶基中两种形态的N原子均参与配位。树脂PVBS-AP,PVBSO-AP中的硫基和亚砜基悬臂中的S原子均参与配位,且树脂中的S原子被部分氧化成亚砜基和砜基。而PVBSO₂-AP树脂中的S原子未参与配位。这类新型的有硫醚、亚砜、砜基悬臂的氨基吡啶螯合树脂,因其带有亲水悬臂,增加了微环境结构体的亲水性和柔顺性,所以与无悬臂的树脂相比更易于捕获水溶液中的金属离子,可用于一些贵金属及有毒金属离子分离、富集、回收。更多还原

【Abstract】 Being an important branch of the polymer science, the chelating resin is a kind of cross-linked functional polymer material, which can form multi-coordinated complex with metal ions. This kind of resin is widely used in the fields of inorganic, metallurgy, analysis, radiation, pharmaceuticals, catalysis, and marine chemistry, etc. Cross-linked polystyrene is one of the most popular skeletons of the chelating resins, but it has the bad hydrophilic; Commonly, sulfur-containing chelating groups, as soft bases, have good adsorption properties for transition metal ions, but they have some hydrophobic properties; pyridine is often used as function group of chelating resin due to its nitrogen atom which can form steady complex with transition metal ions. Moreover, Amino-pyridine can be easily linked to macromolecule carrier through amino group. So that three kinds of novel chelating resins named PVBS-AP,PVBSO-AP,PVBSO2-AP are synthesized by chloromethylated polystyrene. The structure and patterns are characterized by FTIR, XPS, SEM, ES, etc.. The adsorption properties of the three resins for Hg²⁺、Ni²⁺、Pb²⁺、Fe³⁺、Au³⁺、Cu²⁺、Pd²⁺、Cd²⁺、Pt4+、Zn²⁺、Ag+ were studied.The results showed that the resin of PVBS-AP had good adsorption for Hg²⁺、Pd²⁺、Au³⁺、Pt4+、Ni²⁺; the resin of PVBSO-AP had good adsorption for Hg²⁺、Ni²⁺、Pb²⁺、Au³⁺、Cu²⁺、Pd²⁺、Cd²⁺、Pt4+;the resin of PVBSO2-AP had good adsorption for Ni²⁺、Cd²⁺、Pb²⁺、Cu²⁺; the three resins all had good selective properties for Au³⁺, Ag+ and Hg²⁺when the coexisting ions were Ni²⁺,Pb²⁺,Cu²⁺ , Zn²⁺; The experience results also told us that the adsorption properties of PVBS-AP and PVBSO-AP were little affected by acid concentration, except for the resin of PVBSO2-AP; the result of the adsorption kinetics for Hg²⁺ showed that the balance speeds of PVBS-AP and PVBSO2-AP were faster than PVBSO-AP; The thermodynamics results showed that the adsorption of the three resins for Hg²⁺ were good agreement with the Langmuir equation; and all the three resins had good reuseability.The adsorption mechanisms of the resins for Hg²⁺ and Ag+ were confirmed by X-ray photoelectron spectroscopy （XPS）. The result showed that the nitrogen atoms of amino-pyridine were that main electron donors to coordinate with Hg²⁺ and Ag+ in the three resins. The sulfur atoms in the spaces of the PVBS-AP and PVBSO-AP resins took part in coordinating with metal ions. Because of the hydrophilic chain increasing the hydrophilicity of the chelating resins, the novel amino-pyridine chelating resins containing sulfur, sulfoxide, sulfone spacers have good adsorption for the transition metal ions .They can be well used to extract and separate some transition metal ions.更多还原