【作者】 陈权；

【导师】 崔元臣；

【作者基本信息】 河南大学 ， 高分子化学与物理， 2003， 硕士

【摘要】 氨基二硫代甲酸基团是一种优良的螯合剂，对痕量的贵重金属离子有良好的的捕集效果，但不与碱金属和碱土金属络合，故可以定量地回收和富集海水或其它稀溶液中的贵重金属离子。该活性功能团与特定的金属离子络合后，又会产生许多新的物理化学性能，如光敏活性、润滑性能、引发活性和增溶性等。以多胺为主要原料制备了含有活性基团的单体，再通过均聚、共聚或缩聚的方法制备了一系列含有氨基二硫代甲酸基团的聚合物。利用接枝高分子化的方法将螯合基团引入天然或合成的高分子上，制备了田菁胶负载氨基二硫代甲酸基团的聚合物，另外又将含有氨基二硫代甲酸的功能团修饰到石墨电极上，制备成聚合物膜的化学修饰电极。分别考察了某些含有氨基二硫代甲酸功能团聚合物合适的合成条件及其物理化学性能，尤其是它的吸附性能，并进一步研究了各种环境因素如酸碱度、时间以及温度对吸附容量、吸附率及吸附动力学等参数的影响。1、主链型氨基二硫代甲酸基团聚合物有较高的分解温度，环状胺比直链胺具有更高分解温度；苄酯类氨基二硫代甲酸基团聚合物在紫外光的作用下，能有效地引发聚甲基丙烯酸甲酯的嵌段聚合。2、以哌嗪为主要原料合成的氨基二硫代甲酸基团聚合物，在较宽的pH范围内对贵重金属具有较好的吸附性能，对Ag+、Pd2+、Cu2+、Ni2+、Pb2+等金属离子的吸附容量分别为6.50、3.81、2.90、2.21和1.04mmol/g，对Ag+、Cu2+、Ni2+、Pb2+混合金属离子的吸附实验表明：聚合物对贵金属离子Ag+具有较高的选择性，能够定量地吸附Ag+而几乎不吸附其它离子。3、以田菁胶为载体，环氧氯丙烷作为交联剂，通过对田菁胶环氧化、胺化、<WP=5>二硫代羧酸化反应，在伯羟基上引入二硫代氨基甲酸基团而合成田菁胶负载的聚合物。环氧化过程中，最佳反应条件为：碱浓度为11%，环氧氯丙烷用量为1.0ml/g碱化原粉；胺化过程中，最佳的反应温度为80℃。所制得树脂对贵重金属离子有较高的吸附容量，并有吸附速率快，重复性好的特点。对Ag+的吸附2h内可以达到平衡，吸附容量为3.595mmol/g。以有机硅烷偶联剂作为交联剂所制备的聚合物，对贵金属离子具有强的吸附性能和高的选择性，对Ag+和Cu2+的吸附容量分别为5.41mmol/g和2.10mmol/g。4、将二硫代氨基甲酸活性功能团修饰到石墨电极上，在底液为1.0mol.L-1KCl；pH=1.7；富集时间为15min；扫描速度为100mV/s的条件下，对络合Ag+后的修饰电极作循环伏安电势扫描，其峰电流是未修饰前的10倍以上，表明通过化学修饰电极，二硫代氨基甲酸活性功能团对Ag+具有良好的络合作用，对金属离子吸附的灵敏度和选择性也大大提高了。更多还原

【Abstract】 It was known that dithiocarbamate groups were effectived as an excellect chelated agent for the separation and concentration trace amount of noble metal and heavy metal ions, while unacceptable for alkali metal and alkaline-earth metal ions, quantificationally recover and enrichment metal ions from seawater or other dilute solution. By coordinating with specific metal ions the active functional groups wound produce many new performances in physical chemistry, such as photosensitive activity, lubricate, initiation and dissolve aids performances.Monomers containing active functional groups were prepared from polyamine and achieved a series of polymers with dithiocarbamate by homopolymerization, copolymerization or polycondensation methods. The active groups were introduced savageness or synthesize macromolecul by graft macromoleculize methods and also prepared polymers containing sesbanion gum carrier, then the groups were modified to graphite electrode and attained a kind of polymer film chemistry modifying electrode.Some polydithiocarbamate resins were reviewed separately in suituable synthesize appropriate capability, especially their adsorption properity, and more investigate all kinds of conditions such as pH value, adsorption time and adsorption temperature effected absorption capability, absorption rate and absorption dynamics parameters.Polydithiocarbamate backbone polymer beared high decompose<WP=7>temperature, and cyclic amine was higher than linear ones; Benzyl sulfide polydithiocarbamates could availably introduce block copolymerization of MMA under ultraviolet radiation.Polydithiocarbamate resins containing piperazine backbone exhibited high adsorption capacity over the range of broad pH value for metal ions, as Ag+, Pd2+, Cu2+, Ni2+, Pb2+, their adsorption capacity separately were 6.50,3.81, 2.90,2.21and 1.04mmol/g. Disposal experiments for mixture solution containing Ag+, Cu2+, Ni2+and Pb2+, indicated that the polymers had higher selectivity for noble metal ions.Crosslinked sesbanion gum polymers were prepared by epichlorohydrin and introduced dithiocarbamate by alkalization, epoxidation, amination, thioformation to secondary amine groups. The optimum conditions for epoxidation process were also obtained. Alkali concentration was 11%, and the dosage of epichlorohydrin was 1.0mL according to 1.0g basify stock. The amination temperature was 800C. The resins possessed high capacities, rapid rate and preferably repetition for capturing noble metal ions. Polymer crosslinked by organic silane coupling agents exhibited high selectivity and adsorption capacity for metal ions attained 5.41mmol/g to Ag+ and 2.10 mmol/g to Cu2+. Graphite electrode modified with dithiocarbamate active functional groups had been fabricated and applied to the analysis of siliver ion in the aqueous media. The optimum reaction conditions were KCl solution (1.0mol/L), pH value (1.7), enrichment time (15min), scan velocity (100mV/s) and peak current value was 10 times of unmodified electrode. This<WP=8>indicated that active functional groups after chemistry modified had excellect chelation for Ag+ and advanced adsorption sensitivity and selectivity for metal ions greatly.更多还原