测定高分子聚合物-金属配合物稳定常数及平均配位数的新方法

Abstract

建立了基于化学平衡理论模型以及凝胶过滤色谱(gfC)-电感耦合等离子体质谱(ICPMS)联用技术的高分子聚合物-金属配合物稳定常数、平均配位数测定新方法。以聚乙烯亚胺(PEI)和Cu2+为例,对形成的PEI-Cu配合物稳定常数、平均配位数进行测定,以0.02 MOl·l-1 HAC-nAAC为流动相,凝胶色谱柱分离大分子PEI-Cu配合物以及Cu的小分子配合物、游离态离子,最后用ICPMS测定不同形态金属元素的浓度;利用建立的化学平衡理论模型,计算PEI与金属离子形成配合物的稳定常数、平均配位数,测得25℃,PH4.1~5.3时,PEI-Cu配合物稳定常数为109.6~1010.7,平均配位数为1.0~1.3。建立的在线分离、测定方法具有快速、准确的特点,为高分子聚合物-金属配合物的研究提供新的技术手段。

A new method using gel filtration chromatography(GFC) and inductively coupled plasma mass spectrometry(ICPMS) was developed for the measurement of complexation stability constant and average coordination number of the complex of metallic ion with polymer.As an example,the binding of PEI with Cu2+was shown and investigated.The macromolecular PEI-Cu complex and micromolecular species of Cu (Ⅱ) were firstly separated by a low efficiency GFC column with a mobile phase of 0.02 mol·L-1HAc-NaAc buffer,and then directly introduced into ICPMS for elemental analysis.The results of complexation stability constant and average coordination number characterized by putting the concentration of different species of metallic element into the equations of the novel chemical equilibrium model which was developed in this study.The results shown that the complexation stability constants(KPEI-Cu) were between 109.6and 1010.7and the average coordination numbers(n) were in the range of 1.0~1.3 when pH was changed from 4.1 to 5.3 at 25 ℃.This online,rapid and accurate method of GFC-ICPMS is a novel technique for the research of polymer-metallic complex.