氯化铜与非离子聚合物PEG和PVP配合物的合成与表征

B. Bakirova, I. Smagulova, D. Akbayeva
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引用次数: 0

摘要

用电位法测定了氯化铜(II)与聚乙二醇(PEG)和聚乙烯吡咯烷酮(PVP)的聚合物金属配合物的组成。根据测定络合物组成的实验数据,绘制了滴定曲线,并确定了反应组分的最佳摩尔比。计算了Bjerrum的地层函数。得到的数据表明,聚合物铜配合物的形成,其中两个铜离子络合剂中有两个PEG单链(Cu2+-PEG为1:2),PVP为3个(Cu2+-PVP为1:3)。在热力学稳定常数的基础上,利用Vant Hoff和Gibbs的等温线方程和等压线,计算了Gibbs能量(DrG0)、焓(DrH0)和熵(DrS0)的变化。Cu2+-PEG和Cu2+-PEG体系的络合过程表现为负吉布斯能,表明在这些体系中自发形成了聚合物-金属配合物(PMC)。相比之下,铜离子与聚乙二醇的络合作用伴随着较大的正焓值,这表明Cu2+与聚合物官能团的相互作用在能量上是不利的。熵值为正,这可以解释为离子和官能团的脱水,当一个离子与几个官能团结合时,在络合过程中充当配体和螯合作用。用红外光谱对合成的配合物的结构进行了表征。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Synthesis and characterization of copper (II) chloride complexes with non-ionic polymers PEG and PVP
The compositions of polymer-metal complexes based on copper (II) chloride and polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP) have been determined by the potentiometric method. Based on the experimental data, obtained to determine the composition of the complex, the titration curves have been plotted, and the optimal molar ratios of the reacting components have been found. The Bjerrum’s formation functions have been calculated. The obtained data indicate the formation of the polymer copper complexes, in which there are two PEG mono-links per two copper ions-complexing agent (1:2 in the Cu2+-PEG), and in the case of PVP, there are three ones (1:3 in the Cu2+-PVP). On the basis of thermodynamic constants of stability, using isotherm equations and isobars of Vant Hoff and Gibbs, Gibbs’ energy (DrG0), enthalpy (DrH0) and entropy (DrS0) changes have been calculated. The complexation process in the Cu2+-PEG and Cu2+-PEG systems is characterized by negative Gibbs’ energies, which indicates a spontaneous occurrence of the polymer-metal complex (PMC) formation process in these systems. In contrast, the complexation of copper ions with PEG is accompanied by the large positive enthalpy values, which indicate that the interaction of Cu2+ with the functional groups of the polymer is energetically unfavorable. The entropy values ​​are positive, which can be explained by the dehydration of ions and functional groups, acting as ligands and a chelating effect during complexation, when one ion binds to several functional groups. The structure of the synthesized complexes has been investigated by IR spectroscopy.
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