Polymer complexes XXXIV. Potentiometric and thermodynamic studies of monomeric and polymeric complexes containing 2-acrylamidosulphadiazine - ScienceDirect

European Polymer Journal

Volume 38, Issue 3, March 2002, Pages 561-566

European Polymer Journal

https://doi.org/10.1016/S0014-3057(01)00210-5 Get rights and content

Abstract

2-Acrylamidosulphadiazine (ASD) was synthesized and characterized by elemental analyses, IR and $^{1}$ H NMR spectra. Proton–monomeric ligand dissociation and metal–monomeric ligand stability constants of ASD with some metal ions were determined potentiometrically in 0.1 M KCl and 40% (v/v) ethanol–water mixture. In the presence of 2,2^′-azobisisobutyronitrile as initiator, the dissociation and stability constants of ASD were determined in polymeric form (PASD). The influence of temperature on the dissociation of ASD and the stability constants of their complexes in monomeric and polymeric forms were critically studied. The pK₂^H value of PASD was found to be higher than ASD, this means that the vinyl group in the monomeric form decreases the electron density and hence reduces the N–H bond strength. The stability constants of the metal complexes in polymeric form are higher than those of the monomeric form. This is quite reasonable because the ligand in a polymeric form is considered as a better complexing agent.

Introduction

Recently, an important new focus for environmental inorganic chemistry is the selective removal and recovery of metal ions from aqueous solution with organic ligands anchored to modified polymer backbones [1], [2], [3]. Several significant criteria for facile metal ion removal from aqueous solution includes the hydrophilicity of the pendant organic ligand when it is anchored to a hydrophobic, pH stable polymer backbone such as modified, kinetics and thermodynamics of the pendant ligand reaction with the selected metal ion [4], [5].

In this paper we extend our preliminary studies [6] and focus attention on the preparation of polymers as polydentate ligands. Here we describe the synthesis and characterization of 2-acrylamidosulphadiazine (ASD) which possesses one polymerizable vinyl group. Our approach is to study the dissociation of ASD and determine the stability constants of its metal complexes with Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, La³⁺, UO₂²⁺ and Th⁴⁺ in monomeric and polymeric forms, using potentiometric measurements and thermodynamic calculations.

Section snippets

Preparation of the monomer

ASD was prepared [6] by the equimolar amounts of acryloyl chloride (Aldrich) and sulphadiazine (Aldrich) in dry benzene using hydroquinone as inhibitor. The crude material was recrystallized from ethyl alcohol and then dried in a vacuum desiccator over anhydrous calcium chloride. The purity was checked by elemental analysis, IR and $^{1}$ H NMR spectra.

Acid dissociation constants

The average acid dissociation constant of the ligand in monomeric (ASD) and in polymeric (PASD) form at different pH values, $n ̄_{A}$ , were calculated from the titration curves of acid in the absence and presence of ligand. Thus, the formation curves ( $n ̄_{A}$ vs. pH) for the acid systems were constructed and found to extend between (0 and 2) in the $n ̄_{A}$ scale for ASD and PASD. This means that, each of ASD and PASD has two dissociable protons (the enolized hydrogen ions of the amidic proton, CONH and

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