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Vinylimidazole copolymers: coordination chemistry, solubility, and cross-linking as function of Cu<sup>2+</sup> and Zn<sup>2+</sup> complexation

Journal article
Authors Markus Andersson
Örjan Hansson
Lars Öhrström
Alexander Idström
Magnus Nydén
Published in Colloid and Polymer Science
Volume 289
Issue 12
Pages 1361-1372
ISSN 0303-402X
Publication year 2011
Published at Department of Chemistry
Pages 1361-1372
Language en
Keywords Coordinated polymer, 1-vinylimidazole, EPR, DSC, Glass transition, temperature, Vibrational spectroscopy, core/polymer shell microcapsules, internal phase-separation, metal-ions, poly(methyl methacrylate), imidazole complexes, spectra, cu(ii), field, raman, nmr
Subject categories Coordination chemistry, Polymer Chemistry, Molecular biophysics


P(1-VIm-co-MMA) copolymers with 4 or 44 wt.% 1-VIm (abbreviated PVM-4 and PVM-44) where polymerized from 1-VIm (1-vinylimidazole) and methylmethacrylate with azobisisobutyronitrile as initiator and reacted with either Cu(2+) or Zn(2+). The resulting coordinated polymer complexes were studied using ICP-AES, CP/MAS (13)C NMR, conductivity measurements, vibrational spectroscopy (mid-FTIR and far-FTIR), DSC, and EPR. It was established by ICP-AES, CP/MAS (13)C NMR, conductivity, mid-FTIR and EPR measurements that the transition metal ions in the complexes were exclusively coordinated by the imidazole ligand. The coordination geometry is square planar with regard to Cu(II) complexes. The strong interaction between the polymeric imidazole ligand and the transition metal ion cross-links the system, resulting in augmentation of T (g) (the glass transition temperature), especially for copolymers with high relative amount of 1-VIm. The effect of changing metal ion is more complicated and depends on both the strength of the coordinate interaction as well as the coordination number. The solubility of the coordinate polymer complex in conventional solvents is low due to the coordinate cross-links. However, the coordinate polymer complexes are soluble in strongly coordinating solvents such as acetonitrile and dimethylsulfoxide.

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