The preparation of a series of hydrogel copolymer membranes of 2-hydroxyethyl methacrylate with 4-vinyl pyridine (VPy) in the range of0.5-17 wt%, or 4'-vinyl 4-methyl 2,2'-bipyridine (VBpy) in the range 0.5-8 wt%, are described. The membranes are shown to coordinate selected transition metal ions from aqueous solution. Interactions with Cu(n) and Fe(ii) were isolated for individual attention on the basis that, under certain conditions, bands appear in the visible spectra characteristic of the Cu(u) tetra(VPy) and the Fe(n) tris(VBpy) complexes. The complexation of more than one ligand group per metal ion leads to the potential anchoring of two or more previously unconnected polymer chains at a metal-centred cross-link. The effects of 'coordinative cross-linking' on the tensile properties of the hydrogel polymers were studied in elongation at 25°C and 100% humidity, until failure of the membranes occurred. The tensile strengths of both the Cu(n) and Fe01)-coordinated polymers are found to increase in conjunction with copolymer ligand content, as a consequence of a greater degree of coordinative cross-linking. In more classical hydrogel systems, the equilibrium water content of the polymer is caused to fall with degree of cross-linking. Here, this is not the case, as the equilibrium water content remains relatively unchanged owing to the incorporation of further water-structuring groups in the guise of metal complexes. Together with the capability of a reversible crossqinking effect by metal leaching under acid conditions, these ligand-modified systems offer a novel and unique route to the enhancement of mechanical properties in hydrogel-type materials.
Посилання на статтю:
Coordinative cross-linking of pyridyl- and bipyridyl-based hydrogel polymer membranes / Andrew L. Lewis and J. David Miller* // Polymer. – 1993. – Vol 34. – P. 2453-2457.