Résumé
Copolyethers and polyurethanes containing lower and upper rim calix[4]arene units in the fixed cone conformation were prepared in good yield by polycondensation reactions of distal calix[4]arene diols with bisphenol-A/dibromomethane and 2,4-tolylendiisocyanate (TDI), respectively. In a similar way were prepared calix[4]arene-crown-5 and -crown-6 polyurethanes in the fixed 1,3-alternate conformation by condensation of TDI with lower rim calixcrown-5 and calixcrown-6 diols. However, the poor solubility in common organic solvents of the copolyether derivatives (
M
w=11,100–11,600
g/mol) hampered further studies on their ionophoric properties. Aiming to obtain model compounds for the investigation of both extraction abilities and ionophoric properties of the polyurethane materials, several bis-urethanes were also synthesized by reaction of the calix[4]arene diols with
p-tolylisocyanate (TI). The extraction ability measurements of monomeric and polymeric calix[4]arene urethanes (
M
w
=12,300–83,500 g/mol) towards alkali metal cations (Li
+, Na
+, K
+, Rb
+, Cs
+) and Ag
+showed a remarkable efficiency and selectivity of calixcrown-6 polyurethane toward Rb
+, Cs
+and Ag
+.