SYNTHESIS OF FUNCTIONALIZED 12-MEMBERED, 13-MEMBERED AND 14-MEMBERED CROWN-ETHERS BEARING EXOCYCLIC POLYMERIZABLE GROUPS AND THE BINDING-PROPERTIES AND CONDUCTIVITIES OF THEIR LITHIUM-DOPED POLYMERS

The synthesis of a series of [12], [13] and [14]-membered crown ethers bearing an exocyclic polymerisable methacrylate is reported. The spac ing group between the ring and the methacrylate is either a simple alk yl chain, [CH2] or [CH2]6, or an oxydiethylene chain. The relative bin ding ability of the 'mono and di-substituted' macrocyclic rings toward s Li+ is compared by C-13 NMR analysis. Radical polymerisation gives t he amorphous polymers in which the glass transition temperature is pri marily controlled by the nature of the spacer group. In the lithium do ped polymers, for a given glass transition temperature, T(g), the [12] -ring materials show enhanced ionic conductivities over the [14]-ring analogues which may be related to the lower rate of lithium exchange ( in the former series) or to an enhanced tendency of the [12]-ring syst ems to form 2:1 complexes with more effective counterion separation.