A Vandenberg synthesis type has been selected to obtain high molecular weight POP polymers. The principal features of these materials are given in this paper. The ionic behaviour of alkaline complexes based on lithium bis(trifluoromethylsulfonyl) amide abbreviated to LiTFSI, or on potassium bis(trifluoromethylsulfonyl) amide abbreviated to KTFSI, and has been investigated and shows a marked improvement of solubility and conductivity, compared to the usual POP electrolytes.