PREPARATION OF POLY(ALKYLENE H-PHOSPHONATE)S AND THEIR DERIVATIVES BYPOLYCONDENSATION OF DIPHENYL H-PHOSPHONATE WITH DIOLS AND SUBSEQUENT TRANSFORMATIONS

A new method of preparation of poly(alkylene H-phosphonate)s (1) by po lycondensation of diphenyl H-phosphonate with diols such as 1,10-decan ediol or tetra(oxyethylene) glycol is described. These polymers can be converted into poly(alkylene phosphate)s-mimicking backbones of nucle ic acids and other biomacromolecules. The described method is the only one allowing simple preparation of this important class of polymers. This method eliminates the major side reaction taking place when dialk yl H-phosphonates are used and is related to the C-alkylation and form ation of the unreactive ether end groups. Reaction of diphenyl H-phosp honate with alcohols is practically irreversible and can be performed without removing phenol, formed as a byproduct of condensation. It can be carried out in solvent or in bulk at temperature 80-200 degrees C. Removing phenol enhances, however, formation of polymers with higher (M) over bar(n). Polymers with (M) over bar(n) similar to 30 x 10(3) w ere obtained and characterized as such or in the form of their derivat ives. Chlorination of 1 with gaseous Cl-2 leads to corresponding poly( alkylene chlorophosphate)s transformed readily into further derivative s, for instance, poly(alkyl alkylene phosphate)s, poly(alkylene phosph ate) salts, or/and acids, using the poly(alkylene phosphorimidazolide) as the reactive intermediate.