Makromol. Chem., Macromol. Symp. 6,123-153 (1986) zyx 123 zy POLYMERIZATION zyxwvut OF PHOSPHORUS CONTAINING CYCLIC MONOMERS : SYNTHESIS OF POLYMERS RELATED TO BIOPDLYMERS Stanislaw Penczek*, Tadeusz Biela, Pawel Klosinski,and Grzegorz Lapienis Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-362 Lodz, Boczna 5, Poland SUMMARY The mechanism of polymerization i s discussed, i n which cyclic esters of phosphoric acid, and related compounds are converted into linear macromolecules, modelling nucleic and teichoic acid backbones.Struc- tures l i k e deoxyribose polyphosphate and glycerol polyphosphate were prepared from the corresponding cyclic compounds. These polymerizations involve heterolytic breaking zyxw of the P-0 bond i n t h e c y c l i c monomer and proceed by i o n i c mechanism. Both 5- and 6-mem- bered monomers have been polymerized. The thermodynamic parameters of the ring-chain interconversion were determined; the 5-membered rings polymerization i s driven by the exothermicity of the ring-opening, whereas polymerization o f several 6-membered rings i s endothermic and allowed because of the positive change of entropy. Anionic polymerization, and particularly the pseudo(coordinate)anionic polymerization provides, i n contrast to the cationic process, high-mo- lecular-weight polymers with more uniform structure. Anignic polymeri- zation proceeds mostly (at the applied conditions) on the macroion - -pairs. The elementary reactions consist of the nucleophilic attack of the paired macroanions on the phosphorus atom in t h e c y c l i c monomer mo- lecule. Rate constants of the elementary reactions for the model mono - mers will be presented. Stereochemistry of the propagation steps i s shown t o be governed by the statistical ring-opening, leading to the three kinds of polymer units (head-to-tail and two symmetrical units). Apart from the ring-opening,the polyaddition of diepoxides t o phospho- rousand phosphoric acids i s described. Finally,a few examples o f preparation of models of biopolymers are given, namely poly(deoxyribose phosphate) and poly(glycero1 phosphate). INTRODUCTION Polymer chemistry has contributed in various ways to the present pro- gress i n biology, biochemistry and medicine, providing new methods for pre- paring and studying macromolecules as well as providing new, highly speci- fied materials. One of these ways, we are particularly interested in,is the synthesis of new polymers, structurally related to the natural biopolymers with poly(alky1ene phosphate) main chains. We assume, t h a t f o r a number o f applications it i s not necessary to exactly duplicate the actual structure of natural biopolymers in order to provide the desired functions.