Preparation and polymerization of racemic and optically active tert‐butyl thiirane

Preparation and polymerization of tert‐butyl thiirane are described. The racemic monomer was obtained by reaction in aqueous solution of tert‐butyl oxirane and potassium thiocyanate. The levorotatory enantiomer was synthesized from R(−) 3.3‐dimethyl 1.2‐butane diol passing through the intermediate of the cyclic carbonate. Polymerization of the racemic monomer with coordinate type initiators give crystalline, soluble products of high molecular weights and high melting points (close to 205°C). Crystalline, soluble, high molecular weight polymers but of lower melting points (close to 160°C) could also be obtained with the levorotatory enantiomer, either by coordiante or purely anionic initiation. These polymers have high optical activities of positive sign in all the solvents used. NMR measurements show that racemic and optically active crystalline polymers have the same isotactic structure. The differences in melting point and X‐ray diagrams show the existence of several crystalline modifications. These results indicate a strong difference in the behaviour of tert‐butyl thiirane as compared to methyl thiirane.