Abstract
Polyrotaxanes have been synthesized by the radical polymerization of styrene in the presence of a cyclic urethane (CU) derived from triethylene glycol and hexamethylene diisocyanate (CU-B) (Statistical method) and by styrene polymerization in presence of ordered “swarm” complexes of CU-B and ZnCl 2. A mechanism of polyrotaxane formation has been proposed, involving the preliminary swelling of the macro-rings in the monomer. The structure of these compounds was investigated by NMR and X-ray spectroscopy. The number of monomer units in one ring was calculated. A comparison of results obtained with analogous data on polyrotaxane synthesis based on a smaller ring of this homologous series (the CU from diethylene glycol and hexamethylene diisocyanate), permitted an elucidation of the effect of ring size and “swarm” complex dimensions on the degree of “piercing” of the rings by a polymer chain. The mechanisms obtained were explained with the aid of data on formation of complexes of both CUs with ZnCl 2 and the results of studying molecular models of these rings and the polyrotaxanes based on them.
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