Synthesis of cyclic polymers and flaws of the Jacobson–Stockmayer theory

Abstract

Cyclic poly(L-lactide)s were prepared by ring-opening polymerization combined with simultaneous polycondensation (ROPPOC) in bulk at 160 °C with dibutyltin bis(4-cyanophenoxide) as catalyst. It is demonstrated by MALDI TOF mass spectrometry and ¹H NMR end group analyses that cycles are formed by end-to-end cyclization in addition to “back-biting” transesterification. Formation of high molar mass cyclic poly(L-lactide)s by means of several more reactive ROPPOC catalysts presented previously and in new experiments is discussed. These experimental results, together with theoretical arguments, prove that part of the Jacobson–Stockmayer theory is wrong. The critical monomer concentration, above which end-to-end cyclization is seemingly impossible, does not exist and reversible like irreversible polycondensations can theoretically proceed up to 100% conversion, so that finally all reaction products will necessarily adopt a cyclic architecture.