Syntheses of cyclic polylactides and the problem of catenane formation

Cyclic poly(l-lactide)s (PLAs) were prepared in bulk either by ring-expansion polymerization (REP) or by ring-opening polymerization (ROP) with simultaneous polycondensation (ROPPOC). In contrast to REP the latter method involves formation of linear chains and thus, may involve formation of polydisperse catenanes that affect crystallization. The reprecipitated PLAs were annealed at 120 °C and compared with regard to melting temperature (T _m) and melting enthalpy (ΔH _m). For similar molar masses the PLAs prepared by REP and ROPPOC had almost identical T _m's and crystallinities. Furthermore, the influence of REP and ROPPOC catalysts on the morphology of the virgin reaction products was compared.