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Branched Poly(lactide) Synthesized by Enzymatic Polymerization: Effects of Molecular Branches and Stereochemistry on Enzymatic Degradation and Alkaline Hydrolysis
journal contribution
posted on 2007-10-08, 00:00 authored by Keiji Numata, Rajiv K. Srivastava, Anna Finne-Wistrand, Ann-Christine Albertsson, Yoshiharu Doi, Hideki AbeIn this article the effects of the number of molecular branches (chain ends) and the stereochemistry of poly(lactide)s (PLAs) on the enzymatic degradation and alkaline hydrolysis are studied. Various linear and branched
PLAs were synthesized using lipase PS (Pseudomonas fluorescens)-catalyzed ring-opening polymerization (ROP)
of lactide monomers having different stereochemistries (l-lactide, d-lactide, and d,l-lactide). Five different alcohols
were used as initiators for the ROP, and the monomer-to-initiator molar feed ratio was varied from 10 to 100 and
1000 for each branch in the polymer architecture. The properties of branched PLAs that would affect the enzymatic
and alkaline degradations, i.e., the glass transition temperature, the melting temperature, the melting enthalpy,
and the advancing contact angle, were determined. The PLA films were degraded using proteinase K or 1.0 M
NaOH solution, and the weight loss and changes in the number average molecular weight (Mn) of the polymer
were studied during 12 h of degradation. The results suggest that an increase in the number of molecular branches
of branched PLAs enhances its enzymatic degradability and alkali hydrolyzability. Moreover, the change in Mn
of the branched poly(l-lactide) (PLLA) by alkaline hydrolysis indicated that the decrease in Mn was in the first
place dependent on the number of molecular branches and thereafter on the length of the molecular branch of
branched PLA. The branched PLLA, poly(d-lactide) (PDLA), and poly(d,l-lactide) (PDLLA) differed in weight
loss and change in Mn of the PLA segment during the enzymatic degradation. It is suggested that the branched
PDLLA was degraded preferentially by proteinase K.