Background:
The synthesis of the aliphatic polyesters obtained by the ring opening
polymerization has been achieved using as initiators a large amount of organometallic compounds
derivative from: Alkali metals, alkaline earth metals, transition metals and lanthanide metals. Of all
these compounds, the lanthanide derivatives have acquired great importance in the synthesis of aliphatic
polyesters, since these show a greater catalytic activity and also can provide polymer with
characteristics that will be very useful in the design of biomaterials.
Objective:
It was proposed the synthesis of poly(L-lactida) (PL-LA) through a ring opening polymerization
process of L-lactide initiated with samarium(III) acetate (Sm(OAc)3) under solvent-free melt
conditions. The influence of different parameters of reaction, such as temperature, time, molar ratio
monomer to initiator, on typical variables of polymers, e.g., conversion, dispersity, and molar mass,
were analyzed.
Methods:
All polymerizations were carried out under solvent-free melt conditions in ampoules-like
flasks, equipped with a magnetic stirrer. The obtained polyesters were characterized by size exclusion
chromatography (SEC) and 1H-NMR.
Results:
The Sm(OAc)3 induces the polymerization of L-LA at high conversion, and produce polyesters
with number-average molecular weights of 1.00 x 103 to 30.00 x 103 Dalton. The 1H-NMR analysis
indicates a typical polymerization mechanism of coordination-insertion, with a breakdown of the
acyl-oxygen bond of the L-LA.
Conclusion:
Sm(OAc)3 was an effective initiator for the ring-opening polymerization of L-LA. SEC
chromatography showed that, at high temperatures and prolonged reaction times, the molar mass of
the polyester decreases, which is associated with the transesterification collateral reactions that occur
during the polymerization process.
1-n-Butyl-3-methylimidazolium-2-carboxylate: a versatile precatalyst for the ring-opening polymerization of ε-caprolactone and rac-lactide under solvent-free conditions
