Tensile behavior and dynamic mechanical analysis of novel poly(lactide/δ-valerolactone) statistical copolymers

Lactide-co-δ-valerolactone copolymers (PLVL) have not attracted as much research interest as the more popular poly(lactide-co-ε-caprolactone) (PLCL) elastomeric materials. In this work the study of the mechanical performance is focused on the former with the aim of identifying the potential advantages of these thermoplastic elastomers for their application in the biomedical field. Mechanical testing (at 21°C and at 37°C) of at least 5 specimens and dynamic mechanical analysis (DMA) in duplicate were carried out on various PLVL, which include a moderately blocky l-lactide/δ-valerolactone copolymer (~70% of l-LA and R=0.68) and several that showed a random distribution of sequences (R~1): some terpolymers based on l-lactide, d-lactide and δ-valerolactone (with a lactone content of ~25 and ~14%) and a series of copolymers of l-LA and δ-VL having l-LA molar contents ranging from 69 to 74%. In view of the results, it can be concluded that noteworthy improvements in stiffness and strength were achieved by adding δ-VL to the reaction mix instead of ε-CL, although both monomers have analogous chemical properties. For example, a PLVL with a 75:25M composition of l-LA/δ-VL at 21°C presented a secant modulus of 213.7±36.5MPa and σu=14.7±1.4MPa whereas a previously studied PLCL of equal composition had a secant modulus and an ultimate stress value of 19.4±1.3MPa and 3.2±0.6MPa, respectively. At 37°C, the differences in the mechanical properties between the different PLVLs of this work were far less relevant, with most of them showing a fully elastomeric behavior. Referring to the DMA measurements, the reduction in the peak of tan δ (from ~2.5 to 0.5) through the glass transition was a clear indicator that crystalline domains formed during hydrolytic degradation in some of the polymers. However, the more amorphous PLVLs with short l-LA average sequence lengths (ll-LA<2.91) did not undergo changes in the storage modulus and tan δ curves after two weeks submerged in PBS at 37°C.