β-Methyl-δ-valerolactone-containing thermoplastic poly(ester-amide)s: Synthesis, mechanical properties, and degradation behavior

Poly(ester-amide)s (PEAs) have been prepared from (glucose-derived) β-methyl-δ-valerolactone (MVL) by reaction of MVL-derived diamidodiols with diacid chlorides in solution to form poly(ester-amide)s having alternating diester-diamide subunits. The PEAs formed by this method exhibit plastic properties and are of sufficiently high molecular weight to be tough, ductile materials (stress at break: 41-53 MPa, strain at break: 530-640%). The length of the methylene linker unit (n = 1,2,3) between amide groups of the diamidodiols affects the Young's modulus; longer linkers reduce the stiffness of the materials. This allows tuning of the properties by judicious choice of precursors. MVL was also converted to a diacid chloride that was then used to prepare a PEA that is 76 wt% MVL-derived. The degradation rates of suspensions of these new PEAs in basic aqueous media were benchmarked and their instability in aqueous acid was also observed. NMR studies were used to detect the hydrolytic degradation products of both these PEAs as well as a structurally simpler analog.