Block Copolymers From δ‐Tetradecalactone and Lactide: Synthesis, Self‐Assembly, and Ready Biodegradation Test

The synthesis and characterization of novel block copolymers derived from δ‐tetradecalactone (TDL), a biobased lactone, and lactide (LA), using ring‐opening polymerization, was investigated. Poly(δ‐tetradecalactone) (PTDL) macroinitiators were first prepared in bulk via organocatalysis using TBD and subsequently employed as macroinitiators to generate a range of diblock copolymers with poly( l ‐lactide) or poly( d,l ‐lactide) segments. These copolymers exhibit tunable thermal properties and demonstrate the ability to self‐assemble in nonpolar media such as isododecane, with particle formation behavior dependent on the copolymer composition and the preparation method (direct solubilization or nanoprecipitation). The biodegradability of the materials was evaluated under OECD 301F conditions. While copolymers with long PLA blocks showed limited biodegradation, incorporation of short lactide blocks maintained significant biodegradation levels, particularly when aided by a bioavailability improvement method (2,2,4,4,6,8,8‐heptamethylnonane, HMN).