“…Polycaprolactone (PCL), a member of aliphatic polyesters, has garnered growing attention with extensive applications in the biomedical and pharmaceutical fields and as packaging materials owing to the promising biocompatibility and degradability. − Despite its many advantages and commercial availability, PCL still has inherent limitations for practical applications due to its low melting processing temperature and low hydrophilicity. Massive efforts have been devoted to the development of functional PCLs via substitution − on PCL or incorporation of heteroatoms to the main chain. − For example, poly(1,5-dioxepan-2-one) (PDXO) containing both ester and ether functionalities in the polymer backbone was synthesized, and it demonstrated enhanced hydrophilicity compared with PCL. ,,, However, the complete amorphousness of PDXO limits its potential application scope. Besides, sulfur-containing polymers have established a variety of intrinsic merits and potential applications because they possess outstanding optical and electrical features and exhibit potential coordinating ability to heavy metal ions. − The introduction of sulfur atoms into PCL to generate poly(1,4-oxathiepan-7-one) (POTO), an analogue of PDXO, has been reported to display a slightly higher glass transition temperature ( T g ) than PDXO.…”