Empirical Structure–Property Relationships of PLLA-b-PEG-b-PLLA Triblock Copolymers with Tunable Thermal, Tensile, and Swelling Behavior

PLLA-b-PEG-b-PLLA triblock copolymers are promising materials because of their highly tunable properties. However, a systematic understanding of composition–property relationships remains limited. In this study, a series of A-B-A triblock copolymers was synthesized with polyethylene glycol (PEG) as soft center (B) domains and poly(L-lactic acid) (PLLA) as hard end (A) domains via ring-opening polymerization. Copolymer composition and molecular weights were characterized by proton nuclear magnetic resonance spectroscopy (1H NMR) and gel permeation chromatography (GPC). The thermal and mechanical properties of the copolymers were evaluated by differential scanning calorimetry (DSC) and tensile testing. We established quantitative structure–property relationships using empirical data, demonstrating that PLLA block length played a key role in modulating tensile properties, with a near-linear relationship, while PEG molecular weight critically influenced mechanical stability. An approximate minimum PLLA block length of 20 repeat units was found as a threshold required to maintain structural integrity during in vitro 24 h swelling. These findings provide insights and practical guidance for the design of triblock copolymers with tunable thermal, mechanical, and swelling properties of PLLA-b-PEG-b-PLLA triblock copolymers.