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1. Synthesis and Melt Processing of Sustainable Poly(ε-decalactone)- block -Poly(lactide) Multiblock Thermoplastic Elastomers

   https://doi.org/10.1021/sc500412a  

   Martello, Mark T.; Schneiderman, Deborah K.; Hillmyer, Marc A. (October 2014, ACS Sustainable Chemistry & Engineering)
2. Toughening Glassy Poly(lactide) with Block Copolymer Micelles

   https://doi.org/10.1021/acsmacrolett.6b00063  

   Li, Tuoqi; Zhang, Jiuyang; Schneiderman, Deborah K.; Francis, Lorraine F.; Bates, Frank S. (March 2016, ACS Macro Letters)
3. Post-functionalization and Mechanical Properties of Poly(lactide-cyclohexadiene oxide) Block Copolymers

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4. Crazing Mechanism and Physical Aging of Poly(lactide) Toughened with Poly(ethylene oxide)- block -poly(butylene oxide) Diblock Copolymers

   https://doi.org/10.1021/acs.macromol.0c01759  

   McCutcheon, Charles J.; Zhao, Boran; Jin, Kailong; Bates, Frank S.; Ellison, Christopher J. (November 2020, Macromolecules)

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5. Biaxial Toughening in Uniaxially Stretched Films of Block Polymer-Modified Semicrystalline Poly( l -lactide)

   https://doi.org/10.1021/acsapm.4c00670  

   Coote, Jonathan P; Zhao, Boran; McCutcheon, Charles J; Larson, Matthew C; Lyadov, Illya; Bates, Frank S; Ellison, Christopher J (May 2024, ACS Applied Polymer Materials)

   Semicrystalline poly(l-lactide) (PLLA) is a leading biosourced, compostable alternative to conventional plastics but lacks sufficient toughness for many applications. Chain alignment via uniaxial stretching may be used to toughen PLLA but often creates anisotropic materials that are tough in the machine direction (MD) but brittle in the transverse direction (TD). This work reports uniaxially stretched films of PLLA blended with 3 wt % poly(ethylene oxide)-block-poly(butylene oxide) (PEO-PBO), which exhibit as much as a 5-fold increase in toughness in the TD compared to similarly stretched neat PLLA films─and elucidates the impact of PEO–PBO particles on the relationship between stretching, crystallization behavior, and resultant mechanical properties. Faster stretching rates were correlated with higher yield stress and a greater degree of crystallite alignment in the PEO–PBO/PLLA blends. This trend highlights the synergistic relationship between crystallinity and chain alignment and suggests a competing mechanism of heterogeneous crystallite nucleation around PEO–PBO particles. Importantly, PEO–PBO/PLLA exhibited a TD elongation at break of 36%, five times greater than the value of similarly stretched neat PLLA and even greater than the corresponding MD value of either material. Taken together, these findings demonstrate that uniaxial stretching of PEO–PBO/PLLA blends produces biaxially tough films, with the fastest stretching conditions producing the greatest enhancement in TD toughness. 

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