Polylactide (PLA) polymers are the world's foremost 100% biobased resin with both composting and recycling end-of-life options in harmony with Ellen MacArthur Foundation "Circularity Model." It is commercially manufactured by converting lactic acid to lactide, which is then polymerized to PLA. These molecules present unique and intriguing stereochemistry that dictate manufacturing, performance properties, and processability. However, it is seldom discussed and not well understood in the role stereochemistry can play and impact product performance and use. In the current work, we critically review and discuss the stereochemical implications for PLA through studies on different PLA compositions. To-date, it is unclear the origin of D-content present in commercial grade PLA, although it is assumed to originate from D-lactide. In this work, we validate that manufacture of lactide monomer from (L)- lactic acid predominantly results in a mixture of L and meso (DL), not L- and D- lactide. Optical rotation and 1H NMR studies are used to elucidate this stereochemistry. Copolymers of L-lactide and meso-lactide and copolymers of L-lactide and D-lactide are synthesized via bulk polymerization at various compositions. The optical rotation, tacticity, crystallinity, and thermal properties of synthesized copolymers are characterized. The optical rotation of poly(meso-lactide) has also been reported for the first time in this text. Differential scanning calorimetry (DSC) and 1H NMR studies confirm that PLA transitions from a predominantly isotactic, semi-crystalline polymer to a predominantly atactic, amorphous polymer when one copolymerizes greater than 10% meso-lactide with L-lactide. The stereochemical composition, mechanical and rheological properties of commercial grade PLA are measured to elucidate the effect of stereochemistry on the tensile and rheological behavior of PLA. We conclude this section with studies on PLA stereochemistry and its influence on immune cellular response. Hydrolytic degradation of semi-crystalline and amorphous PLA is analyzed via molecular weight characterization and lactic acid abundance. Semi-crystalline and amorphous PLA are then studied as potential carriers for glycolytic inhibitors. The stereochemistry of PLA and its implication on performance properties are further explored in studies on stereocomplex PLA. A pilot-scale continuous manufacturing process of stereocomplex PLA is developed and optimized by melt-blending a 1:1 blend of high molecular weight poly(L-lactide) (PLLA) and high molecular weight poly(D-lactide) (PDLA) in a co-rotating twin screw extruder. Stereocomplexation is first characterized via DSC at different temperatures and times. The optimal reaction temperature and reaction time are found and used to process>95% stereocomplex PLA conversion (melting peak temperature Tpm = 240°C). Stereocomplex PLA is used as an additive to produce 70% PLLA/30% stereocomplex PLA composites. The crystallinity, thermal properties, and tensile properties of composites are then characterized. A study on stereocomplex PLA and its effect on the crystallization kinetics of PLLA is conducted. 5% stereocomplex PLA is blended with 95% PLLA to analyze its use as a nucleating agent. The final section discusses a pilot-scale end-of-life method for PLA via thermal recycling. This study continues previous studies on PLA thermodepolymerization by scaling up the reversible reaction in a pilot-scale batch reactor. PLA is run at various temperatures and times to elucidate the processing conditions that yield the highest lactide conversion. The chemical purity, optical purity, lactide yield and stereoisomeric composition of the final lactide product are characterized by DSC, optical rotation, mass balance, and 1H NMR, respectively.
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