Levulinic Acid as a Versatile Building Block for Plasticizer Design

The large potential of utilizing green platform chemicals such as levulinic acid, glycerol, and ethylene glycol as building blocks for the design of high-performance biobased plasticizers was demonstrated. From these green platform chemicals, esters with ketal or ketone functionalities and linear or branched structures were carefully designed and synthesized via a mild and solvent-free route and characterized by H-1 NMR, C-13 NMR, and FTIR. The effect of the structural combinations on the performance as plasticizers for polylactide (PLA), including migration resistance, was followed by a series of characterization techniques. The levulinates with ketone end-groups exhibited large capability to lower the glass transition temperature (T-g) of PLA (to 15 degrees C by 20 wt % plasticizer). Ketal end-groups provided additional thermal stability to the plasticizers, but their ability to lower T-g was not as good as that of ketone end-groups. Significantly improved flexibility reaching 546% elongation at break was achieved by the addition of 20 wt % ethylene glycol dilevulinate, as compared to 5% elongation at break for neat PLA. The structural differences for the plasticizers resulted in different degrees of hydrophobicity, which influenced the migration tendency of the plasticizers and also the hydrolysis rate of PLA. The branched ester structure with ketal end-groups maintained the processing window of PLA, but also lowered the hydrolysis rate of PLA in an accelerated migration test. In general, performance comparable to that of the reference plasticizer acetyl tributyl citrate (ATBC) was demonstrated, offering promise for a family of plasticizers derivable from green platform chemicals.