Enhancing the Sustainability of Poly(Lactic Acid) (PLA) Through Ketene-Based Chain Extension

The widespread utilization of nonrenewable fossil-based polymers has led to significant environmental damage. Bio-based Poly(lactic acid) (PLA) has garnered substantial academic and industrial interest in the last two decades due to its advantageous characteristics for food packaging applications. Nonetheless, the improper disposal of PLA continues to contribute to the plastic waste problem. PLA recycling mainly involves thermal processes, facing challenges due to PLA’s limited stability. This study aims to enhance PLA’s molecular weight and melt viscosity by using chain extenders to increase its degree of branching. A modular chain extender capable of thermally forming highly reactive ketene intermediates is employed to react with PLA’s hydroxyl and carboxyl end groups in a single step. For this purpose, copolymers of styrene and 2,2,5-trimethyl-5-(4-vinylbenzyl)-1,3-dioxane-4,6-dione were synthesized using free radical polymerization and characterized through ¹H-NMR, TGA, and DSC analyses. The chemical interaction between these chain extenders and molten PLA was also explored, resulting in increased PLA molecular weight and higher melting temperature (T_m), reaching 155.1 for PLA_2.5CE2. Additionally, the branching introduced through this process led to a notable increase in the UV absorption of PLA, suggesting potential applications in the packaging industry. The chemical tunability of this functional ketene-based chain extender holds promise for tailoring PLA’s structure for diverse applications, further advancing its sustainability and utility. Graphical Abstract: (Figure presented.).