Melt Free-Radical Grafting of Maleic Anhydride onto Biodegradable Poly(lactic acid) by Using Styrene as a Comonomer

Maleic anhydride (MA) was grafted onto poly(lactic acid) (PLA) in the presence of styrene (St) by using a free-radical grafting methodology. The grafting degree (Dg) of MA was increased from 0.65 wt % to 1.1 wt % with the St/MA ratio up to 2/1, where the grafting efficiency (Eg) of MA was 27%. However, both Dg and Eg were decreased with further increasing of the St/MA ratio to 4/1. The Dg of MA increased with MA concentration and showed a maximum at 180 °C in the temperature range of 165 °C–190 °C. The grafting mechanisms of MA in the presence of St are analyzed based on titration, thermogravimetric analysis and infrared results, i.e., MA is grafted onto PLA chains via single monomers and a charge-transfer-complex (CTC) at St/MA ratios of ≤ 1/1, while dominantly via St-co-MA oligomers at St/MA ratios of around 2/1. Copolymerization rather than grafting of St and MA occurs at St/MA ratios of around 4/1. The thermal stability of PLA was compromised to a certain extent by the grafting of MA, resulting in reductions in the decomposition temperature (Td-5%) and molecular weight of the PLA. In addition, the crystallization and melting temperatures of the PLA were slightly reduced after the grafting.