Effects of heating rate and temperature on product distribution of poly-lactic acid and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate

In this study, poly-lactic acid (PLA) and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (PHBH) were pyrolyzed at various temperatures (300, 350, 400, 500, 600, and 700 °C) and heating rates (5, 10, 20, 30, and 40 °C min⁻¹) using a pyrolysis–gas chromatograph/mass spectrometer (Py–GC/MS). The results revealed that the main pyrolysis products of PLA were acetaldehyde, lactide (including meso-lactide and d-, l-lactide), and oligomers. Crotonic acid and its oligomers accounted for most of the PHBH pyrolyzates. The pyrolysis temperature significantly correlated with the product distribution, but the heating rate had a small effect on the product distribution. Lactide and crotonic acid were two kinds of high-value chemicals, and their highest yields were obtained at 400 and 600 °C with 29.7 and 72.6 area %, respectively. Secondary reactions could not be neglected at 700 °C, and acetaldehyde and crotonic acid decreased to 65.0 and 69.6 area %, respectively. These results imply that pyrolyzate selectivity can be controlled by temperature management during pyrolysis.