ABSTRACTSynthetic l‐lactide random copolymers can be employed as controlled release materials when prepared using supercritical carbon dioxide (scCO2), since they are biodegradable via hydrolysis. To determine the effects of thermal properties on polymer performance following scCO2 processing, three types of poly(l‐lactide) having different properties were assessed. The Tm of one poly(l‐lactide) sample (H‐100) was found to be approximately 170 °C over the processing pressure range from 8 to 18 MPa, while a second sample (H‐440) also showed a constant value of approximately 152 °C. In contrast, the poly(l‐lactide) REVODE exhibited a Tm of 146 °C prior to processing but a higher value of 147 °C following treatment at 8 MPa. Unlike the H‐100 and H‐440, the Tm value of the REVODE tended to decrease with increasing pressure. The Tg values increased greatly under mild conditions of 8 MPa pressure and a temperature of 40 °C. In particular, the Tg values for the H‐440 and REVODE increased by 4 °C and 5 °C, respectively. All Tg values were lowest at 12 MPa and increased with increasing processing pressure, although the effect of processing temperature was minimal. The Χc DSC of the H‐100 was 18% initially but increased to 20% upon scCO2 processing at 40 °C and 14 MPa, and showed further increases at higher processing temperatures. Although the relationship between processing temperature and Χc DSC values for the H‐440 showed the same trend as observed with the H‐100, a different trend was seen for the REVODE. The Χc XRD values obtained from the XRD analyses differed from the values generated by DSC analysis, and showed a maximum degree of crystallinity following processing at 80 °C both with and without scCO2 treatment. ATR FT‐IR analyses identified peaks due to semicrystalline regions in poly(l‐lactide) samples treated with scCO2, even when applying low temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44006.