PLGA Barrier Materials from CO2. The influence of Lactide Co-monomer on Glycolic Acid Polyesters

Maria A Murcia Valderrama; Robert-Jan van Putten; Gert-Jan M Gruter

doi:10.1021/acsapm.0c00315

PLGA Barrier Materials from CO₂. The influence of Lactide Co-monomer on Glycolic Acid Polyesters

ACS Appl Polym Mater. 2020 Jul 10;2(7):2706-2718. doi: 10.1021/acsapm.0c00315. Epub 2020 Jun 24.

Authors

Maria A Murcia Valderrama¹, Robert-Jan van Putten^{1

2}, Gert-Jan M Gruter^{1

2}

Affiliations

¹ Van't Hoff Institute for Molecular Sciences, University of Amsterdam, P. O. Box 94720, 1090 GS Amsterdam, The Netherlands.
² Avantium Chemicals BV, Zekeringstraat 29, 1014 BV Amsterdam, The Netherlands.

Abstract

The combination of the predicted polymer market growth and the emergence of renewable feedstocks creates a fantastic opportunity for sustainable polymers. To replace fossil-based feedstock, there are only three alternative sustainable carbon sources: biomass, CO₂, and existing plastics (via mechanical and/or chemical recycling). The ultimate circular feedstock would be CO₂: it can be electrochemically reduced to formic acid derivatives that subsequently can be converted into useful monomers such as glycolic acid. This work is part of the European Horizon 2020 project "Ocean" in which the steps from CO₂ to glycolic acid are developed. Polyglycolic acid (PGA) and poly(lactide-co-glycolide) (PLGA) copolyesters with high lactic acid (LA) content are well-known. PGA is very difficult to handle due to its high crystallinity. On the other hand, PLGAs with high LA content lack good oxygen and moisture barriers. The aim of this work is to understand the structure-property relationships for the mostly unexplored glycolic acid rich PLGA copolymer series and to assess their suitability as barrier materials. Thus, PLGA copolymers with between 50 and 91 mol % glycolic acid were synthesized and their properties were evaluated. Increased thermal stability was observed with increasing glycolic acid content. Only those containing 87 and 91 mol % glycolic acid were semicrystalline. A crystallization study under non-isothermal conditions revealed that copolymerization reduces the crystallization rate for PLGA compared to polylactic acid (PLA) and PGA. While PGA homopolymer crystallizes completely when cooled at 10 °C·min^-1, the copolymers with 9 and 13% lactic acid show almost 10 times slower crystallization, which is a huge advantage vis-à-vis PGA for processing. The kinetics of this process, modeled with the Jeziorny-modified Avrami method, confirmed those observations. Barrier property assessment revealed great potential for these copolymers for application in barrier films. Increasing glycolic acid content in PLGA copolymers enhances the barrier to both oxygen and water vapor. At room temperature and a relative humidity below 70% the PLGA copolymers with high glycolic acid content outperform the barrier properties of polyethylene terephthalate.