To meet EU CO2 emission targets, we need to replace most fossil-derived plastics with renewable alternatives. To stop endless pollution by accumulating non degradable plastics we need future plastics to be closed-loop recyclable and/or biodegradable.
The one-pot catalytic reductive etherification of furfural to 2-methoxymethylfuran (furfuryl methyl ether, FME), a valuable bio-based chemical or fuel, is reported. A large number of commercially available hydrogenation heterogeneous catalysts based on nickel, copper, cobalt, iridium, palladium and platinum catalysts on various support were evaluated by a high-throughput screening approach. The reaction was carried out in liquid phase with a 10% w/w furfural in methanol solution at 50 bar of hydrogen. Among all the samples tested, carbon-supported noble metal catalysts were found to be the most promising in terms of productivity and selectivity. In particular, palladium on charcoal catalysts show high selectivity (up to 77%) to FME. Significant amounts of furfuryl alcohol (FA) and 2-methylfuran (2-MF) are observed as the major by-products.
4 January 2022 in Science of The Total Environment
In order to reduce the plastic accumulation in the environment, biodegradable plastics are attracting interest in the plastics market. However, the low thermal stability of most amorphous biodegradable polymers limits their application. With the aim of combining high glass transition temperature (Tg), with good (marine) biodegradation a family of novel fully renewable poly(isosorbide-co-diol) oxalate (PISOX-diol) copolyesters was recently developed. In this study, the biodegradability of a representative copolyester, poly(isosorbide-co-1,6-hexanediol) oxalate (PISOX-HDO), with 75/25 mol ratio IS/HDO was evaluated at ambient temperature (25 °C) in soil and marine environment by using a Respicond system with 95 parallel reactors, based on the principle of frequently monitoring CO2 evolution. During 50 days incubation in soil and seawater, PISOX-HDO mineralised faster than cellulose. The ready biodegradability of PISOX-HDO is related to the relatively fast non-enzymatic hydrolysis of polyoxalates. To study the underlying mechanism of PISOX-HDO biodegradation, the non-enzymatic hydrolysis of PISOX-HDO and the biodegradation of the monomers in soil were also investigated. Complete hydrolysis was obtained in approximately 120 days (tracking the formation of hydrolysis products via 1H NMR). It was also shown that (enzymatic) hydrolysis to the constituting monomers is the rate-determining step in this biodegradation mechanism. These monomers can subsequently be consumed and mineralised by (micro)organisms in the environment much faster than the polyesters. The combination of high Tg (>100 °C) and fast biodegradability is quite unique and makes this PISOX-HDO copolyester ideal for short term applications that demand strong mechanical and physical properties.
The predicted growth in plastic demand and the targets for global CO2 emission reductions require a transition to replace fossil-based feedstock for polymers and a transition to close- loop recyclable, and in some cases to, biodegradable polymers. The global crisis in terms of plastic littering will furthermore force a transition towards materials that will not linger in nature but will degrade over time in case they inadvertently end up in nature. Efficient systems for studying polymer (bio)degradation are therefore required. In this research, the Respicond parallel respirometer was applied to polyester degradation studies. Two poly(lactic-co-glycolic acid) copolyesters (PLGA12/88 and PLGA6/94) were tested and shown to mineralise faster than cellulose over 53 days at 25 °C in soil: 37% biodegradation for PLGA12/88, 53% for PLGA6/94, and 30% for cellulose. The corresponding monomers mineralised much faster than the polymers. The methodology presented in this article makes (bio)degradability studies as part of a materials development process economical and, at the same time, time-efficient and of high scientific quality. Additionally, PLGA12/88 and PLGA6/94 were shown to non-enzymatically hydrolyse in water at similar rates, which is relevant for both soil and marine (bio)degradability.