High-throughput experimentation for discovery of biodegradable polyesters

Abstract

The consistent rise of plastic pollution has stimulated interest in the development of biodegradable plastics. However, the study of polymer biodegradation has historically been limited to a small number of polymers due to costly and slow standard methods for measuring degradation, slowing new material innovation. High-throughput polymer synthesis and a high-throughput polymer biodegradation method are developed and applied to generate a biodegradation dataset for 642 chemically distinct polyesters and polycarbonates. The biodegradation assay was based on the clear-zone technique, using automation to optically observe the degradation of suspended polymer particles under the action of a single Pseudomonas lemoignei bacterial colony. Biodegradability was found to depend strongly on aliphatic repeat unit length, with chains less than 15 carbons and short side chains improving biodegradability. Aromatic backbone groups were generally detrimental to biodegradability; however, ortho- and para-substituted benzene rings in the backbone were more likely to be degradable than metasubstituted rings. Additionally, backbone ether groups improved biodegradability. While other heteroatoms did not show a clear improvement in biodegradability, they did demonstrate increases in biodegradation rates. Machine learning (ML) models were leveraged to predict biodegradability on this large dataset with accuracies over 82% using only chemical structure descriptors.

Highly transparent polyurethane thermosets with tunable properties and enzymatic degradability derived from polyols originating from hemicellulosic sugars

“…Here, aliphatic condensation polymers are expected to have higher susceptibility to biodegradation compared to aromatic ones. 60,61 For preliminary evaluation of the susceptibility of our aliphatic PU networks to biodegradation, all synthesized aliphatic PU networks with different crosslinking degrees were subjected to enzymatic degradation assays in aqueous solution using Candida rugosa lipase and lipase from Aspergillus niger as enzymes. These enzymes have been commonly used to evaluate the enzymatic degradability of polyesters, polyurethanes and polyester-urethanes.…”

Ring-Opening Polymerization of Lactones to Prepare Closed-Loop Recyclable Polyesters

“…Reineke and co-workers reported the synthesis and polymerization of a novel disubstituted valerolactone, β-acetoxy-δ-methyl­valerolactone, which was derived from the renewable feedstock triacetic acid lactone (TAL). The ROP thermodynamic behavior was examined, and the resultant amorphous material displayed a T g of 25 °C (Table , run 15). Li et al prepared a series of poly­(ester–amide)­s (PEAs) by the ROP of morpholino-2,5-dione derivatives (MDs), which can be synthesized from α-hydroxy acids and α-amino acids. , These amorphous PEAs can also be directly depolymerized to pristine MDs under an amberlyst 15 ion-exchange resin.…”

“…The heteroatom substitutions in the main chain can affect the polarity, crystallinity, mechanical properties and chemical recyclability of polyesters . Recently, the incorporation of heteroatoms into the polymer backbone has become an efficient tool to accelerate degradation and construct chemical recyclable polyesters .…”

“…The heteroatom substitutions in the main chain can affect the polarity, crystallinity, mechanical properties and chemical recyclability of polyesters. 173 Recently, the incorporation of heteroatoms into the polymer backbone has become an efficient tool to accelerate degradation and construct chemical recyclable polyesters. 174 For example, Wang et al have been engaged in investigation of ROP of 1,4-dioxan-2-one (pDO) to produce degradable and chemical recyclable (co)polyesters over ten years.…”

Synthesis of Statistical Multiblock Copolymers through Chain Shuttling Copolymerization with a Thermomechanical Switch Behavior

“…High-throughput experimentation (HTE) platforms and workflows in material science can help to discover new materials and widen the field of applications of polyolefins. − In a recent paper, a multidisciplinary high-throughput approach covering the entire chain of knowledge, was introduced to build sound and reliable databases for quantitative structure–property relation (QSPR) investigations and to prepare new materials. , In particular, it was demonstrated that HTE protocols implemented for the high-temperature and high-pressure synthesis of statistical multiblock copolymers (MBCs) with chain shuttling copolymerization (CSC) technology allow the production of MBCs, mimicking the commercial Dow INFUSE materials in all industrially relevant aspects.…”