Sustainable Polythioesters via Thio(no)lactones: Monomer Synthesis, Ring-Opening Polymerization, End-of-Life Considerations, and Industrial Perspectives.

As the environmental effects of plastics are of ever greater concern, the industry is driven towards more sustainable polymers. Besides sustainability, our fast-developing society imposes the need for highly versatile materials. Whereas aliphatic polyesters (PEs) are widely adopted and studied as next-generation biobased and (bio)degradable materials, their sulfur-containing analogs, polythioesters (PTEs), only recently gained attention. Nevertheless, the introduction of S atoms is known to often enhance thermal, mechanical, electrochemical, and optical properties, offering prospects for broad applicability. Furthermore, thanks to their thioester-based backbone, PTEs are inherently susceptible to degradation, giving them a high sustainability potential. The key route to PTEs is through ring-opening polymerization (ROP) of thio(no)lactones. This Review critically discusses the (potential) sustainability of the most relevant state-of-the-art in every step from sulfur source to end-of-life treatment options of PTEs, obtained through ROP of thio(no)lactones. The benefits and drawbacks of PTEs versus PEs are highlighted, including their industrial perspective.

Boosting PLA melt strength by controlling the chirality of co-monomer incorporation.

Bio-based and degradable polymers such as poly(lactic acid) (PLA) have become prominent. In spite of encouraging features, PLA has a low melt strength and melt elasticity, resulting in processing and application limitations that diminish its substitution potential vis-a-vis classic plastics. Here, we demonstrate a large increase in zero shear viscosity, melt elasticity, elongational viscosity and melt strength by random co-polymerization of lactide with small amounts, viz. 0.4-10 mol%, of diethylglycolide of opposite chiral nature. These enantiomerically pure monomers can be synthesized using one-step zeolite catalysis. Screening of the ester linkages in the final PLA chains by the ethyl side groups is suggested to create an expanding effect on the polymer coils in molten state by weakening of chain-chain interactions. This effect is suspected to increase the radius of gyration, enabling more chain entanglements and consequently increasing the melt strength. A stronger melt could enable access to more cost-competitive and sustainable PLA-based biomaterials with a broader application window. Amongst others, blow molding of bottles, film blowing, fiber spinning and foaming could be facilitated by PLA materials exhibiting a higher melt strength.