Enhanced generation of bio-based materials is vital to replace current synthetic polymers obtained from petroleum with more sustainable options. By using Nature’s own bio-functionalization, enzymes can be used as green catalysts for the valorization of abundant terpenes from pine-wood extractives. By combining <i>in vitro</i> synthetic biology and polymer chemistry, we have generated a novel class of bio-based polymers, starting from a naturally abundant terpene found in biomass. As a showcase, we unlock the inherent monomer reactivity of norcamphor, a bicyclic ketone used as a monoterpene-model system, to afford polyesters with unprecedented backbones. One of the potential uses of these previously unreported polymers is polymeric networks. However, these materials are not readily deformable once cured; they lack re-fabrication ability after crosslinking, and can’t be reprocessed or repaired after fracture. To overcome such issues, stimuli-responsive polymers have become a chief/major topic in the field of material science and engineering in the last several decades.<br/>Temperature-dependent crosslinking/reverse crosslinking can be performed by the Diels-Alder reaction (DA). The temperature serves an important role in determining the favoured equilibrium. Materials based on star-shaped poly(ε-caprolactone) (PCL) exhibited outstanding thermo-reversible properties such as high recovery ratios and recyclability. Poly(norcamphor lactone) (PNCL) can be used as a green alternative to PCL. We prepared polymer networks based on star-shaped PNCL functionalized with furan moieties and allowed it to form a thermo-reversible network by DA chemistry (Scheme 1). We were able to demonstrate that the use of enzymatic or chemo-enzymatic processes is ideal to convert terpenes into highly versatile polymeric materials. The designed networks display promising molecular and synthetic features for the production of high-performance temperature-responsive polymer networks from renewable resources.

Enzymatic route for the synthesis of norcamphor lactone and its polymerization for applications as thermo-sensitive networks

2019 Fall National Meeting

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