Polymers play an essential role in everyday life as materials in automotive, packaging and electronics and as compounds in medicine. Today most polymeric materials are based on fossil sources, and reducing this fossil dependency, while propelling the transition to renewable resources, is one of the main challenges in the contemporary society. Renewable natural products from forestry, especially hemicelluloses and terpenes, offer a highly versatile platform for green building blocks. By using Nature’s own biofunctionalizations, enzymes can be used as green catalysts for the valorization of abundant terpenes from pinewood extractives. Enzymatic biotransformations enable mild processes for “activating” inert molecular building blocks in a highly controlled manner to afford renewable monomers. By combining <i>in vitro</i> synthetic biology and polymer chemistry, we have generated a new biobased polymer, starting from a naturally abundant terpene found in wood. Specifically, methacrylation of the terpene sobrerol, which can be achieved both enzymatically and by traditional organic chemistry, yielded a suitable monomer for radical polymerization. We were able to demonstrate that the enzymatic functionalization under benign conditions showed superior properties concerning yield, stereoselectivity and workup procedures of the methacrylated sobrerol, SobMa. Further, SobMA could be polymerized using both traditional and enzymatic procedures enabling a completely green route from a natural abundant compound to a highly versatile polymer. Due to the functional groups in the side chain, polySobMA provides a variety of possibilities for post-functionalization reactions and crosslinking. Polymeric films were obtained by crosslinking reactions using either the ene- or the hydroxyl functionality of the sobrerol unit, and the properties of the films were evaluated. Thus, the orthogonal second functionality, left unaffected during crosslinking, can be used for a broad range of further modifications to produce tailor-made polymer films targeting different applications. In conclusion, we were able to demonstrate that the use of enzymatic or chemo-enzymatic processes is an ideal approach to convert terpenes into highly versatile polymeric coating materials.

New chemo-enzymatic pathways for sustainable terpene-based polymeric materials

2019 Spring National Meeting

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