Accessing SUstainable polyCArbonates from bio-based diols via organo- and biocatalytic Ring-Opening Polymerization (ASUCAROP)

The aim of the ASUCAROP project is the synthesis of structurally diverse, circular, aliphatic polycarbonates (APCs) from renewable-based monomers, relying exclusively on inherently sustainable organo- and biocatalytic polymerization/depolymerization processes. This strategy contributes to broaden the scope and applications of added-value bioderived materials, entering APCs characterised by aliphatic bridging units with variable length and/or degree of substitution suitable for depolymerization under controlled conditions. APCs will be synthesised by an innovative route starting from readily available 1,n-diols, derived from renewable-based platform chemicals. Initially, the selected diols will be transformed in the corresponding cyclic carbonates (CCs), upon reaction with synthetically relevant linear organic carbonates. The resulting CCs will be then employed as monomers for ring-opening (co)polymerization [RO(CO)P], leading to the selective formation of desired APCs products. Both processes will be carried out in presence of suitable organo- or biocatalysts, aiming at developing a one-pot, two step protocol. We selected a series promising 1,n-diols to be employed for the synthesis of large cyclic carbonates (LCCs), also using an extensive literature survey exercise as a starting point. Starting from these substates, the formation of LCCs was studied applying both organo-catalytic and a biocatalytic approaches, respectively based on superbases and lipases as the catalysts. In particular, the formation of 1,3-dioxan-2-one and linear dicarbonates was achieved, using green carbonylating agents such as DMC, that can be used for the synthesis of APCs by either ROCOP or polycondensation reactions.