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

ASUCAROP aims at synthesizing 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 bio-derived 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 (n = 3-5), 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. After initial optimization in batch conditions, CCs and APCs syntheses will also be optimized in a continuous flow setup, critically evaluating the effect of reaction conditions on the processes productivities and on physico-chemical properties of the resulting products. Importantly, the end-of-life fate of the resulting polycarbonates will be evaluated upon selective depolymerization to the starting cyclic monomers under controlled catalytic conditions, in order to assess a circular and tuneable, reversible polymerization process. ASUCAROP will benefit of the complementary expertise of the different research units involved in the project, which are all currently investigating sustainable chemistry relevant research topics. In particular ASUCAROP represents a unique opportunity to merge established competences in homogeneous and heterogeneous organo- and biocatalysis for biomass valorisation and apply them to the preparation of novel added-value bio-based molecular building blocks and materials, ultimately developing (de)polymerization processes. All the researchers involved will acquire broader interdisciplinary competences, developing catalytic processes at the interface between molecules and materials and using sustainable catalytic strategies as a key enabling tool for biomass valorisation. We envisage a broad societal impact of both technical and complementary objectives of the proposal, including timely and relevant interdisciplinary training opportunities for two early career researchers. In particular, the successful implementation of ASUCAROP project will address relevant open challenges in the development of circular economy highlighted within the emerging topics of Horizon Europe, and will contribute to development of environmentally benign technologies for the responsible consumption and production of chemical products (UN’s SDG 12).