Functional polyesters and polycarbonates preparation through catalytic ring-opening copolymerization of fatty acid epoxides Arianna Brandolese University of Birmingham, UK Raw materials derived from renewable resources are of growing interest to the chemical industry. 1 Nowadays, a great challenge is the production of polymers based on renewable feedstock and of special attention are natural oil-based monomers. 2 Among the readily available renewable biocompounds, fatty acids, after a preliminary conversion into the corresponding epoxides, embody a promising monomer for the ring opening copolymerization (ROCOP) along with cyclic anhydrides or with CO 2 . 3 Herein, we report on the ring-opening alternating copolymerization of epoxy fatty acids with various cyclic anhydrides using metal aminotriphenolate complexes including bio-based ones to afford polyesters (with M n up to 16.0 kg/mol) of narrow molecular weight distributions ( Đ = 1.2−1.5). 4 The reported methodology constitutes a way to synthesize a variety of polyesters from oleic acid, including those with alkyne and furan functionalities that are potentially useful in post-polymerization modifications. Therefore, we explored the possibility of functionalizing these new materials through the preparation of irreversible and thermo- reversible cross-linked polyesters. Similarly, terminal epoxides from fatty acids were employed as monomers in the ROCOP with CO 2 under the same catalytic system to access biobased polycarbonates (with M n up to 20.0 kg/mol) of narrow molecular weight distributions ( Đ = 1.2−1.5). 5 The organocatalytic depolymerization of fatty acid-based polycarbonates was additionally explored along with the possibility to introduce further functional groups in the side chains of the polymeric formulations. References 1. Biermann, U.; Bornscheuer, U.; Meier, M. A.; Metzger, J. O.; Schäfer, H. J. Chem. Int. Ed. 2011 , 50 , 3854−3871. 2. Meier, M. A. R.; Metzger, J. O.; Schubert, S. Chem. Soc. Rev. 2007 , 36 , 1788-1802;
3. Montero de Espinosa, L.; Meier, M. A. R. Eur. Polym. J . 2011 , 47 , 837–852. 4. Brandolese, A.; Kleij, W. Acc. Chem. Res. 2022 , 55, 12, 1634−1645. 5. Brandolese, A.; Della Monica, F.; Pericàs, M. A.; Kleij, A. W. Macromolecules 2022 , 55 , 2566−2573. 6. Brandolese A.; Lamparelli, D. H; Grimaldi, I.; Kleij, A. W., manuscript under preparation .
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