Fluoride-promoted carbonylation polymerization: a facile step-growth technique to polycarbonates
IdentifiersPermanent link (URI): http://hdl.handle.net/10017/35220
AffiliationUniversidad de Alcalá. Departamento de Química Orgánica y Química Inorgánica. Unidad docente Química Inorgánica
Chemical Science, 2017, v. 8, n. , p. 4853-4857
info:eu-repo/grantAgreement/Swedish ResearchCouncil/VR-2011-5358 2010-435/Knut and Alice Wallenberg Foundation-2012-0196/Marcus and Amalia Wallenberg foundation/H2020/Marie Sklodowska-Curie Grant Agreement/655649
Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
© Royal Society of Chemistry, 2017
Fluoride-Promoted Carbonylation (FPC) polymerization is herein presented as a novel catalytic polymerization methodology that complements ROP and unlocks a greater synthetic window to advanced polycarbonates. The overall two-step strategy is facile, robust and capitalizes on the synthesis and step-growth polymerization of bis-carbonylimidazolide and diol monomers of 1,3- or higher configurations. Cesium fluoride (CsF) is identified as an efficient catalyst and the bis-carbonylimidazolide monomers are synthesized as bench-stable white solids, easily obtained on 50&#-100 g scales from their parent diols using cheap commercial 1,1&;8242#-carbonyldiimidazole (CDI) as activating reagent. The FPC polymerization works well in both solution and bulk, does not require any stoichiometric additives or complex settings and produces only imidazole as a relatively low-toxicity by-product. As a proof-of-concept using only four diol building-blocks, FPC methodology enabled the synthesis of a unique library of polycarbonates covering (i) rigid, flexible and reactive PC backbones, (ii) molecular weights 5&#-20 kg mol&;8722#1, (iii) dispersities of 1.3&#-2.9 and (iv) a wide span of glass transition temperatures, from &;8722#45 up to 169 °C.