Fluoride-promoted carbonylation polymerization: a facile step-growth technique to polycarbonates

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-g...

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Detalhes bibliográficos
Autores: García Gallego, Sandra|||0000-0001-6112-0450, Olsson, Johan V., Hult, Daniel, Malkoch, Michael
Formato: artículo
Fecha de publicación:2017
País:España
Recursos:Universidad de Alcalá (UAH)
Repositorio:e_Buah Biblioteca Digital Universidad de Alcalá
Idioma:inglés
OAI Identifier:oai:ebuah.uah.es:10017/35220
Acesso em linha:http://hdl.handle.net/10017/35220
https://dx.doi.org/10.1039/C6SC05582F
Access Level:acceso abierto
Palavra-chave:Cesium Fluoride
polymerization
1,1'-carbonyldiimidazole
polycarbonates
Química
Chemistry
Descrição
Resumo: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.