The application of N-heterocyclic carbene (NHC) catalysis to the polycondensation of diols and dialdehydes under oxidative conditions is herein presented for the synthesis of polyesters using fossil-based (ethylene glycol, phthalaldehydes) and bio-based (furan derivatives, glycerol, isosorbide) monomers. The catalytic dimethyl triazolium/1,8-diazabicyclo[5.4.0]undec-7-ene couple and stoichiometric quinone oxidant afforded polyester oligomers with a number-average molecular weight (Mn) in the range of 1.5–7.8 kg mol−1 as determined by NMR analysis. The synthesis of a higher molecular weight polyester (polyethylene terephthalate, PET) by an NHC-promoted two-step procedure via oligoester intermediates is also illustrated together with the catalyst-controlled preparation of cross-linked or linear polyesters derived from the trifunctional glycerol. The thermal properties (TGA and DSC analyses) of the synthesized oligoesters are also reported.

Oxidative NHC-Catalysis as Organocatalytic Platform for the Synthesis of Polyester Oligomers by Step-Growth Polymerization

Daniele Ragno
Primo
;
Graziano Di Carmine
Secondo
;
Arianna Brandolese;Olga Bortolini;Pier Paolo Giovannini;Giancarlo Fantin;BERTOLDO, Monica
Penultimo
Membro del Collaboration Group
;
Alessandro Massi
Ultimo
2019

Abstract

The application of N-heterocyclic carbene (NHC) catalysis to the polycondensation of diols and dialdehydes under oxidative conditions is herein presented for the synthesis of polyesters using fossil-based (ethylene glycol, phthalaldehydes) and bio-based (furan derivatives, glycerol, isosorbide) monomers. The catalytic dimethyl triazolium/1,8-diazabicyclo[5.4.0]undec-7-ene couple and stoichiometric quinone oxidant afforded polyester oligomers with a number-average molecular weight (Mn) in the range of 1.5–7.8 kg mol−1 as determined by NMR analysis. The synthesis of a higher molecular weight polyester (polyethylene terephthalate, PET) by an NHC-promoted two-step procedure via oligoester intermediates is also illustrated together with the catalyst-controlled preparation of cross-linked or linear polyesters derived from the trifunctional glycerol. The thermal properties (TGA and DSC analyses) of the synthesized oligoesters are also reported.
2019
Ragno, Daniele; DI CARMINE, Graziano; Brandolese, Arianna; Bortolini, Olga; Giovannini, Pier Paolo; Fantin, Giancarlo; Bertoldo, Monica; Massi, Alessa...espandi
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11392/2410178
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