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

Daniele Ragno; Graziano Di Carmine; Arianna Brandolese; Olga Bortolini; Pier Paolo Giovannini; Giancarlo Fantin; Monica Bertoldo; Alessandro Massi

doi:10.1002/chem.201903557

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

Daniele Ragno, Graziano Di Carmine, Arianna Brandolese, Olga Bortolini, Pier Paolo Giovannini, Giancarlo Fantin, Monica Bertoldo, Alessandro Massi^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

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 (M_n) 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.

Original language	English
Pages (from-to)	14701-14710
Number of pages	10
Journal	Chemistry - A European Journal
Volume	25
Issue number	64
DOIs	https://doi.org/10.1002/chem.201903557
Publication status	Published - 18 Nov 2019

Bibliographical note

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

carbenes
organocatalysis
oxidation
polyesters
polymerization

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1002/chem.201903557

Cite this

@article{4b60643619a340a19773ea7ad922d5fa,

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

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.",

keywords = "carbenes, organocatalysis, oxidation, polyesters, polymerization",

author = "Daniele Ragno and {Di Carmine}, Graziano and Arianna Brandolese and Olga Bortolini and Giovannini, {Pier Paolo} and Giancarlo Fantin and Monica Bertoldo and Alessandro Massi",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = nov,

day = "18",

doi = "10.1002/chem.201903557",

language = "English",

volume = "25",

pages = "14701--14710",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "64",

}

TY - JOUR

T1 - Oxidative NHC-Catalysis as Organocatalytic Platform for the Synthesis of Polyester Oligomers by Step-Growth Polymerization

AU - Ragno, Daniele

AU - Di Carmine, Graziano

AU - Brandolese, Arianna

AU - Bortolini, Olga

AU - Giovannini, Pier Paolo

AU - Fantin, Giancarlo

AU - Bertoldo, Monica

AU - Massi, Alessandro

PY - 2019/11/18

Y1 - 2019/11/18

N2 - 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.

AB - 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.

KW - carbenes

KW - organocatalysis

KW - oxidation

KW - polyesters

KW - polymerization

UR - http://www.scopus.com/inward/record.url?scp=85074554936&partnerID=8YFLogxK

U2 - 10.1002/chem.201903557

DO - 10.1002/chem.201903557

M3 - Article

C2 - 31486558

AN - SCOPUS:85074554936

SN - 0947-6539

VL - 25

SP - 14701

EP - 14710

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 64

ER -

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

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Fingerprint

Cite this