Exploring Oxidative NHC-Catalysis as Organocatalytic Polymerization Strategy towards Polyamide Oligomers

Daniele Ragno; Arianna Brandolese; Graziano Di Carmine; Sara Buoso; Giada Belletti; Costanza Leonardi; Olga Bortolini; Monica Bertoldo; Alessandro Massi

doi:10.1002/chem.202004296

Exploring Oxidative NHC-Catalysis as Organocatalytic Polymerization Strategy towards Polyamide Oligomers

Daniele Ragno, Arianna Brandolese, Graziano Di Carmine, Sara Buoso, Giada Belletti, Costanza Leonardi, Olga Bortolini, Monica Bertoldo, Alessandro Massi^*

^*Corresponding author for this work

Chemistry

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

9 Citations (Scopus)

Abstract

The polycondensation of diamines and dialdehydes promoted by an N-heterocyclic carbene (NHC) catalyst in the presence of a quinone oxidant and hexafluoro-2-propanol (HFIP) is herein presented for the synthesis of oligomeric polyamides (PAs), which are obtained with a number-average molecular weight (M_n) in the range of 1.7–3.6 kg mol⁻¹ as determined by NMR analysis. In particular, the utilization of furanic dialdehyde monomers (2,5-diformylfuran, DFF; 5,5’-[oxybis(methylene)]bis[2-furaldehyde], OBFA) to access known and previously unreported biobased PAs is illustrated. The synthesis of higher molecular weight PAs (poly(decamethylene terephthalamide, PA10T, M_n = 62.8 kg mol⁻¹; poly(decamethylene 2,5-furandicarboxylamide, PA10F, M_n = 6.5 kg mol⁻¹) by a two-step polycondensation approach is also described. The thermal properties (TGA and DSC analyses) of the synthesized PAs are reported.

Original language	English
Pages (from-to)	1839-1848
Number of pages	10
Journal	Chemistry - A European Journal
Volume	27
Issue number	5
Early online date	28 Sept 2020
DOIs	https://doi.org/10.1002/chem.202004296
Publication status	Published - 21 Jan 2021

Bibliographical note

Publisher Copyright:
© 2020 Wiley-VCH GmbH

Keywords

carbenes
organocatalysis
oxidation
polyamides
polymerization

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1002/chem.202004296

Cite this

@article{e8ba6d887524451ba2bba61e8407e799,

title = "Exploring Oxidative NHC-Catalysis as Organocatalytic Polymerization Strategy towards Polyamide Oligomers",

abstract = "The polycondensation of diamines and dialdehydes promoted by an N-heterocyclic carbene (NHC) catalyst in the presence of a quinone oxidant and hexafluoro-2-propanol (HFIP) is herein presented for the synthesis of oligomeric polyamides (PAs), which are obtained with a number-average molecular weight (Mn) in the range of 1.7–3.6 kg mol−1 as determined by NMR analysis. In particular, the utilization of furanic dialdehyde monomers (2,5-diformylfuran, DFF; 5,5{\textquoteright}-[oxybis(methylene)]bis[2-furaldehyde], OBFA) to access known and previously unreported biobased PAs is illustrated. The synthesis of higher molecular weight PAs (poly(decamethylene terephthalamide, PA10T, Mn = 62.8 kg mol−1; poly(decamethylene 2,5-furandicarboxylamide, PA10F, Mn = 6.5 kg mol−1) by a two-step polycondensation approach is also described. The thermal properties (TGA and DSC analyses) of the synthesized PAs are reported.",

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

author = "Daniele Ragno and Arianna Brandolese and {Di Carmine}, Graziano and Sara Buoso and Giada Belletti and Costanza Leonardi and Olga Bortolini and Monica Bertoldo and Alessandro Massi",

note = "Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

year = "2021",

month = jan,

day = "21",

doi = "10.1002/chem.202004296",

language = "English",

volume = "27",

pages = "1839--1848",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "5",

}

TY - JOUR

T1 - Exploring Oxidative NHC-Catalysis as Organocatalytic Polymerization Strategy towards Polyamide Oligomers

AU - Ragno, Daniele

AU - Brandolese, Arianna

AU - Di Carmine, Graziano

AU - Buoso, Sara

AU - Belletti, Giada

AU - Leonardi, Costanza

AU - Bortolini, Olga

AU - Bertoldo, Monica

AU - Massi, Alessandro

PY - 2021/1/21

Y1 - 2021/1/21

N2 - The polycondensation of diamines and dialdehydes promoted by an N-heterocyclic carbene (NHC) catalyst in the presence of a quinone oxidant and hexafluoro-2-propanol (HFIP) is herein presented for the synthesis of oligomeric polyamides (PAs), which are obtained with a number-average molecular weight (Mn) in the range of 1.7–3.6 kg mol−1 as determined by NMR analysis. In particular, the utilization of furanic dialdehyde monomers (2,5-diformylfuran, DFF; 5,5’-[oxybis(methylene)]bis[2-furaldehyde], OBFA) to access known and previously unreported biobased PAs is illustrated. The synthesis of higher molecular weight PAs (poly(decamethylene terephthalamide, PA10T, Mn = 62.8 kg mol−1; poly(decamethylene 2,5-furandicarboxylamide, PA10F, Mn = 6.5 kg mol−1) by a two-step polycondensation approach is also described. The thermal properties (TGA and DSC analyses) of the synthesized PAs are reported.

AB - The polycondensation of diamines and dialdehydes promoted by an N-heterocyclic carbene (NHC) catalyst in the presence of a quinone oxidant and hexafluoro-2-propanol (HFIP) is herein presented for the synthesis of oligomeric polyamides (PAs), which are obtained with a number-average molecular weight (Mn) in the range of 1.7–3.6 kg mol−1 as determined by NMR analysis. In particular, the utilization of furanic dialdehyde monomers (2,5-diformylfuran, DFF; 5,5’-[oxybis(methylene)]bis[2-furaldehyde], OBFA) to access known and previously unreported biobased PAs is illustrated. The synthesis of higher molecular weight PAs (poly(decamethylene terephthalamide, PA10T, Mn = 62.8 kg mol−1; poly(decamethylene 2,5-furandicarboxylamide, PA10F, Mn = 6.5 kg mol−1) by a two-step polycondensation approach is also described. The thermal properties (TGA and DSC analyses) of the synthesized PAs are reported.

KW - carbenes

KW - organocatalysis

KW - oxidation

KW - polyamides

KW - polymerization

UR - http://www.scopus.com/inward/record.url?scp=85097819790&partnerID=8YFLogxK

U2 - 10.1002/chem.202004296

DO - 10.1002/chem.202004296

M3 - Article

C2 - 32986909

AN - SCOPUS:85097819790

SN - 0947-6539

VL - 27

SP - 1839

EP - 1848

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 5

ER -

Exploring Oxidative NHC-Catalysis as Organocatalytic Polymerization Strategy towards Polyamide Oligomers

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Fingerprint

Cite this