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 (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.