Polyesters and Poly(ester-urethane)s from Biobased Difuranic Polyols

Abstract

This contribution investigates the impact of rigid and flexible difuranic polyols on the resulting polyester (PE) and poly(ester-urethane) (PEU) properties. Three biobased difuranic polyol monomers, 5,5′-bihydroxymethyl furil (BHMF), 5,5′-dihydroxymethyl furoin (DHMF), and bis[5-(hydroxymethyl)furan-2-yl)methyl]adipate (BHFA), all derived from the biomass platform chemical 5-hydroxymethylfurfural (HMF), were employed for the synthesis of a series of new linear and cross-linked PEs as well as amorphous and semicrystalline PEUs. The polycondensations of diols (rigid BHMF and flexible BHFA) with various diacyl chlorides afford linear PEs, whereas the rigid triol (DHMF) reacts with diacyl chlorides to form cross-linked PEs. Among these difuranic PEs, the most intriguing PE is the one containing C═C double bonds, derived from BHFA and fumaryl chloride, which exhibits the unique self-curing ability via the Diels–Alder reaction. Furthermore, the catalyzed polyaddition of BHFA with various diiscyanates produces novel PEUs, the most interesting of which is the one derived from BHFA and hexamethylene diisocyanate, a semicrystalline material displaying a high melting-transition temperature of 135.8 °C.