Semi-Crystalline and Amorphous Polyesters Derived from Biobased Tri-Aromatic Dicarboxylates and Containing Cleavable Acylhydrazone Units for Short-Loop Chemical Recycling

Abstract

Recycling polymers by site-specific scission into short-chain oligomers/polymers, followed by recoupling these to form the original polymer presents an energetically more favorable shorter-loop chemical recycling in comparison to recycling into monomers. Here, we present the synthesis and polymerization of tri-aromatic diesters to prepare polyesters with acylhydrazone units as weak structural links. Two diester monomers were prepared by combining methyl 5-chloromethyl-2-furoate, obtainable from 5-chloromethylfurfural, with potentially biobased hydroquinone and resorcinol, respectively. The two diesters have a central phenyl ring flanked by two furan rings, and were polymerized with 1,6-hexanediol and 1,4-butanediol, respectively, together with controlled amounts of monofunctional ethyl levulinate to form telechelic ketone-terminated polyesters. Subsequent reactions of these telechelic polyesters with adipic dihydrazide yielded the corresponding chain-extended polyesters with increased molecular weights ([η] = 0.29–0.52 dL g–1) with acylhydrazone units in the backbone. Thermogravimetric analysis showed a high thermal stability of the polyesters with thermal decomposition only above 275 °C. The polyesters containing the linear hydroquinone units were found to be semi-crystalline materials with melting points at 158 and 192 °C, respectively, while those containing the kinked resorcinol units were fully amorphous with glass transition temperatures at 35 and 44 °C, respectively. Initial investigations of the chemical recyclability of the polyesters demonstrated that acylhydrazone units could be selectively cleaved to recover the original telechelic ketone-terminated polyesters, which could again be chain-extended to obtain a recycled polymer with molecular weights and properties very similar to those of the original material.