Short-Loop Chemical Recycling via Telechelic Polymers for Biobased Polyesters with Spiroacetal Units

Abstract

Spirocyclic acetal structures have recently received growing attention in polymer science due to their dual potential to raise the glass transition temperature (Tg) and enable chemical recycling of biobased polymers. In the present work, a vanillin-based diol with a spirocyclic acetal structure was incorporated in a series of rigid amorphous polyesters based on neopentyl glycol and dimethyl terephthalate (DMT). Up to 50 mol % of spirocyclic diol (with respect to DMT) could be incorporated in the copolyesters, but a reasonably high molecular weight was only achieved when ≤30 mol % of the spirocyclic diol was used. The presence of the spiroacetal units in the polyesters not only enhanced the Tg (up to 103 °C) and thermal stability (T5 ≥ 300 °C) but also the oxygen barrier of solution-cast films. We found that the acetal units in the copolyesters could be selectively hydrolyzed under acidic conditions while virtually retaining all of the ester bonds in the polymer backbone. After acidic hydrolysis, telechelic polymers exclusively terminated by two aldehyde end groups were obtained. In this work, we have demonstrated that these telechelic polyesters can be conveniently converted back into poly(acetal-ester)s via cycloacetalization reactions with pentaerythritol.