# Enhancing Biopolyester Backbone Rigidity with an Asymmetric Furanic Monomer

## TL;DR

Scientists created a new biobased polyester with a rigid backbone using an asymmetric furan monomer, which could lead to better performance materials.

## Contribution

The novel contribution is the development of poly(5-hydroxymethyl furanoate) with enhanced backbone rigidity from an asymmetric furan monomer.

## Key findings

- PHMF exhibits a higher glass transition temperature than poly(ethylene furanoate).
- PHMF has slower crystallization kinetics and lower amorphous mobility due to its rigid backbone.
- The amorphous phase of PHMF is denser due to noncovalent interchain interactions.

## Abstract

Biobased furanic polyesters can exhibit performance advantages
over petroleum-derived polyesters, primarily due to their rigid furan-containing
backbones. Herein, we develop two strategies to polymerize methyl
5-hydroxymethyl furanoate to poly­(5-hydroxymethyl furanoate) (PHMF),
a furan-based polyester with even greater backbone rigidity than poly­(ethylene
furanoate). Thermal, spectroscopic, and computational investigations
of PHMF alongside analogous furan-based and phenyl-based polyesters
suggest that the high furan content of PHMF leads to its high glass
transition temperature, slow crystallization kinetics, and low amorphous
mobility. Molecular dynamics simulations suggest that while the backbone
of PHMF is exceptionally rigid, its amorphous phase is denser than
its phenyl analog due to noncovalent interchain interactions. Together,
these results highlight how asymmetric furan-based monomers can modulate
key properties in biobased polyesters.