Reactive phenolic solvents applied to the synthesis of renewable aromatic polyesters with high isosorbide content.

High boiling point phenolic reactive solvents like p-cresol could play a key role in improving the synthesis of aromatic polyesters with a high content of secondary diols such as isosorbide. Previously, our group showed that this method significantly improves the synthesis of poly(isosorbide succinate). In this work, terephthalic acid and 2,5-furandicarboxylic acid were used as building blocks for the synthesis of high Tg polyesters with high isosorbide content (>30 mol% of diols) and high molecular weight (Mn > 24 kg mol-1). A number of reactive and non-reactive solvents were tested in this work, and the results clearly point to a significant improvement when using reactive solvents, in terms of molecular weight and polycondensation time, especially for the case of p-cresol. The synthesis method was successfully scaled to 1 kg, showing promise for production at industrial scale. A method to remove these solvents (including end groups) from the polymers, which uses small excesses of isosorbide (1.5-3.0%) in the feed, is also presented.

Overcoming the low reactivity of biobased, secondary diols in polyester synthesis.

Shifting away from fossil- to biobased feedstocks is an important step towards a more sustainable materials sector. Isosorbide is a rigid, glucose-derived secondary diol, which has been shown to impart favourable material properties, but its low reactivity has hampered its use in polyester synthesis. Here we report a simple, yet innovative, synthesis strategy to overcome the inherently low reactivity of secondary diols in polyester synthesis. It enables the synthesis of fully biobased polyesters from secondary diols, such as poly(isosorbide succinate), with very high molecular weights (Mn up to 42.8 kg/mol). The addition of an aryl alcohol to diol and diacid monomers was found to lead to the in-situ formation of reactive aryl esters during esterification, which facilitated chain growth during polycondensation to obtain high molecular weight polyesters. This synthesis method is broadly applicable for aliphatic polyesters based on isosorbide and isomannide and could be an important step towards the more general commercial adaption of fully biobased, rigid polyesters.