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

Abstract

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.

Oxalic acid hydrogenation to glycolic acid: heterogeneous catalysts screening

“…17,18,63,64 Next to oxalic acid as monomer itself (which thermal instability can be overcome by using appropriate ester derivatives) it can also be the starting material for other monomers. [65][66][67] One of those is glycolic acid for which one of the acid groups is reduced to an alcohol. Effectively this can be done by first converting the oxalic acid into an ester and then reducing the ester to glycolic acid.…”

Alpha‐ketoglutaric acid based polymeric particles for cutaneous wound healing

“…Notably, polymers with 1,8‐Octanediol, or 1,10‐Decanediol, or 1,12‐Dodecanediol might impart different properties to the polymers including solubility, biodegradability, hydrophobicity and ability to generate particles. In fact, it has been demonstrated using different metabolites such as fumarate, and succinate that different diol based monomers modulate the polymer characteristics, which can be exploited for biological applications 26,27 …”

Design and synthesis of isosorbide‐based copolycarbonates with high transparency and low hygroscopicity for optical applications

“…However, the hydrophilic groups in the PIC chain can easily form hydrogen bonds with water molecules as well as a cage‐like hydration molecule through the solvation of water 13 . This hydration means the polymer is able to absorb and retain large amounts of water 14 . Meanwhile, the special structure of the two thickened furan rings of ISB connected in a V‐shape creates a large steric hindrance, which further facilitates the storage of large quantities of water molecules 15,16 .…”

“…13 This hydration means the polymer is able to absorb and retain large amounts of water. 14 Meanwhile, the special structure of the two thickened furan rings of ISB connected in a V-shape creates a large steric hindrance, which further facilitates the storage of large quantities of water molecules. 15,16 Noteworthy, the water absorption of polycarbonate leads to the hydrolysis of hydrophilic groups in the molecular chain, which breaks the chain and creates polar phenolic hydroxyl groups that further exacerbate the hydrolysis.…”