Vanillin derived a carbonate dialdehyde and a carbonate diol: novel platform monomers for sustainable polymers synthesis

Abstract

Vanillin has been regarded as one of the important biomass-based platform chemicals for aromatic polymers synthesis. Herein, novel symmetric bis(4-formyl-2-methoxyphenyl)carbonate (BFMC) and bis(4-(hydroxymethyl)-2-methoxyphenyl)carbonate (BHMC) polymeric monomers have been synthesized in high yields using vanillin as a raw chemical, which have been submitted for polymer synthesis <i>via</i> well-established polymeric strategies. A new class of poly(carbonate ester)s oligomers with amide moieties in their side chain can be prepared by using the BFMC as one of monomers <i>via</i> the Passerini three compound reaction (3CR). A new class of poly(carbonate ester)s oligomers and poly(carbonate urethane)s can be prepared <i>via</i> reactions between BHMC with dicarboxylic acid chlorides and diisocyanates, respectively. Their structure have been confirmed by ¹H NMR, ¹³C NMR and FTIR, and the gel permeation chromatograph (GPC) analysis shows that the Mn of poly(carbonate ester)s oligomers ranges from 3100 to 7900 with PDI between 1.31 and 1.65, and the Mn of poly(carbonate urethane)s ranges from 16 400 to 24 400 with PDI ranging from 1.36 to 2.17. The DSC analysis shows that the poly(carbonate ester)s oligomers have relative low <i>T</i> _g ranging from 37.4 to 74.1 °C, and the poly(carbonate urethane)s have <i>T</i> _g ranging from 97.3 to 138.3 °C, mainly correlating to the structure of dicarboxylic acid chlorides and diisocyanates used.