Renewable Unsaturated Polyesters from Muconic Acid

Nicholas Rorrer, Derek Vardon, Gregg Beckham, John Dorgan, Chelsea Martinez, Yuan Yang

Research output: Contribution to journalArticlepeer-review

77 Scopus Citations

Abstract

cis,cis-Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis-muconate is synthesized and subsequently incorporated into poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the case of poly(butylene succinate), utilization of neat muconic acid yields substoichiometric incorporation consistent with a tapered copolymer structure, whereas the muconate diester exhibits stoichiometric incorporation and a random copolymer structure based on thermal and mechanical properties. Prototypical fiberglass panels were produced by infusing a mixture of low molecular weight poly(butylene succinate-co-muconate) and styrene into a woven glass mat and thermally initiating polymerization resulting in thermoset composites with shear moduli in excess of 30 GPa, a value typical of commercial composites. The increased glass transition temperatures with increasing mucconic incorporation leads to improved composites properties. We find that the molecular tunability of poly(butylene succinate-co-muconate) as a tapered or random copolymer enables the tunability of composite properties. Overall, this study demonstrates the utility of muconic acid as a monomer suitable for direct use in commercial composites.

Original languageAmerican English
Pages (from-to)6867-6876
Number of pages10
JournalACS Sustainable Chemistry and Engineering
Volume4
Issue number12
DOIs
StatePublished - 5 Dec 2016

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

NREL Publication Number

  • NREL/JA-5100-67274

Keywords

  • Composites
  • Muconic Acid
  • Poly(butylene succinate)
  • Unsaturated Polyester

Fingerprint

Dive into the research topics of 'Renewable Unsaturated Polyesters from Muconic Acid'. Together they form a unique fingerprint.

Cite this