Sustainable Synthesis and Polycondensation of Levoglucosenone-Cyrene-Based Bicyclic Diol Monomer: Access to Renewable Polyesters

Florian Diot-Néant; Louis Mouterde; Sami Fadlallah; Stephen A Miller; Florent Allais

doi:10.1002/cssc.202000680

Sustainable Synthesis and Polycondensation of Levoglucosenone-Cyrene-Based Bicyclic Diol Monomer: Access to Renewable Polyesters

ChemSusChem. 2020 May 22;13(10):2613-2620. doi: 10.1002/cssc.202000680. Epub 2020 May 15.

Authors

Florian Diot-Néant^{1

2}, Louis Mouterde¹, Sami Fadlallah¹, Stephen A Miller², Florent Allais^{1

3}

Affiliations

¹ URD Agro-Biotechnologies Industrielles (ABI), CEBB, AgroParisTech, 51110, Pomacle, France.
² The George and Josephine Butler Laboratory for Polymer Research, Department of Chemistry, University of Florida, Gainesville, FL, 32611-7200, USA.
³ Department of Chemistry, University of Florida, Gainesville, FL, 32611-7200, USA.

PMID: 32237202
DOI: 10.1002/cssc.202000680

Abstract

The already-reported, low-yielding, and non-sustainable Et₃ N-mediated homocoupling of levoglucosenone (LGO) into the corresponding LGO-Cyrene^TM diketone has been revisited and greened-up. The use of methanol as both a renewable solvent and catalyst and K₂ CO₃ as a safe inorganic base improved the reaction significantly with regards to yield, purification, and green aspects. LGO-Cyrene^TM was then subjected to a one-pot, H₂ O₂ -mediated Baeyer-Villiger oxidation/rearrangement followed by an acidic hydrolysis to produce a new sterically hindered bicyclic monomer, 2H-HBO-HBO. This diol was further polymerized in bulk with diacyl chlorides to access new promising renewable polyesters that exhibit glass transition temperatures (T_g ) from -1 to 81 °C and a good thermostability with a temperature at which 50 % of the mass is lost (T_{d50 %} ) of 349-406 °C.

Keywords: biomass; dimerization; oxidation; polymers; synthesis design.