Regioselective synthesis of renewable bisphenols from 2,3-pentanedione and their application as plasticizers

Abstract

2,3-Pentanedione (2,3-PD), a bio-based chemical derived from lactic acid, has the potential to serve as a precursor for the synthesis of novel bisphenols. We developed a solvent-free catalytic strategy for the condensation of phenol with 2,3-PD by using acid catalysts at temperatures ranging from 323 to 373 K. Various soluble and solid acids exhibit high activity, while a high chemoselectivity to bisphenol requires a high phenol to 2,3-PD molar ratio. Bisphenol yields as high as 84% are for instance reported in an excess of phenol in the presence of Nafion NR50. Recycling of the Nafion catalyst after washing with ethanol at room temperature is demonstrated. The regioselectivity in the bisphenol fraction is influenced by the acid strength. A clear trend is presented in which the regioselectivity towards the desired p,p′-isomers increases with increasing acid strength, showing p,p′/o,p′-isomer ratios as high as 100. A tentative mechanism is discussed based on the ionic versus non-ionic pathway. The purified 2,3-PD-derived p,p′-bisphenols are assessed as plasticizers for polyethylene terephthalate (PET), showing promising properties similar to that of the reference bisphenol A, but with a broader processing window due to the lower melting point and higher thermal stability under an inert atmosphere.