The Etherification of HMF: One Step to Create Renewable Tunable Polymers from HMF There is a desire to use biomass to replace oil as the feedstock for modern chemicals and products. In this study, we seek to create tunable polymers using 5-hydroxymethylfurfural (HMF) as a renewable platform chemical. The properties of the final polymer can be tuned by modifying the side-chain of the monomer, which is added by the etherification of HMF. Several different catalysts with a variety of active sites and pore structures were evaluated for their activity in the etherification reaction. We have also evaluated the interplay of R-group identity and active site structure on the etherification kinetics. Catalysts possessing Brønsted acid sites showed the highest selectivities to the ether product. Catalysts without Brønsted sites were an order of magnitude less active and selective than those with Brønsted sites. The improved selectivity observed for H-BEA-Zeolite, compared with Amberlyst-15, is hypothesized to be due to the ability of the zeolite to stabilize reaction intermediates.1 When the rate of production of the ether product was evaluated for BEA Zeolite and Amberlyst-15 it was found that although the consumption rates were comparable, the ether production rate depends on catalyst identity. Increasing the size of the alcohol decreases the production rates, and the rate of production of all ether products was consistently higher for H-BEA Zeolite for all alcohols tested. Based on these results, we hypothesize that the structure of H-BEA Zeolite leads to improved activity for etherification. We suggest that Brønsted acidity is needed for etherification, and catalyst morphology may also be significant. Sources: 1. K. Barbera, P. Lanzafame, A. Pistone, S. Millesi, G. Malandrino, A. Gulino, S. Perathoner and G. Centi, J. Catal., 2015, 323,19–32.

Faculty Mentor: Thomas Schwartz