Synthesis of Butyl-Exchanged Polyoxymethylene Ethers as Renewable Diesel Blendstocks with Improved Fuel Properties

Methyl-terminated polyoxymethylene ethers (MM-POMEs), having the formula CH₃O−(CH₂O)_n−CH₃ (n = 3−5), are a high-cetane, low-sooting group of oxygenates that have recently attracted attention as potential diesel blendstocks. Despite these attractive fuel properties, MM-POMEs have shortcomings due to their low energy density and high water solubility. Guided by a computational fuel property assessment for POMEs with longer end-groups, the most promising improvements in the desired compression ignition fuel properties were observed for butyl-terminated POMEs. Here, an acid-catalyzed transacetalization reaction was developed to exchange the methyl end-groups of MM-POMEs (n = 3−6) with butyl end-groups. The reaction utilizes an ion-exchange resin as the acid catalyst at mild reaction conditions of 60 °C and atmospheric pressure. Approximately 100 mL of butyl-exchanged POMEs in the diesel boiling range were produced, enabling laboratory-scale fuel property testing. The butyl-terminated POME mixture possesses the advantaged fuel properties of the parent MM-POMEs (low-soot, high-cetane) while exhibiting improved energy density (lower heating value (LHV) of 30 MJ/kg) and substantially reduced water solubility (7.3 g/L) compared to the parent MM-POME mixture (LHV of 19 MJ/kg, water solubility of 258 g/L).