Ring opening of epoxidized methyl oleate using a novel acid-functionalized iron nanoparticle catalyst

Abstract

Hydroxyl soybean oils, also called soy polyols, are biobased chemicals designed to replace petroleum-based polyols mainly for polyurethane (PU) applications. Soy polyols are obtained by acid-catalyzed ring opening of expoxidized soybean oils or other epoxidized plant oils by nucleophilic SN2 attack of methanol. Recyclable heterogeneous catalysts are preferred for the ring-opening reactions over non-recyclable homogeneous catalysts because they minimize environmental impact. The drawbacks of current solid catalysts such as SAC 13 and Amberlite 15 are low production yield and high energy consumption. Here, we demonstrate a greener synthetic pathway of soy polyols with low energy consumption and excellent atom economy and environment (E) factor by using novel sulfamic acid-functionalized iron (iron/iron oxide core shell) nanoparticles (NPs) as a heterogeneous catalyst. The excellent selectivity of the reaction with the recyclable NPs was confirmed by 1H NMR, 1H-1H COSY NMR, and ESI-MS comparable to non-recyclable H2SO4. The synthetic route with the NPs resulted in higher product yield (almost 100%) as H2SO4 at room temperature for 30 min over the SAC 13 (83% yield at 60 °C for 60 min) and Amberlite 15 (87% yield at 60 °C for 100 min). Life cycle assessment (LCA) revealed that the NP synthetic technology for soy polyol production is superior or equal to the competing routes (H2SO4, SAC 13, and Amberlite 15 methods) with respect to 9 environmental impacts (acidification potential, ozone depletion potential, smog formation potential, global warming potential, human toxicity by ingestion, human toxicity by inhalation, persistence, bioaccumulation, and abiotic resource depletion potential).