Selective defunctionalization of citric acid to tricarballylic acid as a precursor for the production of high-value plasticizers

Abstract

Strong concerns about the toxicity and endocrine disrupting properties of widespread phthalate plasticizers stimulate the demand for safe and preferably biobased alternatives. Citric acid forms in this respect an excellent and abundant platform chemical for the production of valuable plasticizers. Here, we report a new and direct synthesis route for propane-1,2,3-tricarboxylic acid (PTA) from citric acid via a sequential one pot dehydration–hydrogenation process. This saturated triacid can serve as a basis for the production of tricarballylate esters via esterification, which have been shown to possess excellent plasticizing properties in vinyl resins. In the presence of a solid acid H-Beta zeolite and Pd/C hydrogenation catalyst, yields up to 85% of PTA were obtained under mild reaction conditions and in water as a green solvent. Partial dealumination of the H-Beta zeolite by citric acid could be counteracted by reincorporating aluminium into the framework of the recycled H-Beta zeolite through realumination, regenerating a significant fraction of the initial activity of the catalytic system. The success of the realumination procedure was verified via MAS NMR spectroscopy.