Disproportionation of Rosin Driven by 4,4′-Thio-bis(3-Methyl-6-Tert-Butylphenol): Kinetic Model Discrimination

Abstract

Herein, a phenomenological kinetic modeling of the disproportionation of rosin with a well-known antioxidant and bleaching agent, antioxidant 300, also known as 4,4′-thio-bis(3-methyl-6-tert-butylphenol) under thermal conditions adequate for rosin esterification with polyols such as glycerol or pentaerythritol, is studied. The temperature was varied in the 260–280 °C range, while the catalyst was either absent or added till a 2% w/w amount relative to rosin. The composition of the reaction liquid was followed by GC-MS to identify the rosin acids present in each sample and GC-FID to quantify them. Gas chromatography analyses indicated that abietic acids were involved in dehydrogenation, isomerization and disproportionation reactions, while pimaric acid underwent a number of isomerization reactions, dehydroabietic acid being the main product of the disproportionation process, while abietic acid almost disappeared in the more reactive conditions. Several kinetic models featuring direct hydrogenation, disproportionation, isomerization, and dehydrogenation reactions were proposed and fitted, step by step, to all relevant data. Physicochemical and statistical discrimination allowed for the selection of the most adequate model, which includes abietic, neoabietic and palustric acid dehydrogenation to dehydroabietic acid, abietic acid disproportionation to di- and dehydroabietic acid, and pimaric acid isomerization. In any case, a model with isomerization of all abietic-type acids towards abietic acid before its further transformation via dehydrogenation and disproportionation reactions seems statistically valid as well.