| Resumo: | In this study, we report the use of clay-based catalysts in the methoxylation of -pinene, for the selective synthesis of -terpinyl methyl ether, TME. The main reaction products and intermediates were identified by GC–MS. The reaction conditions (stirring rate and catalystload)that afford a kinetic regime were estab lished. SAz-1 (Cheto, Arizona, USA) source clay and a montmorillonite (SD) from Porto Santo, Madeira Archipelago, Portugal, were modified by ion-exchange with Al3+ to produce catalysts with markedly different acidities and textural properties. The catalysts based on the high layer-charge SAz-1 montmo rillonite proved to be the most active. Ion-exchange with Al3+, followed by thermal activation at 150 ◦C, afforded the highest number of Brønsted acid sites – a significant proportion of which were located in the clay gallery – and this coincided with the maximum catalytic activity. The influence of various reac tion conditions, to maximize -pinene conversion and selectivity, was studied over AlSAz-1. When the reaction was performed for 1 h at 60 ◦C, the conversion reached 65% with 65% selectivity towards the mono-ether, TME. Similar conversions and selectivities required up to 50 h over zeolites and other solid acid catalysts. The kinetic dependencies of this reaction on temperature and reagent concentration, over the selected clays were also investigated. It was established that, in the temperature and reagent con centration regime studied, the reaction was first order with respect to -pinene. The apparent activation energies over the two catalysts, calculated from Arrhenius plots, were almost identical at 72 kJ mol−1.
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