Nucleophilic degradation of diazinon in thermoreversible polymer-polymer aqueous biphasic systems

resumo

Although aqueous biphasic systems have been largely investigated in the separation and/or purification of biocompounds, their potential as reaction media to design integrated reaction-separation processes has been less explored. In this work aqueous biphasic systems (ABSs) composed of polypropylene glycol of molecular weight 400 g mol(-1) (PPG 400) and different polyethylene glycols (PEGs) were characterized, and investigated for integrated reaction-separation processes, i.e. in the nucleophilic degradation of diazinon and further separation of reaction products by taking advantage of the lower-critical solution temperature (LCST) behaviour of these ABSs. The nucleophilic degradation of diazinon was carried out in the monophasic regime at 298 K, after which an increase in temperature (up to 313 K) allowed the product separation by two-phase formation (thermoreversible systems). The reaction kinetics and reaction pathways have been determined. The reaction kinetic increases as the PEG molecular weight decreases, with the half-life values obtained being competitive to those previously reported using volatile organic solvents as solvent media and significantly higher than under alkaline hydrolysis. One reaction pathway occurs in ABSs comprising PEGs of higher molecular weights, whereas in the ABS composed of PEG 600 two reaction pathways have been identified, meaning that the reaction pathways can be tailored by changing the PEG nature. ABSs formed by PEGs of lower molecular weights were identified as the most promising option to separate the pesticide degradation products by simply applying changes in temperature.

categoria

Chemistry, Physical; Physics, Atomic, Molecular & Chemical

autores

Millan, D; Almeida, MR; Rufino, AFCS; Coutinho, JAP; Freire, MG

nossos autores

agradecimentos

This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 and UIDP/50011/2020 financed by national funds through the Portuguese Foundation for Science and Technology/MCTES, D. Millan thanks Fondecyt projects 3150122 and 11170569 and also the NMR facility in the Unidad Central de Investigacion at the Pontificia Universidad Catolica de Chile for NMR support. A. F. C. S. Rufino acknowledges FCT for the PhD grant SFRH/BD/138997/2018.

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