RESUMO
In this study, two homologous series of novel herbicidal ionic liquids (HILs) were synthesized in a simple metathesis reaction between alkyl[2-(2-hydroxyethoxy)ethyl]dimethylammonium bromides and alkali metal salts of 4-chloro-2-methylphenoxyacetic acid (MCPA) or 3,6-dichloro-2-methoxybenzoic acid (dicamba), known as popular herbicides from the class of growth regulators. These HILs were subsequently mixed to prepare double-salt herbicidal ionic liquids (DSHILs). The DSHILs were characterized by substantially altered parameters of viscosity, refractive index, glass transition temperatures and surface activity compared to the average values expected for ideal mixtures of their individual components (HILs). Interestingly, DSHILs possessed superior physicochemical properties such as relatively low viscosity or facilitated formation of micelles, which emphasizes the complex nature of multi-ion interactions in the microstructures of ionic liquid mixtures. The biological tests showed improved efficiency of DSHILs against tested weeds compared to the reference herbicides and parent HILs.
RESUMO
In the framework of this study a synthesis methodology and characterization of long alkyl herbicidal ionic liquids (HILs) based on four commonly used herbicides (2,4-D, MCPA, MCPP, and dicamba) are presented. New HILs were obtained with high efficiency (>95%) using an acid-base reaction between herbicidal acids and hexadecyltrimethylammonium, octadecyltrimethylammonium, and behenyltrimethylammonium hydroxides in alcoholic medium. Among all synthesized salts, only three compounds comprising the MCPP anion were liquids at room temperature. Subsequently, the influence of both the alkyl chain length and the anion structure on their physicochemical properties (thermal decomposition profiles, solubility in 10 representative solvents, surface activity, density, viscosity, and refractive index) was determined. All HILs exhibited high thermal stability as well as surface activity; however, their solubility notably depended on both the length of the carbon chain and the structure of the anion. The herbicidal efficacy of the obtained salts was tested in greenhouse and field experiments. Greenhouse testing performed on common lambsquarters (Chenopodium album L.) and flixweed (Descurainia sophia L.) as test plants indicated that HILs were characterized by similar or higher efficacy compared to commercial herbicides. The results of field trials confirmed the high activity of HILs, particularly those containing phenoxyacids as anions (MCPA, 2,4-D, and MCPP).
