Transesterification or polymerization? Reaction mechanism and kinetics of 2-(diethylamino)ethyl methacrylate with methanol and the competitive effect on free-radical polymerization†
Judith Cabello-Romero, Román Torres-Lubián, Javier Francisco Enríquez-Medrano, Adrián Ochoa-Terán, Jesús Jara-Cortés and Iván Zapata-González
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引用次数: 0
Abstract
Transesterification of 2-(diethylamino)ethyl methacrylate (DEAEMA) with methanol leads to the formation of methyl methacrylate (MMA) and 2-(diethylamino)ethanol; this alcoholysis reaction is studied by Density Functional Theory (DFT) calculations and in situ1H-NMR measurements. The transesterification mechanism involves the cooperative effect of methanol. Second-order transesterification kinetics and Arrhenius parameters (A and Ea) are reported. Furthermore, the competition between transesterification and (co)polymerization between DEAEMA and the MMA transesterification product, using 2,2-azobis (2-methylpropionitrile) (AIBN) as an initiator at 70 °C, has been analysed. In experiments with a DEAEMA : methanol molar ratio of 1 : 46 the copolymerization results in a large proportion of the MMA copolymer composition (FMMA) of 60 mol%; with an equimolar ratio the transesterification is avoided and the FMMA is only 2 mol%. FMMA can also be tuned by modification of the DEAEMA : AIBN molar ratio. Therefore, this work provides guidelines for the synthesis of well-defined poly(DEAEMA) and poly(DEAEMA-co-MMA) in primary alcohols.
期刊介绍:
Reaction Chemistry & Engineering is a new journal reporting cutting edge research into all aspects of making molecules for the benefit of fundamental research, applied processes and wider society.
From fundamental, molecular-level chemistry to large scale chemical production, Reaction Chemistry & Engineering brings together communities of chemists and chemical engineers working to ensure the crucial role of reaction chemistry in today’s world.