Behavior of Acrylamide in the Presence of Cyclohexanone and Methyl Ethyl Ketone

Abstract

Reactions of acrylamide (AAm) were carried out in the presence of cyclohexanone, methyl ethyl ketone and its derivatives in tetrahydorafuran at various reaction temperatures. Interactions between the carbonyl oxygen of ketones and the amide group were found to enhance the reactivity of AAm. No reactions of AAm occurred in the absence of the ketones under the same condition. Interactions of carbonyl group in the ketone with AAm could be examined directly using the 13C NMR spectra of a mixture of AAm and t-butyl methyl ketone or poly (methyl vinyl ketone).

Study on Copolymerization of Acrylamide With Styrene Initiated by Methyl Ethyl Ketone and Its Derivatives in Comparison With Conventional Radical Initiator

“…As shown in Figure 3 = 1). It is also in good agreement with the result of our previous reports [16,17] that the higher electronic density of the carbonyl oxygen atom in ketone results in the stronger interaction of the monomer with the ketone. The following two overlapped effects can be responsible for this fact: the formation of a reactive complex between AAm and ketones which results in the generation for the radical of AAm, and the retardation of the radical copolymerization by the chain transfer reaction [24].…”

“…In all the copolymerization systems, the r 1 (AAm) value is greatly smaller than that of the r 2 (St) value, and the r 1 value in the copolymerization systems initiated by the ketones is higher than by the conventional radical initiator, AIBN. The initiating radicals in these copolymerization systems in the presence of the ketones probably generated from the AAm monomer which formed a complex with the ketone (Scheme 3), as we reported in the homopolymerization systems of AAm in previous papers [16,17]. This fact may be explained on the basis of the strong hydrogen bonding ability of ketones to the amide group, which is assumed to affect the AAm monomer association [21], and consequently disturbs the keto/enol equilibrium of AAm [22].…”

“…The reactivity coefficient data are represented in Table 6. The r 1 values increased as the order: MEK < MIK < tBMK, that is the same order as the electronic density of carbonyl oxygen atom for ketones [16,17]. In all the copolymerization systems, the r 1 (AAm) value is greatly smaller than that of the r 2 (St) value, and the r 1 value in the copolymerization systems initiated by the ketones is higher than by the conventional radical initiator, AIBN.…”

“…A similar type of interaction between methyl methacrylate (MMA) and ketones such as cyclohexanone (CHn) [6,7], cyclopentanone, cycloheptanone, and acetylacetone [9], was also proposed by A. However, in all of the literature, the major investigation point was the effect of the polarity of solvents, not the structure of the initiators (ketones) . We have recently been studying the interaction between the amide group of AAm and the carbonyl group of the template polymer [14] or ketones [15][16][17] in the homopolymerization system of AAm in the presence of poly(methyl methacrylate), CHn, methyl ethyl ketone (MEK), methyl isopropyl ketone (MIK), and t-butyl methyl ketone (tBMK). However, in all of the literature, the major investigation point was the effect of the polarity of solvents, not the structure of the initiators (ketones) . We have recently been studying the interaction between the amide group of AAm and the carbonyl group of the template polymer [14] or ketones [15][16][17] in the homopolymerization system of AAm in the presence of poly(methyl methacrylate), CHn, methyl ethyl ketone (MEK), methyl isopropyl ketone (MIK), and t-butyl methyl ketone (tBMK).…”