Spontaneous polymerization of amphiphilic vinyl monomers, 4. Spontaneous polymerization of methacrylic derivatives of quaternary ammonium bromides with a long alkyl chain

Abstract

Amphiphilic surface active vinyl monomers (alkyl-2-methacryloyloxyethyldimethylammonium bromides) with a long alkyl chain (C8, C,,, C,,, C,,, and CIS) were investigated with respect to their polymerization behavior in the absence of an initiator. These monomers polymerized spontaneously in water, through a free-radical mechanism, except for the 'C, monomer'. In the polymerization of the 'C,, monomer', the polymer yield depended on polymerization temperature, and the intrinsic viscosity of the resulting polymer varied with the initial concentration of the monomer just like in ordinary polymerization. The 'C ,8 monomer', having low reactivity, became highly polymerizable upon mixing with a quaternary surfactant (dodecyl-2-isobutyryloxyethyldimethylammonium bromide) in a particular mole ratio, owing to a change in the monomer aggregation state. In benzene, all of the quaternary methacrylates polymerized spontaneously, too. It is obvious that formation of monomer aggregates, micelles or reverse micelles is essential for the spontaneous polymerization. The spontaneous polymerization of other quaternary monomers, having a hexadecyl group and a polymerizable acryloyl, acrylamido, or methacrylamido moiety, did also occur, yet with lower rate than in case of the methacrylate. a) Parts 1, 2 and 3: cf. refs. b,

Polymerized Ionic Amphiphiles: Synthesis and Effects in the Enantioselective Hydrogenation of an Amino Acid Precursor

“…[22][23][24][25][26] Under these circumstances the polymerization of certain methacrylic derivatives can proceed spontaneously without any initiators. [6] Of course, the position of the activated double bond influences the reactivity: being localized at the end of a hydrophobic alkyl chain ("tail-end"position) the activated double bond is more reactive than in the hydrophilic "head" position. [27] Additionally, the polymerization rate in spheric micelles increases with the decrease of counterion size in the "head" and/or increase of the length of the "tail" in the monomer.…”

“…Sodium methacryloyloxydodecanoate (5) and sodium methacryloyloxyoctadecanoate (6) were prepared in analogy to the literature. [16] Sodium 10-undecenylsulfate (7).…”

Spontaneous Polymerization of Micelle-Forming Styryl Ammonium Derivatives in Water

“…The results mentioned above were quite similar to those obtained in the case of quaternary ammonium amphiphiles derived from a methacrylic ester (DMAEMA-RBr). 7 CHa CHa CH2=C-c;;:-o-CH2CH2-N+-CnH2n+1 Br-…”

Molecular concepts, self-organisation and properties of polysoaps

“…Thus, vinylic surfactant homopolymers of other than "tail end" geometry should be of very limited use as polysoaps. In fact, very few exceptions to the geometry controlled model of solubility have been reported [82,106,128,225,[289][290][291]. In these examples, the chemical integrity of the polymers prepared, the attributed structures, or the polymeric nature may be questioned considering the results obtained for very similar compounds [115,232,309].…”