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- W2049523111 abstract "Abstract A number of novel polymerizable quaternary ammonium (meth)acrylates have been polymerized in water at concentrations both above and below their critical micelle values, and also in isotropic alcohol solutions. Oligomeric species with DP n up to 25 are formed readily from micellized solutions using both photochemical and thermal initiation systems. Below critical micelle concentrations, however, polymerization seems very inefficient and conversions are very low. Even in isotropic alcohol solutions, polymerization remains sluggish and DP n values are typically very low, ∼2–4. In dilute aqueous solution and in alcohols, it appears that charge repulsion is an obstacle to propagation, both for monomers where the cationic charge is located near the polymerizable group and for those where the charge is more remote. Radical transfer is probably more favoured. On micellization, this charge repulsion is overcome by the favourable thermodynamics of micelle formation and monomers are closely orientated to allow bimolecular radical reaction to proceed. Despite this, radical transfer remains favoured. The effective local concentration of monomer in the micellar state approaches that of the bulk state, and this simple concentration (rather than orientation) factor is probably most important in allowing polymerization. The rate of exchange of monomer surfactant between micelles is much faster than the rate of oligomer propagation and so a topochemical polymerization of a micelle is extremely unlikely, i.e. the occurrence of ‘polymerized micelles’ can be discounted. However, oligomeric species can be formed which display micellar-like physical properties and these show a great tendency to aggregate into large units and, indeed, to phase separate." @default.
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- W2049523111 date "1987-02-01" @default.
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- W2049523111 title "Novel quaternary ammonium amphiphilic (meth)acrylates: 2. Thermally and photochemically initiated polymerizations" @default.
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- W2049523111 doi "https://doi.org/10.1016/0032-3861(87)90427-7" @default.
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