Radical Polymerisation in the Associated Species of Ionogenic Surface-active Monomers in Water

Abstract

The radical polymerisation in water of ionogenic monomers of the cationic and anionic type exhibiting surface-active properties is discussed. Together with kinetic phenomena, which can be accounted for within the framework of the hypothesis of a homophase course of the process, effects which require the assumption of the possibility of the association of the monomeric molecules are observed in the polymerisation of monomers with a low surface activity in aqueous solutions. The polymerisation of monomers with a high surface activity in micellar dispersions differs from the processes in solutions by a number of features associated with the influence of structure formation in the monomer on the kinetics of polymerisation and the macrostructure of the polymer formed. The kinetic effects induced by the increasing concentration and microviscosity of the monomer solutions and also by the change in the relative positions of its molecules in the associated species compared with the solution are discussed. Examples of the influence of processes involving the rearrangement of the associated speices on the process kinetics are presented. The possibility, in principle, of the fixation of the structure of the associated species (micelles) as a consequence of polymerisation is noted. The kinetics of the polymerisation process in micellar and vesicular dispersions of two-chain surface-active monomers and also in monolayers at the water-gas interface are discussed. The bibliography includes 118 references. CONTENTS

Aryl (meth)acrylates and polymers based on them

“…22 PMA with substituents in the aromatic ring containing the aldehyde and ketone, 23 carboxy, 24,25 benzyl, 26 tetracyanocyclobutyl 27 and dioxolane 28 groups have been described. Special mention should be made of (meth)acrylates of hydroxyphenylacetic 29 and hydroxybenzoic 24,25 acids as well as of surfactant salts 30 of the general formula CH 2 =CMeC(O)OC 6 H 4 (CH 2 ) n X [n = 3, 7; X = CO 2 Na, N + (C n H 2n+1 ) 3 Z 7 ; Z = Cl, Br, I, MeSO 4 ].…”

Effect of the Association of Nitrogen-Containing (Meth) Acrylic Monomers on their Radical Polymerisation in Aqueous Solutions

“…It must be mentioned straight away that so-called surface-active NMMs (containing a salt group and a C 9 or higher hydrocarbon fragment), which are in fact classical surfactants, are not included in this review. Features of the micelle formation and polymerisation of these compounds have been well studied and generalised in earlier reviews [1,2]. Table 1 presents the formulae and nomenclature of the main monomers discussed in the present work.…”

“…Data presented in reference [18] indicate a multimolecular structure of AA associates rather than a dimeric structure -on the VCD Figure 1. Isotherms of surface tension for aqueous solutions of DMAEM.DMS (1), DMAPMA.SK (2), and DMAPMA (3). Temperature 20°C [13] Figure 2.…”

“…Temperature 20°C [13] Figure 2. Influence of the concentration of monomeric sulphonic acids Na-ASSK (1,3) and AMPSK (2) on the electrical conductivity (1,2) and specific viscosity (3) of aqueous solutions. Temperature 20°C [14,15] of the monomer, as the solution is concentrated, several inflections can be clearly traced (at an AA concentration of about 6, 22, and 32%), which is normally attributed to change in the structure of aggregates.…”

“…Concentrated aqueous solutions of a number of vinyl monomers are characterised not only by the anormally rapid radical reactions noted above but also by a Figure 5. Influence of the concentration of monomers (c) on the ratio of constants k g (2fk h /k 0 ) 0.5 (A) during the polymerisation of DMAPMA.KhK (1) and DMAEM.KhK (2) in the presence of PSK, 50°C [13] capacity for arbitrary (self-initiated) polymerisation. The main feature of this reaction is that it proceeds only in concentrated solutions.…”