Micro emulsion polymerisation

Emulsion, mini-emulsion and micro-emulsion polymerisations... 

Details are given of the preparation of SAN latexes by micro-emulsion polymerisation using sodium dodecyl sulphate as an anionic surfactant. Kinetics of copolymerisation was studied at different temperatures using different concentrations of potassium persulphate and hydrogen peroxide/ascorbic acid. The latexes were characterised for particle size and number of particles by dynamic light scattering and TEM. Products were examined using NMR and thermal analysis. 20 refs. INDIA... 

In latex technology, a submicro scopic aggregation of oriented molecules in polymer technology it is synonymous with crystallite. The term is also applied to the aggregates of soap molecules formed in emulsion polymerisation. Micro... 

Microemulsions are used as reaction media for a variety of chemical reactions. The aqueous droplets of water-in-oil micro emulsions can be regarded as minireactors for the preparation of nanoparticles of metals and metal salts and particles of the same size as the starting microemulsion droplets can be obtained [1-3]. Polymerisation in micro emulsions is an efficient way to prepare nanolatexes and also to make polymers of very high molecular weight. Both discontinuous and bicontinuous micro emulsions have been used for the purpose [4]. Microemulsions are also of interest as media for enzymatic reactions. Much work has been done with lipase-catalysed reactions and water-in-oil microemulsions have been found suitable for ester synthesis and hydrolysis, as well as for transesterification [5,6]. 

Within the last 30 years, micro emulsions have also become increasingly significant in industry. Besides their application in the enhanced oil recovery (see Section 10.2 in Chapter 10), they are used in cosmetics and pharmaceuticals (see Chapter 8), washing processes (see Section 10.3 in Chapter 10), chemical reactions (nano-particle synthesis (see Chapter 6)), polymerisations (see Chapter 7) and catalytic reactions (see Chapter 5). In practical applications, micro emulsions are usually multicomponent mixtures for which formulation rules had to be found (see Chapter 3). Salt solutions and other polar solvents or monomers can be used as hydrophilic component. The hydrophobic component, usually referred to as oil, may be an alkane, a triglyceride, a supercritical fluid, a monomer or a mixture thereof. Industrially used amphiphiles include soaps as well as medium-chained alcohols and amphiphilic polymers, respectively, which serve as co-surfactant. 

Micro-emulsion Swollen monomer micelles dispersed in a continuous phase fairly large concentrations of surfactants required initiator dissolved in continuous phase Polymerisation initiated in the course of nucbation of monomer micelbs process characterised by continuous nucleation during entire reactbn fast rate of polymerisation (< 30 min) Particbs of very small si (diameter <100 nm) and narrow distribution polymer with ultra-high molecular weight (> 10 g/mol) copolymers with well-defined, homogenous composition... 

Micro-emulsion is another variant of emulsion polymerisation. Such emulsions are thermodynamically stable systems including swollen monomer micelles dispersed in a continuous phase. In general, they require fairly large concentrations of surfactants to be produced compared with the other dispersed polymerisation systems. Hence, the interfacial tension of the oil/water is generally close to zero. Polymers with ultra-high molecular weight, i.e. above 10 g/mol, can be obtained, as can copolymers with a very well-defined, homogenous composition. Whereas polymerisation can take 24-48 h in the normal emulsion process, it proceeds at a fast rate in micro-emulsion, as total conversion can be obtained in less than 30 min. Polymer particles of very small size (diameter < 100 nm) and narrow distribution can be obtained by this process. 

Water-containing nanocapsules can be obtained by interfacial polymerisation of ACA in water-in-oil micro-emulsion. In such a system, water-swollen micelles of surfactants of small and uniform size are dispersed in... 

Branching is usually greater with emulsion polymers than is really desirable. Solution polymers may be either completely linear or contain a controlled degree of branching. The two polymer types are also different in the amount of gel that is present. Emulsion polymers contain micro-gel (extensively in hot rubbers and moderately in cold rubbers) as a result of the very nature of the free-radical emulsion polymerisation process, whereas the gel content of solution polymers is very small. Rather interestingly, there have been deliberate attempts recently to incorporate controlled amounts of gel into the SBR in order to improve polymer green strength as will also be discussed later (see Section 5.2). 

Metal ion-imprinted microspheres were prepared as follows [14,15]. Seed emulsion was obtained by the polymerisation of styrene, butyl acrylate and methacrylic acid in water. Divinylbenzene, butyl acrylate and water were further added to the polymerisation mixture (seed emulsion) and the emulsion was left for a defined time so that the seed microspheres became swollen. The emulsion was combined with a metal ion solution to achieve complexation between the metal ion and the carboxyl group on the surface. Then the divinylbenzene-containing emulsion was polymerised by the use of y-rays at room temperature. The micro-spheres obtained by centrifugation were washed with a hydrochloric acid solution to remove the metal ion. The microspheres obtained were then dried under vacuum. Non-imprinted microspheres (as a reference) were synthesised similarly, but without a metal ion. 

Inverse opals are formed by the use of micro- or nanospheres to template a structure containing spherical cavities. One way of doing this is to use monodisperse latex spheres. These latex spheres are prepared by slow addition of an aqueous precursor solution into a reservoir of hydrophobic silicone liquid, forming emulsion droplets. The size of the droplets is controlled by the concentration of the aqueous latex, the speed at which the suspension is stirred and ratio between the silicone liquid and latex. Polymerisation results in latex spheres of well defined size of the order of a few hundred nanometers, and spherical shape. As the concentration of the latex spheres increases to its critical concentration... 

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