Micelle polymerisation

The reaction is considerably modified if the so-called emulsion polymerisation technique is used. In this process the reaction mixture contains about 5% soap and a water-soluble initiator system. The monomer, water, initiator, soap and other ingredients are stirred in the reaction vessel. The monomer forms into droplets which are emulsified by some of the soap molecules. Excess soap aggregates into micelles, of about 100 molecules, in which the polar ends of the soap molecules are turned outwards towards the water whilst the non-polar hydrocarbon ends are turned inwards (Figure 2.17). 

Monomer molecules, which have a low but finite solubility in water, diffuse through the water and drift into the soap micelles and swell them. The initiator decomposes into free radicals which also find their way into the micelles and activate polymerisation of a chain within the micelle. Chain growth proceeds until a second radical enters the micelle and starts the growth of a second chain. From kinetic considerations it can be shown that two growing radicals can survive in the same micelle for a few thousandths of a second only before mutual termination occurs. The micelles then remain inactive until a third radical enters the micelle, initiating growth of another chain which continues until a fourth radical comes into the micelle. It is thus seen that statistically the micelle is active for half the time, and as a corollary, at any one time half the micelles contain growing chains. 

As reaction proceeds the micelles become swollen with monomer and polymer and they eject polymer particles. These particles which are stabilised with soap molecules taken from the micelles become the loci of further polymerisation, absorbing and being swollen by monomer molecules. 

In the case of emulsion polymerisation, half the micelles will be reacting at any one time. The conversion rate is thus virtually independent of radical concentration (within limits) but dependent on the number of micelles (or swollen polymer particles). 

An increase in the rate of radical production in emulsion polymerisation will reduce the molecular weight since it will increase the frequency of termination. An increase in the number of particles will, however, reduce the rate of entry of radicals into a specific micelle and increase molecular weight. Thus at constant initiator concentration and temperature an increase in micelles (in effect in soap concentration) will lead to an increase in molecular weight and in rate of conversion. 

Emulsion polymerisation represents the next stage in development from the suspension technique and is a versatile and widely used method of polymerisation. In this technique droplets of monomer are dispersed in water with the aid of an emulsifying agent, usually a synthetic detergent. The detergent forms small micelles 10-100 /im in size, which is much smaller than the droplets that can be formed by mechanical agitation in suspension polymerisation. These micelles contain a small quantity of monomer, the rest of the monomer being suspended in the water without the aid of any surfactant. 

Emulsion polymerisation is initiated using a water-soluble initiator, such as potassium persulfate. This forms free radicals in solution which may initiate some growing chains in solution. These radicals or growing chains pass to the micelles and diffuse into them, which causes the bulk of the polymerisation to occur in these stabilised droplets. 

After more than 20 years, Walde et al. (1994) returned in a way to coacervate experiments, although using other methods. Walde (from the Luisi group) repeated nucleotide polymerisation of ADP to give polyadenylic acid, catalysed by polynucleotide phosphorylase (PNPase). But instead of Oparin s coacervates, the Zurich group used micelles and self-forming vesicles. They were able to demonstrate that enzyme-catalysed reactions can take place in these molecular structures, which can thus serve as protocell models. Two different supramolecular systems were used ... 

The reason why the hybrid micelles evolve from sphere to cylinder is not yet completely understood, but it results from the fact that when silica species are adsorbed onto the surface of the micelles, the average curvature of the micelles is decreasing [9], Polymerisation of silica species by condensation leads to precipitation of the ordered hexagonal mesoporous material. 

The monomers get absorbed in micelles resulting in their swelling. Water soluble initiators are used which form free radicals. Inorganic persulphates are commonly used as initiators. The initiator diffuses into a micelle and polymerisation proceeds. As more monomer is polymerised monomers from outside the micelle diffuse inside and the process continues when another radical enters the micelle the polymerisation stops. This technique can give high Molecular weight polymers. 

It is well known that AB diblock copolymers form micelles in solvents that are selective for one of the blocks. By varying the nature of the solvent, it is also possible to form micelles with the A block in the core or with the B block in the core. However, we have recently demonstrated that certain hydrophilic AB diblock copolymers can form either A-core micelles or B-core micelles in aqueous media. In the original example, both blocks were based on tertiary amine methacrylates and the diblock copolymer was prepared by group transfer polymerisation, a special type of anionic polymerisation which is particularly... 

Microemulsions with different structures, like micelles, reverse micelles or bicontinuous networks, can be used for several inorganic, organic [72] or catalytic reactions which require a large contact area between oil and water. Besides enzyme catalysis, this can be the formation of nanoparticles [54, 73, 74], hydro-formylation reactions [75] or polymerisations [76-78]. 

The mechanism of emulsion polymerisation is complex. The basic theory is that originally proposed by Harkins21. Monomer is distributed throughout the emulsion system (a) as stabilised emulsion droplets, (b) dissolved to a small extent in the aqueous phase and (c) solubilised in soap micelles (see page 89). The micellar environment appears to be the most favourable for the initiation of polymerisation. The emulsion droplets of monomer appear to act mainly as reservoirs to supply material to the polymerisation sites by diffusion through the aqueous phase. As the micelles grow, they adsorb free emulsifier from solution, and eventually from the surface of the emulsion droplets. The emulsifier thus serves to stabilise the polymer particles. This theory accounts for the observation that the rate of polymerisation and the number of polymer particles finally produced depend largely on the emulsifier concentration, and that the number of polymer particles may far exceed the number of monomer droplets initially present. 

Monodispersed sols containing spherical polymer particles (e.g. polystyrene latexes22"24, 135) can be prepared by emulsion polymerisation, and are particularly useful as model systems for studying various aspects of colloidal behaviour. The seed sol is prepared with the emulsifier concentration well above the critical micelle concentration then, with the emulsifier concentration below the critical micelle concentration, subsequent growth of the seed particles is achieved without the formation of further new particles. 

It is also possible to prepare chiral PANI by in situ polymerisation with CSA, and in this case the reaction can afford chiral nanotubes [63]. The optically active materials contain nanotubes with 80 to 200 nm outer diameter and an internal diameter of between 20 and 40 nm, as revealed through microscopy images. A self-assembly process was proposed in which anilinium cations and CSA anions form micelles which act as templates for the growing polymer chains. Nanotubes are also formed when (R)- or (S)-2-pyrrolidone-... 

Emulsions made by agitation of pure immiscible liquids are usually very unstable and break within a short time. Therefore, a surfactant, mostly termed emulsifier, is necessary for stabilisation. Emulsifiers reduce the interfacial tension and, hence, the total free energy of the interface between two immiscible phases. Furthermore, they initiate a steric or an electrostatic repulsion between the droplets and, thus, prevent coalescence. So-called macroemulsions are in general opaque and have a drop size > 400 nm. In specific cases, two immiscible liquids form transparent systems with submicroscopic droplets, and these are termed microemulsions. Generally speaking a microemulsion is formed when a micellar solution is in contact with hydrocarbon or another oil which is spontaneously solubilised. Then the micelles transform into microemulsion droplets which are thermodynamically stable and their typical size lies in the range of 5-50 nm. Furthermore bicontinuous microemulsions are also known and, sometimes, blue-white emulsions with an intermediate drop size are named miniemulsions. In certain cases they can have a quite uniform drop size distribution and only a small content of surfactant. An interesting application of this emulsion type is the encapsulation of active substances after a polymerisation step [25, 26]. 

The present chapter is concerned only with catalysis at the solid/liquid interface and will not deal with microheterogeneous catalysis by enzymes, micelles and polyelectrolytes even though the resulting kinetics are closely similar [4], Moreover, little reference will be made to catalytic processes involving gases as these have been the subject of Vols. 19-21 of this series, nor to catalytic polymerisations which have been treated in Vols. 14, 14A, and 15. 

Figure 19.24. Degree of polymerisation in Tg cross-linked casein micelles and caseinate (Bonisch et al. 2007).

The reason for this behaviour is obscure it is not apparently due to the presence of peroxides in the surfactant. However, it is perhaps significant that an emulsion polymerisation reaction in which the rate of polymerisation is first-order with respect to surfactant level is consistent with Smlth-Ewart "Case 2" kinetics for a system in which the surfactant functions as an initiator as well as a micelle generator. 

It appears that the presence of polar molecules such as water is essential If significant decomposition Is to occur. It therefore seems likely that the aqueous-phase polymerisation of butadiene Is Initiated through the decomposition of cobalt(III) acetylacetonate which Is dissolved In the true aqueous phase. That fraction of the initiator which Is dissolved In the monomer phase Is presumably Ineffective. So also, presumably. Is the fraction which is solubilised within the surfactant micelles, since the Interiors of the latter are essentially non-polar In nature. 

Polymer nanoparticles with diameters of 50-500 nm are now widely used. As with microspheres and microcapsules, one can differentiate between solid polymeric spheres (nanoparticles) and those spheres with thin polymeric walls (nanocapsules). The locus of polymerisation is not an emulsion droplet as in microencapsulation, hut a micelle. The process involves the soluhilisation of a water-soluhle monomer such as acrylamide along with the dmg or other agent such as antigen to he encapsulated. An organic liquid such as n-hexane serves as the outer phase. Polymerisation is induced hy irradiation (y-rays. X-rays, UV light), exposure to visible light or heating with an initiator. 

Polymerized Microemulsion Systems. A microemulsion of styrene and divinylbenzene with CTAB + hexanol may readily be made, and subsequently polymerized to form a polymerized microemulsion (5,6,7). This system exhibits two sites of solubilisation for photosystems such as pyrene, one in the surfactant skin layer, and the other in the polymerized styrene-divinylbenzene core. Photochemical reactions induced in the surfactant skin are very similar to those observed in micelles and are not immediately of concern to us at this stage. However, photochemical reactions induced in the rigid polymerized core are of interest, as they essentially confine reactants to a small region of space where movement is restricted as compared to a fluid non-polymerised microemulsion or a micelle. Thus, diffusion is minimised, and it may be possible to investigate reactions which occur over a distance rather than reactions which occur by diffusion. In order to eliminate reactions in the surfactant skin a microemulsion can be constructed which contains cetyl pyridinium chloride in place of CTAB. The pyrene that resides in the surfactant skin layer is immediately quenched by the pyridinium group following excitation. 

The role of the surfactants is two-fold first, to provide a locus for the monomer to polymerise, and second, to stabilise the polymer particles as they are formed. In addition, surfactants aggregate to form micelles (above the cmc), and these can solubilise the monomers. In most cases a mixture of anionic and nonionic surfactant is used for the optimum preparation of polymer latexes. Cationic surfactants are seldom used, except for specific applications where a positive charge is required on the surface of the polymer particles. 

Micelle formation has been studied for sodium salts of fatty acids containing terminal double bonds using electrical conductivity . Here two critical micelle concentration points were observed of which the first point at 0.044 moles litres" was critical in terms of the number average degree of polymerisation of the polymers produced. At concentrations up to the second point the molecular weight change was significantly smaller. The photopolymerisation of acrylamide in reverse micelles was found to be first order with respect to monomer concentration whilst the order was found to depend upon the oil concentration in the... 

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