Polymer emulsifier concentration

Most synthetic latices contain 5—10 wt % of nonelastomeric components, of which more than half is an emulsifier or mixture of emulsifiers. One reason for this relatively high emulsifier concentration as compared with natural latex is that emulsifier micelles containing solubiHzed monomer play a principle role in the polymerization process. A high emulsifier concentration is usually necessary to achieve a sufficiently rapid rate of polymerization. Secondly, a considerable fraction of the surface of the polymer particles must be covered by adsorbed soap or equivalent stabilizer to prevent flocculation... 

Achieving steady-state operation in a continuous tank reactor system can be difficult. Particle nucleation phenomena and the decrease in termination rate caused by high viscosity within the particles (gel effect) can contribute to significant reactor instabilities. Variation in the level of inhibitors in the feed streams can also cause reactor control problems. Conversion oscillations have been observed with many different monomers. These oscillations often result from a limit cycle behavior of the particle nucleation mechanism. Such oscillations are difficult to tolerate in commercial systems. They can cause uneven heat loads and significant transients in free emulsifier concentration thus potentially causing flocculation and the formation of wall polymer. This problem may be one of the most difficult to handle in the development of commercial continuous processes. 

Elnulsifler Magg Balance. The overall emulsifier concentration in the system, Cgt. is constant however, it is distributed among the aqueous liiase (Cg ), the polymer particles and the monomer droplets intertaces (Cga) and the micellar aggregates (Cgm), according to the sinple balance ... 

Figure 4-5 shows the viscosity-average molecular weights in the emulsion polymerizations of styrene of Fig. 4-3. The results are in line with Eq. 4-7 in that the polymer size increases with the emulsifier concentration.

Smith and Ewart calculated the number of particles having been formed at the end of the first stage of polymerization. The number of particles is affected by the initiator decomposition rate (or radical formation rate) and total surface area of emulsifier to stabilize polymer-monomer particles. Smith and Ewart concluded that the number of particles is proportional to the 0.4 power of the initiator concentration and the 0.6 power of the emulsifier concentration, assuming that the surface area of total polymer-monomer particles is equal to the total surface area of emulsifier molecules when the last micelle disappears. 

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. 

Another method to increase the number of polymer particles produced in the first stage reactor with initiator and emulsifier concentrations fixed is to employ a plug flow type reactor such as a tubular reactor for the first stage. The minimum residence time of a plug flow reactor 6 necessary to produce the same number of polymer particles as in E batch reactor is tc. Thus, from Eq.(31) We have ... 

Figures 6, 7 and 8 show experimental verification of Eq.(40) in batch emulsion polymerization of styrene ( 14). The number of polymer particles was measured by electron micrscopy, not at finite but at 1 hour after the start of polymerization. Figure 6 represents the effect of lowering the initial monomer concentration, Mq on the number of polymer particles formed at fixed initial initiator and emulsifier concentrations. The number of polymer particles formed is constant even if M is lowered to the critical value Mc. This is because normal°condition that micelles disappear before the disappearance of monomer droplets is satisfied in the range of monomer concentration above Mc. The value of Mc can be calculated by the following equation obtained by equating XMc, the monomer conversion where micelles disappear, to XMc2, the monomer conversion where monomer droplets disappear.

The preparation of biodegradable microspheres by a solvent evaporation process using sodium oleate as the emulsifier was described in previous publications (1.21. A number of process parameters (such as drug loading, polymer molecular weight, polymer composition and initial polymer solution concentration) were studied to determine their effects on the release of drugs from biodegradable microspheres. 

In some areas, for example in crop protection, moving away from solvents simply required the development of new forms of delivery, e.g. concentrated emulsions or suspo-emulsions progressively displaced the emulsifiable concentrates. A change in the surfactant system was obviously necessary, but the new formulations could be made using commercially available products. In other instances, for example in the field of emulsion polymers, new colloidal species were developed and are still the subject of extensive research the reactive surfactants. 

At low emulsifier concentrations near the CMC, an increase in the degree of agitation results in a reduction of the emulsifier used for the formation of polymer particles (like micelles). This is because the monomer droplets become smaller as the degree of agitation is increased, and so the amount of emulsifier adsorbed onto the surfaces of the monomer droplets increases in proportion to the increased surface area of the monomer droplets. This brings about a decrease in the number of polymer particles produced, and so a decrease in the rate of polymerization. 

The investigation of polymer rate dependence on Initiator concentration C. (with ionic strength of the solution equalized) and emulsifier concentration C (for various molecular structures of emulsifier) pennltted us tb establish that it can be described by the following equation ... 

Effect of emulsifier concentration upon the number of polymer particles and the progress of polymerization ... 

Fig, 4 shows the effect of initial emulsifier concentration on the number of polymer particles produced. From the log-log... 

Initial emulsifier concentration 5 19/tti.ater] Fl9e23 Comparison between the ooservetf and calculat ed number of polymer particles at various Initial emu-... 

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