Polymerization polymer particles, formation

Equations 10.1 and 10.4 show that the number of polymer particles is crucial in determining both the rate and degree of polymerization. The mechanism of polymer particle formation indicates clearly that the number of polymer particles will depend on the emulsifier, its initial concentration (which determines the number of micelles), and the rate of generation of primary radicals. Smith and Ewart have shown that... 

Surfactant—polymer systems have additional technological significance since surfactants are normally used in the emulsion polymerization of many materials, often involving the solubilization of monomer in micelles prior to polymerization and particle formation. Surfactants have also been shown to increase the solubility of some polymers in aqueous solution. The combined actions of the surfactant as a locus for latex particle formation (the micelle) in some cases, particle stabilization by adsorbed surfactant, and as a solubilizer for monomer permit us to expect quite complex relationships between the nature of the surfactant and that of the resulting latex. 

Suspension polymerization of VDE in water are batch processes in autoclaves designed to limit scale formation (91). Most systems operate from 30 to 100°C and are initiated with monomer-soluble organic free-radical initiators such as diisopropyl peroxydicarbonate (92—96), tert-huty peroxypivalate (97), or / fZ-amyl peroxypivalate (98). Usually water-soluble polymers, eg, cellulose derivatives or poly(vinyl alcohol), are used as suspending agents to reduce coalescence of polymer particles. Organic solvents that may act as a reaction accelerator or chain-transfer agent are often employed. The reactor product is a slurry of suspended polymer particles, usually spheres of 30—100 pm in diameter they are separated from the water phase thoroughly washed and dried. Size and internal stmcture of beads, ie, porosity, and dispersant residues affect how the resin performs in appHcations. 

Among the various suspension systems mentioned, the details of oil-inwater (o/w) suspension polymerizations are fully known. The criteria of droplet formation, droplet stabilization, and droplet hardening, as will be discussed for the o/w suspension system, can apply equally to the preparation of beaded polymer particles in w/o systems. 

Emulsion polymerizations most often involve the use of water-soluble initiators (e.g. persulfate see 33.2.6.1) and polymer chains are initiated in the aqueous phase. A number of mechanisms for particle formation and entry have been described, however, a full discussion of these is beyond the scope of this book. Readers are referred to recent texts on emulsion polymerization by Gilbert4 and Lovell and El-Aasser43 for a more comprehensive treatment. 

The precipitation polymerization literature is reviewed with particular attention to the influence of particle formation and growth, autoaccelerating polymerization rates, and copolymer composition drift on polymer reactor design. 

The number of polymer particles is the prime determinant of the rate and degree of polymerization since it appears as the first power in both Eqs. 4-5 and 4-7. The formation (and stabilization) of polymer particles by both micellar nucleation and homogeneous nucleation involves the adsorption of surfactant from the micelles, solution, and monomer droplets. The number of polymer particles that can be stabilized is dependent on the total surface area of surfactant present in the system asS, where as is the interfacial surface area occupied by a surfactant molecule and S is the total concentration of surfactant in the system (micelles, solution, monomer droplets). However, N is also directly dependent on the rate of radical generation. The quantitative dependence of N on asS and R,- has been derived as... 

Modification of mortar and concrete in the presence of a latex occurs by concurrent cement hydration and formation of a polymer film (coalescence of polymer particles and the polymerization of monomers). Cement... 

However, emulsion polymerizations involve the formation of colloidal polymer particles that are essentially permanently suspended in the reaction medium. The reaction mechanism involves the migration of monomer molecules from liquid monomer droplets to sites of polymerization that originate in micelles consisting of surface-active agent molecules surrounding monomer molecules. Emulsion polymerizations are usually characterized by the requirement of surfactants during the initiation of the process and by the use of water-soluble initiators. This process also permits good control of the exothermic nature of the polymerization. 

The inter-relationship between colloid and polymer chemistries is completed by colloidal polymer particles. The formation of 50-nm-diameter, 100- to 200-nm-long polyaniline fibrils in a poly(acrylic acid)-template-guided polymerization, similar in many ways to those produced from polymerized SUVs (see above), provides a recent example of polymer colloids [449], The use of poly(styenesulfonic acid) as a template yielded globular polyaniline particles which were found to be quite different morphologically from those observed in the regular chemical synthesis of polyaniline [449]. 

In emulsion polymerization the compartmentalization of reaction loci and the location of monomer in polymer particles favor the growth and slow down termination events. The contribution of solution polymerization in the continuous phase is strongly restricted due to the location of monomer in the monomer droplets and/or polymer particles. This gives rise to greatly different characteristics of polymer formation in latex particles from those in bulk or solution polymerization. In emulsion polymerization, where polymer and monomer are mutually soluble, the polymerization locus is the whole particle. If the monomer and polymer are partly mutually soluble, the particle/water interfacial region is the polymerization locus. 

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