Free-radical dispersion polymerization constant

If an oil-soluble monomer is dispersed in a continuous aqueous phase without the use of surfactants, suspension polymerization results. The viscosity of the resulting suspension will remain essentially constant over the course of the polymerization. Oil-soluble free radical initiators are used to effect polymerization. The monomer is dispersed into beads by the action of an agitator. Since little or no surfactant is used, no emulsification takes place, and, if the agitation is stopped, the monomer will form a separate bulk phase, usually above the aqueous phase. The monomer is polymerized by the initiator within the droplets, forming polymer beads of approximately the same size as the monomer droplets (0.1-10 mm diameter). The product can be readily separated from the aqueous phase (via filtration or decantation) in the form of macroscopic particles or beads, which can be easily packaged and/or transported. Heat transfer is facihtated by the presence of the continuous aqueous phase. Blocking agents such as clays or talcs are used to prevent particle ag-... 

Figure 3.33 lists a recipe for emulsion polymerization of polystyrene in a water dispersion of monomer droplets and soap micelles [20]. The reaction is started by light-sensitive, water-soluble initiators, such as benzoyl peroxide. If one compares the sizes of the dispersed droplets, one notices that the small soap micelles that contain also styrene in their interior are most likely to occasionally initiate a polymerization of the monomer on absorption of a free radical. Once initiated, the reaction continues until a second free radical molecule enters the micelle. Then the reaction is terminated, until a third radical starts another molecule. Monomers continuously add to the micelles, so that the polymerization continues. Keeping the free radical generation constant, a relatively narrow molar mass distribution can be obtained. 

The free radical then has the possibility to react with monomer dispersed in the system in several states, the most significant of which is micelles (18). Micelles are monomer droplets stabilized by the emulsifying agent. An emulsifying agent contains both oil-soluble and water-soluble parts in its molecular structure, and hence forms the interphase between the water and the dispersed monomeric phase. At the start of phase I, a typical system contains 10 micelles/mL and the initiation rate is around 10 radicals/(mL s). As the radicals enter the particles, the polymerization proceeds in the usual manner at a rate rp with a propagation rate constant k-g and the monomer concentration [M] in the particle (3-5,9). 

Water as diluent has obvious advantages and has been developed for many free-radical polymerizations. Thus suspension polymerization involves the dispersion of the non-miscible monomer in water as droplets (0.1-5 mm diameter) by means of agitation and protective colloids or dispersing agents (e.g. polyvinyl alcohol, PVAL), and adding a monomer-soluble initiator. The polymer ends up approximately the same size as the original droplets and the system can be viewed as many small bulk polymerizations. As water is the continuous phase the viscosity remains constant and good heat transfer occurs. This process is used for PVC. 

In the case of free radical polymerization (figure 13.2) the dispersion index D at low degrees of conversion appears to be 1.5. In a batch or plug flow reactor D increases as the degree of conversion goes up. The reason is that the propagationrinitiation ratio decreases as the monomer is consumed. For a segregated CSTR the effect is enhanced by the residence time distribution. For a well mixed CSTR D remains constant and low. This is explained by the fact that all polymer molecules are made under identical conditions. 

Emulsion polymerization of vinyl chloride is initiated by a water-soluble initiator such as potassium persulfate. Initially in the reactor, monomer droplets are dispersed in the aqueous phase (continuous phase) containing initiator and surfactant (emulsifier). As the reactor content is heated, the initiator decomposes into free radicals. When the surfactant concentration exceeds the critical micelle concentration (CMC), micelles are formed. Free radicals or oligomers formed in the aqueous phase are then captured by these micelles. Vinyl chloride monomer is slightly soluble in water. As the monomer dissolved in water diffuses into micelles containing radicals, polymerization occurs. With an increase in monomer conversion in the polymer particles, separate monomer droplets become smaller and eventually they disappear. The monomer concentration in polymer particles is constant as long as liquid monomer droplets exist. The rate of emulsion polymerization is represented by... 

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