Particle monomer concentration

Using this model, the dependence of particles (monomers) concentration decay, equal to (1-Q), on temporal scale of polymerization t can be constmcted. Such dependence in donble logarithmic coordinates for fonr values c is presented in Fig. 26. As one can see, the adduced dependences at large enough t can be described by the following relationship [51] ... 

During Stage I the number of polymer particles range from 10 to 10 per mL. As the particles grow they adsorb more emulsifier and eventually reduce the soap concentration below its critical micelle concentration (CMC). Once below the CMC, the micelles disappear and emulsifier is distributed between the growing polymer particles, monomer droplets, and aqueous phase. 

During Stage II the growing particles maintain a nearly constant monomer concentration. The concentration of monomer is particle-size dependent, with smaller particles having lower concentrations (28). 

The monomer concentration within the forming latex particles does not change for a long period due to the diffusion of monomer from the droplets to the polymerization loci. Therefore, the rate of the propagation reaction does not change and a constant polymerization rate period is observed in a typical emulsion polymerization system. 

We have studied the effect of monomer concentration in the dispersion polymerization of styrene carried out in alcohol-water mixtures as the dispersion media. We used AIBN and poly(acrylic acid) as the initiator and the stabilizer, respectively, and we tried isopropanol, 1-butanol, and 2-butanol as the alcohols [89]. The largest average particle size values were obtained with the highest monomer-dispersion medium volumetric ratios in 1-butanol-water medium having the alcohol-water volumetric ratio of 90 10. The SEM micrographs of these particles are given in Fig. 15. As seen here, a certain size distribution by the formation of small particles, possibly with a secondary nucleation, was observed in the poly-... 

In this equation, Mp is the monomer concentration within forming particles, pa is the adsorption rate of oligomeric radicals by the forming particles, Vp is the volume fraction of forming particles within the system, and kp and k, are the rate constants of propagation and termination, respectively. 

The polymerizations were conducted in a 20-liter stainless steel reactor with a pitched-blade turbine agitator and four side-wall baffles. The monomer was polymerized at the same temperature, initiator and monomer concentration in two different inert diluents. The data (Figure 6) illustrate the substantial lowering of the overall heat transfer coefficient for the system with the more highly swollen particles. 

First, the water soluble initiator decomposes to form free radicals in the aqueous phase. These free radicals then add to comonomers dissolved in the aqueous phase to start a free radical oligomer chain. If the monomers are present to a greater concentration than the saturation concentration, they form a separate comonomer droplet phase. This phase then acts as a reservoir to feed the polymerization which occurs in the polymer (latex) particles. Monomers diffuse into the aqueous phase, diffuse into the polymer particles, and polymerize. 

Let the monomer concentration [M] be 5 molar both in the bulk phase and in the emulsion particles. The comparison is set forth below ... 

Models for emulsion polymerization reactors vary greatly in their complexity. The level of sophistication needed depends upon the intended use of the model. One could distinguish between two levels of complexity. The first type of model simply involves reactor material and energy balances, and is used to predict the temperature, pressure and monomer concentrations in the reactor. Second level models cannot only predict the above quantities but also polymer properties such as particle size, molecular weight distribution (MWD) and branching frequency. In latex reactor systems, the level one balances are strongly coupled with the particle population balances, thereby making approximate level one models of limited value (1). 

Combining then a balance for the rate of change of the free (unpolymerized) monomer concentration Mmon(0 with one for the total concentration of monomer units Mxoi(t) (bounded and unbounded), assuming that the rate of polymerization in the polymer particles is dominant and differentiating equation (1-6), one obtains ... 

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