Suspension polymerization termination kinetics

Polymerization Kinetics of Mass and Suspension PVC. The polymerization kinetics of mass and suspension PVC are considered together because a droplet of monomer in suspension polymerization can be considered to be a mass polymerization in a very tiny reactor. During polymerization, the polymer precipitates from the monomer when the chain size reaches 10—20 monomer units. The precipitated polymer remains swollen with monomer, but has a reduced radical termination rate. This leads to a higher concentration of radicals in the polymer gel and an increased polymerization rate at higher polymerization conversion. 

The concentration of monomers in the aqueous phase is usually very low. This means that there is a greater chance that the initiator-derived radicals (I ) will undergo side reactions. Processes such as radical-radical reaction involving the initiator-derived and oligomeric species, primary radical termination, and transfer to initiator can be much more significant than in bulk, solution, or suspension polymerization and initiator efficiencies in emulsion polymerization are often very low. Initiation kinetics in emulsion polymerization are defined in terms of the entry coefficient (p) - a pseudo-first order rate coefficient for particle entry. 

The kinetics of termination in suspension polymerization is generally considered to be the same as for solution or bulk polymerization under similar conditions and will not be discussed further. A detailed discussion on the kinetics... 

A mathematical model for styrene polymerization, based on free-radical kinetics, accounts for changes in termination coefficient with increasing conversion by an empirical function of viscosity at the polymerization temperature. Solution of the differential equations results in an expression that calculates the weight fraction of polymer of selected chain lengths. Conversions, and number, weight, and Z molecular-weight averages are also predicted as a function of time. The model was tested on peroxide-initiated suspension polymerizations and also on batch and continuous thermally initiated bulk polymerizations. 

In current industrial practice, most often all monomer is added at once, and thus is completely absorbed in the Y-droplets before the polymerization starts. In this case the kinetics may resemble that of a suspension polymerization system. The main differences from suspension kinetics may result from a possible interdroplet transport of radicals and a possible aqueous-phase termination. 

To form a dispersion, the monomer must be quite insoluble in the suspension system. To decrease the solubility and to sometimes also increase the particle size of the resultant polymer bead, partially polymerized monomers or prepolymers may be used. Optimum results are obtained with initiators that are soluble in the monomer. Often, no differences in rates are observed between polymerization in bulk and suspension. Kinetic studies of styrene suspension polymerization have shown that all the reaction steps, initiation, propagation, and termination, occur inside the particles. ... 

In suspension polymerization each droplet can be considered as a small batch reactor. The water phase serves as a suspension medium, and also as a heat transfer medium. A cooling jacket takes care of the heat removal from the reactor. The polymerization rate in the droplets is mostly determined by the kinetics of initiation, propagation and termination reactions. At a certain degree of conversion, the Trommsdorff or gel-effect may occur (see section 13.3.1). Towards the end of the reaction, also the propagation step may be hindered by diffusion... 

The formation of primary radicals governs the rate of initiation and particle population. Because radical generation occurs in the aqueous phase, whereas radical termination occurs in the polymer particles, the polymerization rate and molecular weight can be increased at the same time. In vinyl chloride emulsion polymerization, the emulsifier greatly affects the polymerization kinetics and the physicochemical and colloidal properties of the polymer. The average polymer particle size is of the order 0.1-0.3 p,m, which is the size of primary particle nuclei in bulk and suspension polymerizations. The following is a summary of the typical kinetic features of batch vinyl chloride emulsion polymerization [61] ... 

Equations, which are also applicable to suspension, solution, and bulk polymerization, form an extension of the Smith-Ewart rate theory. They contain an auxiliary parameter which is determined by the rate of initiation, rate constant of termination, and volume of the porticles. The influence of each variable on the kinetics of emulsion polymerization is illustrated. Two other variables are the number of particles formed and monomer concentration in the particles. Modifications of the treatment of emulsion polymerization are required by oil solubility of the initiator, water solubility of the monomer, and insolubility of the polymer in the monomer. 

Kinetics models are useful for designing commercial reactors and for studying the fundamental mechanisms of the important reactions. The free-radical polymerization that takes place in emulsion systems is characterized by three main reactions initiation, propagation, and termination. Various radical transfer reactions can also be important. The rate of polymerization for bulk, solution, and suspension processes can be expressed as shown by Equation 2 ... 

When solid polymer precipitates fiom bulk, solution, suspension, or emulsion polymerizations by a chain mechanism, the kinetics of the reaction and properties of the product may change sharply. If the solid phase is not swollen by the reaction mixture, the active site of the polymerization is isolated from possible termination reactions and may produce pronounced auto acceleration and increases in molecular weight of polymer formed. This behavior was quantified for one chain reaction polymer, polyvinyl chloride, covered in this book. Micldey (9) showed that polyvinyl chloride synthesis in bulk followed a two term kinetics equation with the second term representing incremental increases in polymerization rate due to accelerated polymerization in precipitated particles of polymer. 

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