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Kinetic Modeling of Irreversible Polycondensations

In his pioneering study of nonlinear polycondensation [7], Stockmayer has already checked his statistical solution [Eq. (5)] by solving the mass balance equations in a batch reactor for the concentrations of functional groups A and the set of isomeric polymer molecules P with x repeating units X [Eqs. (122)]. [Pg.129]

The two solutions are identical. Hence, for a long time no importance was attributed to the use of a kinetic approach for describing batch polycondensations starting from monomers, and the statistical approach was preferred. Of course, chemical engineers had to deal with semi-batch and continuous stirred tank reactors where the statistical approach, although possible, is cumbersome and error-prone, so a few papers appeared in the 1960s dealing with kinetically controlled linear polycondensations [274—276]. [Pg.129]

It is possible to obtain a rate equation for the members of each dass by adding the contributions of the various condensation reactions, leading to a version of Smoluchowski s coagulation equation. [Pg.130]

The rate of formation of groups requires a modification of Eq. (68), since it is no longer possible to include breakage or exchange reactions. Adding the unimolecular reactions defined above, the new general rate equation becomes Eq. (124). [Pg.130]

The multiple sums in the rate of formation of P(x), which will not be presented, are simplified through consideration of its generating function [Eqs. (125), (126)] [Pg.130]


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