Kinetic model of the thermoinitiated polymerization

We propose the following kinetic equation, which allows us a quantitative description of the 3-D polymerization of the polyfunctional oligomers in bulk in the entire interval of transformation level [8-10]  

Kinetic equation (5.1) shows a S-shaped dependence of P on / with ordinate Pq being the point of inflection, which is determined from the condition d P/d f=0 

The estimates [8] of the maximum rate of the process Wo=(dP/dr)max corresponding to ordinate Po, point of inflection of the kinetic curve P=P(t), show that the principal contribution to the kinetics of the process is made by the second term in equation (5.1). Therefore, without a significant error, the expression in square brackets in equation (5.2) may be considered equal to dP/dt. From the expression Vi=-dc/dt=k C, in which c is concentration of the initiator and k, is the rate constant of its decomposition, follows dv/Vid =- i, Thus, the solution of equation (5.2) can be written as 

From this equation follows, that at a h and P Vi, then W k2v/A. This allows us to estimate on Wa directly. In accepted terms of a normalized rate of the process we have -d(ln(l-F))/df. Its maximum corresponds to the point of inflection of the kinetic curve 

Solution of the equation (5,5) does not limit the values of P in the area of positive P 0 this also agrees with the experimental data [ 1 ]. 

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