Experimental verification of the kinetic model for the reaction yielding linear polyurethanes,claiming dependence of oligomer reactivities on molecular weights. III

Taking advantage of the algorithm developed earlier which makes it possible to calculate rate constants for the parallel-subsequent reactions of the kinetic model for the diisocyanate and diol polyaddition process, a mathematical model was developed for this process which then was subjected to mathematical decomposition. The procedure adopted allowed me to numerically resolve the obtained system of differential equations and to perform the numerical simulation of the polymerization process studied. For the reactions of 2,4-TDI and 1,4-butanediol, the results obtained were compared to experimental concentrations of urethane oligomer fractions found by means of GPC. It was found that the model suggested provides a better fit than does the model claiming dependence of chemical activity of oligomers solely on reactivity specifications for their functional groups. © 1996 John Wiley & Sons, Inc.