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By C. H. Bamford

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Extra info for Comprehensive Chemical Kinetics Degradation of Polymers

Example text

Some of the conclusions are summarized in Fig. 9*. xO(ks + k * R )t Fig. 9. Random chain scission initiation, initial “most probable” distribution [ 191. The effect of chain transfer on weight remaining against time. , (l/y)Ixo. At each zip length ratio, curves forJhree-values of the fraction of the initial weight loss rate due to chain transfer, F = k I R / ( k l R + k s ) , are plotted. 3 Random chain scission initiation; combination termination The degradation behaviour in this case cannot be obtained from the preceding equations, which are restricted to first-order termination or second-order disproportionation termination.

165-1 7 3 46 20 40 % Volatilization 60 80 Fig. 24. Application of Gordon’s theory (continuous line) to Grassie and Kerr’s experimental points for the molecular weight changes during depolymerization of polystyrene [69]. K e n [67] very well (Figs. 24 and 25). Madorsky and co-workers have also made an extensive study of polystyrene degradation (see Ref. 59)’ and agree with Gordon’s degradation mechanism. A further argument against the weak link theory of Jellinek can be deduced from the results of Wall [70] on deuteropolystyrene.

3 Method involving more than one thermogram at different heating rates [ 31-33] If the constant rate of heating is changed from run to run and the other conditions are maintained constant, different thermograms are obtained (Fig. 15). From eqn. ( 7 2 ) In R , = In A - E/RT + n ln W (76) E and In A + n In W can thus be calculated from a plot of In R , against 1/T, for constant W. Furthermore, at In R , = 0, E/RTo = l n A + n l n W (77) and one can get a value for n. 0- 60- TemperaturePC) Fig. 15.

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