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Comprehensive Chemical Kinetics Degradation of Polymers by C. H. Bamford

By C. H. Bamford

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Graph of A, the first derivative of the thermogravimetric curve dwldt, and 0, the weight of reactant W, as a function of reciprocal absolute temperature for the degradation of polythene in vacuum [ 27 I . 29 thermobalance while the temperature is continuously increased at a programmed rate. This method has been reviewed by Reich et al. [21, 261. Dynamic thermogravimetric methods offer many advantages when compared with the usual isothermal methods. The thermal behaviour of a polymer can be characterized rapidly over a wide range of temperature in one experiment using a small amount of sample.

This proves that weak links are absent in this polymer. The molecular weight distribution at various stages in the degradation was determined by Nakajima et al. [76]. The initial polymer was shown t o have a logarithmic normal molecular weight distribution. The molecular weight distribution of the degraded polymer could be explained on the basis of a mechanism of random References pp. 165-1 73 48 scission. On the contrary, conventional (radical) polystyrene, on degradation gave values of 01 which showed an appreciable ordinate intercept when plotted according t o eqn.

Random initiation followed by depropagation competing with inter- and intramolecular transfer was proposed by these authors. This intramolecular transfer was further investigated by Tsuchiya and Sumi [ 561 by means of a careful analysis of the volatile products formed. These authors have shown that the amount of products formed by radical transfer to primary carbon atoms was much greater than that formed by transfer to secondary carbon atoms. It is suggested that the low reactivity of the hydrogen atoms attached to secondary carbons is due to the steric effect of the methyl groups.

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