Abstract

AbstractAn apparatus is described which permits reasonably uniform heat treatment of fairly large samples of PVC blends in controlled atmospheres, at preset temperatures, and for predetermined lengths of time. Experiments are described in which portions of a plasticised PVC blend, and also portions of an unplasticised PVC blend, were heated under nitrogen at 180 °C for various lengths of time up to those stages when Congo Red tests showed hydrogen chloride to be liberated. Each blend contained the basic lead carbonate “plumbonacrite”, 6PbCO3. 3Pb(OH)2.PbO, as stabiliser, and stearic acid as milling lubricant. Carbon dioxide evolved during the stabilising reactions was measured, and the crystalline solids in each heated PVC blend sample were studied by X‐ray diffraction.The results obtained show that the plumbonacrite stabiliser in each PVC blend was used continuously and completely during the effective stabilisation period. The rates of carbon dioxide evolution were found to differ markedly between the plasticised and unplasticised blends, but in each case they could be described in terms of first order reaction kinetics. Correlation of these carbon dioxide measurements with the X‐ray diffraction results led to the conclusion that the stabilising reactions in the plasticised PVC blend took place mainly in solution, whereas these reactions in the unplasticised PVC blend seemed to take place within the plumbonacrite crystals themselves.It is shown that these findings are consistent with previous work in these laboratories which has led to the idea that soluble lead compounds are formed by reaction of the basic lead stabiliser crystals with stearic acid milling lubricant, and that these compounds are in some way responsible for stabilising polyvinyl chloride against thermal decomposition. Further, it is suggested that the present results show that basic lead compounds act as thermal stabilisers for PVC in the true sense of the word. Considering in particular a radical chain mechanism for the thermal dehydrochlorination of polyvinyl chloride, a theory is proposed which explains how basic lead compounds can stabilise this polymer.

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