The Thermal Degradation Mechanism of Polystyrene¹

Pyrolysis of anionic and thermally prepared polystyrenes

“…The two National Bureau of Standards Standard Reference Polymers 705 and 706 were also studied in more detail than previously [13].…”

“…Until recently the shapes of the experimental thermal volatilization curves for polystyrene have not been produced by a fully a priori theory. However, with the use of computer evaluation the original theory [1,2] was shown [13] to be able to nearly reproduce the experimental rate and molecular weight behavior. The results indicate that intermolecular transfe r, end initiation, and zip lengths of the order of 5 are operative.…”

“…An important discrepancy was the existence of somewhat higher values for the viscosity average degree of polymerization of the degraded polymer at conversions of 20 to 60 percent, than predicted from the level of the theoretical values for the weight average degree of polymerization. In the previous work [13] the distribu-' v= tion computed for the mechanism deduced from the then available experimental rate and molecular weight data was presented in terms of plots of the ratio of weight to number average degree of polymerization as a function of conversion (see fig. 1).…”

“…The dashed sections of the c urves were drawn to this limit intuitively. The full lines are computer calculated [13]. The ~urprising result is that with even the highest initial r!…”

Thermolysis of polystyrene

“…First order kinetics was used in this work because random scission was assumed to be negligible. [8,15,20,29,35,45,[50][51][52][53][54] as shown in Table 6 . • • [20] up to 180 min.…”