The plastic samples of 3P/PVC/HIPS-Br mixed with PET were subjected to thermal decomposition. Another series of pyrolysis experiments were carried out in the presence of Ca-C catalyst applying vapor phase contact. The pyrolysis of plastic mixtures was performed in a Pyrex glass reactor (length: 35 cm; i.d. 3 cm) under atmospheric pressure by batch operation using the experimental conditions and temperature program shown in Fig. 1. Approximately, 10 g of plastics were loaded into the reactor for the thermal decomposition and also for the catalytic experiments. The solid catalyst (1 mm average diameter) was loaded into the reactor 10 cm above the plastic bed whereas the plastic sample was kept at the bottom of the reactor. In a typical run, the reactor was purged with nitrogen gas at a flow rate of 30 ml min−1 and held at 120 °C for 60 min to remove the physically adsorbed water from the catalyst and plastic sample. The reactor temperature was increased to the decomposition temperature (430 °C) at a heating rate of 3 °C min−1. The temperature of the plastic bed was measured and it was taken as the temperature of the decomposition. The vapor products were condensed (using a cold water condenser) to liquid products and trapped in a measuring cylinder. The hydrogen bromide evolved during pyrolysis was trapped in a flask containing ion-exchanged water (trap A). Organic bromine compounds cannot be trapped in the above flask, therefore these volatile products were passed through a furnace heated to 900 °C and flushed with air. Thus, the organic bromine products were converted into HBr and trapped in ion-exchanged water (trap B).