Asymmetrical Bifunctional Organic Peroxides as Initiators for the High-Pressure Polymerization of Ethylene

As a follow-up to earlier investigations into the high-pressure polymerization of ethylene with symmetrically substituted bifunctional peroxides, the suitability of 2,5-dimethylhexane-2-t-butylperoxy-5-perpivalate, a peroxide with different substituents on both O—O groups, has been tested. The polymerization tests were carried out in continuous operation in a stirred autoclave at 1700 bar, 240–285°C, a residence time of 60 s, and an initiator concentration of 3–25 mol ppm in the feed. Conversions of up to 30% were achieved. The specific initiator consumption was 0.2–1 g initiator per kg polyethylene. The density of the polymers obtained was 0.915–0.925 g/mL, their average molecular weight was 40 × 10³ to 60 × 10³, and their melt flow index was 0.001–100 g/10 min. On the basis of the molecular weight distribution, polydispersities of 4–7 were obtained.