ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Cross-linking of polyethylene with benzoyl peroxide. II. The mechanism of the decomposition reaction of the peroxide

R. Rado and M. Lazár

Slovak Academy of Sciences, Bratislava

Abstract: cf. CA 55, 17074e. From the kinetic analysis of the decompn. of Bz₂O2 in the polyethylene (I) at 60 to 90° and from the decompn. products, BzOH and CO₂, the mechanism of this chain reaction is described. The first reaction is spontaneous decompn. of Bz₂O₂ with the formation of 2 BzO which in the induction decompn. react with mols. of Bz₂O₂. During this reaction, BzO is regenerated with the formation of CO₂ and PhOBz. The major part of BzO radicals carry their activity into I with the formation of polymer radicals and BzOH. The termination of the chain process occurring at 60 to 90° is caused by mutual deactivation, that is by the interaction of 2 polymer radicals and by the reaction of the primary radical with the polymer. The formation of polymer radicals is caused by the carry-over reaction of BzO radicals with I. The activation energy of carry-over reaction detd. graphically is 17.3 kcal./mol. The const. is K = 3.6 × 109 exp (-17,300/RT) mole/kg.

Full paper in Portable Document Format: 152a95.pdf (in Slovak)

Chemical Papers 15 (2) 95–101 (1961)