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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)

Tuesday, March 19, 2024

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