RADICAL FORMATION DURING 3-METHYL-3-TERT-BUTYLPEROXY-1-BUTYNYLSILVER THERMAL-DECOMPOSITION

A mechanism for 3-methyl-3-tert-butylperoxy-1-butynylsilver (PBS) ther molysis involving the decomposition of a coordinated complex of four P BS molecules followed by the homolytic rupture of the C-Ag bond to giv e colloid silver is proposed. The colloid silver acts as a catalyst, w hich results in an autocatalytic reaction acceleration. PBS thermolysi s results in the formation of electrophilic (CH3)(2)((CH3)(3)COO)CC=C radicals. At 393-413 K, peroxide bond dissociation contributes signifi cantly to radical generation. The rate constant for the hydrogen-atom abstraction from n-decane by the (CH3)(2)((CH3)(3)COO)CC=C radical is estimated to be 3.8 x 10(3) l mol(-1) s(-1).