Butylperoxy interaction

This in accordance with the mechanism shown in Figure 14.5. In a preequilibrium two 2-propoxide anions are replaced by a tertiary-butylperoxy anion and an allyloxy anion, as follows clearly from the kinetic equation. This intermediate has a very low concentration and has not been observed directly. From here on we can only speculate on the interactions leading to a preferred attack on either of the enantiotopic faces of the alkene. 

Isobutane reacts with O2 by a free radical chain process similar to the one for n-butane except that cage combinations of r-butoxy radicals produced by terminating interactions of f-butylperoxy radicals gives di-t-butylperoxide . r-Butoxy radicals which escape the solvent cage undergo )8-scission to give methyl radicals and acetone ... 

Percent product distribution acetone 24.5 5.1, 2-methyl-2-propanol 18.8 4.0, 2-methyl-2-hydroperoxypropane 36.7 7.5, 2-methyl-propanal 14.0 3.9, 2-methyl-propanol 4.4 1.3, tertiary butylperoxide < 1.7. The peroxy radicals involved are primary 2-methyl-1-propylperoxy, primary methylperoxy and tertiary 2-methyl-2-propylperoxy. The relatively large yield of tertiary butanol is due to the interaction between CH3OO and tertiary butylperoxy radicals. Computer simulations based on the known rate coefficients for the self-reactions of these radicals [2] gave = 3 x 10" cm molecule s for the cross combination reaction. To simulate the observed ratio of primary alcohol and aldehyde requires a rate coefficient p 3 x 10" cm molecule s for the interaction between 2-methyl-1-propylperoxy and tertiary 2-methyl-2-propyl-peroxy radicals. The oxidation mechanism is quantitatively well understood. 

Another route to modify interfacial interactions combines the coverage of the filler surface with a polymer layer (see Section VII.C) and the subsequent polymerization of a monomer, or chemical reaction with the matrix [135], A peroxidic oligomer is prepared by the copolymerization of various components, e.g., maleic acid, 2-t-butylperoxy-2-methyl-5-hexen-3-in and styrene. The surface of a filler, usually CaC03, is covered with the oligomer from an aqueous solution. The decomposition of the peroxidic groups in the presence of monomers leads to a composite, where the filler is evenly distributed in the polymer matrix and adhesion of the components is excellent. Up to now. 

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