Manabu Kikuta

Studies of the Polymerization of Diallyl Compounds. XL. Correlation between Addition Modes and Evolution of Carbon Dioxide in the Polymerization of Diailyl Oxalate

Abstract The occurrence of head-to-head (HH) addition in the radical polymerization of diallyl oxalate (DAO) was examined under various polymerization conditions. The content of HH linkage in poly (DAO) was reduced in comparison with allyl acetate and diallyl succinate; this may be ascribed to the high polarity of DAO inducing a polar effect on the intermolecular propagation of the growing polymer radical, resulting in reduced HH addition. The correlation between addition modes and evolution of carbon dioxide characteristic of DAO polymerization at elevated temperatures is mechanistically discussed in detail, with special focus on the solvent effect and the reduced dismutation of the cyclized radical compared to the uncyclized one.