Alkyllithium and alkali metal tert‐butoxide as polymerization initiator

We have shown that the presence of other alkali metal alkoxides in the alkyllithium‐initiated polymerization drastically increases the rate of polymerization and vinyl unsaturation in polybutadiene. Mechanistically, the propagating center is the dynamic equilibriums between carbon–metal bonds and oxygen–metal bonds. With potassium, rubidium, and cesium salts it reaches a limiting anionic behavior.