Polybutadiene was successfully metalated by use of tert‐butyllithium activated with alkoxides of Group I metals without chain degradation. The metalated polymer was grafted with styrene and 1,3‐butadiene to give novel graft copolymers of varying microstructure. This metalating system was found to be highly efficient; however, its catalyst effectiveness is less than that of organolithium‐TMEDA metalation agent.
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