Polymerization of norbornene with a pendent sulfonyl fluoride group catalyzed by palladium complex bearing tBu3P ligand

The combination of palladium complex (tBu3P)Pd(Me)Cl (1) and NaB[3,5‐(CF3)2C6H3]4 (NaBAr4) catalyzed homopolymerization of a novel monomer, norbornene (NB) with a pendent 2‐fluorosulfonyltetrafluoroethoxymethyl chain (NBSF). Catalytic activities of 1/NaBAr4 were higher than those of previously reported palladium or nickel catalysts, probably, because the palladium center with electron donative tBu3P ligand was barely poisoned by the sulfonyl fluoride coordination. Thus, 1/NaBAr4 is the current best catalyst system for NBSF polymerization. The catalyst system also gave copolymers of NB with NBSF. The obtained copolymers have high sulfonyl‐fluoride incorporation and a narrow molecular weight distribution. Present catalyst system could control incorporation ratio of NBSF by changing a feed monomer ratio with slow addition of NB solution.