Polymerization of norbornene with a pendent sulfonyl fluoride group catalyzed by palladium complex bearing <i>^t</i>Bu₃P ligand

Abstract

Abstract The combination of palladium complex ( t Bu 3 P)Pd(Me)Cl ( 1 ) and NaB[3,5‐(CF 3 ) 2 C 6 H 3 ] 4 (NaBAr 4 ) catalyzed homopolymerization of a novel monomer, norbornene (NB) with a pendent 2‐fluorosulfonyltetrafluoroethoxymethyl chain (NBSF). Catalytic activities of 1 /NaBAr 4 were higher than those of previously reported palladium or nickel catalysts, probably, because the palladium center with electron donative t Bu 3 P ligand was barely poisoned by the sulfonyl fluoride coordination. Thus, 1 /NaBAr 4 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. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5133–5141, 2008