Controlled Synthesis of Polyfluorenes via Kumada Catalyst Transfer Polycondensation with Ni(acac)2/dppp as the Catalyst

A new catalyst system, i.e., nickel acetylacetonate/1,3-bis(diphenylphosphino)propane (Ni(acac)(2)/dppp), was explored to catalyze the Kumada catalyst transfer polycondensation (KCTP) of three fluorene monomers with different substituents at 9-position. The living nature of the polymerization was confirmed by polymerization kinetic studies, monomer addition experiment and block copolymerizations. As a result, poly(9,9-dioctylfluorene)s (PF8s) with the number-average molecular weights (M(n)s) in the range 2.8-62.2 kDa and polydispersity indices (PDIs) of similar to 1.20 were successfully synthesized in a controlled manner. The syntheses of fluorene-fluorene and fluorene-thiophene diblock copolymers with M(n)s up to 46 kDa were also demonstrated. A complex, i.e. Ni(dppp)(acac)(2), with an octahedral coordination geometry was isolated and confirmed by X-ray crystallographic analysis. The polymerization experiments indicated that the in situ formed Ni(dppp)(acac)(2) should be the active catalyst. To the best of our knowledge, this is the first report on the controlled synthesis of polyfluorenes (PFs) via KCTP.