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 (Mns) in the range 2.8–62.2 kDa and polydispersity indices (PDIs) of ∼1.20 were successfully synthesized in a controlled manner. The syntheses of fluorene-fluorene and fluorene-thiophene diblock copolymers with Mns 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...

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