Synthesis of hyperbranched poly(m-phenylene)s via suzuki polycondensation of a branched AB₂ monomer

An efficient synthesis of hyperbranched poly(m-phenylene)s is achieved by Suzuki polycondensation of a m-terphenyl-derived branched AB₂ monomer. The resulting hyperbranched polymers show high molecular weight and relatively low polydispersity and are readily soluble in common organic solvents. A catalyst system composed of Pd(OAc)₂ and S-Phos was found to be highly active in the present Suzuki polycondensation protocol. The molecular weight and polydispersity of the polymer are controllable by varying the catalyst loading and the starting monomer concentration. Experimental results are consistent with a pseudo-chain-growth pathway that involves intramolecular catalyst transfer during polymerization. Furthermore, the triflate end groups of the hyperbranched poly(m-phenylene)s can be efficiently converted to other functionalities via in situ Suzuki-Miyaura cross-couplings.