A Novel Type of Polycondensation Utilizing Transition Metal-Catalyzed C–C Coupling. I. Preparation of Thermostable Polyphenylene Type Polymers

Abstract Transition metal compounds including NiCl2(bpy) (bpy=2,2′-bipyridine), NiBr2(PPh3)2 (PPh3=triphenylphosphine), PdCl2(bpy), NiCl2, CoCl2, FeCl2, and FeCl3 catalyze polycondensation of di- and polyhalogenated organic aromatic compounds by dehalogenation with magnesium under mild conditions. Poly(p-phenylene), poly(m-phenylene), poly(oxybiphenylene), and poly(phenylenemethylene) were prepared from p-dihalobenzene, m-dichlorobenzene, bis(p-bromophenyl) ether, and α,p-dichlorotoluene. They have a high degree of polymerization and high thermal stability. Poly(p-phenylene), poly(oxybiphenylene), and poly(phenylenemethylene) have regularly repeated structures as proved by IR spectroscopy and X-ray powder diffraction. Polymerization of polyhalogenated aromatic compounds (1,3,5-trichlorobenzene and hexachlorobiphenyl) in tetrahydrofuran (THF) gave copolymers having aromatic nuclei and THF units. Polymerization of the haloaromatic compounds is considered to proceed through a mechanism in which consecutive cycles of oxidative addition of haloaromatic compounds (R–X) to the transition metal catalyst take place so as to cause alkylation (arylation) by the Grignard reagent formed in the system (R′MgX) and elimination of R–R′ from an active transition metal compound having R and R′ groups.