Ferrocene‐based polymers have drawn much attention in the past decades due to their unique properties and promising applications. However, the synthesis of hyperbranched polymers is still a great challenge. Here, two ferrocene‐based hyperbranched polytriazoles with high molecular weights are facilely prepared by the click polymerization reactions of ferrocene‐containing diazides ( 1 ) and tris(4‐ethynylphenyl)amine ( 2 ) using Cu(PPh3)3Br as catalyst in dimethylformamide at 60 °C for 5 and 9 h in satisfactory yields of 54.0% and 52.3%. The resulting polytriazoles are soluble in common organic solvents and thermally stable, with 5% weight loss temperatures up to 307 °C. They can be used as precursors to produce nanostructured ceramics with good magnetizability by pyrolysis at elevated temperature.
Summary: Novel hyperbranched poly([1,2,3]‐triazole)s were synthesized from several AB2 monomers by a 1,3‐dipolar cycloaddition reaction. The compound 3,5‐bis(propargyloxy)benzyl azide was polymerized thermally at room temperature leading to 1,4‐ and 1,5‐disubstituted poly([1,2,3]‐triazole) and catalytically leading only to the 1,4‐disubstituted poly([1,2,3]‐triazole). Only the thermal reaction led to fully soluble products. The AB2 monomers containing an internal alkyne A unit could be autopolymerized thermally under mild reaction conditions leading to soluble, high‐molecular‐weight hyperbranched poly([1,2,3] triazole)s. All products were characterized by detailed NMR investigations.
