Reactivity-controlled synthesis of A2 + B3 type soluble hyperbranched polymers from aromatic diamines and cyanuryl chloride via a coupled monomer method

Abstract High molecular weight hyperbranched poly(guanamine)s (hb-PGs) based on cyanuric chloride (CyC) with various aromatic diamine monomers were successfully prepared via a coupled monomer (CM) method. The reaction of a diamine (A2 type monomer) with CyC (B3 type monomer) solution at −20 °C resulted in the corresponding (AB2)x type soluble intermediate, whose reaction then proceeded with an additional diamine monomer resulting in two- or three-component hb-PG polymers. A thick film was successfully prepared from a hb-Poly(BisAAF-CyC-mPDA) polymer solution that exhibits the exceptionally high Tg of 325 °C (as determined by thermomechanical analysis (TMA)) compared with that of the linear-type PG (l-PG) polymer such as poly(anilinodichloro-s-triazine-BisAAF) (Tg =191 °C). This hb-PG is miscible with the l-PG to a desired extent. Thus, blended polymer films were prepared, and their Tg values were measured by TMA. The blended films with hb-PG weight fractions of 85 %, 90 %, and 95 % exhibit the Tgs of 201, 212, and 228 °C, respectively. Contrary to the homo l-PGs, the blended films still exhibit stiffness above Tg at temperatures up to 400 °C. This may suggest that the prepared hb-PG could play an effective roll in binding linear PG polymers to afford supramolecular networks with amino functions at the periphery.