Excellent performance of aromatic polyguanamines induced by multiple hydrogen bondable tetraazacalix[2]arene[2]-triazine ring in their main chain

A series of poly(guanamine) (c-PG)s containing tetraazacalix[2]arene[2]-triazine (mPDA(2)CyC(2)) were successfully prepared by solution polycondensation of mPDA(2)CyC(2) with various aromatic diamines in an aprotic organic solvent with a lithium chloride additive (5 wt%) at 150 °C for 6 hours. The number-average molecular weights (M(n))s of these c-PG polymers reached up to 31 500, with a relatively broad molecular weight distribution (M(w)/M(n)) of 5.3. They showed good solubility in aprotic organic solvents, such as N-methylpyrrolidone and N,N-dimethylacetamide at a concentration of 2 mg mL(−1). The glass transition temperatures (T(g)) of the c-PG polymers were in the range 359 °C–392 °C, approximately 160 °C higher than those of counterpart polymers (i.e., with no aza-calixarene-based PG (l-PG)). The coefficients of thermal expansion (CTEs) of the c-PG polymers were 29.7–48.1 ppm K(−1) (at 100 °C–150 °C), much lower than those of l-PG samples, i.e., 59.1–85.1 ppm K(−1). Transparent and almost colorless c-PG films were successfully prepared by a solution casting method, showing maximum tensile strength (σ(S)), modulus (E(γ)), and elongation at break (E(b)) values of 151 MPa, 6.3 GPa, and 4.4%, respectively, for the c-PG polymer from mPDA(2)CyC(2) and 4,4′-oxydianiline monomers. The corresponding l-PG film exhibited σ(S), E(γ), and E(b) values of just 76 MPa, 5.4 GPa, and 1.6%, respectively. These outstanding thermal and mechanical properties of the c-PG polymers can be attributed to their multiple hydrogen bonding interaction between mPDA(2)CyC(2) residues in the polymer backbone. This interaction was identified by infrared spectroscopy measurements at the broad absorption band around 3000–3400 cm(−1).