Sasaki H, Kotaki T, Fujimori A, Tsukamoto T, Suzuki E, Oishi Y, Shibasaki Y
Department of Chemistry & Biological Sciences, Faculty of Science & Engineering, Iwate University 4-3-5 Ueda Morioka Iwate 020-8551 Japan
Graduate School of Science and Engineering, Saitama University 255 Shimo-okubo, Sakura-ku Saitama 338-8570 Japan.
RSC Adv. 2020 Jan 8;10(3):1361-1370. doi: 10.1039/c9ra09136j. eCollection 2020 Jan 7.
A series of poly(guanamine) (-PG)s containing tetraazacalix[2]arene[2]-triazine (PDACyC) were successfully prepared by solution polycondensation of PDACyC 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 ( )s of these -PG polymers reached up to 31 500, with a relatively broad molecular weight distribution ( / ) of 5.3. They showed good solubility in aprotic organic solvents, such as -methylpyrrolidone and ,-dimethylacetamide at a concentration of 2 mg mL. The glass transition temperatures ( ) of the -PG polymers were in the range 359 °C-392 °C, approximately 160 °C higher than those of counterpart polymers (, with no aza-calixarene-based PG (-PG)). The coefficients of thermal expansion (CTEs) of the -PG polymers were 29.7-48.1 ppm K (at 100 °C-150 °C), much lower than those of -PG samples, , 59.1-85.1 ppm K. Transparent and almost colorless -PG films were successfully prepared by a solution casting method, showing maximum tensile strength ( ), modulus ( ), and elongation at break ( ) values of 151 MPa, 6.3 GPa, and 4.4%, respectively, for the -PG polymer from PDACyC and 4,4'-oxydianiline monomers. The corresponding -PG film exhibited , , and values of just 76 MPa, 5.4 GPa, and 1.6%, respectively. These outstanding thermal and mechanical properties of the -PG polymers can be attributed to their multiple hydrogen bonding interaction between PDACyC residues in the polymer backbone. This interaction was identified by infrared spectroscopy measurements at the broad absorption band around 3000-3400 cm.
通过在150℃下，将四氮杂杯[2]芳烃[2] - 三嗪（PDACyC）与各种芳香族二胺在含有5 wt%氯化锂添加剂的非质子有机溶剂中进行溶液缩聚反应6小时，成功制备了一系列含四氮杂杯[2]芳烃[2] - 三嗪的聚胍胺（-PG）。这些-PG聚合物的数均分子量（ ）高达31500，分子量分布相对较宽（ / ）为5.3。它们在非质子有机溶剂中表现出良好的溶解性，例如在浓度为2 mg/mL时，能溶解于N-甲基吡咯烷酮和N,N-二甲基乙酰胺中。-PG聚合物的玻璃化转变温度（ ）在359℃ - 392℃范围内，比相应的聚合物（不含基于氮杂杯芳烃的PG（-PG））高约160℃。-PG聚合物的热膨胀系数（CTEs）在100℃ - 150℃时为29.7 - 48.1 ppm K，远低于-PG样品（59.1 - 85.1 ppm K）。通过溶液浇铸法成功制备了透明且几乎无色的-PG薄膜，对于由PDACyC和4,4'-氧二苯胺单体制备的-PG聚合物，其最大拉伸强度（ ）、模量（ ）和断裂伸长率（ ）值分别为151 MPa、6.3 GPa和4.4%。相应的-PG薄膜的 、 和 值分别仅为76 MPa、5.4 GPa和1.6%。-PG聚合物这些优异的热性能和机械性能可归因于聚合物主链中PDACyC残基之间的多重氢键相互作用。这种相互作用通过红外光谱测量在3000 - 3400 cm附近的宽吸收带得以确认。
