Synthesis of tetraazacalix[2]arene[2]triazine-containing poly(dimethylsiloxane) with elastic property induced by pinning effect of the calixarene ring
Synthesis of tetraazacalix[2]arene[2]triazine-containing poly(dimethylsiloxane) with elastic property induced by pinning effect of the calixarene ring
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杯芳环钉扎效应诱导的含四氮杂杯[2]芳烃[2]三嗪的聚二甲基硅氧烷的合成
DOI：
10.1016/j.eurpolymj.2021.110890
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发表时间：
2022
影响因子：
6
通讯作者：
Shibasaki Yuji
中科院分区：
文献类型：
--
作者：
Shibata Ryota;Ishihara Tsutomu;Tsukamoto Tadashi;Oishi Yoshiyuki;Fujimori Atsuhiro;Shibasaki Yuji
通过溶液缩聚，将四氮杂环芳烃[2]三嗪二氯与具有nh2末端的远旋聚（二甲基硅氧烷）s （PDMSx，聚合度x= 8,18,38）进行聚合，得到相应的含氮杂环芳烃聚合物ACAT-PDMSx，收率较高。计算出ACAT- pdms聚合物的硬ACAT部分（fHS）分别为33.0%、20.4%和11.6%。聚合物的数平均分子量（Mn）在20 ~ 32 kDa之间，通过溶剂浇铸法制备了独立式坚韧薄膜。以2-苯胺-4,6-二氯-1,3,5-三嗪（AnDCT）与PDMS8溶液聚合制备了不含偶氮胞芳烃的聚合物（AnDCT- pdms），其mnh值分别为21 kDa和19.8%。虽然andct - pdms8和acat - pdms18的fhs值相似，但在室温下，前者得到的膜比后者更柔软、更粘。有趣的是，acat - pdms18薄膜的抗拉强度为2.7 MPa，模量为2.0 MPa，断裂伸长率为200%。根据热力学和动态力学分析，acat - pdmsx薄膜的玻璃化转变温度在77 ~ 105℃之间。广角x射线衍射和偏振光学显微镜研究表明，azazalixarene单元首先通过多个氢键在acat - pdmsx膜内局部聚集，然后在加热时分散在膜中。在实验浓度低于100 μg/mL时，ACAT-PDMS聚合物对HeLa和IMR-90细胞无细胞毒性。
Tetraazacalix[2]arene[2]triazine dichloride was polymerized with telechelic poly(dimethylsiloxane)s having NH2terminals (PDMSx; degree of polymerizationx= 8, 18, 38) via solution polycondensation to give the corresponding azacalixarene-containing polymers (ACAT-PDMSx) in good yield. The fraction of the hard ACAT moiety (fHS) of the ACAT-PDMS polymers was calculated to be 33.0%, 20.4%, and 11.6% forxof 8, 18, and 38, respectively. The number-average molecular weight (Mn) of the polymers ranged from 20 to 32 kDa, and freestanding tough films were successfully fabricated via solvent cast method. As a control sample, a polymer not containing azacalixarene (AnDCT-PDMS) withMnandfHSvalues of 21 kDa and 19.8%, respectively, was prepared via the solution polymerization of 2-anilino-4,6-dichloro-1,3,5-triazine (AnDCT) with PDMS8. Although thefHSvalues of AnDCT-PDMS8and ACAT-PDMS18were similar, the film obtained from the former polymer was much softer and sticky at room temperature than that from the latter. Interestingly, the ACAT-PDMS18film exhibited a tensile strength of 2.7 MPa, a modulus of 2.0 MPa, and an elongation at break of 200%. The glass transition temperature of the ACAT-PDMSxfilms ranged from 77 °C to 105 °C according to thermomechanical and dynamic mechanical analyses. Wide-angle X-ray diffraction and polarized optical microscopy studies indicated that the azacalixarene units were first locally aggregated via multiple hydrogen bonds within the ACAT-PDMSxfilms and then were well dispersed in the film on heating. The ACAT-PDMS polymer showed no cytotoxicity to HeLa and IMR-90 cells in the experimental concentration of below 100 μg/mL.