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中文摘要: 通过5，10，15，20 四(4-羧基苯基)（TCPP）卟啉单体与含螺环结构的二胺单体(Spiro-DA)的缩聚反应，实现了含螺环结构的卟啉基固有微孔材料的定向合成（PIM-Spiro）。同时在相同的工艺条件下,以对苯二胺（PPDA），4，4'-二氨基二苯醚(ODA)作为二胺单体分别制备了相应的聚酰胺(PA)网络材料。采用傅里叶红外光谱（FT-IR）、扫描电子显微镜（SEM）、热重分析(TG)、氮气吸附等分析测试手段对3种聚酰胺材料的网络结构和物理化学性能进行了表征。结果表明：螺环扭曲结构的引入可以有效提高微孔卟啉聚合物网络的比表面积，同时在溶剂中表现出很强的溶胀特性；所制备的聚酰胺网络材料中的卟啉基和酰胺键所含的高密度N—H键，赋予材料良好的碱性催化特性。
中文关键词: 固有微孔卟啉聚合物网络 螺环扭曲结构 聚酰胺 协同作用 Knoevenagel缩合
Abstract:A new porphyrin based polyamide(PA) network with intrinsic microporosity (PIM-Spiro) is synthesized by the condensation of 3,3,3',3'-tetramethyl 1,1'- spirobisindane(Spiro-DA) and 5,10,15,20-tetra(4-carboxyphenyl) porphyrin(TCPP). PA-PPDA, PA-ODA polyamide networks are also synthesized using p- phenylenediamine(PPDA)、4,4'-oxybisbenzenamine(ODA) as monomers under the same synthesis condition. The microporous structure and physicochemical properties are characterized by FT-IR, SEM, TG and nitrogen adsorption test. Results show that spiro structure of diamine monomer can improve the PA networks BET surface effectively and give the PIM-Spiro excellent swellable property in solvent. The PA networks have high efficiency basic catalytic property owing to the rich N—H covalent of porphyrin group and amide bonds.
keywords: porphyrin based polyamide network with intrinsic microporosity spiro structure polyamide synergistic effect Knoevenagel condensation
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基金项目:国家自然科学基金(20974069，21174089) ；聚合物分子工程国家重点实验室(K2013 23)
引用本文：
王建英1,吴琦1,江意1,张朝良2,刘习奎1.基于螺环结构桥连的固有微孔卟啉聚合物网络的制备与表征及其催化Knoevenagel缩合反应[J].功能高分子学报,2015,28(1):.
WANG Jian ying1,WU Qi1,JIANG Yi1,ZHANG Chao liang2,LIU Xi kui1.Preparation and Characterization of Spirobisindane Linked Porphyrin Based Polyamide Networks with Intrinsic Microporosity and Catalyst of Knoevenagel Condensation[J].Journal of Functional Polymers,2015,28(1):.
王建英1,吴琦1,江意1,张朝良2,刘习奎1.基于螺环结构桥连的固有微孔卟啉聚合物网络的制备与表征及其催化Knoevenagel缩合反应[J].功能高分子学报,2015,28(1):.
WANG Jian ying1,WU Qi1,JIANG Yi1,ZHANG Chao liang2,LIU Xi kui1.Preparation and Characterization of Spirobisindane Linked Porphyrin Based Polyamide Networks with Intrinsic Microporosity and Catalyst of Knoevenagel Condensation[J].Journal of Functional Polymers,2015,28(1):.
