采用二氯马来酰亚胺与芳香胺的亲核取代聚合反应合成有机多孔聚合物

Preparation of Porous Organic Polymer through Nuclephilic Substitution Polymerization between Dichloromaleimide and Aromatic Amine

首先以二氯马来酸酐和1,2-环己二胺为原料合成了卤代烃1,2-双(3,4-二氯马来酰亚胺)基环己烷;然后通过该卤代烃与1,3,5-三(4-氨基苯基)苯的亲核取代聚合反应,制备了一种有机多孔聚合物(POP)。采用扫描电子显微镜(SEM)、热重分析(TG)、氮气吸附-脱附等测试手段对聚合物的形貌、稳定性以及孔结构进行了研究。结果表明:该多孔聚合物具有独特的棒状结构、优良的热稳定性(初始分解温度达400℃)、较大的比表面积(404m^2/g),且具有多级孔(介孔和微孔)结构。

Porous organic polymer(POP)has attracted great interests due to its excellent pore tunability and diverse synthetic methods,and has been widely used in the fields of gas storage,carbon capture,separation,catalysis,sensing,energy storage and conversion.However,most of the POPs are prepared from expensive monomers and noble metal catalysts which usually require complicated workup thus rise the cost and reduce the synthetic efficiency.It is necessary to explore some novel precious-metal-free and workup-easy polymerization reactions to obtain POP efficiently.In this work,the monomer 1,2-bis(3,4-dichloromaleimidyl)-hexane was firstly synthesized from the reaction of 1,2-diaminocyclohexane and dichloromaleic anhydride.The POP was further synthesized through nucleophilic substitution polymerization between 1,2-bis(3,4-dichloromaleimidyl)-hexane and 1,3,5-tris-(4-aminophenyl)with acetic acid as solvent.Fourier Transform Infrared spectroscopy(FT-IR)indicates the formation of C-N bonds between dichloromale imide and aromatic amine units.Nitrogen adsorption-desorption isotherm shows that the prepared POP has a high surface area(404m^2/g)and a wide range of pore size distribution from 1 nm to 6 nm(containing micropore and mesopore).In addition,Scanning Electron Microscopy(SEM)shows that the prepared POP has a regular rod structure(diameter,1-5μm).The thermogravimetric analysis(TG)reveales that the POP has excellent thermal stability(degration temperature is up to 400℃).As a novel catalyst-free and workup-easy C-N coupling reaction,the developed nucleophilic substitution polymerization between dichloromale imide and aromatic amine works well to synthesize maleic amide-based POP efficiently,and it is an eco-friendly C-N crossing strategy which can provide people another choice to obtain the targeted POP free of catalysts efficiently.