基于三蝶烯的微孔聚二胺磷腈  

Triptycene-Based Microporous Poly(diaminophosphazene)

作　　者：李慧[1] 姜美洋 王求 李中华[2] 陈琦[1] 韩宝航[1] 

机构地区：[1]国家纳米科学中心,北京100190 [2]华中师范大学化学与化工学院,武汉430079

出　　处：《化学学报》2015年第6期617-622,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.21274033和21374024);科技部国家重大科研项目(No.2014CB932200)资助~~

摘　　要：近年来有机多孔聚合物材料由于其在气体吸附分离、气体存储及非均相催化等多个领域具有优良性质而受到国内外科学家们广泛的关注.三蝶烯是一类具有D3h刚性对称骨架结构的化合物,同时它特有的结构特点及其丰富的反应性能使其成为一类构筑有机多孔材料的优良建筑块.基于六氨基三蝶烯盐酸盐和六氯环三磷腈,通过N-P型一步聚合法制备了两种聚二胺磷腈多孔材料Trp POP-1和Trp POP-2.材料的结构通过固体核磁共振碳谱、磷谱和红外光谱等进行了表征.氮气吸脱附等温线表明两种聚合物均具有永久的微孔性质,Trp POP-1和Trp POP-2的BET比表面积分别为790和640 m2·g-1,主要孔径分别在0.63和0.59 nm左右.孔径分布较窄的多孔聚合物能与小分子气体有更好的相互作用,因此,我们对这两种材料的小分子气体(氢气、二氧化碳和甲醛)吸附性能进行了研究.Trp POP-1的氢气吸附量在77 K和1.0 bar条件下为1.30 wt%,二氧化碳吸附量在273 K和1.0 bar条件下为16.2 wt%.材料Trp POP-2对甲醛的吸附量在298 K为5.5 mg·g-1.Porous materials have recently drawn much attention owing to their potential applications in gas storage, separations, and heterogeneous catalysis. As a D3h-symmetric rigid structure, triptycene and its derivatives can be used as suitable building blocks to prepare porous materials with high porosities. Based on the air-stable hexaammoniumtriptycene hexachloride and hexachlorocyclotriphosphazene, porous polymers(Trp POP-1 and Trp POP-2) were prepared via one-step polymerization through N-P linkage. The two polymers were characterized at the molecular level by 13 C NMR and 31 P NMR as well as IR. The two polymers possess type I nitrogen gas sorption isotherm according to the IUPAC classification. Both Trp POP-1 and Trp POP-2 show permanent microporous nature with the Brunauer-Emmett-Teller specific surface area of 790 and 640 m2g-1 and exhibit narrow pore size distribution, with dominant pore size locating at 0.59 and 0.63 nm, respectively. Porous polymers with a narrow pore distribution may interact attractively with small gas molecules through improved molecular interaction. Their gas(hydrogen and carbon dioxide) adsorption capacities were measured based on the obtained gas physisorption isotherms. The hydrogen uptake of Trp POP-1 is 1.30 wt% at 77 K and 1.0 bar, and the carbon dioxide uptake is up to 16.2 wt% at 273 K and 1.0 bar. The higher carbon dioxide loading capacity of Trp POP-1 may be attributed to its higher charge density at the nitrogen sites of networks that can facilitate local-dipole/quadrupole interactions with carbon dioxide. Meanwhile, the adsorption capacity of the obtained materials for poisonous and harmful organic vapors such as formaldehyde was also investigated. Trp POP-2 shows a better formaldehyde uptake, which is 5.5 mgg-1 at 298 K. Formaldehyde, as a volatile organic compound, is a major air pollutant indoor, therefore, the uptake performance of Trp POP-2 for formaldehyde would be very promising to remove harmful indoor air pollutant in the environment.

关 键 词：三蝶烯 气体储存 微孔聚合物 聚二胺磷腈 

分 类 号：TQ317[化学工程—高聚物工业] TB383.4[一般工业技术—材料科学与工程]