摘要
设计合成了醛基或酮基功能化的咔唑9-(4-联苯)-3-甲醛基咔唑(CM-2)、9-(4-联苯)-4-乙酮基咔唑(CM-3)和9-(4-联苯)-2,6-二氟-3-乙酮基咔唑(CM-4).分别以CM-2,CM-3和CM-4为单体,以FeCl_3为催化剂,采用一步法制备了超交联多孔聚咔唑:聚[9-(4-联苯)-3-甲醛基咔唑](HPP-2)、聚[9-(4-联苯)-4-乙酮基咔唑](HPP-3)和聚[9-(4-联苯)-2,6-二氟-3-乙酮基咔唑](HPP-4).反应中间体和聚咔唑的结构由核磁共振波谱(~1H NMR,^(13)C NMR)、魔角旋转交叉固体核磁共振波谱(^(13)C CP/MAS NMR)、红外光谱(IR)和质谱(MS)进行表征,研究了聚咔唑的热稳定性及气体(氮气、二氧化碳和甲烷)吸附性能.结果表明,3种聚咔唑在400℃左右开始分解,450~550℃出现明显失重,然后逐渐趋于平缓,800℃时的热失重均小于25%,表明材料有很好的热稳定性;HPP-2,HPP-3和HPP-4的BET比表面积分别为330,420和660 m^2/g,孔径分别为0.98,0.96和1.07 nm,对二氧化碳的吸附质量分数分别为6.90%,8.30%和9.80%,对甲烷的吸附质量分数分别为1.10%,1.30%和1.60%,表明所得聚合物的孔主要为微孔,且对二氧化碳和甲烷气体有良好的吸附能力.
Three novel carbazoles CM-2,CM-3 and CM-4 were designed and synthesized by ketone-or aldehyde-functionalization of carbazole.Then a series of hypercrosslinked porous polycarbazoles(HPP-2,HPP-3 and HPP-4)was prepared using CM-2,CM-3 and CM-4 as monomers under the catalysis of FeCl 3.The structures of the novel carbazoles and the hypercrosslinked porous polycarbazoles(HPPs)were characterized by nuclear magnetic resonance(1 H NMR,13 C NMR),magic angle spinning nuclear magnetic resonance(MAS NMR),infrared(IR)and mass spectrometry(MS).The thermal stability and the gas(nitrogen,carbon dioxide and methane)adsorption properties of the obtained HPPs were also investigated.The results show that the structures of the novel carbazoles and the polymers are consistent with the molecular design.Three kinds of HPPs begin to degrade around 400℃and render a mass loss less than 25%at 800℃,denoting that these materials have a good thermal stability.HPP-2,HPP-3 and HPP-4 present BET specific surface areas of 330,420 and 660 m 2/g,with pore sizes mainly distributed at 0.98,0.96 and 1.07 nm,respectively.The adsorption capacities of CO 2 on HPP-2,HPP-3 and HPP-4 are 6.90%,8.30%and 9.80%,while those of CH 4 on HPP-2,HPP-3 and HPP-4 are 1.10%,1.30%and 1.60%,respectively.The results show that the obtained polymers possess mainly micropores and present high adsorption capacity for CO 2 and CH 4.This work provides a new approach for the synthesis of hypercrosslinked porous polycarbazoles.
作者
张荣荣
袁光明
罗卫华
ZHANG Rongrong;YUAN Guangming;LUO Weihua(College of Material Science and Engineering,Central South University of Forestry and Technology,Changsha 410004,China;Hunan Provincial Collaborative Innovation Center for High-efficiency Utilization of Wood and Bamboo Resources,Central South University of Forestry and Technology,Changsha 410004,China)
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2018年第9期2105-2112,共8页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:31770606)
国家林业公益性行业科研专项(批准号:201504503)
湖南省自然科学基金(批准号:2015JJ2200)资助~~
关键词
醛基咔唑
酮基咔唑
超交联聚合物
多孔性
气体吸附
Aldehyde-modified carbazole
Ketone-modified carbazole
Hypercrosslinked polymer
Porosity
Gas adsorption
作者简介
罗卫华,男,博士,教授,主要从事功能高分子材料研究.E-mail:lwh6803@163.com
