氨基硫脲修饰卟啉基聚合物的制备及对CO_(2)和Hg^(2+)的吸附  

Preparation of Thiosemicarbazide-decorated Porphyrin-based Polymers and Their Adsorption of CO_(2) and Hg^(2+)

作　　者：王小梅[1] 郭江飞 王立志 黄健涵[2] Xiao-mei Wang;Jiang-fei Guo;Li-zhi Wang;Jian-han Huang(College of Biology and Chemical Engineering,Changsha University,Changsha 410003;College of Chemistry and Chemical Engineering,Central South University,Changsha 410083)

机构地区：[1]长沙学院生物与化学工程学院,长沙410003 [2]中南大学化学化工学院,长沙410083

出　　处：《高分子学报》2023年第4期520-528,共9页Acta Polymerica Sinica

基　　金：湖南省自然科学基金(基金号2019JJ50690);湖南省教育厅科技项目(项目号21A0543);国家自然科学基金(基金号51974374)项目资助。

摘　　要：利用四苯基卟啉和三种酰基化交联剂(草酰氯、对苯二甲酰氯和均苯三甲酰氯)经Friedel-Crafts酰基化反应,制备了卟啉基聚合物中间体,进一步用氨基硫脲与之发生席夫碱反应,得到了氨基硫脲修饰卟啉基聚合物.结果发现,聚合物的交联结构使其具有高比表面积和丰富的超微孔,显示出优异的CO_(2)吸附(138 mg/g,273 K,10^(5)Pa)及CO_(2)/N_(2)选择性.同时,聚合物表面氨基和硫脲的引入使得其对Hg^(2+)的吸附量可达311.0 mg/g,吸附机理也证实了N和S对Hg^(2+)的配位作用.The hyper-cross-linked polymers(HCPs)are considered one of the most famous porous organic polymers for their great advantages of high Brunauer-Emmett-Teller(BET)surface area(SBET),abundant micropores,and tunable porosity.Furthermore,the extensive aromatic monomers,inexpensive Lewis acid catalysts,and simply construction process make the HCPs developed greatly.In this way,the Friedel-Crafts alkylation was widely used for the construction of HCPs.However,the shortage of functional groups and reaction sites make the HCPs limited in the adsorption performance.The Friedel-Crafts acylation would take ketone carbonyl to the resulting polymers,which will performed well in the adsorption performance after the post-functionalization.However,it is still difficult to construct the HCPs with high SBETthrough Friedel-Crafts acylation.Therefore,in this work,a series of porphyrin-based polymers with high specific surface area was constructed through the Friedel-Crafts acylation reaction by using three different acylated crosslinking agents(p-phthaloyl chloride,trimesoyl chloride,and oxalyl chloride)and 5,10,15,20-tetraphenylporphyrin.The polymers show abundant ketone carbonyl groups.Therefore,thiosemicarbazide,which has amino and thiourea structure,was used for post-functionalization through Schiff-based reaction and a series of functionalized porphyrin-based polymers were obtained.Due to the hyper-cross-linked structure of the polymer with high SBETand abundant micropores,The polymer showed remarkable CO_(2)adsorption performance(138 mg/g,273 K,10~5 Pa)and excellent CO_(2)/N_(2)selectivity.Remarkable,the post-functionalization of thiosemicarbazide decreased the SBETand the Vmicroof the polymers,the introducing of the N and S heteroatoms greatly improved the CO_(2)adsorption capacity for the strong interaction between the heteroatoms and the CO_(2)moleculars.Especially for HTMb-TSC,the post-functionalization make the CO_(2)capture capacity increased from 37 mg/g to 91 mg/g(273 K,10^(5) Pa).At the same time,the adsorption capacit

关 键 词：FRIEDEL-CRAFTS酰基化反应 席夫碱反应 卟啉 CO_(2) Hg^(2+) 

分 类 号：O631.5[理学—高分子化学] O647.33[理学—化学] X70[环境科学与工程—环境工程]