应用化学 ›› 2022, Vol. 39 ›› Issue (7): 1083-1089.DOI: 10.19894/j.issn.1000-0518.210231

• 研究论文 • 上一篇    下一篇

卟啉基超交联聚合物的合成及其对二氧化碳和汞(Ⅱ)离子的吸附

王小梅1(), 郭江飞2, 王立志2, 黄健涵2   

  1. 1.长沙学院生物与环境工程学院,长沙 410003
    2.中南大学化学化工学院,长沙 410083
  • 收稿日期:2021-05-13 接受日期:2021-11-23 出版日期:2022-07-01 发布日期:2022-07-11
  • 通讯作者: 王小梅
  • 基金资助:
    湖南省自然科学基金青年基金(2019JJ50690);湖南省教育厅重点项目(21A0543┫湖南省大学生创新训练项目┣S202011077021);长沙学院“青年英才支持计划”(2019JJ50690)

Porphyrin⁃Based Hyper⁃cross⁃Linked Polymer: Preparation and Adsorption of Carbon Dioxide and Hg(Ⅱ) Ion

Xiao-Mei WANG1(), Jiang-Fei GUO2, Li-Zhi WANG2, Jian-Han HUANG2   

  1. 1.Department of Bioengineering and Environmental Science,Changsha University,Changsha 410003 China
    2.College of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China
  • Received:2021-05-13 Accepted:2021-11-23 Published:2022-07-01 Online:2022-07-11
  • Contact: Xiao-Mei WANG
  • About author:wxm11@ccsu.edu.cn
  • Supported by:
    the Youth Foundation of Natural Science Foundation of Hunan Province(2019JJ50690);the Science and Technology Project of Hunan Provincial Education Department(21A0543);the Innovation Training Program for College Students in Hunan Province(S202011077021);the Young Talents Support Program of Changsha University(2019JJ50690)

摘要:

超交联聚合物(HCPs)具有较高的比表面积和独特的孔结构,且制备方法简单、合成原料广泛,是多孔有机聚合物的研究热点之一。卟啉是一类由4个吡咯类亚基的α-碳原子通过次甲基桥互联形成的大分子杂环化合物,可与多种金属形成稳定的配合物,在重金属的吸附与检测、气体的吸附与分离等方面具有很好的应用。卟啉结构的HCPs也有了较多的报道,然而当前报道的卟啉结构HCPs几乎均是通过Friedel-Crafts烷基化反应构筑的。Friedel-Crafts酰基化反应在卟啉结构HCPs上报道较少。而通过Friedel-Crafts酰基化反应制备的聚合物表面含大量羰基,为其进一步功能化提供了可能。但是,这类聚合物的比表面积低、孔结构差,而其优良孔结构的构建是亟待解决的问题。为此,本文在四苯基卟啉与1,2,4,5-苯四甲酸酐通过Friedel-Crafts酰基化反应制备的聚合物的基础上,进一步通过席夫碱反应,用含刚性三嗪环的三聚氰胺将其进一步交联,合成了三聚氰胺修饰的卟啉基超交联聚合物。结果发现,三聚氰胺的引入不仅实现了超交联聚合物孔结构的支撑,使得聚合物比表面积极大增长(从2 m2/g增加到118 m2/g),且具有优良的多级孔结构。三聚氰胺修饰卟啉基超交联聚合物的高氮质量分数(46.28%)和多级孔结构使其对CO2(93 mg/g, 273 K, 101 kPa)和Hg2+(494.1 mg/g, 298 K)具有较好的吸附。

关键词: 三聚氰胺, 卟啉, Friedel-Crafts酰基化, 二氧化碳捕获, 汞离子(Ⅱ)去除

Abstract:

Hyper-cross-linked polymers (HCPs) have been one of the hotspots of the porous organic polymers because of their high Brunauer-Emmett-Teller (BET) surface area (SBET) and unique porosity. Moreover, their simple synthetic procedure of one-pot Friedel-Crafts reaction and various aromatic monomers make HCPs one of the hotspots of porpous organic polymers. Porphyrins are a kind of macromolecular heterocyclic compounds formed by the interlinking of four α-carbon atoms of pyrrole subunits via submethyl bridges. It can form stable complexes with a variety of metals, and has good applications in the adsorption and detection of heavy metals, adsorption and separation of gases, etc. However, the reported porphyrin-based HCPs in the literature are almost fabricated according to the Friedel-Crafts alkylation, while the Friedel-Crafts acylation reaction is rarely reported. The ketone-functionalized porphyrin-based HCPs based on the Friedel-Crafts acylation possess plentiful acyl groups, which offers a potential prospect for their further functionalization. However, these ketone-functionalized HCPs own very poor porosity, and their construction of unique porosity for this kind of HCPs is of great significance. Herein, the Friedel-Crafts acylation was performed for tetraphenylporphyrin and pyromellitic dianhydride, and the synthesized ketone-functionalized HCPs were further carried out for the Schiff-base reaction using melamine as the reactant. The resulting melamine-modified porphyrin-based HCPs exhibit medium SBET (118 m2/g), excellent hierarchical porosity, and high N content (46.28%), indicative of its outstanding CO2 capture and Hg2+ removal, the CO2 uptake is 93 mg/g at 273 K and 101 kPa, and the Hg2+ adsorption reaches equilibrium within 30 min with the maximum capacity of 494.1 mg/g.

Key words: Melamine, Porphyrin, Friedel-Crafts acylation, Carbon dioxide capture, Hg(Ⅱ) ion removal

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