β-酮烯胺类手性共价有机框架的合成及在毛细管气相色谱中的应用

doi:10.7503/cjcu20200206

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (9): 1996.doi: 10.7503/cjcu20200206

β-酮烯胺类手性共价有机框架的合成及在毛细管气相色谱中的应用

严逸伦, 黄晓玲, 范军, 蔡松亮(), 郑盛润(), 章伟光

华南师范大学化学学院, 广州市生物医药分析化学重点实验室，广州 510006

收稿日期:2020-04-15 出版日期:2020-09-10 发布日期:2020-09-02
通讯作者: 蔡松亮 E-mail:songliangcai@m.scnu.edu.cn;zhengsr@scnu.edu.cn
作者简介:郑盛润, 男, 博士, 副教授, 主要从事共价有机框架和金属有机框架材料研究. E-mail: zhengsr@scnu.edu.cn
基金资助:
国家自然科学基金(21603076)

Synthesis of a β-Ketoenamine-linked Chiral Covalent Organic Framework and Its Application in Capillary Gas Chromatography

YAN Yilun, HUANG Xiaoling, FAN Jun, CAI Songliang(), ZHENG Shengrun(), ZHANG Weiguang

School of Chemistry, Guangzhou Key Laboratory of Analytical Chemistry for Biomedicine, South China Normal University, Guangzhou 510006, China

Received:2020-04-15 Online:2020-09-10 Published:2020-09-02
Contact: CAI Songliang E-mail:songliangcai@m.scnu.edu.cn;zhengsr@scnu.edu.cn
Supported by:
Supported by the National Natural Science Foundation of China(21603076)

摘要/Abstract

摘要：

利用2,4,6-三羟基-1,3,5-苯三甲醛(Tfp)和(S)-2,5-双(2-甲基丁氧基)对苯二甲酸二酰肼(Mth)作为单体, 通过席夫碱反应合成了新型的β-酮烯胺类手性共价有机框架(COF)材料TfpMth COF. 采用粉末X射线衍射、红外光谱、热重分析及氮气吸附-脱附等手段对制备的TfpMth COF粉末进行了表征, 结果表明其具有良好的结晶度、高的孔隙率和优异的热稳定性. 基于此, 以该COF为新型固定相采用原位生长法制备了TfpMth COF键合毛细管柱, 成功分离了一系列直链与支链的烷烃和醇类, 以及苯/环己烷、乙苯/苯乙烯混合物. 该结果为β-酮烯胺类COF在色谱分离中的应用提供了新思路, 也为研究新型气相色谱固定相提供了参考.

关键词: 共价有机框架, β-酮烯胺连接型, 气相色谱分离

Abstract:

A new β-ketoenamine-linked chiral covalent organic framework(COF), namely TfpMth COF, was prepared by the reaction of 1,3,5-triformylphloroglucinol(Tfp) with (S)-2,5-bis(2-methylbutoxy)terephthalohydrazide(Mth). The obtained TfpMth COF powder was characterized by various techniques such as powder X-ray diffraction analysis, Fourier transform infrared spectrometer(FTIR), thermogravimetric analysis(TGA), nitrogen adsorption-desorption measurement and so on, indicating its virtue of good crystallinity, high porosity, and excellent thermostability. Thus, we used TfpMth COF as a new stationary phase to prepare the TfpMth COF-bound capillary column by an in situ growth method. A series of linear and branched alkanes and alcohols, as well as mixtures of benzene and cyclohexane, ethylbenzene and styrene can be separated using the TfpMth-bound capillary column. This result provides a new idea for the application of β-ketoenamine-linked COF in chromatographic separation, and also gives a reference for the study of novel gas chromatographic stationary phases.

Key words: Covalent organic framework, β-Ketoenamine-linked, Gas chromatography separation

中图分类号:

O657.7

TrendMD:

严逸伦, 黄晓玲, 范军, 蔡松亮, 郑盛润, 章伟光. β-酮烯胺类手性共价有机框架的合成及在毛细管气相色谱中的应用. 高等学校化学学报, 2020, 41(9): 1996.

YAN Yilun, HUANG Xiaoling, FAN Jun, CAI Songliang, ZHENG Shengrun, ZHANG Weiguang. Synthesis of a β-Ketoenamine-linked Chiral Covalent Organic Framework and Its Application in Capillary Gas Chromatography. Chem. J. Chinese Universities, 2020, 41(9): 1996.

图/表 8

Scheme 1 Synthesis of TfpMth COF

Scheme 2 In situ synthesis of TfpMth COF?bound capillary column

Fig.1 PXRD patterns of TfpMth COF(A), eclipsed AA packing and staggered AB packing structures of TfpMth COF(B) and Pawley refined PXRD patterns of TfpMth COF(C)(A) a. Experimental; b. AA packing; c. AB packing. (C) a. Experimental; b. pawely refined; c. bragg position; d. difference.

Fig.2 FTIR spectra of TfpMth COF, Tfp and Mth(A), solid?state 13C NMR spectrum(B), TGA curve(C), SEM image(D), N2 adsorption(●) and desorption(○) isotherms(E), and pore size distribution(F) of TfpMth COF

Fig.3 FTIR spectra(A) and PXRD patterns(B) of the TfpMth COF powder(a) and the COF material collected from the inner wall of the TfpMth COF?bound short capillary column(b), SEM images(C, D) of the cross section of TfpMth COF?bound column with different magnifications

Table 1 McReynolds constants of the TfpMth/min-bound capillary column measured at 120 ℃*

Sample	X	Y	Z	U	S	Average
McReynolds constant	7	204	142	167	163	137

Fig.4 Optimized gas chromatograms on the TfpMth COF?bound capillary column for separation of Grobs reagent(A), n?alkanes(B), octane isomers(C), n?alcohol(D), propanol isomers(E), butanol isomers(F), ethylbenzene and styrene(G), benzene and cyclohexane(H)(A) Peak 1. n?dodecane; peak 2. nonanal; peak 3. n?octanol; peak 4. 2,6?dimethylphenol; peak 5. methyl deca? noate; peak 6. dicyclohexylamine. Column conditions: 80 ℃ for 1 min, then 15 ℃/min to 200 ℃ under a N2 flow rate of 1.2 mL/min; (B) 60 ℃ for 1 min, then 10 ℃/min to 180 ℃ under a N2 flow rate of 1.5 mL/min; (C) N2 flow rate of 1.2 mL/min under 120 ℃; (D) 60 ℃ for 1 min, then 10 ℃/min to 150 ℃ under a N2 flow rate of 1.5 mL/min; (E) N2 flow rate of 1.5 mL/min under 100 ℃; (F) N2 flow rate of 1.5 mL/min under 125 ℃; (G) N2 flow rate of 1.5 mL/min under 130 ℃; (H) N2 flow rate of 1.2 mL/min under 100 ℃.

Fig.5 GC separation of benzene and cyclohexane on TfpMth COF-bound capillary column after being used for 2—6 months on the same column: selectivity(a), resolution(b)N2 flow rate: 1.2 mL/min; column temperature: 100 ℃.

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β-酮烯胺类手性共价有机框架的合成及在毛细管气相色谱中的应用

Synthesis of a β-Ketoenamine-linked Chiral Covalent Organic Framework and Its Application in Capillary Gas Chromatography

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