Research on crosslinking of epichlorohydrin and ionic liquids

doi:10.11949/0438-1157.20200804

Abstract

Abstract:

Ionic liquid supported liquid membranes have shown high CO₂ selective separation performance, but their low pressure resistance greatly limits their industrial applications. From the viewpoint of high cost and complex synthesis of crosslinkers used for crosslinking ILs, preparing IL-based gels by crosslinking diamino protic ionic liquids (PILs) with epichlorohydrin (ECH) was proposed in this work. The feasibility of this conception was confirmed via monitoring dynamical information of reaction system. The effects of protonation, reaction temperature and ECH-to-PIL molar ratio on the conversion of epoxy and chloride groups were systematically investigated. The gel transition property of these crosslinked PILs and the possible crosslinking mechanism were studied. Moreover, CO₂ permeation performance in crosslinked ILs was preliminarily tested.

Key words: ionic liquid, crosslinking, dynamics, membrane, carbon capture

摘要：

鉴于目前离子液体交联反应所用交联剂存在的高成本、难制备的问题，提出以廉价易得的环氧氯丙烷交联二胺质子型离子液体制备离子液体凝胶的设想。基于此，通过监测反应体系动力学信息证明了反应的可能性，同时研究了与酸中和顺序、反应温度、交联比例对环氧基团和氯基团转化率的影响。探究了环氧氯丙烷-二胺交联体系的凝胶转变性能以及可能的反应机理。并且初步测试了交联产物的CO₂分离性能。

关键词: 离子液体, 交联, 动力学, 膜, 碳捕集

CLC Number:

TQ 028.8

Zhuoheng TU,Mingzhen SHI,Xiaomin ZHANG,Youting WU,Xingbang HU. Research on crosslinking of epichlorohydrin and ionic liquids[J]. CIESC Journal, 2020, 71(11): 4971-4980.

涂卓恒,史名珍,张效敏,吴有庭,胡兴邦. 环氧氯丙烷与离子液体的交联过程研究[J]. 化工学报, 2020, 71(11): 4971-4980.

Figures/Tables 10

Fig.1 Chemical structures of DMAPA-based PIL and crosslinking agent used in this work

Fig.2 Illustration of two synthetic methods used in this work

Fig.3 Plots of pH (a) and conversion of chloride group (b) in the equimolar reaction system of ECH with [DMAPAH][MOAc] as a function of time at different temperatures

Fig.4 Plots of pH (a), conversion of chloride group (b) and conversion of epoxy group (c) in the reaction systems with different ECH-to-DMAPA molar ratio as a function of time at 25℃

Fig.5 Plots of pH (a), conversion of chloride group (b) and conversion of epoxy group (c) in the equimolar reaction systems of ECH with DMAPA as a function of time at different temperatures

Fig.6 Plots of viscosities(a), logarithms of viscosity (b) in reaction systems with 1.0 of ECH-to-DMAPA molar ratio as a function of time at different temperatures

Fig.7 One possible mechanism of ECH crosslinking with [DMAPAH][MOAc]

Fig.8 FT-IR spectra of ECHn-DMAPA with different ECH-to-DMAPA molar ratio (reaction temperature = 55℃, reaction time =2 h)

Fig.9 Possible chemical structures associcated to the peaks found in ESI-MS spectra of CPILs

Fig.10 Plots of permeability of CO2 and CO2/N2 selectivity in ECH0.5-[DMAPAH][MOAc] of 20%(mass) water as a function of transmembrane pressure difference under humidified condition at 40℃

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