Pathway modulation and substrate partitioning for CO2-assisted hydration of ethylene oxide catalyzed by swelling poly(ionic liquid)s

被引：9

作者：

Zhang, Jingshun

Dang, Lulu

Lai, Tong

Yuan, Huixia

Zhang, Dawei

Gao, Guohua ^{[1
]}

机构：

[1] East China Normal Univ, Sch Chem & Mol Engn, Shanghai Key Lab Green Chem & Chem Proc, Shanghai 200062, Peoples R China

来源：

FUEL | 2024年 / 355卷

基金：

中国国家自然科学基金;

关键词：

Amine-functionalized poly(ionic liquid)s; Swelling; Enrichment ability; CO2-assisted hydration; Ethylene oxide; Spatially isolate; LIPOPHILIC POLYELECTROLYTE GELS; IONIC LIQUID; POLYMERS; EPOXIDES; ACID; HYDROGELS; CO2;

D O I：

10.1016/j.fuel.2023.129521

中图分类号：

TE [石油、天然气工业]; TK [能源与动力工程];

学科分类号：

0807 ; 0820 ;

摘要：

Amine-functionalized swellable poly(ionic liquid)s (poly[BAVIm]Br-DVIm-n%) were synthesized by free radical copolymerization of amine-functional vinyl imidazolium ionic liquids and ionic cross-linker 1,8-triethylene glycoldiyl-3,3 '-divinylimidazolium (DVIm). Poly[BAVIm]Br-DVIm-n% exhibited excellent swelling ability in the water, ethylene carbonate (EC), and ethylene glycol (MEG), and the swelling ratio (Q) decreased with the increase of the content of the crosslinker. The swollen state of poly[BAVIm]Br-DVIm-2.5% in water observed by cryogenic scanning electron microscopy (cryo-SEM) presented densely packed and interconnected pores (0.2-11 mu m). Poly[BAVIm]Br-DVIm-n% were used to catalyze CO2-assisted hydration of ethylene oxide (EO) at a low H2O/EO ratio of 1:1, in which poly[BAVIm]Br-DVIm-2.5% with the highest Q in water gave the highest yield (87%) and selectivity (97%) of MEG. Moreover, EC was produced and subsequently disappeared during the process of CO2-assisted hydration of EO. A cascade reaction including the cycloaddition of CO2 with EO (EO + CO2 -> EC) and the hydrolysis of the resulting EC (EC + H2O. MEG + CO2) in situ was elaborated. Poly[BAVIm] Br-DVIm-n% containing amine group and imidazolium ionic liquid synergistically catalyzed this cascade reaction, exhibiting a bifunctional effect. Poly[BAVIm]Br-DVIm-2.5% with the H2O, EC, and MEG enrichment ability in H2O/EO, EC/EO, and MEG/EO could spatially isolate EO and H2O, EC, MEG. The substrate partitioning of poly [BAVIm]Br-DVIm-2.5% could promote the two sequential reactions to be orthogonal and inhibit the sidereactions between MEG and EO, thus resulting in a higher reaction rate of poly[BAVIm]Br-DVIm-2.5% (0.0141 h 1) than that of homogeneous catalyst ([BAVIm]Br) (0.0074 h 1). Furthermore, poly[BAVIm]Br-DVImn% had good generality and could be reused effectively at least seven times without a significant decrease of its initial activity.

引用

页数：8