氯化1-氨基聚醚-3-甲基咪唑离子液体的制备与催化性能

doi:10.16085/j.issn.1000-6613.2017.02.025

化工进展 ›› 2017, Vol. 36 ›› Issue (02): 581-587.DOI: 10.16085/j.issn.1000-6613.2017.02.025

氯化1-氨基聚醚-3-甲基咪唑离子液体的制备与催化性能

郭立颖, 马秀云, 王立岩, 邓莉莉, 金先超

沈阳工业大学石油化工学院, 辽宁辽阳 111003

收稿日期:2016-06-03 修回日期:2016-08-23 出版日期:2017-02-05 发布日期:2017-02-05
通讯作者: 郭立颖(1981-),女,博士,硕士生导师,主要从事离子液体结构设计与制备及其改性高分子材料或工业催化等方面研究。E-mail:lyguo1981@163.com。
作者简介:郭立颖(1981-),女,博士,硕士生导师,主要从事离子液体结构设计与制备及其改性高分子材料或工业催化等方面研究。E-mail:lyguo1981@163.com。
基金资助:
辽宁省科技厅自然科学基金（201602537）及辽宁省教育厅一般项目（L2014037）。

Preparation and catalytic properties of chloride 1-amino polyether-3-methyl imidazole ionic liquid

GUO Liying, MA Xiuyun, WANG Liyan, DENG Lili, JIN Xianchao

School of Petrochemical Engineering, Shenyang University of Technology, Liaoyang 111003, Liaoning, China

Received:2016-06-03 Revised:2016-08-23 Online:2017-02-05 Published:2017-02-05

摘要/Abstract

摘要： 首先以环氧氯丙烷为原料，通过开环聚合得聚环氧氯丙烷（PECH），再通过溴化和氨化等方法得到端氨基的聚环氧氯丙烷，再将其与N-甲基咪唑反应，制备氯化1-氨基聚醚-3-甲基咪唑离子液体（[H₂N-PECH-MIM]Cl）催化剂，并利用红外（IR）和核磁（NMR）对其化学结构进行表征，利用热重分析仪（TGA）和凝胶渗透色谱仪（GPC）对其热性能和分子量进行了测试。然后用制备的高分子离子液体[H₂N-PECH-MIM]Cl催化环氧丙烷与二氧化碳合成碳酸丙烯酯，以纯度、转化率、选择性和转化频率为考察指标，研究催化温度、压力、循环使用次数对催化性能的影响，并比较了其与溴化1-乙胺基-3-甲基咪唑离子液体[AeMIM]Br的催化性能。结果表明，制备的高分子催化剂[H₂N-PECH-MIM]Cl结构正确，产率为71%，其催化性能远远优于小分子离子液体[AeMIM]Br，可在不用助催化剂的温和条件下即可高效完成催化过程，且循环使用10次基本不影响其催化活性。当催化温度为90℃，压力为1.8MPa，用量为1.0%时，纯度为99.0%，转化率为100%，选择性高达96.9%，转化频率TOF为3848h^-1。

关键词: 离子液体, 催化剂, 二氧化碳

Abstract: Polyepichlorohydrin(PECH)was synthesized by ring-opening polymerization with epoxy chloropropane. Then the amino-terminal polyepichlorohydrin was obtained by bromination and ammonification,and the polymer catalyst of chloride 1-amino polyether-3-methyl imidazole ionic liquid([H₂N-PECH-MIM]Cl) was prepared from the amino-terminal polyepichlorohydrin and N-methyl imidazole. Finally,IR and NMR were used to characterize the chemical structure of [H₂N-PECH-MIM]Cl,while TGA and GPC were used to determinate the thermal properties and molecular weight. Propylene carbonate was synthesized from propylene epoxide and carbon dioxide with the catalyst of [H₂N-PECH-MIM]Cl. The effects of temperature,pressure and the number of recycles on catalytic properties were studied in terms of purity,conversion,selectivity and the turnover frequency(TOF). The catalytic performance of [H₂N-PECH-MIM]Cl and [AeMIM]Br was compared. The results showed that the chemical structure of the prepared[H2N-PECH-MIM]Cl was right,and the yield was 71% and the catalytic performance was far better than that of the organocatalyst of [AeMIM]Br.[H₂N-PECH-MIM]Cl could achieve the catalytic process efficiently without assistant catalyst and could be used 10 times under mild conditions. The purity,conversion rate,the selectivity and TOF were 99.0%,100%,96.9% and 3848h^-1 respectively at 90℃,and 1.8MPa with the catalyst dosage of 1.0%.

Key words: ionic liquid, catalyst, carbon dioxide

中图分类号:

郭立颖, 马秀云, 王立岩, 邓莉莉, 金先超. 氯化1-氨基聚醚-3-甲基咪唑离子液体的制备与催化性能[J]. 化工进展, 2017, 36(02): 581-587.

GUO Liying, MA Xiuyun, WANG Liyan, DENG Lili, JIN Xianchao. Preparation and catalytic properties of chloride 1-amino polyether-3-methyl imidazole ionic liquid[J]. Chemical Industry and Engineering Progree, 2017, 36(02): 581-587.

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氯化1-氨基聚醚-3-甲基咪唑离子液体的制备与催化性能

Preparation and catalytic properties of chloride 1-amino polyether-3-methyl imidazole ionic liquid

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