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新型聚合酸性离子液体作为绿色催化剂用于通过甲缩醛与三氧杂环己烷的缩醛化反应制备聚甲醛二甲醚。

Novel polymeric acidic ionic liquids as green catalysts for the preparation of polyoxymethylene dimethyl ethers from the acetalation of methylal with trioxane.

作者信息

Song Heyuan, Jin Fuxiang, Kang Meirong, Chen Jing

机构信息

State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou 730000 China

出版信息

RSC Adv. 2019 Dec 9;9(69):40662-40669. doi: 10.1039/c9ra07765k. eCollection 2019 Dec 3.

Abstract

A series of micro-mesoporous polymeric acidic ionic liquids (PAILs) have been successfully synthesized and subsequently characterized using Fourier transform-infrared spectroscopy, N adsorption-desorption isotherms, scanning electron microscopy and thermogravimetry. Furthermore, the catalytic performance of the synthesized PAILs was investigated for the acetalation of methylal (DMM) with 1,3,5-trioxane (TOX), micro-mesoporous PAILs copolymerized by divinylbenzene with cations and anions exhibited moderate to excellent catalytic activities for the acetalation. In particular, VIMBs-AMPs-DVB, with higher specific surface area (25.51 m g) and total pore volume (0.15 cm g) displayed an elevated conversion of formaldehyde (82.2%) and selectivity for polyoxymethylene dimethyl ethers (CHO(CHO) CH; PODE or DMM ) = 3-8 (52.6%) at 130 °C, 3.0 MPa for 8 h. Moreover, the influence of various reaction parameters was investigated by employing VIMBs-AMPs-DVB as the catalyst and it demonstrated high thermal stability and easy recovery.

摘要

一系列微介孔聚合物酸性离子液体(PAILs)已成功合成,并随后通过傅里叶变换红外光谱、N吸附-脱附等温线、扫描电子显微镜和热重分析进行了表征。此外,研究了合成的PAILs对甲缩醛(DMM)与1,3,5-三氧杂环己烷(TOX)缩醛化反应的催化性能,由二乙烯基苯与阳离子和阴离子共聚的微介孔PAILs对缩醛化反应表现出中等至优异的催化活性。特别是,具有较高比表面积(25.51 m²/g)和总孔体积(0.15 cm³/g)的VIMBs-AMPs-DVB在130℃、3.0 MPa下反应8小时,甲醛转化率提高到82.2%,对聚甲醛二甲醚(CHO(CH₂O)ₙCH₃;PODEₙ或DMMₙ,n = 3 - 8)的选择性为52.6%。此外,以VIMBs-AMPs-DVB为催化剂研究了各种反应参数的影响,结果表明其具有高热稳定性且易于回收。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d5/9076234/0bb5049c2c07/c9ra07765k-s1.jpg

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