Mechanistic study for the formation of polyoxymethylene dimethyl ethers promoted by sulfonic acid-functionalized ionic liquids
文献类型：期刊论文
| 作者 | Wang F(王芳) ; Zhu GL(朱刚利); Li Z(李臻); Zhao F(赵峰); Xia CG(夏春谷); Chen J(陈静); Xia CG(夏春谷)
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| 刊名 | Journal of Molecular Catalysis A: Chemical
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| 出版日期 | 2015 |
| 卷号 | 408页码:228-236 |
| 关键词 | Polyoxymethylene dimethyl ethers Sulfonic acid-functionalized ionic liquids Mechanism DFT |
| ISSN号 | 1381-1169 |
| 通讯作者 | 夏春谷 |
| 英文摘要 | Polyoxymethylene dimethyl ethers (DMMn), which are ideal additives for diesel fuel, are mainly synthesized from the condensation of methanol (MeOH) or dimethoxymethane (DMM) with 1,3,5-trioxane (TOX) or paraformaldehyde (PF) promoted by different acid catalysts. However, up to date, few studies have been reported to examine the formation mechanism of DMMn which is essential in understanding the reaction and valuable in designing improved catalysts. In this work, using the density functional theory (OFT) calculations combined with experiment studies, we evaluate the formation mechanism of DMMn, which is promoted by sulfonic acid-functionalized ionic liquids (SO3H-FILs). Our calculated results indicate TOX and PF should dissociate into formaldehyde monomers firstly and then to react with MeOH or DMM. However, their decomposition process is different where the dissociation of TOX proceeds along a two-step mechanism while it follows a one-step mechanism for PF dissociation. As for the formation of DMMn, the reaction proceeds along a hemiacetal-carbocation pathway when MeOH is selected as the capping group provider, while the reaction follows a carbocation pathway when DMM is chosen. The origination for the product distribution pattern has also been discussed in detail. The cations and anions of ionic liquids are found synergistically promote the condensation reaction by proton transfer and simultaneously stabilizing the formed intermediated and transition states. Moreover, all the processes related to the decomposition of TOX and PF and the condensation reaction are reversible. |
| 学科主题 | 物理化学与绿色催化 |
| 收录类别 | SCI |
| 资助信息 | National Basic Research Program of China (973 Program, No. 2011CB201404);National Natural Science Foundation of China (Project No. 21203218;21133011;21473225) |
| 语种 | 英语 |
| WOS记录号 | WOS:000361254400026 |
| 源URL | [http://210.77.64.217/handle/362003/18199]  |
| 专题 | 兰州化学物理研究所_OSSO国家重点实验室 |
| 通讯作者 | Xia CG(夏春谷) |
| 作者单位 | Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Suzhou Res Inst, Lanzhou 730000, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wang F,Zhu GL,Li Z,et al. Mechanistic study for the formation of polyoxymethylene dimethyl ethers promoted by sulfonic acid-functionalized ionic liquids[J]. Journal of Molecular Catalysis A: Chemical,2015,408:228-236. |
| APA | Wang F.,Zhu GL.,Li Z.,Zhao F.,Xia CG.,...&夏春谷.(2015).Mechanistic study for the formation of polyoxymethylene dimethyl ethers promoted by sulfonic acid-functionalized ionic liquids.Journal of Molecular Catalysis A: Chemical,408,228-236. |
| MLA | Wang F,et al."Mechanistic study for the formation of polyoxymethylene dimethyl ethers promoted by sulfonic acid-functionalized ionic liquids".Journal of Molecular Catalysis A: Chemical 408(2015):228-236. |
入库方式： OAI收割
来源：兰州化学物理研究所
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