| Mechanistic study for the formation of polyoxymethylene dimethyl ethers promoted by sulfonic acid-functionalized ionic liquids | |
| Department | OSSO国家重点实验室 |
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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| 2015 | |
| Source Publication | Journal of Molecular Catalysis A: Chemical
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| ISSN | 1381-1169 |
| Volume | 408Pages:228-236 |
| Abstract | 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. |
| Keyword | Polyoxymethylene Dimethyl Ethers Sulfonic Acid-functionalized Ionic Liquids Mechanism Dft |
| Subject Area | 物理化学与绿色催化 |
| DOI | 10.1016/j.molcata.2015.07.028 |
| Funding Organization | National Basic Research Program of China (973 Program, No. 2011CB201404);National Natural Science Foundation of China (Project No. 21203218;21133011;21473225) |
| Indexed By | SCI |
| If | 3.958 |
| Language | 英语 |
| Funding Project | 分子催化与技术课题组;均相催化课题组 |
| compositor | 第一作者单位 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/18199 |
| Collection | 羰基合成与选择氧化国家重点实验室（OSSO） |
| Corresponding Author | Xia CG(夏春谷) |
| Affiliation | Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Suzhou Res Inst, Lanzhou 730000, Peoples R China |
| Recommended Citation 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. |
| Files in This Item: | ||||||
| File Name/Size | DocType | Version | Access | License | ||
| 王芳2015JMC.pdf（2085KB） | 期刊论文 | 作者接受稿 | 开放获取 | CC BY-NC-SA | View Application Full Text | |
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