DOI: 10.1016/j.jcou.2018.12.001
Scopus记录号: 2-s2.0-85058196597
论文题名: Highly selective, sustainable synthesis of limonene cyclic carbonate from bio-based limonene oxide and CO2: A kinetic study
作者: Rehman A. ; López Fernández A.M. ; Gunam Resul M.F.M. ; Harvey A.
刊名: Journal of CO2 Utilization
ISSN: 22129820
出版年: 2019
卷: 29 起始页码: 126
结束页码: 133
语种: 英语
英文关键词: Activation energy
; Cyclic carbonates
; Kinetic study
; Limonene oxide
; Stereoselective epoxidation
; Tetrabutylammonium halide
Scopus关键词: Activation energy
; Carbon dioxide
; Carbonates
; Catalysts
; Chlorine compounds
; Free energy
; Gibbs free energy
; Isomers
; Kinetic theory
; Kinetics
; Monoterpenes
; Stereoselectivity
; Temperature distribution
; Cyclic carbonates
; Kinetic study
; Limonene oxide
; Stereo-selective
; Tetrabutylammonium
; Reaction kinetics
英文摘要: Bio-derived cyclic carbonates are of significant research interest as building blocks for non-isocyanate polyurethanes (NIPUs). Cyclic carbonates from limonene are bio-renewable monomers for the production of fully bio-based polymers from citrus waste; however, there are currently very few reports on their synthesis. This work reports the synthesis of five-membered cyclic carbonates from bio-based limonene oxide (LO) and CO2 catalysed by commercially available inexpensive, tetrabutylammonium halides (TBAX). The cycloaddition of CO2 with commercial LO mixture of cis/trans-isomers (40:60) is highly stereoselective and the trans-isomer exhibits considerably higher conversion than the cis-isomer. Therefore, a stereoselective method of (R)-(+)-limonene epoxidation was performed to achieve a significantly higher yield of the trans-isomer (87 ± 2%) than cis-isomer, which leads to high conversion and yield to the corresponding cyclic carbonates. The catalytic effect of halide anions (X) and the influence of operational reaction parameters such as temperature, pressure, and catalyst amount were studied. High conversion (87%) was obtained after 20 h at 120 °C, 40 bar CO2 using 6 mol% tetrabutylammonium chloride (TBAC) catalyst. A detailed study of the reaction kinetics revealed the reaction to be first-order in epoxide (LO), CO2 and catalyst (TBAC) concentrations. Moreover, the temperature dependence of the reaction was studied using Arrhenius and Eyring equations. The activation energy (Ea) of the reaction was calculated to be 64 kJ mol-1. The high positive value of Gibbs free energy (ΔG‡ = 102.6 kJ mol-1) and negative value of activation entropy (ΔS‡ = -103.6 J mol-1) obtained as result of the thermodynamic study, indicate that the reaction was endergonic and kinetically controlled in nature. © 2018 Elsevier Ltd. All rights reserved. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/117321
Appears in Collections: 气候变化与战略
There are no files associated with this item.
Recommended Citation:
Rehman A.,López Fernández A.M.,Gunam Resul M.F.M.,et al. Highly selective, sustainable synthesis of limonene cyclic carbonate from bio-based limonene oxide and CO2: A kinetic study[J]. Journal of CO2 Utilization,2019-01-01,29