Citation: DENG Ping, ZHANG Hai-Dong, JIANG Jun-Hao, JIANG Qi-Hua. Reaction Mechanism for Propylene Carbonate Prepared by KI/NH₃ Catalysis from Propylene Oxide and CO₂[J]. Acta Physico-Chimica Sinica, ;2011, 27(06): 1386-1392. doi: 10.3866/PKU.WHXB20110615 shu

Reaction Mechanism for Propylene Carbonate Prepared by KI/NH₃ Catalysis from Propylene Oxide and CO₂

1.
1. Pharmaceutical School, Chongqing Medical University, Chongqing 400016, P. R. China;
2. Engineering Research Centre for Waste Oil Recovery Technology and Equipment, Ministry of Education, Chongqing Technology and Business University, Chongqing 400067, P. R. China

Received Date: 11 February 2011
Available Online: 28 April 2011

The reaction mechanisms for the preparation of propylene carbonate (PC) from propylene oxide (PO) and CO₂ in the absence of a catalyst or by catalysis using KI or KI/NH₃ were studied in detail using density functional theory (DFT) at the B3LYP/6-311++G^** level (I atom using the MIDIX basis set). The geometric configurations of the reactants, intermediates, transition states, and products were optimized. Vibration analysis and the intrinsic reaction coordinate (IRC) of the reactions proved that the intermediates and transition states predicted were present. The natural bond orbital (NBO) and atoms in molecules (AIM) theories were used to determine the orbital interactions and the bond nature at the same level. The results reveal that PO+CO₂→M0a→TS0c→M0c→TS0c′→PC is the main reaction channel in the absence of the catalyst and it has a high energy barrier of 200.65 kJ·mol^-1. The energy barrier is reduced to 187.40 kJ·mol^-1 in the presence of KI, and it has a slow reaction rate. However, the energy barrier is reduced to 154.64 kJ·mol^-1 and the reaction rate increases considerably upon promotion by KI/NH₃, possibly because of the formation of hydrogen bonds between H in NH₃ and O in CO₂ or PO, which is in od agreement with the experimental results.
- KI,
- NH₃,
- Catalysis,
- Propylene oxide,
- Propylene carbonate,
- Reaction mechanism
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沈阳化工大学材料科学与工程学院沈阳 110142

Reaction Mechanism for Propylene Carbonate Prepared by KI/NH3 Catalysis from Propylene Oxide and CO2

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通讯作者: 陈斌, bchen63@163.com

Reaction Mechanism for Propylene Carbonate Prepared by KI/NH₃ Catalysis from Propylene Oxide and CO₂