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| Study on the Ring–opening Pyrolysis Mechanism of Furfuryl–alcohol Resin |
| JI Huiling1, JIANG Nan2, WANG Jigang1 |
1. Jiangsu Key Laboratory of Advanced Metallic Materials, School of Materials Science and Engineering, Southeast University, Nanjing 211189
2. School of Pharmacy, Nanjing Medial University, Nanjing 210029 |
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Cite this article:
JI Huiling JIANG Nan WANG Jigang. Study on the Ring–opening Pyrolysis Mechanism of Furfuryl–alcohol Resin. Chin J Mater Res, 2011, 25(6): 585-590.
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Abstract Based on the Density Functional Theory (DFT), the ring-opening mechanisms of monocyclic segment of furfuryl-alcohol resin were investigated by QST2 (Quadratic Synchronous Transit) and IRC (Intrinsic Reaction Coordinate) methods. Gaussian 03 software package was employed in this study. In order to investigate the influence of water on the ring-opening, the reactions were respectively analyzed with the participation and absence of water. The ring-opening mechanisms were discussed according to the analysis of Mulliken charges as well as the energies calculated at B3LYP/6–31G** and QCISD/6–31G** levels. Results showed that water molecules exhibit importance influence on the ring-opening process. For the reaction with the participation of water, hydrogen bonding will be formed between the oxygen atom on the furan ring and the water molecule. Because of the influence of water, the conjugation of C–O bond was weakened, and gradually resulting in the ring-opening of furan ring. Though such path, only one transition state was experienced and a chain-type saturated ketone structure was finally obtained. According to the distance between oxygen atom on the furan ring and the allyl hydrogen atom on the adjacent aliphatic hydrocarbon, there were two ring-opening paths without the attendance of water. (1) If the hydrogen atom is close to the oxygen atom, the allyl hydrogen radical will bond with the oxygen atom firstly, results in the obtaining of an intermediate that is characterized by enol as well as diene structures. Subsequently, the hydrogen atom on the hydroxyl group will migrate again, and leading to the formation of a chain-type unsaturated ketone. (2) If the hydrogen atom is far from the oxygen atom, the allyl hydrogen radical migrates to the adjacent carbon directly. The data of activity energies indicated that the incorporation of water benefits in the ring-opening reaction. For the reaction with the participation of water, the activity energies calculated at B3LYP and QCISD levels were 299.29 kJ/mol and 343.25 kJ/mol, respectively. In contrast, without attendance of water, the activity energies of route 1 were 312.3 kJ/mol and 353.11 kJ/mol, while whose of route 2 were 354.24 kJ/mol and 378.82 kJ/mol. Therefore, the decrease of water benefits in the retarding of ring-opening degradation reaction.
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Received: 10 August 2010
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| Fund: Supported by National Nature Science Foundation of China No.20874011, Scientific Research Foundation for the Returned Overseas Chinese Scholars sponsored by State Education Ministry, and Scientific Research Foundation of Southeast No.XJ2008321. |
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