材料研究学报  2011, Vol. 25 Issue (6): 585-590

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糠醇树脂的开环热裂解机理研究

季慧玲1, 蒋南2, 王继刚1

1.东南大学材料科学与工程学院~江苏省先进金属材料重点实验室 南京 211189 2.南京医科大学药学院 南京 210029

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

季慧玲 蒋南 王继刚. 糠醇树脂的开环热裂解机理研究[J]. 材料研究学报, 2011, 25(6): 585-590.
, , . Study on the Ring–opening Pyrolysis Mechanism of Furfuryl–alcohol Resin[J]. Chin J Mater Res, 2011, 25(6): 585-590.

摘要 参考文献 相关文章 Metrics 全文: PDF(905 KB)   摘要: 基于密度泛函理论, 利用Gaussian 03程序包, 通过QST2(Quadratic Synchronous Transit)和IRC(Intrinsic Reaction Coordinate)方法, 研究了糠醇树脂单呋喃环片段在有H$_{2}$O分子和无H$_{2}$O分子参与两种情况下的开环反应路径, 同时分别在B3LYP/6--31G**和QCISD/6--31G**水平下计算开环过程中的能量变化,并结合Mulliken电荷的变化来解析反应机理。结果表明: 对于有H2O分子参与的开环反应, 呋喃环上O原子将与H2O分子形成氢键; 在H2O诱导影响下, 呋喃环上C--O的结合弱化直至断键, 最终导致呋喃环的开环和形成链式饱和酮结构, 此过程只需经历一个过渡态就完成了开环。在无H2O分子情况下, 主要是通过呋喃环相邻脂肪链上产生的烯丙基H自由基迁移至呋喃环上的C原子而促成开环。根据H自由基与呋喃环上O原子的距离不同, 无H2O分子条件下的开环将呈现出两种途径：当H自由基与O原子较近时, 则先与O原子相结合。伴随着O原子的电负性增加, 环上C--O键断开, 呋喃环开环并得到以烯醇和连二双键为结构特征的中间体。该结构不稳定, 羟基上的氢原子将再次迁移, 并最终得到链式不饱和酮结构。当H自由基与O原子较远时, 则可直接迁移至呋喃环上的C原子, 并导致C--O键断裂和呋喃环开环。在B3LYP和QCISD水平下的活化能比较显示, H2O的存在有利于开环裂解。有H2O参与时的开环反应活化能分别为299.29 kJ/mol和343.25 kJ/mol; 而无H2O时, 反应路径1的活化能分别为312.3 kJ/mol和353.11 kJ/mol; 反应路径2的活化能分别为354.24 kJ/mol和378.82 kJ/mol。因此, 降低H2O的含量, 有助于延缓糠醇树脂的开环裂解。 关键词 ： 高分子材料,  开环机理,  Gaussian 03,  糠醇树脂     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. Key words： polymer materials    ring-opening mechanism    Gaussian 03    furfuryl–alcohol resin 收稿日期: 2010-08-10      ZTFLH:  TB324   基金资助: 国家自然科学基金20874011, 教育部留学回国人员科研启动基金和教育部高等学校博士学科点基金20100092110030资助项目。 服务 把本文推荐给朋友 加入引用管理器 E-mail Alert RSS 作者相关文章 季慧玲 蒋南 王继刚 44.8K 链接本文: https://www.cjmr.org/CN/      或      https://www.cjmr.org/CN/Y2011/V25/I6/585 1 C.F.Cullis, A.C.Norris, The pyrolysis of organic compounds under conditions of carbon formation, Carbon, 10(5), 525(1972) 2 E.Fitzer, W.Schafer, S.Yamada, The formation of glasslike carbon by pyrolysis of polyfurfuryl alcohol and phenolic resin, Carbon, 7(6), 643(1969) 3 J.G.Wang, N.Jiang, H.Y.Jiang, Effect of the evolution of phenol-formaldehyde resin on the high-temperature bonding, International Journal of Adhesion & Adhesives, 29(7),718(2009) 4 H.Y.Jiang, J.G.Wang, S.Q.Wu, B.S.Wang, Z.Z.Zhong, Pyrolysis kinetics of phenol-formaldehyde resin by nonisothermal thermogravimetry, Carbon, 48(2), 352(2010) 5 K.A.Trick, T.E.Saliba, 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