中间相沥青的聚合动力学及组分控制

Polymerization kinetics and control of the components of a mesophase pitch

  • 摘要: 增加中间相沥青中吡啶可溶物含量对于提高其可纺性具有重要意义。本研究以萘系各向同性沥青为原料,使用直接热缩聚合成中间相沥青,分析了聚合产物族组成随时间的变化;结合偏光显微镜和元素分析结果,研究了聚合温度、时间和原料组成对中间相沥青合成反应的影响;并用连串反应模型计算了反应动力学常数。结果表明,400℃预聚10 h后,430℃下反应20 h得到族组成分布相对均一的沥青。中间相沥青合成反应具有很明显的加速效应,即重组分的反应速度常数较轻组分大。在合成反应后期,随着沥青分子量增加,其反应速率也越来越快。因此起始组成、反应温度与时间对族组成的分布有决定性的影响。

     

    Abstract: It is important to increase the content of pyridine soluble in mesophase pitch to improve its spinnability. A naphthalene isotropic pitch was used as the raw material to prepare mesophase pitch by polymerization. The components of the polymerized products were analyzed by solvent extraction with benzene and pyridine, and classified as benzene soluble (BS), pyridine insoluble (PI) and benzene insoluble but pyridine soluble (BI-PS). The effects of polymerization temperature, time and the components of the raw material on the distribution of the components and optical texture of the mesophase pitch were investigated. The reaction kinetic constants were calculated assuming a consecutive reaction from BS to BI-PS, then to PI. Results show that a mesophase pitch with a relatively uniform distribution of components is obtained after reaction at 430 oC for 20 h from an isotropic pitch pre-polymerized at 400 oC for 10 h. The mesophase pitch synthesis reaction has a significant auto-acceleration effect in that the reaction rate constant of a heavy component is larger than a light one. The reaction rate becomes faster and faster as the molecular weight of the pitch increases in the latter stage of the synthesis reaction. Therefore, the initial component of raw pitch, reaction temperature and time have a decisive influence on the distribution of components in the mesophase pitch.

     

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