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题名	聚合物体系相平衡热力学与数据库的研究
作者	温浩
学位类别	博士
答辩日期	2003
授予单位	中国科学院过程工程研究所
授予地点	中国科学院过程工程研究所
导师	许志宏
关键词	聚合物溶液 共混聚合物 相平衡 数据库
其他题名	Study on the Phase Equilibrium Thermodynamics and Database for Polymer Containing Systems
学位专业	化学工艺
中文摘要	在聚合物加工和应用领域中，聚合物溶液是纺丝、成膜、涂料一、各种助剂、溶液聚合等过程的基本物料，对已有聚合物材料的共混改性也已成为开发新型聚合物材料的一种卓有成效的手段。如何描述聚合物溶液和共混聚合物的相态行为是上述过程中的一个基本问题。由于聚合物在分子尺度、结构、多分散性上存在的巨大差异，使之具有区别于小分子溶液相平衡问题的显著特点。因此，描述聚合物溶液和共混聚合物相平衡行为的数据和热力学模型对理论和应用都是必要且重要的基础性研究。本文着重讨论的是聚合物溶液和共混聚合物相平衡热力学研究与数据库开发。在相平衡热力学研究方面：一用气相色谱法测定了聚乙二醇中部分有机溶剂的无限稀释活度系数，本文测定的 数据扩展了已有数据在聚乙二醇摩尔质量上的覆盖范围，并与其他文献数据之间 有着良好的规律性和一致性。一系统考察了UNIQUAC模型用于汽一液平衡数据关联的能力，该模型对局部组成的描述反映出溶液微观结构的非均匀性，常可获得较Flory-Huggins模型更高的关联精度，使之成为聚合物溶液相平衡数据库的关联模型。一采用Chiew硬球链方程和Cllen-Kxeglewski引力相互作用解析表达，发展了微扰硬球链状态方程，本文发展的微扰硬球链状态方程对汽一液平衡数据的关联能力好于SAFT方程，预测能力表现出明显优势。在相平衡数据库开发方面：一与丹麦技术大学、意大利的里亚斯特大学合作开发了聚合物溶液相平衡数据库，该数据库可提供汽一液平衡、液一液平衡和溶剂无限稀释活度系数的完整描述。以此为基础，在DECHEMA Chemistry Data Series第XIV卷中，用3个分册编著出版了数据手册Polymer Solution Data collection。一与美国国家标准与技术研究院合作开发了共混聚合物相容性数据库，该数据库可提供共混聚合物相容性数据的完整描述。进而尝试将理论计算作为数据质量评价的方法，该方法独立于实验测定，有可能为用户提供相容性数据质量的参考。一作为工程化学数据库的组成部分，聚合物溶液相平衡数据库和共混聚合物相容性数据库已纳入中国科学院科学数据库及其应用系统。
英文摘要	In the fields of polymer processing and application, polymer solutions are performed as the essential materials in the processes of fibre spinning, membrane forming, coating, auxiliaries and solution polymerization, preparing polymer blends by blending different existing polymers is employed also as an effective method for developing new polymeric materials. One of the fundamental topics in above-mentioned processes is the description of the phase behaviors of polymer solutions and blends. Phase equilibrium of polymer solutions and blends present different features from those of mixtures of small molecules because of the molecular structure, molecular size and their polymolecularity of macromolecules. It is essential and important to develop the thermodynamic models and data of phase equilibrium for polymer solutions and blends from both theoretical and practical points of view. The discussions in this dissertation focus on the phase equilibrium thermodynamics studies and related databases developments for polymer solutions and blends. In the phase equilibrium thermodynamics studies, Weight fraction activity coefficients at infinite dilution of some organic solvents in poly(ethylene glycol) are measured by gas chromatography. The measured data in this dissertation extend the data coverage for poly(ethylene glycol) of different molar mass, and present good regularity and consistency with those from other publications. The performance of UNIQUAC model on data correlation is systematically studied for vapor-liquid equilibrium. Better correlation results can be obtained by UNIQUAC model than by Flory-Huggins because of the non-homogeneity on microstructure of polymer solution presented by the local composition expression in UNIQUAC model. The UNIQUAC model is selected to be the correlation model in the Polymer Solution Phase Equilibrium Database for its performance in data correlation. A new perturbed hard-sphere chain equation of state is developed in this dissertation with Chiew's hard-sphere chain equation and Chen-Kreglewski's expression of attractive interaction. The equation of state developed in this dissertation shows better performance on data correlation and evident advantage on data prediction than the S AFT equation of state does for polymer solution vapor-liquid equilibrium. In the phase equilibrium database developments, The Polymer Solution Phase Equilibrium Database is developed as the collaboration with Danmarks Tekniske Htejskole and Universita degli Studi di Trieste, from which people can obtain the full data information of polymer solution vapor-liquid equilibrium, liquid-liquid equilibrium and solvent activity coefficients at infinite dilution in polymers. The data handbook of Polymer Solution Data Collection is published in 3 parts based on this database, as the Volume XIV in DECHEMA Chemistry Data Series. The Polymer Blend Miscibility Database is developed as the collaboration with the National Institute of Standards and Technology of United States, from which people can obtain the full data information of polymer blend miscibility. Furthermore, a trial is performed for evaluating the data quality by a theoretical calculation method. This method is independent to the experimental measurements, and presents the possibility to be the reference of data quality. As the components of the Engineering Chemistry Database, the Polymer Solution Phase Equilibrium Database and the Polymer Blend Miscibility Database provide their data services via the Scientific Database and its application system of the Chinese Academy of Sciences.
语种	中文
公开日期	2013-09-16
页码	210
内容类型	学位论文
源URL	[http://ir.ipe.ac.cn/handle/122111/1414]
专题	过程工程研究所_研究所（批量导入）
推荐引用方式 GB/T 7714	温浩. 聚合物体系相平衡热力学与数据库的研究[D]. 中国科学院过程工程研究所. 中国科学院过程工程研究所. 2003.

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