分子模拟研究逐步聚合过程中的高分子结晶行为

项目名称： 分子模拟研究逐步聚合过程中的高分子结晶行为

项目编号： No.21204011

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 高分子科学

项目作者： 马禹

作者单位： 东华大学

项目金额： 25万元

中文摘要： 可结晶高分子在逐步聚合反应中，链状分子结构和分子密堆的结晶结构同时形成，两个过程相互竞争，共同决定了高分子的链结构和凝聚态结构。一方面，结晶的形成导致发生非均相的缩聚反应；另一方面，分子链的增长过程改变了结晶动力学和结晶形态。在本课题中，我们将利用分子模拟的方法，从聚合诱导结晶成核和生长的角度探索反应速率常数、溶剂的混合相互作用参数、主链构象能及分子链的密堆能等热力学条件如何协同影响高分子的链结构，如分子量和分子量分布，以及晶体结构，如结晶形貌、取向和缺陷等。目标是建立起聚合反应与结晶过程协同进行的分子尺度模型，并提炼聚合时高分子初生晶体形态调控的热力学方法。本项基础性课题的研究，扩展了经典高分子化学和高分子物理的研究领域。同时，对调控芳纶、聚酰亚胺、聚芳酯等高性能纤维聚合物原料的结构和开发其未来新型加工方法提供必要的前期理论探索。

中文关键词： 分子模拟；逐步聚合；结晶；反应动力学；共聚物序列

英文摘要： During step polymerization of crystalline polymers, the long chain molecular structure and closed packing crystalline structure was constructed simultaneously. Two main effects could be incurred by the interplay of chain growth process and crystal growth process. In one hand, polymerization has to occurr within both solution and crystals after the formation of crystallites; on the other hand, crystal growth kinetics and morphology could be intensively altered by the chain growing process. In this project, we will employ molecular simulation as our main technique to investigate how the thermodynamic conditions, i.e. reaction kinetics, Flory-Huggins interactions, collinear interaction along the chain and parallel packing energy, influence the chain structure and crystal structure, such as molecule weight and its distribution, crystal morphology, orientation and defects etc. We are aim to build the molecule model of polymerization induced crystallization, and therefore propose a thermodynamic method to control structures of nacent crystal. This fundamental research project will expand the scope of classical polymer chemistry and polymer physics. Meanwhile, it's also a valuable tentative study for the controlled synthesis of polymer of high performance fiber, for example, Kevlar, Polyimide, Polyarylate etc., and for

英文关键词： Molecular simulation；stepwise polymerization；crystallization；reaction kinetics；comonomer sequence