Chlorinated Poly (Vinyl Chloride) with High-Performance Properties and the Detection of Labile Structures in Vinylidene Chloride Polymers

9610361 Starnes所提出的研究的最终目标是获得具有上级性能的有用聚合物。 设想开展两个平行项目。 它们在某种意义上是相关的，即都与氯化聚合物和自由基化学有关。 其中一个项目涉及新形式氯化聚氯乙烯的制备，这些树脂具有特殊的物理特性，可作为高性能材料使用。 在这种情况下，一个具体的合成目标是聚（1，2-二氯乙烯）（PDCE），其玻璃化转变温度已被预测为远高于目前的商业CPVC的。 制备PDCE和其他新型CPVC的方法包括：（a）在各种能络合氯原子的溶剂存在下，用分子氯氯化聚氯乙烯（PVC），（B）用选择性不寻常的其他试剂氯化PVC，和（c）通过不发生实质性氯化的替代路线合成。 这项工作将最终扩展到其他新的含氯聚合物材料的制备。 另一个项目旨在识别和列举偏二氯乙烯聚合物（PVDC）中的异常（缺陷）结构，并阐明这些结构在聚合过程中形成的机制。 将特别注意热不稳定的结构，因为它们的形成机制可能会建议的方式修改的聚合程序，以创建聚合物的稳定性大大提高。 %%% 这项研究可能导致制备重要的新材料，这些材料在技术上非常有用，并且属于含有PVC的聚合物家族，PVC是世界上第二大使用最广泛的热塑性塑料。 这项工作还将通过培训高级研究人员和所有在全国首屈一指的本科学校之一的化学学生在国际公认的小组中进行前沿研究，为科学教育做出重大贡献。 ***

9610361 Starnes The proposed research is directed toweard the ultimate goal of obtaining useful polymers with superior properties. Two parallel projects are envisaged. They are related in the sense that both are concerned with chlorinated polymers and with free-radical chemistry. One project deals with the preparation of new forms of chlorinated poly(vinyl chloride) (CPVC) having unusual physical properties that should make these resins excellent candidates for utilization as high performance materials. In this context, a specific synthetic target is poly(1,2-dichloroethylene)(PDCE), whose glass transition temperature has predicted to be much higher than those of the current commercial CPVC's. Approaches to the preparation of PDCE and other new CPVC's will include (a) the chlorination of poly(vinyl chloride)(PVC) with molecular chlorine in the presence of various solvents that can complex chlorine atoms, (b) the chlorination of PVC with other reagents whose selectivities are unusual, and ( c) synthesis by alternative routes in which no substantive chlorination occurs. This work will be extended eventually to the preparation of other new chlorine-containing polymeric materials. The other project is designed to identify and enumerate the anomalous (defect) structures in vinylidene chloride polymers (PVDC's) and to elucidate the mechanisms by which these structures are formed during polymerization. Particular attention will be paid to thermally labile structures, because their mechanisms of formation may suggest ways of modifying the polymerization procedures in order to create polymers whose stabilities are greatly enhanced. %%% This research could lead to the preparation of important new materials that are very useful technologically and are in the family of polymers that contains PVC, the world's second most widely used thermoplastic. The work also will make a major contribution to science education by training advanced researchers and by all owing Chemistry students at one of the nation's premier undergraduate schools to do research in a frontier with an internationally recognized group. ***