Solid-State Polymerization Processes

这项研究的目的是发展新的方法 用于大分子的受控合成。 具体地说， 将尝试开发固态聚合 生产不能由其它方法合成的聚合物的方法 方法. 这部作品分为四个主要主题福尔斯。 (1)不饱和 有机单体分子将在分子水平上被包合 由某些结晶固体形成的隧道系统。 单体 然后在隧道中通过暴露在高能量下 辐射或通过化学引发。 立体定向 在某些情况下预期聚合。 (2)尝试将 制备一维金属骨架聚合物， 使用相同的隧道包合技术。 (3)环状 以适当的晶体堆积结晶的磷腈 将通过γ-辐射方法聚合排列。 它 预计这条路线将产生无法获得的聚合物， 通过常规的热熔融聚合途径。 (4)其他 在合适的空间群中结晶的环状无机体系 也将通过伽马辐照方法进行研究。 这些系统 包括杂元素磷腈、硼-氮-、硫- 氮和其它杂环。 大多数系统将 经研究证明，它能抵抗传统的热环- 开放聚合方法。 本工作制备的聚合物应具有新的大分子 结构和新的性能组合， 可用于电子、光学、磁性和其它应用。

The objective of this research is the development of new methods for the controlled synthesis of macromolecules. Specifically, attempts will be made to develop solid-state polymerization processes to yield polymers that cannot be synthesized by other methods. The work falls into four main topics. (1) Unsaturated organic monomer molecules will be clathrated in the molecular level tunnel systems formed by certain crystalline solids. The monomers will then be polymerized in the tunnels by exposure to high energy irradiation or by chemical initiation. Stereospecific polymerizations are expected in some cases. (2) Attempts will be made to prepare one-dimensional metallo-backbone polymers by the use of the same tunnel clathration technique. (3) Cyclic phosphazenes which crystallize in appropriate crystal packing arrangements will be polymerized by gamma-irradiation methods. It is expected that this route will generate polymers not accessible by the conventional thermal melt polymerization route. (4) Other cyclic inorganic systems that crystallize in suitable space groups will also be studied by gamma-irradiation methods. These systems include heteroelement phosphazenes, boron-nitrogen-, sulfur- nitrogen-, and other heterocyclic rings. Most of the systems to be studied have proved to be resistant to conventional thermal ring- opening polymerization methods. The polymers prepared in this work should have new macromolecular structures and new combinations of properties that are potentially useful in electronic, optical, magnetic, and other applications.