Solid-State Polymerization Processes

本研究的目的是开发新的方法来控制大分子的合成。具体来说，将尝试开发固态聚合工艺，以产生其他方法无法合成的聚合物。这项工作主要分为四个主题。(1)不饱和有机单体分子会在某些结晶固体形成的分子级隧道体系中被笼化。然后，单体将通过暴露于高能辐射或化学引发在隧道中聚合。在某些情况下，预计会发生立体特异性聚合。(2)将尝试使用相同的隧道笼合技术制备一维金属骨架聚合物。(3)以适当的晶体排列方式结晶的环状磷腈将通过伽马辐照方法聚合。预计这条路线将产生传统热熔聚合路线无法获得的聚合物。(4)其他在合适空间群中结晶的循环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杂烯、硼氮杂环、硫氮杂环和其他杂环。所研究的大多数体系已被证明能够抵抗传统的热开环聚合方法。在这项工作中制备的聚合物应该具有新的大分子结构和新的性质组合，在电子，光学，磁性和其他应用中具有潜在的用途。

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.