Towards moisture and light stable polystannanes

直到最近，对14族元素的聚合物的研究主要局限于那些含有碳的聚合物。虽然对基于较重的14族元素、聚硅烷、聚日耳曼和聚锡烷的聚合物的独特性能的研究兴趣不断增加，但这些材料的应用却相当有限。较高的14族聚合物通常对光和湿气都敏感，这使得它们比传统的聚合物系统更难制备、分离和使用。14族金属的最高聚合物（Sn, Pb）代表了一个相对未开发的研究领域，与链状铅聚合物，聚铅醚，仍然未知。高14族聚合物的独特性质之一是由主链上元素轨道重叠形成的广泛的离域sigma-sigma键网络，使这些产物在光学和电子上都很有趣。用锡和铅的均聚物制造高导电薄膜、一维量子线和可印刷电子产品的潜力尚未得到探索。这项研究将解决以前这些独特材料的合成缺点，并提供第一个湿、光稳定的聚锡烷的例子。光稳定性将通过引入光稳定侧基（UV吸收剂（UVA），受阻胺光稳定剂（HALS））来保护骨架免受光分裂反应的影响。湿稳定性将通过在锡原子上使用庞大的疏水或环状结构来提供，以提高对水分和其他亲核试剂的抵抗力。上述单体的聚合将通过烷基或芳基锡二氢化物的脱氢偶联和Wurtz偶联以及烷基或芳基锡二氯化物的电聚合来完成。金属催化插入不饱和烃，（炔或苯）到这些聚合物的主链也将被研究。还将进行这些新聚合物的表征和应用测试。

Until relatively recently, studies of polymers of Group 14 elements have been largely limited to those containing carbon. While research interest into the unique properties of polymers based on heavier Group 14 elements, polysilanes, polygermanes, and polystannanes has continued to increase, applications with these materials has been considerably more limited. Higher Group 14 polymers are in general both light and moisture sensitive, making them more difficult to prepare, isolate and use compared to conventional polymer systems. The highest polymers of Group 14 metals (Sn, Pb) represent a relatively untapped research area with catenated lead polymers, polyplumbanes, still unknown. One of the unique properties of higher Group 14 polymers is the extensive delocalized sigma-sigma bond network created from overlap of elemental orbitals along the backbone, making these products optically and electronically interesting. The potential to make highly conductive films, one-dimensional quantum wires and printable electronics with homopolymers of Sn and Pb have not been explored. This research will address the previous synthetic shortcomings of these unique materials and deliver the first examples of moisture and light stable polystannanes. Light stability will be accomplished by the introduction of light stabilizing side groups (UV absorbers (UVA), hindered amine light stabilizers (HALS)) to protect the backbone from photoscission reactions. Moisture stability will be provided by the use of bulky hydrophobic or ring structures on the tin atom to improve resistance to moisture and other nucleophiles. Polymerization of the above described monomers will be accomplished by dehydrogenative coupling of alkyl or aryl tin dihydrides and Wurtz coupling and electropolymerization of alkyl or aryl tin dichlorides. Metal catalyzed insertion of unsaturated hydrocarbons, (alkynes or benzynes) into the backbone of these polymers will also be investigated. Characterization and applications testing of these new polymers will also be undertaken.