Captodative Initiators and Monomers: A New Synthetic Approach to High Polymers

这项研究涉及到一种新的自由基引发聚合方法的开发，该方法基于碳原子稳定的概念，以及基于环碳原子自由基的可逆二聚的新的引发体系的使用。将合成新的单体，以评估自由基稳定性和反应性之间的平衡。脱氢丙氨酸衍生物(已知是高活性的自由基单体)将首先被检测，以评估其规整性、共聚性以及通过偶联产生自由基嵌段共聚物的可逆终止的使用。然后将合成脱氢丙氨酸的类似物，其中封端基包括腈、硝酸盐、磺酸盐或膦酸衍生物与胺、羟基、巯基或硅基官能团的组合。单体和中间体的键强度和电荷分布将被计算并与经验数据相关联。

This research involves development of a new approach to radical initiated polymerization based on the concept of captodative stabilization, and the use of new initiating systems based on reversible dimerization of cyclic captodative radicals. New monomers will be synthesized that will allow evaluation of the balance between radical stabilization and reactivity. Dehydroalanine derivatives (which are known to be highly active radical monomers) will be examined first to evaluate tacticity, copolymerizability, and the use of reversible termination by coupling to generate radical block copolymers. Analogs of dehydroalanines will then be synthesized in which the captodative groups include combinations of nitrile, nitrate, sulfonate, or phosphonate derivatives with amine, hydroxyl, sulfhydryl, or silyl functionality. Bond strengths and charge distributions of monomers and intermediates will be calculated and correlated with empirical data.