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

这项研究涉及开发一种新的方法， 自由基引发聚合的概念， 捕获稳定和使用新的引发系统 基于环状捕获自由基的可逆二聚化。 将合成新的单体，这将允许评估 自由基稳定和反应性之间的平衡。 脱氢丙氨酸衍生物（已知其具有高活性 自由基单体）将首先进行检查以评价立构规整度， 可共聚性，以及使用可逆终止， 偶联以生成自由基嵌段共聚物。 的类似物 然后将合成脱氢丙氨酸，其中捕获剂 基团包括腈、硝酸盐、磺酸盐或它们的组合。 具有胺、羟基、巯基的膦酸酯衍生物，或 甲硅烷基官能度。 的键强度和电荷分布 将计算单体和中间体，并与 经验数据

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.