Atom Transfer Radical Polymerization of Dienes

通过这个奖项，化学系的大分子、超分子和纳米化学项目正在支持康涅狄格大学的Alexandru Asandei教授开发合成二烯基聚合物的新方法。聚合物在日常生活中有许多重要的应用。一种广泛使用的聚合物是由二烯类单体制备的。二烯基聚合物是汽车轮胎合成橡胶和高冲击塑料的重要组成部分。Asandei教授的目标是开发一种可持续的替代方法，以较低的生产成本合成基于二烯的聚合物，这种方法的目标是使用生物可再生单体。这个基础研究项目涵盖了广泛的技术和方法，为研究生和本科生的教育和研究培训提供了一个多学科的环境。还计划向来自各种背景的高中生提供服务。合成上，无规二烯共聚物的生产得益于乳液自由基聚合，而相应的热塑性弹性体嵌段共聚物的合成则需要昂贵的、对水敏感的阴离子/配位聚合。因此，廉价、耐水、可控的自由基聚合（CRPs）将是非常有益的。在这项研究中，Asandei教授和他的同事们旨在对二烯的原子转移自由基聚合（ATRP）进行定量的了解，这一过程具有简单、低成本、催化性质、可调和耐水性等潜在优势。该研究项目需要在廉价的加压玻璃管中进行详细的动力学研究，从而实现光化学和快速，经济高效的优化。这些研究有望提供有关二烯结构、ATRP类型、温度、引发剂、溶剂、催化剂、配体、添加剂和试剂配比对相关聚合的分子量、多分散性、速率、副反应和链端官能团的影响的信息。这些知识有望促进乳液二烯ATRP的发展，并促进复杂的聚二烯共聚物结构的合成。

With this award, the Macromolecular, Supramolecular and Nanochemistry Program of the Division of Chemistry is supporting Professor Alexandru Asandei of the University of Connecticut to develop new approaches for the synthesis of diene-based polymers. Polymers have many important applications in everyday life. One type of widely used polymer is prepared from monomers that belong to the diene class. Diene-based polymers are important components of synthetic rubbers in tires of automobiles and high-impact plastics. Professor Asandei aims to develop a sustainable alternative to the synthesis of diene-based polymers at lower production cost in an approach that targets the use of biorenewable monomers. This fundamental research project spans a wide variety of techniques and methods, providing a multi-disciplinary environment for the education and research training of graduate students and undergraduate coworkers. Outreach to high school students from a variety of backgrounds is also planned.Synthetically, while the production of random diene copolymers benefits from emulsion radical polymerizations, the synthesis of corresponding thermoplastic elastomer block copolymers involves expensive, water sensitive anionic/coordination polymerizations. Thus, inexpensive, water tolerant, controlled radical polymerizations (CRPs) would be highly beneficial. In this research, Professor Asandei and coworkers aim to provide quantitative understanding of the atom transfer radical polymerization (ATRP) of dienes, a process that offers the potential advantages of simplicity, low cost, catalytic nature, tunable, and water tolerance. This research project entails detailed kinetic investigations carried out in inexpensive pressurized glass tubes, which enable both photochemistry and a fast, cost efficient optimization. These studies are expected to provide information on the effect of diene structure, ATRP type, temperature, initiator, solvent, catalyst, ligand, additives and reagent ratios on the molecular weight, polydispersity, rate, side reactions and chain end functionality of associated polymerizations. Such knowledge is expected to enable the development of emulsion diene ATRP, and facilitate the synthesis of complex polydiene-copolymer architectures.