Structure-Reactivity Correlation in Atom Transfer Radical Polymerization and Addition Processes

有机和大分子化学项目支持卡内基梅隆大学化学系Krzysztof Matyjaszewski教授进行原子转移自由基聚合的研究，该研究基于使用自由基聚合将单体转化为聚合物。本研究旨在对过渡金属催化的原子转移自由基聚合（ATRP）和加成反应（ATRA）进行系统的机理研究，主要目的是确定ATRP和ATRA中催化剂和中间体物种的结构，并建立烷基、（拟）卤素、过渡金属、和配体组分。ATRP和ATRA产生良好控制的产物的能力在很大程度上取决于这些动力学参数，因此它们的测定在开发新的和更有效的催化剂中是至关重要的。系统地研究ATRA和ATRP中所涉及的物种的结构和反应性将导致对这些反应的更深入的理解。这将促进和优化两种合成方法，例如开发更有效的催化剂，并将可聚合单体的范围扩大到α-烯烃、乙酸乙烯酯和丙烯酸，这将使新材料的生产效率更高，产量和选择性更大。有机和大分子计划支持卡内基梅隆大学化学系的Krzysztof Matyjaszewski教授，具有重大的技术和经济意义。活性自由基聚合可用于生产新型先进材料，用于电子，制造和环境用途。这项研究的基础研究结果将影响包括传感器在内的许多技术的进步，这些技术对安全问题至关重要。该项目还将继续在聚合物化学和材料科学的几个技术重要领域教育和培训学生。

The Organic and Macromolecular Chemistry Program support Professor Krzysztof Matyjaszewski of the Department of Chemistry at Carnegie Mellon University for research on atom transfer radical polymerization, which is based on the use of radical polymerization to convert monomer to polymer. The purpose of the proposed research is to perform a systematic mechanistic investigation into the transition metal catalyzed atom transfer radical polymerization (ATRP) and addition (ATRA).The main goal is to determine the structure of the catalytic and intermediate species in both ATRP and ATRA, and to build a comprehensive structure-reactivity relationship for alkyl, (pseudo)halogen, transition metal, and ligand components of these reactions under different conditions. The ability of ATRP and ATRA to produce well-controlled products depends heavily on these kinetic parameters, and therefore their determination is of vital importance in the development of new and more efficient catalysts. The systematic investigation of the structures and reactivities of the species involved in ATRA and ATRP will lead to a greater depth of understanding of these reactions. This will advance and optimize both synthetic methods, such as the development of more effective catalysts, and expansion of the range of polymerizable monomers to alpha-olefins, vinyl acetate and acrylic acid, which will allow new materials to be produced more efficiently and with greater yields and selectivity.The Organic and Macromolecular Program supports Professor Krzysztof Matyjaszewski of the Department of Chemistry at Carnegie Mellon University whose research program has substantial technological and economic significance. Living radical polymerization can be used to produce new classes of advanced materials for applications in electronics, fabrication, and environmental uses. Results from the fundamental studies emerging from this research will impact advances in many technologies including sensors, which are important to security issues. This project will also continue to educate and train students in several technologically significant areas of polymer chemistry and material science.