Enhancing Efficiency of Atom Transfer Radical Polymerization

聚合物广泛应用于家用电器、家具、汽车零部件、电子产品、医疗器械和制药等产品。原子转移自由基聚合(ATRP)是合成规整聚合物的重要方法。ATRP已经被世界各地的几家公司用于商业用途，因此，提高聚合过程的效率并将其对环境的影响降至最低是至关重要的。化学系的大分子、超分子和纳米化学项目支持卡内基-梅隆大学(CMU)的Matyjaszewski教授的研究，以加深我们对ATRP催化剂结构和活性之间关系的基本了解。这项研究的结果可能会导致更有效的催化剂和在良性介质(如水)中的新型催化剂，并影响由ATRP制造的明确定义的聚合物的商业生产。所产生的信息通过及时的出版物、在(国际)国家会议上和在债务工具中央理事会的网站上传播。所获得的知识也通过受控自由基聚合(CRP)联盟与业界共享。此外，该项目为本科生和研究生提供教育和研究培训机会，为他们在学术界或聚合物行业的职业生涯做好准备。拟议的研究活动包括设计、合成和评价新型高活性、选择性和稳定性的铜(铜)和铁(铁)基ATRP催化剂。该项目包括计算建模、动力学和力学研究，以及聚合物的合成和表征。研究了水介质中铜(0)和铜(I)的还原(同比例/歧化)和活化过程的机理。新型催化剂在良性介质中的活性和效率的提高，可以通过获得具有更好控制结构的复杂(共)聚合物来影响聚合物科学的各个领域。新的活性铁基催化剂应该比铜基体系更便宜，毒性更低，还有可能扩大可聚合单体的范围，并为合成用于高级应用的定义明确的聚合物开辟新的途径。

Polymers are used in a wide range of products including household appliances, furniture, automotive components, electronics, medical devices, and pharmaceuticals. Atom transfer radical polymerization (ATRP) is an important method for synthesis of well-defined polymers. ATRP is already commercially used by several companies world-wide and therefore, it is critically important to enhance efficiency of the polymerization process and minimize its environmental impact. The Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division supports research of Prof. Matyjaszewski of Carnegie-Mellon University (CMU) to increase our fundamental understanding of the correlation between structure and activities of ATRP catalysts. The results of this research could lead to more efficient catalysts and new catalysts in benign media, such as water, and affect commercial production of well-defined polymers made by ATRP. The generated information is disseminated via timely publications, at (inter)national meetings, and at CMU web-site. The knowledge gained is also shared with industry through the Controlled Radical Polymerization (CRP) Consortium. In addition, this project provides education and research training opportunities to undergraduate and graduate students, preparing them for careers in academia or polymer industry. The proposed research activities include design, synthesis and evaluation of new highly active, selective and stable copper(Cu)- and iron(Fe)-based ATRP catalysts. The project encompasses computational modeling, kinetic and mechanistic studies, and polymer synthesis and characterization. The mechanism of reduction (comproportionation/disproportionation) and activation processes by Cu(0) and Cu(I)in aqueous media are investigated. Improved livingness and efficiency of new catalyst in benign media can impact various areas of polymer science by giving access to complex (co)polymers with better controlled architecture. New active iron-based catalysts should be less expensive and less toxic than copper-based systems, and potentially can also expand range of polymerizable monomers and open new avenues for synthesis of well-defined polymers for advanced applications.