CAREER: Advanced Molecular Architectures for Electronically-Active Radical Polymers

非技术总结新电子材料的开发对从国防应用到个人电子设备到生物医学监测和药物输送的许多技术领域至关重要。该项目将开发轻质、灵活、可拉伸的新型塑料电子材料。特别是，它将确定如何将这种聚合物用于下一代柔性电子设备。除了具有坚固的机械性能外，这些塑料还可以按照与喷墨打印等低成本生产技术一致的方式进行沉积。此外，这些努力将把新合成材料的机械性能与塑料材料的电子性能联系起来。为了实现这一目标，该项目将能够建立基本的设计原则，允许在一些能量转换、能量存储和生物医学设备中实施新型塑料导体，这将有助于国家和个人消费者。此外，这一努力将支持基础和应用聚合物科学领域的研究生、本科生和高中生的培训。特别是，将实施一项高中研究计划，以吸引更多来自经济困难家庭的学生进入聚合物科学领域，从而增加即将到来的科学家和工程师群体的多样性。此外，由于开发了一门专注于聚合物合成和应用的大型开放式在线课程(MOOC)，普通公众将有机会接触到这些相同类型的聚合物科学课程。通过这种方式，本文提出的努力将对聚合物科学、聚合物工程和教育产生重大影响，从而在短期和长期内促进新型塑料电子材料的发展。技术和电子活性大分子因其在许多先进的能量转换和储能模块中的应用而受到密切研究。到目前为止，关于这些聚合物材料和基于聚合物的器件的大部分工作都集中在沿着其大分子骨架含有相当高共轭程度的闭壳聚合物上。然而，最近，一类新的氧化还原活性(氧化还原活性)的非共轭有机实体被称为自由基聚合物(即由非共轭主链组成的大分子和带有稳定自由基位的侧基)，由于其在电解质支持和固态有机电子器件应用中的相对较高的性能而引起了人们的极大关注。然而，越来越明显的是，如果没有关于开壳大分子的聚合物化学和聚合物物理的基础性进展，尽管自由基聚合物相对于共轭聚合物体系具有潜在的优势，但自由基聚合物体系的真正潜力是不可能建立的。这项工作将通过将聚合物合成与基础聚合物物理测量和这些设计的大分子的电学表征相结合来解决这些问题。特别是，PI和他的团队将：(1)合成一套包含精选骨架、立体规则和开壳结构的目标大分子；(2)评估这些新合成材料的结构、热和流动性质；(3)将新型自由基聚合物的电子性质与它们的化学、热和结构性质相关联；以及(4)改进大分子的设计，以阐明它们的基本结构-性质-性能关系。通过这种方式，这一努力将提供设计原则，使自由基聚合物能够转化为商业相关的商品材料。反过来，这也将使开壳大分子在不断增长的有机电子工业中发挥更大的作用。

NON-TECHNICAL SUMMARYThe development of new electronic materials is critical to a number of technological fields that range from defense applications to personal electronic devices to biomedical monitoring and drug delivery. This project will develop new kinds of plastic electronic materials that are lightweight, flexible, and stretchable in nature. In particular, it will establish how such polymers can be used in next-generation flexible electronic devices. In addition to having robust mechanical properties these plastics also can be deposited in a manner that is consistent with low-cost production techniques like inkjet printing. Furthermore, these efforts will correlate the mechanical properties of the newly-synthesized materials with electronic properties of plastic materials. In achieving this goal, the project will be able to establish the fundamental design principles that will allow for a new class of plastic conductors to be implemented in a number of energy conversion, energy storage, and biomedical devices, which will aid the nation and individual consumers. Additionally, this effort will support the training of graduate, undergraduate, and high school students in the realm of fundamental and applied polymer science. In particular, a high school research program will be implemented in order to attract a larger number of students from economically-disadvantaged families to the polymer science field so as to increase the diversity of the upcoming population of scientists and engineers. Also, the general public will have access to these same types of polymer science lessons due to the development of a massive open online course (MOOC) that will be focused on polymer synthesis and application. In this way, the effort presented here will offer significant fundamental polymer science, polymer engineering, and educational impacts that will allow for the advancement of new plastic electronic materials in both the near and long terms.TECHNICAL SUMMARYElectronically-active macromolecules have been of intense investigation for their application in a number of advanced energy conversion and energy storage modules. To date, the majority of the effort regarding these polymeric materials and polymer-based devices has focused on closed-shell polymers containing a rather high degree of conjugation along their macromolecular backbones. Recently, however, a new class of oxidation-reduction-active (redox-active), non-conjugated organic entities known as radical polymers (i.e., macromolecules comprised of non-conjugated backbones and with pendant groups bearing stable radical sites) have attracted a great deal of attention for their relatively high performance in electrolyte-supported and solid-state organic electronic device applications. However, it is becoming apparent that, without fundamental advances regarding the polymer chemistry and polymer physics of open-shell macromolecules, the true potential of radical polymer systems will not be established despite the potential advantages that radical polymers could have relative to conjugated polymer systems. This effort will address these issues through the coupling of polymer synthesis with fundamental polymer physics measurements and the electrical characterization of these designer macromolecules. In particular, the PI and his group will: (1) synthesize a suite of targeted macromolecules containing select backbones, stereoregularities, and open-shell architectures; (2) evaluate the structural, thermal, and flow properties of these newly-synthesized materials; (3) correlate the electronic properties of the novel radical polymers to their chemical, thermal, and structural properties; and (4) refine the design of the macromolecules in order to elucidate their fundamental structure-property-performance relationships. In this way, this effort will provide the design principles that should allow for the radical polymers to be translated into commercially-relevant, commodity materials. This, in turn, also will allow open-shell macromolecules to play a larger part in the growing organic electronics industry.