Controlled Interphases by ATRP: Polymeric Brushes and Functional Networks

非技术概述：材料研究部支持卡内基梅隆大学的Krzysztof Matyjaszewski教授制备和研究液体或固体基底表面与原子转移自由基聚合（ATRP）合成的定义良好的聚合物之间的受控界面。衬底包括液态金属，如共晶镓铟合金（EGaIn），锂金属电池中的人工固体电解质界面和固体聚合物电解质，以及膨胀的纳米凝胶、大凝胶和囊泡表面。两种主要的ATRP技术将被使用，嫁接-从和嫁接-到。由于可用材料非常少，因此对界面的精确控制具有挑战性。然而，界面定义了许多至关重要的性质，这些性质与亚微米层的稳定性、与相邻相的相互作用、纳米颗粒的分散性、传输现象、（生物）相容性、摩擦和其他影响宏观性能的性质有关。根据基材的不同，本项目中准备的材料应该有几个有趣的应用。液态金属功能化系统可以找到潜在的用途，以增强用于软机器人的材料的性能，并作为锂金属电池的固体电解质。高功能树脂颗粒将作为新型的可回收载体用于固相聚合物的合成和生物偶联物的合成。除了这些科学活动外，这项工作还通过教育和外联产生更广泛的影响。在这个项目中，Matyjaszewski教授将在聚合物合成和聚合物界面相方面培训博士后、研究生和本科生，这些聚合物界面相在储能、软机器人和生物偶联方面有潜在的应用。他还将通过教学网页和视频向公众提供有关受控界面的准备和重要性的教育。技术总结：在材料研究部的支持下，Matyjaszewski教授和他的团队将探索通过ATRP合成的液体或固体底物表面和定义良好的聚合物之间的受控界面的制备。他将研究在聚合物生长之后，在功能化聚合物链或ATRP（宏观）引发剂的基底表面进行精确锚定的效果，以及它们对界面相性质的影响。他将使用在低聚（环氧乙烷）链和聚合物主链之间有醚连接的聚丙烯酸酯，它比众所周知的低聚（环氧乙烷）链由酯段连接的异构聚甲基丙烯酸酯水解稳定得多。这将提高聚合物和相关网络的稳定性，并为在聚合物骨架中引入其他官能团（如酸、酰胺、肼、醇和其他一些特定应用的部分）提供额外的可能性。Matyjaszewski教授还将介绍聚合物接枝的分支和人造固体电解质界面的交联，以抑制锂枝晶的生长，提高锂金属电池的性能。ATRP的接枝和接枝将应用于可膨胀凝胶和液态金属。因此，他将使用ATRP从共晶镓铟合金的液滴、膨胀的纳米和宏观颗粒以及囊泡中接枝不同结构的聚合物链（线性、支链和交联）。高功能树脂颗粒将作为新型的可回收载体用于固相聚合物的合成，并作为易于移动的牺牲引发剂用于特殊生物偶联物的合成。因此，对固体和液体基质界面聚合物的精确控制将为软机器人技术和能源或生物相关应用提供有吸引力的材料。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

NON-TECHNICAL SUMMARY:The Division of Materials Research supports Professor Krzysztof Matyjaszewski at Carnegie Mellon University to prepare and study controlled interphases between the surface of liquid or solid substrates and well-defined polymers synthesized by atom transfer radical polymerization (ATRP). The substrates include liquid metals such as eutectic gallium-indium alloy (EGaIn), artificial solid electrolyte interphases and solid polymer electrolytes in lithium metal batteries, as well as surfaces of swollen nanogels, macrogels, and vesicles. Two main ATRP techniques will be used, grafting-from and grafting-onto. Precise control of interphases is challenging due to a very small amount of available materials. However, the interphases define many critically important properties related to stability of the sub-micrometer layer, interactions with both neighboring phases, dispersability of nanoparticles, transport phenomena, (bio)compatibility, friction and other properties affecting macroscopic performance. Materials prepared in this project should have several interesting applications depending on the substrates. Liquid metal functionalized systems could find potential uses to enhance properties of materials used for soft robotics and as solid electrolytes for lithium metal batteries. Highly functional resin particles will be used as novel recyclable supports for solid phase polymer synthesis and also in synthesis of bioconjugates. In addition to these scientific activities, this work has broader impacts through education and outreach. In this project, Professor Matyjaszewski will train postdoctoral fellows, graduate, and undergraduate students in polymer synthesis and polymer interphases with potential applications in energy storage, soft robotics, and bioconjugations. He will also provide public education about preparation and importance of controlled interphases via instructional webpages and videos. TECHNICAL SUMMARY:With support from the Division of Materials Research, Professor Matyjaszewski and his team will explore preparation of controlled interphases between the surface of liquid or solid substrates and well-defined polymers synthesized by ATRP. He will investigate the effect of precise anchoring on the substrate surface of either functionalized polymer chains or ATRP (macro)initiators followed by polymer growth, as well as their influence on the properties of interphases. He will use polyacrylates with ether linkers between oligo(ethylene oxide) chain and polymer backbone, which are much more hydrolytically stable than well-known isomeric polymethacrylate with oligo(ethylene oxide) chains linked by ester moiety. This will provide enhanced stability of polymers and related networks and an additional possibility of introducing to the polymer backbones other functional groups, such as acids, amides, hydrazides, alcohols and several other moieties for specific applications. Professor Matyjaszewski will also introduce branching to polymeric grafts and crosslinking to artificial solid electrolyte interphases to suppress growth of lithium dendrites and enhance performance of lithium metal batteries. The grafting-from and grafting-onto by ATRP will be applied to swellable gels and liquid metals. Thus, he will use ATRP to graft polymer chains of different architecture (linear, branched and crosslinked) from liquid droplets of eutectic gallium-indium alloys, swollen nano- and macroparticles, and vesicles. Highly functional resin particles will be used as novel recyclable supports for solid phase polymer synthesis and as easily removable sacrificial initiators in synthesis of specialized bioconjugates. Therefore, the precise control of polymers at interphases at solid and liquid substrates will provide attractive materials for soft robotics and for energy- or bio-related applications. .This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.