Controlled Interphases by ATRP: Polymeric Brushes and Functional Networks

非技术摘要：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质表面和通过原子转移自由基聚合(ATRP)合成的明确定义的聚合物之间的受控中间相。衬底包括液态金属，如共晶镓铟合金(Egain)、人造固体电解质中间相和锂金属电池中的固体聚合物电解质，以及膨胀的纳米凝胶、宏凝胶和囊泡的表面。将使用两种主要的ATRP技术，嫁接自和嫁接到上面。由于可用的材料非常少，对InterPhase的精确控制是具有挑战性的。然而，中间相定义了许多关键的性质，涉及亚微米层的稳定性、与两个相邻相的相互作用、纳米颗粒的分散性、传输现象、(生物)兼容性、摩擦和其他影响宏观性能的性质。根据基材的不同，在这个项目中制备的材料应该有几个有趣的应用。液态金属功能化系统可能会发现潜在的用途，以增强用于软机器人的材料的性能，并用作锂金属电池的固体电解液。高性能的树脂颗粒将作为新型的可回收载体用于固相聚合物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宣传产生了更广泛的影响。在这个项目中，Matyjaszewski教授将培训博士后研究员、研究生和本科生了解聚合物合成和聚合物中间相在能量储存、软机器人和生物结合方面的潜在应用。他还将通过教学网页和视频提供关于受控InterPhase的准备和重要性的公众教育。技术摘要：在材料研究部的支持下，Matyjaszewski教授和他的团队将探索在液体或固体基质表面和通过ATRP合成的明确定义的聚合物之间制备受控中间相。他将研究在聚合物生长之前，在功能化高分子链或ATRP(宏观)引发剂的衬底表面上精确锚定的效果，以及它们对中间相性能的影响。他将使用在低聚(环氧乙烷)链和聚合物主链之间带有乙醚连接物的聚丙烯酸酯，这种聚丙烯酸酯比众所周知的具有通过酯部分连接的低聚(环氧乙烷)链的异构体聚甲基丙烯酸甲酯更稳定。这将增强聚合物和相关网络的稳定性，并增加向聚合物主链引入其他官能团的可能性，例如酸、酰胺、肼、醇和其他几个用于特定应用的部分。Matyjaszewski教授还将介绍支化到聚合物接枝和交联化到人造固体电解质中间相，以抑制锂树枝晶的生长和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、膨胀的纳米和宏观粒子以及囊泡中嫁接不同结构的聚合物链(线性的、支化的和交联的)。高性能的树脂颗粒将作为新型的可回收载体用于固相聚合物合成，以及作为易于移除的牺牲性引发剂用于合成特殊生物偶联物。因此，在固体和液体衬底上精确控制中间相聚合物将为软机器人以及与能源或生物相关的应用提供有吸引力的材料。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势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.