Controlled Interphases by ATRP: Polymeric Brushes and Functional Networks

ATRP 控制的相间：聚合物刷和功能网络

• 批准号: 2202747
• 负责人: Krzysztof Matyjaszewski
• 金额: $ 100万
• 依托单位: Carnegie-Mellon University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-06-01 至 2027-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2202747&HistoricalAwards=false
• 关键词: Controlled; Interphases; ATRP; Polymeric; Brushes

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.

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与原子转移自由基聚合（ATRP）合成的明确聚合物之间的受控界面。所述基底包括液态金属，例如低共熔镓-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，以及溶胀的纳米凝胶、大凝胶和囊泡的表面。将使用两种主要的ATRP技术，嫁接和嫁接。由于可用材料的量非常少，因此界面的精确控制具有挑战性。然而，界面限定了与亚微米层的稳定性、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）相容性、摩擦和影响宏观性能的其他性质相关的许多至关重要的性质。在这个项目中制备的材料应该有几个有趣的应用取决于基板。液态金属功能化系统可以找到潜在的用途，以提高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。高功能性树脂颗粒将被用作固相聚合物合成和生物缀合物合成的新型可回收载体。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教授将培训博士后研究员，研究生和本科生在聚合物合成和聚合物界面与潜在的应用在能量存储，软机器人和生物共轭。他还将通过教学网页和视频提供有关准备和受控间期重要性的公众教育。在材料研究部门的支持下，Matyjaszewski教授和他的团队将探索液体或固体基质表面与ATRP合成的定义明确的聚合物之间的受控界面的制备。他将研究功能化聚合物链或ATRP（宏观）引发剂随后聚合物生长的基底表面上的精确锚定效果，以及它们对界面性质的影响。他将使用在低聚（环氧乙烷）链和聚合物主链之间具有醚连接基的聚丙烯酸酯，其比具有通过酯部分连接的低聚（环氧乙烷）链的众所周知的同分异构聚甲基丙烯酸酯水解稳定得多。这将提供聚合物和相关网络的增强的稳定性以及向聚合物主链引入其它官能团的额外可能性，所述其它官能团例如酸、酰胺、酰肼、醇和用于特定应用的若干其它部分。Matyjaszewski教授还将介绍聚合物接枝的支化和人工固体电解质界面的交联，以抑制锂枝晶的生长并提高锂金属电池的性能。ATRP的接枝自和接枝到将被应用于可溶胀的凝胶和液体金属。因此，他将使用ATRP从低共熔镓铟合金的液滴、溶胀的纳米颗粒和大颗粒以及囊泡中接枝不同结构（线性、支化和交联）的聚合物链。高功能性树脂颗粒将被用作固相聚合物合成的新型可回收载体，以及在专门的生物缀合物合成中作为易于去除的牺牲引发剂。因此，在固体和液体基质的界面处精确控制聚合物将为软机器人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NSF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。

项目成果

Kinetic comparison of isomeric oligo(ethylene oxide) (meth)acrylates: Aqueous polymerization of oligo(ethylene oxide) methyl ether methacrylate and methyl 2‐(oligo(ethylene oxide) methyl ether)acrylate macromonomers

• DOI: 10.1002/pol.20220086
• 发表时间: 2022-04
• 期刊: Journal of Polymer Science
• 影响因子: 3.4
• 作者: Michael R. Martinez;Sylwia Dworakowska;Adam Gorczyński;Grzegorz Szczepaniak;Ferdinando de Luca Bossa;K. Matyjaszewski

Controlling Size and Surface Chemistry of Cationic Nanogels by Inverse Microemulsion ATRP

通过反相微乳液 ATRP 控制阳离子纳米凝胶的尺寸和表面化学

• DOI: 10.1002/macp.202200210
• 发表时间: 2022
• 期刊: Macromolecular Chemistry and Physics
• 影响因子: 2.5
• 作者: Simakova, Antonina;Averick, Saadyah;Jazani, Arman Moini;Matyjaszewski, Krzysztof
• 通讯作者: Matyjaszewski, Krzysztof

Alternating Methyl Methacrylate/ n -Butyl Acrylate Copolymer Prepared by Atom Transfer Radical Polymerization

原子转移自由基聚合制备甲基丙烯酸甲酯/丙烯酸正丁酯交替共聚物

• DOI: 10.1021/acsmacrolett.2c00517
• 发表时间: 2022
• 期刊: ACS Macro Letters
• 影响因子: 7.015
• 作者: Yin, Rongguan;Zhao, Yuqi;Gorczyński, Adam;Szczepaniak, Grzegorz;Sun, Mingkang;Fu, Liye;Kim, Khidong;Wu, Hanshu;Bockstaller, Michael R.;Matyjaszewski, Krzysztof
• 通讯作者: Matyjaszewski, Krzysztof

Depolymerization of Polymethacrylates by Iron ATRP

• DOI: 10.1021/acs.macromol.2c01712
• 发表时间: 2022-11-28
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Martinez, Michael R.;Schild, Dirk;Matyjaszewski, Krzysztof
• 通讯作者: Matyjaszewski, Krzysztof

Miniemulsion SI-ATRP by Interfacial and Ion-Pair Catalysis for the Synthesis of Nanoparticle Brushes

界面和离子对催化细乳液 SI-ATRP 合成纳米颗粒刷

• DOI: 10.1021/acs.macromol.2c01114
• 发表时间: 2022
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Yin, Rongguan;Chmielarz, Paweł;Zaborniak, Izabela;Zhao, Yuqi;Szczepaniak, Grzegorz;Wang, Zongyu;Liu, Tong;Wang, Yi;Sun, Mingkang;Wu, Hanshu
• 通讯作者: Wu, Hanshu