CAREER: Using electrostatic interactions to guide microstructure and mechanical properties in block polyelectrolytes

职业：利用静电相互作用指导嵌段聚电解质的微观结构和机械性能

• 批准号: 1848454
• 负责人: Matthew Green
• 金额: $ 51.91万
• 依托单位: Arizona State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-06-01 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1848454&HistoricalAwards=false
• 关键词: CAREER; Using; electrostatic; interactions; guide

NON-TECHNICAL SUMMARY: Polyelectrolytes are polymeric materials containing electrically charged chemical groups and have been implemented in a number of important technologies. These include separations membranes (e.g., gas or water purification), energy storage and harvesting devices (e.g., Li-ion batteries, ion exchange membranes, or organic photovoltaics), and materials for biomedical applications. The polymers utilized in these applications require organization and assembly at the nanometer scale, which is often difficult to predict and control in polyelectrolyte systems. This limitation often stems from difficulties related to controlling polyelectrolyte synthesis as well as inconsistencies in polymer characteristics that appear in the literature. As a consequence, surveying the literature precludes an empirical prediction of polyelectrolyte behavior. This CAREER project will utilize a modular synthetic strategy to reproducibly control the amount and type of charged groups within the polyelectrolyte, thus enabling correlations between polymer characteristics and application-specific criteria, such as nanoscale assembly features and mechanical properties. Additionally, educational materials related to polymer science will be delivered to local K-12 teachers, who will also be trained in integrating problem-based learning into their curricula. Furthermore, this project will engage undergraduate and graduate students, and highlight the importance and impact of polymer science to the surrounding public community.TECHNICAL SUMMARY:Establishing empirical structure-property design rules for polyelectrolytes through a survey of the literature is impractical due to the variations in synthetic platforms, molecular weight distributions, and absolute molecular weights reported. Recent theoretical work has identified ion entropy, ion solubility, and molecular-range electrostatic interactions as key parameters that synergistically influence the morphology of block polyelectrolytes. Therefore, this project will employ living anionic polymerization to prepare a diblock tetrapolymer (i.e., two blocks, four monomers) precursor with tunable molecular weight and narrow molecular weight distributions. Subsequently, the precursor will undergo orthogonal post-polymerization functionalization to controllably introduce various charge types (e.g., combinations of sulfonate, ammonium, and triazolium ions) at various charge densities. This approach enables experimental correlation of charge type, charge density, and backbone composition to ion solvation, counterion entropy, and electrostatic cohesion and ultimately to microphase separation and rheological properties. Thus, the outcome of this work will demonstrate strategies, in the form of empirical design rules that complement recent theoretical outcomes, to design application-specific performance based on counterion entropy, ion solvation, and long-range Coulombic interactions in polyelectrolyte materials.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：聚电解质是含有带电化学基团的聚合材料，并已在许多重要技术中得到应用。 其中包括分离膜（例如气体或水净化）、能量存储和收集装置（例如锂离子电池、离子交换膜或有机光伏）以及生物医学应用材料。这些应用中使用的聚合物需要纳米级的组织和组装，这在聚电解质系统中通常难以预测和控制。这种限制通常源于与控制聚电解质合成相关的困难以及文献中出现的聚合物特性的不一致。因此，查阅文献排除了对聚电解质行为的实证预测。该CAREER项目将利用模块化合成策略来可重复地控制聚电解质内带电基团的数量和类型，从而实现聚合物特性和特定应用标准（例如纳米级组装特征和机械性能）之间的相关性。 此外，与聚合物科学相关的教育材料将交付给当地 K-12 教师，他们还将接受将基于问题的学习融入课程的培训。此外，该项目将吸引本科生和研究生，并强调高分子科学对周围公共社区的重要性和影响。技术摘要：由于存在差异，通过文献调查建立聚电解质的经验结构-性能设计规则是不切实际的报告了合成平台、分子量分布和绝对分子量。最近的理论工作已确定离子熵、离子溶解度和分子范围静电相互作用是协同影响嵌段聚电解质形态的关键参数。因此，本项目将采用活性阴离子聚合来制备具有可调分子量和窄分子量分布的二嵌段四聚物（即两个嵌段、四个单体）前驱体。随后，前体将进行正交后聚合官能化，以各种电荷密度可控地引入各种电荷类型（例如磺酸根、铵和三唑鎓离子的组合）。这种方法能够实现电荷类型、电荷密度和主链组成与离子溶剂化、反离子熵和静电内聚力以及最终与微相分离和流变特性的实验关联。因此，这项工作的成果将以补充最新理论成果的经验设计规则的形式展示策略，以设计基于反离子熵、离子溶剂化和聚电解质材料中的长程库仑相互作用的特定应用性能。反映了 NSF 的法定使命，并通过使用基金会的智力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

Thermodynamics and Structure–Property Relationships of Charged Block Polymers

带电嵌段聚合物的热力学和结构-性能关系

• DOI: 10.1002/macp.202200036
• 发表时间: 2022-05
• 期刊: Macromolecular Chemistry and Physics
• 影响因子: 2.5
• 作者: Grim, Bradley J.;Green, Matthew D.
• 通讯作者: Green, Matthew D.

Covalently integrated silica nanoparticles in poly(ethylene glycol)-based acrylate resins: thermomechanical, swelling, and morphological behavior

聚乙二醇丙烯酸酯树脂中的共价结合二氧化硅纳米颗粒：热机械、膨胀和形态行为

• DOI: 10.1039/d1sm01377g
• 发表时间: 2022-02
• 期刊: Soft Matter
• 影响因子: 3.4
• 作者: Hocken, Alexis;Beyer, Frederick L.;Lee, Jae Sang;Grim, Bradley J.;Mithaiwala, Husain;Green, Matthew D.
• 通讯作者: Green, Matthew D.

Synthesis of PEG and Quaternary Ammonium Grafted Silicone Copolymers as Nanoemulsifiers

聚乙二醇和季铵接枝有机硅共聚物纳米乳化剂的合成

• DOI: 10.1021/acsapm.0c00103
• 发表时间: 2020-04-08
• 期刊: IETE Journal of Research
• 影响因子: 1.5
• 作者: Srishti Gupta;Pummy Singh;Babak Moghadas;Bradley J. Grim;V. Kodibagkar;M. Green
• 通讯作者: M. Green