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：聚电解质是包含电动化学基团的聚合物材料，并且已在许多重要技术中实施。 其中包括分离膜（例如气体或水净化），能源存储和收获设备（例如，锂离子电池，离子交换膜或有机光伏电池）以及用于生物医学应用的材料。在这些应用中使用的聚合物需要以纳米量表进行组织和组装，这通常很难预测和控制聚电解质系统。这种限制通常源于与控制多电解质合成以及文献中出现的聚合物特征的不一致有关的困难。结果，对文献进行调查排除了聚电解质行为的经验预测。该职业项目将利用模块化的合成策略来重复控制聚电解质中带电组的数量和类型，从而在聚合物特征和特定于应用特定的标准（例如纳米级组件特征和机械性能）之间实现相关性。 此外，与聚合物科学有关的教育材料将交付给本地的K-12教师，他们还将接受将基于问题的学习整合到其课程中的培训。此外，该项目将吸引本科生和研究生，并强调聚合物科学对周围公共社区的重要性和影响。技术摘要：通过对文献调查的调查来确定多电解质的经验结构 - 培训设计规则，这是由于综合平台的变化而导致的。最近的理论工作已经确定了离子熵，离子溶解度和分子范围静电相互作用是关键参数，从而在块多电解质的形态上交织在一起。因此，该项目将采用活的阴离子聚合化来制备具有可调分子量和窄分子量分布的二嵌段四环聚合物（即两个块，四个单体）前体。随后，前体将经历正交后聚合功能化功能，以在各种电荷密度下可控引入各种电荷类型（例如，磺酸盐，铵和三唑离子的组合）。这种方法使电荷类型，电荷密度和主链组成与离子溶剂化，反子熵以及静电凝聚力的实验相关性，最终与麦粒分离和流变特性相关。因此，这项工作的结果将以经验设计规则的形式展示策略，这些规则补充了最新的理论结果，以设计基于相反的熵，离子溶剂化和远距离库仑相互作用的多发材料中的远距离相互作用的特定申请性能，这反映了NSF的法定任务和审查的范围，这是通过评估的范围来进行评估的，这表明了范围的范围。

项目成果

Synthesis of PEG and Quaternary Ammonium Grafted Silicone Copolymers as Nanoemulsifiers

• DOI: 10.1021/acsapm.0c00103
• 发表时间: 2020-05-01
• 期刊: ACS APPLIED POLYMER MATERIALS
• 影响因子: 5
• 作者: Gupta, Srishti;Singh, Pummy;Green, Matthew D.
• 通讯作者: Green, Matthew D.

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
• 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

• DOI: 10.1039/d1sm01377g
• 发表时间: 2022-01-03
• 期刊: SOFT MATTER
• 影响因子: 3.4
• 作者: Hocken, Alexis;Beyer, Frederick L.;Green, Matthew D.
• 通讯作者: Green, Matthew D.