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.

非技术性总结：聚电解质是含有带电化学基团的聚合物材料，并且已经在许多重要技术中实施。 这些包括分离膜（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致发光材料）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在纳米尺度上组织和组装，这通常难以在纳米系统中预测和控制。这种限制通常源于与控制聚合物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，调查文献排除了经验预测的行为。该CAREER项目将利用模块化合成策略来可重复地控制聚合物内带电基团的数量和类型，从而实现聚合物特性与特定应用标准（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提供给当地K-12教师，他们还将接受将基于问题的学习纳入课程的培训。此外，该项目将吸引本科生和研究生，并强调聚合物科学的重要性和影响周围的公众community.Technical摘要：通过文献调查建立经验的聚电解质的结构性能设计规则是不切实际的，由于在合成平台，分子量分布，和绝对分子量的变化报告。最近的理论工作已经确定了离子熵，离子溶解度，和分子范围的静电相互作用的关键参数，协同影响的形态嵌段聚电解质。因此，本项目将采用活性阴离子聚合制备二嵌段四聚物（即，两个嵌段，四个单体）前体，其具有可调的分子量和窄的分子量分布。随后，前体将经历正交后聚合官能化以可控地引入各种电荷类型（例如，磺酸盐、铵和三唑鎓离子的组合）。这种方法使实验相关的电荷类型，电荷密度，和骨干组成的离子溶剂化，反熵，静电凝聚力，并最终微相分离和流变性能。因此，这项工作的结果将展示策略，以经验设计规则的形式补充最近的理论成果，以设计基于反熵，离子溶剂化，和长-该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的知识价值和更广泛的影响审查进行评估来支持的搜索.

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.