Chain Growth Polycondensation via Substituent Effects for the Synthesis of Functional Rigid Rod Polymer Brushes

通过取代基效应进行链增长缩聚合成功能性硬棒聚合物刷

• 批准号: 2024448
• 负责人: Stephen Boyes
• 金额: $ 28.71万
• 依托单位: George Washington University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-01 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2024448&HistoricalAwards=false
• 关键词: Chain; Growth; Polycondensation; via; Substituent

The modification of surfaces with polymers is widely used in the development of new technologies or the improvement of existing technologies, ranging from sensors to smart coatings. Coating by physically adsorbing polymers on surfaces is a more versatile approach, but it suffers from the issue of leaching. Chemically attaching polymers on surfaces provides more robust and longer lasting coatings, but current synthetic techniques limit the molecular structures and architectures of polymers that can be attached. To tackle this problem, Professors Boyes and Vyas of the Colorado School of Mines are developing a new surface-initiated polymerization technique for "growing" polymers of desired architectures and properties directly from a variety of different surfaces. A potential application of this synthetic methodology is the preparation of novel membranes for the removal of salt from seawater. Access to clean drinking water is a critical problem facing many people across the globe and the removal of salt from seawater or brackish water has become an important technique for providing drinking water to regions that suffer from limited sources of fresh water. This project also provides research opportunities to graduate and undergraduate students. In addition, outreach programs to local high schools are established to educate and stimulate the next generation of scientists and engineers.In this project, the research team focuses on developing a new surface-initiated polymerization technique based on the chain growth polycondensation via substituent effects mechanism (SECGP) for preparing aromatic polymer brushes with well-defined structures and properties. The specific objectives of the project are: 1) to design and synthesize N-substituted aminobenzoate monomers with a variety of ester leaving groups, amino groups, and substituents on the aromatic ring; 2) to investigate the effects of monomer structures and polymerization conditions on reaction kinetics and properties (such as molecular weight and solubility) of the resulting aromatic polyamides; 3) to perform density functional theory (DFT) calculations to elucidate the steric and electronic effects of the monomer structures on the polymerization mechanism and kinetics; 4) to conduct surface initiated SECGP on silica substrates, investigate the effect of surface properties on the formation of aromatic polymer brushes (including block copolymer brushes), and probe the structure-property relationships of these new polymer brushes; and 5) to prepare aromatic polyamide brushes on ceramic membranes and test their performance in water desalination. A potential application is in reverse osmosis membranes, where these new brushes can overcome issues with coating instability, biofouling, and reduced flux capacity that limit current polymer membranes.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.

用聚合物对表面的修饰广泛用于开发新技术或改进现有技术，从传感器到智能涂料。通过物理吸附的聚合物在表面上涂层是一种更通用的方法，但它遭受了浸出问题的困扰。 化学连接的聚合物在表面上提供了更坚固，更持久的涂层，但是当前的合成技术限制了可以连接的聚合物的分子结构和结构。为了解决这个问题，科罗拉多州矿业学院的博伊斯教授和Vyas正在开发一种新的表面启动聚合技术，用于直接从各种不同的表面“种植”所需的建筑和特性的聚合物。 这种合成方法的潜在应用是准备新的膜从海水中去除盐。 获得清洁饮用水是全球许多人面临的关键问题，从海水或咸水中去除盐已成为为饮用水提供饮用水的重要技术，以遭受有限来源的淡水来源。 该项目还为研究生和本科生提供了研究机会。此外，还建立了向当地高中的外展计划，以教育和刺激下一代科学家和工程师。在该项目中，研究小组致力于开发一种基于链生长的链化效应机制（SECGP）基于链条生长量化（SECGP）的新型表面发射的聚合技术（SECGP），以制备具有芳香的聚合物刷，并具有良好定义的结构和物业。 该项目的具体目标是：1）设计和合成N-取代的氨基苯甲酸酯单体，并在芳环上使用各种酯离开组，氨基组和取代基； 2）研究所得芳族聚酰胺的单体结构和聚合条件对反应动力学和性能（例如分子量和溶解度）的影响； 3）执行密度功能理论（DFT）计算以阐明单体结构对聚合机理和动力学的空间和电子效应； 4）要进行表面启动二氧化硅底物的SECGP，请研究表面特性对芳族聚合物刷的形成（包括块共聚物刷）的影响，并探测这些新聚合物刷的结构 - 特性关系； 5）在陶瓷膜上制备芳族聚酰胺刷，并测试其在水脱盐中的性能。 潜在的应用是在反渗透膜上，这些新刷子可以克服涂层不稳定性，生物污染和降低通量容量的问题，从而限制了当前的聚合物膜。该奖项反映了NSF的法定任务，并被认为是通过该基金会的知识分子和宽广的影响来评估的支持，并被认为是值得的。

项目成果

New methods in polymer brush synthesis: Non-vinyl-based semiflexible and rigid-rod polymer brushes

• DOI: 10.1016/j.progpolymsci.2021.101361
• 发表时间: 2021
• 期刊: Progress in Polymer Science
• 影响因子: 27.1
• 作者: Caleb J. Reese;S. Boyes

Chain‐growth polycondensation via the substituent effect: Investigation in to the role of initiator and base on the synthesis of poly( N ‐octyl benzamide)

取代基效应链增长缩聚：聚（N-辛基苯甲酰胺）合成中引发剂和碱作用的研究

• DOI: 10.1002/pol.20200436
• 发表时间: 2020
• 期刊: Journal of Polymer Science
• 影响因子: 3.4
• 作者: Prehn, Frederick C.;Etz, Brian D.;Price, Daniel;Trainor, Amanda;Reese, Caleb J.;Vyas, Shubham;Boyes, Stephen G.
• 通讯作者: Boyes, Stephen G.

Aromatic Polyamide Brushes for High Young’s Modulus Surfaces by Surface-Initiated Chain-Growth Condensation Polymerization

• DOI: 10.1021/acs.macromol.1c02088
• 发表时间: 2022-03
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Caleb J. Reese;Yarong Qi;Dustin T. Abele;Maximillian D. Shlafstein;Rhys J. Dickhudt;Xun Guan;M. Wagner;Xitong Liu;S. Boyes

Chain‐growth polycondensation via the substituent effect: Investigation of the monomer structure on synthesis of poly(N‐octyl‐benzamide)

取代基效应的链增长缩聚：聚(N-辛基-苯甲酰胺)合成中单体结构的研究

• DOI: 10.1002/pol.20200435
• 发表时间: 2020
• 期刊: Journal of Polymer Science
• 影响因子: 3.4
• 作者: Prehn, Jr, Frederick C.;Etz, Brian D.;Reese, Caleb J.;Vyas, Shubham;Boyes, Stephen G.
• 通讯作者: Boyes, Stephen G.