Collaborative Research: Next Generation Rigid Rod Polymers through Combined Computation and Experimentation

合作研究：通过计算和实验相结合的下一代刚性棒聚合物

• 批准号: 1949318
• 负责人: Emily Pentzer
• 金额: $ 21.6万
• 依托单位: Texas A&M Engineering Experiment Station
• 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: 2019-08-15 至 2021-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1949318&HistoricalAwards=false
• 关键词: Collaborative; Research; Next; Generation; Rigid

Polymers impact nearly every part of daily life - from the bristles on a toothbrush to the packaging that protects food. The chemical composition of a polymer dictates its properties including strength, flexibility, recyclability, etc., which define applications. In this research project, Prof. Pentzer at Case Western Reserve University and Prof. Lambrecht at University of Pittsburgh explore the use of ketenes, a class of under-utilized monomers, for preparing novel polymers with high mechanical strength, and yet high solubility for facile processing. Computational prediction is integrated with synthesis and characterization to enable cost- and time-efficient discovery of such new polymers. This multidisciplinary project provides research training to undergraduate and graduate students, preparing the future generation of skilled workforce in science and engineering fields. The research team studies the chain growth polymerization of silyl ketenes, (R3Si(H)C=C=O), which form solution processable polymers with variable backbone and side groups that behave as rigid rod polymers (RRPs). Since silyl ketenes can yield three different polymer backbone chemistries as well as mixtures thereof, the challenge addressed in this work is formation of materials with specific structure and rigidity. The Lambrecht group develops computational approaches for predicting the contributions of "synthons" on reaction energetics and polymer properties from first principles; computational prediction informs synthesis performed in Pentzer's laboratory by proposing rational modifications, including solvent polarity and counterion choice. The Pentzer group evaluates the impact of experimental conditions on polymerization, synthesizes and characterizes new polymers, and closes the feedback loop by generating empirical data to validate and refine computational approaches of Lambrecht. The research activities include 1) identifying the fundamental reactivity patterns of silyl ketenes as relevant to chain growth polymerization, 2) controlling the formation of well-defined oligomers, and 3) preparing each of the new polymer chemistries individually and establishing their properties and applications. Further, Pentzer and Lambrecht offer annually a two-day workshop on how to successfully combine research in computation and experiment.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.

聚合物几乎影响到日常生活的每一个部分-从牙刷上的刷毛到保护食品的包装。 聚合物的化学组成决定了其性能，包括强度、柔韧性、可回收性等，定义应用程序。 在这个研究项目中，凯斯西储大学的Pentzer教授和匹兹堡大学的Lambrecht教授探索了烯酮的用途，这是一类未被充分利用的单体，用于制备具有高机械强度的新型聚合物，并且具有易于加工的高溶解度。 计算预测与合成和表征相结合，以实现成本和时间效率高的新聚合物的发现。 这个多学科项目为本科生和研究生提供研究培训，为科学和工程领域的未来一代熟练劳动力做好准备。该研究小组研究了甲硅烷基烯酮（R3 Si（H）C=C=O）的链增长聚合，该聚合物形成具有可变主链和侧基的可溶液加工聚合物，其表现为刚性棒聚合物（RRP）。由于甲硅烷基烯酮可以产生三种不同的聚合物主链化学以及它们的混合物，因此在这项工作中解决的挑战是形成具有特定结构和刚性的材料。Lambrecht小组开发了计算方法，用于从第一性原理预测“质子”对反应能量学和聚合物性质的贡献;计算预测通过提出合理的修改，包括溶剂极性和反式选择，通知在Pentzer实验室进行的合成。 Pentzer小组评估实验条件对聚合的影响，合成和表征新聚合物，并通过生成经验数据来验证和改进Lambrecht的计算方法来关闭反馈回路。研究活动包括1）确定与链增长聚合相关的甲硅烷基乙烯酮的基本反应模式，2）控制明确定义的低聚物的形成，以及3）单独制备每种新聚合物化学物质并确定其性质和应用。此外，Pentzer和Lambrecht每年提供一个为期两天的研讨会，讨论如何成功地将联合收割机研究与计算和实验结合起来。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智力价值和更广泛的影响审查标准进行评估来支持。

项目成果

Lewis Acid-Activated Reactions of Silyl Ketenes for the Preparation of α-Silyl Carbonyl Compounds

路易斯酸活化硅烷烯酮反应制备α-硅烷基羰基化合物

• DOI: 10.1021/acs.joc.9b01859
• 发表时间: 2019
• 期刊: The Journal of Organic Chemistry
• 作者: Mitchell, Sarah M.;Xiang, Yuanhui;Matthews, Rachael;Amburgey, Alexis M.;Pentzer, Emily B.
• 通讯作者: Pentzer, Emily B.

Polymerization of Cumulated Bonds: Isocyanates, Allenes, and Ketenes as Monomers

• DOI: 10.1021/acsmacrolett.0c00396
• 发表时间: 2020-07-21
• 期刊: ACS MACRO LETTERS
• 影响因子: 7.015
• 作者: Mitchell, Sarah M.;Sachinthani, K. A. Niradha;Pentzer, Emily B.
• 通讯作者: Pentzer, Emily B.