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RUI: Creation and Application of Nucleophile-Induced retro Diels-Alder LinKages in Dynamic-Covalent Polymeric Systems

RUI：亲核试剂诱导的逆狄尔斯-阿尔德连接在动态共价聚合物体系中的创建和应用

基本信息

批准号：
2003459
负责人：
Philip Costanzo
金额：
$ 29.75万
依托单位：
California Polytechnic State University Foundation
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2020
资助国家：
美国
起止时间：
2020-09-01 至 2024-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2003459&HistoricalAwards=false
关键词：
RUI Creation Application Nucleophile Induced

项目摘要

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professors Philip Costanzo and Daniel Bercovici of the Department of Chemistry at the California Polytechnic State University, San Luis Obispo, are developing synthetic approaches to prepare novel polymers that are responsive to externally applied temperatures. Synthetic polymers are commonly referred to as plastics and are widely used in our daily lives. Polymers are long chain macromolecules consisting of many repeating chemical units linked with carbon-carbon bonds. Their properties are controlled by their chemical structures which can be tailored for different applications. In this research, a number of chemically-distinct small molecules that trigger temperature response are first prepared and their physical properties investigated. These molecules are then incorporated into polymer chains at precise locations. This efficient strategy allows the design of polymer strands with chemical structures that can be pulled apart at one temperature and snapped back together at a different temperature. The chemistry associated with this award is broadly transferrable to many other polymerization systems and useful to materials chemistry and any other fields in which thermally-responsive plastics are of interest. This research is having a broader impact by providing unique opportunities for undergraduate students to receive cutting edge research training and education in organic and polymer chemistry. Apart from incorporating the results associated with this award into chemistry laboratory courses at the university, an outreach program called the Macromolecular Alliance of Community, Resources and Outreach (MACRO) is initiated. The goal of this program is to create a depository of outreach materials through which individuals can spread their passion and knowledge of science to the general population. This work is focused on the development of dynamic-covalent linkages that can be incorporated into polymer systems to enable switchability in polymer topology and bestow thermal responsive properties. Several studies are carried out in order to achieve this goal. The first objective focuses on the development of Diels-Alder linkage systems with novel dienes and dienophiles and systematic understanding of the thermal stability of the prepared adducts. In the second objective, the unsaturated adducts are undergoing 1,4-Michael addition which favors the retro-Diels-Alder cleavage followed by incorporation within polymeric structures using copper catalyzed atom transfer radical polymerization. The last aim explores dynamic covalent chemistry effects on the polymer topology and physical properties with special emphasis on responsive polymer surfactants. Using nucleophiles such as thiols to modulate bond-cleaving temperature is applicable to a variety of other polymerization techniques and has the potential to generate a wide range of new smart soft materials of industrial importance.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.

在这个由化学系大分子、超分子和纳米化学项目资助的项目中，圣路易斯奥比斯波州立大学理工大学加州化学系的Philip Costanzo和丹尼尔Bercovici教授正在开发合成方法，以制备对外部温度敏感的新型聚合物。合成聚合物通常被称为塑料，广泛应用于我们的日常生活中。聚合物是由许多重复的化学单元通过碳-碳键连接而成的长链高分子。它们的性质由它们的化学结构控制，可以针对不同的应用进行定制。在这项研究中，首先制备了一些化学性质不同的小分子，触发温度响应，并研究了它们的物理性质。然后这些分子在精确的位置并入聚合物链中。这种有效的策略允许设计具有化学结构的聚合物链，这些化学结构可以在一个温度下被拉开，并在不同的温度下迅速恢复。与该奖项相关的化学可广泛应用于许多其他聚合体系，并可用于材料化学和任何其他感兴趣的热响应塑料领域。这项研究通过为本科生提供独特的机会来获得有机和聚合物化学的前沿研究培训和教育，从而产生更广泛的影响。除了将与该奖项相关的结果纳入大学的化学实验室课程外，还启动了一项名为社区，资源和外联高分子联盟（MACRO）的外联计划。该计划的目标是创建一个外展材料的存放处，通过它，个人可以将他们的热情和科学知识传播给普通大众。这项工作的重点是动态共价键的发展，可以纳入聚合物系统，使开关在聚合物拓扑结构和赋予热响应性能。为了实现这一目标，进行了几项研究。第一个目标的重点是发展狄尔斯-阿尔德连接系统与新的二烯和亲二烯体和系统的了解所制备的加合物的热稳定性。在第二个目标中，不饱和加合物进行1，4-Michael加成，这有利于逆Diels-桤木裂解，然后使用铜催化的原子转移自由基聚合并入聚合物结构中。最后一个目的是探讨动态共价化学对聚合物拓扑结构和物理性质的影响，特别强调响应性聚合物表面活性剂。使用亲核试剂如硫醇来调节键裂温度适用于各种其他聚合技术，并有可能产生广泛的新的智能软材料的工业重要性。该奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。