Design and Synthesis of New Interlocked Polymers

新型互锁聚合物的设计与合成

基本信息

批准号：
2304633
负责人：
Stuart Rowan
金额：
$ 67万
依托单位：
University of Chicago
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2023
资助国家：
美国
起止时间：
2023-07-01 至 2027-06-30
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2304633&HistoricalAwards=false
关键词：
Design Synthesis New Interlocked Polymers

项目摘要

With the support of the Macromolecular, Supramolecular and Nanochemistry (MSN) program in the Division of Chemistry (CHE) and the Polymers program in the Division of Materials Research (DMR), Professor Stuart J. Rowan of the University of Chicago is developing synthetic methodologies for the preparation of poly[n]catenanes and poly[n]rotaxanes. Catenanes and rotaxanes consist of two or more components that are interlocked together and held in place by the mechanical bond. Catenanes are comprised of interlocked rings while rotaxanes consist of a ring that is interlocked with a dumbbell (a thread-like molecule with stoppers on either end large enough to prevent dethreading of the ring) component. Macromolecular or polymeric versions of these species are particularly intriguing as they offer new polymeric architectures in which the relative motions of the different components allow access to new and unique properties. While architectures such as poly[2]catenanes and main-chain poly[n]rotaxanes have been prepared, synthetic methodologies to poly[n]catenanes and doubly threaded slide ring gels have received much less attention. In such architectures, the mechanical bond is part of the polymer backbone and allows the macromolecules to expand/contract without significant activation energy. As a result, such polymers can exhibit unusual viscoelastic properties. This research will explore new synthetic protocols that will allow access to these intriguing macromolecules. The proposed research will mix different disciplines within the chemistry arena, from synthetic organic and metal coordination chemistry to polymer science and characterization. This integrated research approach will provide students at all levels with broad educational experiences covering these topics. Additionally, the integrated high school and undergraduate research and outreach activities will be designed to increase the fraction of underrepresented minorities in science and engineering. Specifically, the planned activities will involve high school students from Chicago’s south side. This research will focus on developing synthetic routes to new interlocked polymers based on catenanes and rotaxanes. A strong emphasis will be placed on synthetic methodologies that utilize metal-ligand coordination as the thermodynamic driving force to preorganize the organic components, followed by a covalent fixing either through ring-closing metathesis to access the poly[n]catenanes, or high-yielding, catalyst-free click chemistries to access the doubly-threaded slide ring gels. This project will also provide systematic investigation on how the structure of the building components can be used to impact product distribution, molecular weight, as well as the resulting properties of these unique polymers. Results associated with this work have the potential to advance polymer chemistry by addressing fundamental questions about mechanical linkages in polymeric systems. Moreover, doubly-threaded slide ring gels are expected to be of broad scientific interest as they serve both as models of networks with trapped entanglements as well as potential sources of materials with unusual mechanical and functional properties.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.

在大分子，超分子和纳米化学（MSN）方案的支持下（CHE）和聚合物材料研究部（DMR）的聚合物计划（DMR），芝加哥大学的Stuart J. Rowan教授正在开发用于制备Poly [N] Catenanes and Polyaxanes and Polyaxanes rotaxanes rotaxanes rotaxanes rotaxans rotaxans rotaxans of [n]旋转旋转的方法。 Catenanes和Rotaxanes由两个或多个组成组成，它们互锁并通过机械键将其固定在适当的位置。 Catenanes由互锁的环组成，而Rotaxanes由与哑铃互锁的环组成（螺纹状的分子在任一端的螺纹状分子，足以防止戒指的读取）组件。这些物种的大分子或聚合物版本特别有趣，因为它们提供了新的聚合结构，其中不同组件的相对运动允许访问新的和独特的特性。尽管已经制备了诸如聚[2] catenanes和主链聚[N]旋转烷之类的体系结构，但对聚[N] Catenanes的合成方法和双螺纹滑动环凝胶的关注较少。在这样的体系结构中，机械键是聚合物主链的一部分，可使大分子在没有明显的激活能量的情况下扩展/收缩。结果，这样的聚合物可以提取异常的粘弹性特性。这项研究将探索新的合成方案，以允许访问这些有趣的大分子。拟议的研究将在化学领域中混合不同学科，从合成有机和金属配位化学到聚合物科学和表征。这种综合研究方法将为各级学生提供涵盖这些主题的广泛教育经验。此外，综合的高中和本科研究和外展活动将旨在增加科学和工程中代表性不足的少数群体的比例。具体而言，计划的活动将涉及来自芝加哥南侧的高中学生。这项研究将着重于基于Catenanes和Rotaxanes开发新的互锁聚合物的合成路线。将对合成方法的强烈重视，该方法利用金属 - 配体配位作为热力学驱动力来预组织有机组件，然后通过闭环转移来访问poly [n] catenanes，或者是高收益的cathalyst chemisties coptery offleclyst chemistries，可以访问cateralyst chemistries，以获取双重旋转式旋转式旋转式环圈，以访问poly [n] catenanes，以访问poly [n] catenanes，以访问poly [n] catenanes，以访问poly [n] catenanes。该项目还将为如何使用建筑物组件的结构来影响产品分布，分子量以及这些独特聚合物的产生特性。与这项工作相关的结果有可能通过解决有关聚合物系统中机械链接的基本问题来推动聚合物化学。此外，预计双线线幻灯片凝胶将具有广泛的科学兴趣，因为它们既充当具有纠缠的网络的模型，又是具有不寻常的机械和功能属性的潜在材料来源。这奖反映了NSF的法定任务，并且通过该基金会的知识优点和广泛的影响来评估NSF的法定任务。