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Increasing Control Over Photoredox-Mediated Ring-Opening Metathesis Polymerization through Improved Mechanistic Understanding and Chain Transfer

通过改进机理理解和链转移增强对光氧化还原介导的开环复分解聚合的控制

基本信息

批准号：
2002886
负责人：
Andrew Boydston
金额：
$ 45万
依托单位：
University of Wisconsin-Madison
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：
2020-06-01 至 2023-05-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2002886&HistoricalAwards=false
关键词：
Increasing Control Over Photoredox Mediated

项目摘要

With this award, the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry is funding Professor Andrew J. Boydston of the Department of Chemistry at University of Wisconsin-Madison to investigate metal-free ring opening metathesis polymerization. This research enables the synthesis of precision plastics that are used in light-weighting of vehicles to improve energy efficiency, ballistic impact resistant compositions, and even 3D printing. In this research, systematic studies are performed to gain understanding of how this reaction works. Factors needed to optimize polymerization conditions to prepare plastics with properties that complement or exceed specifications are also investigated. This research provides training and education to undergraduate and graduate students in synthetic polymer chemistry as well collaborative research opportunities with the Army Research Laboratory. Outreach activities focus on workshops for middle school visitors at the University of Wisconsin-Madison, and at the Educators Open House to increase interest in STEM at local high schools. This research is focused on the mechanistic understanding of photoredox-mediated ring opening metathesis polymerization initiated by vinyl ethers. The technique provides access to classes of polymers that are challenging to produce using metal-based initiators. Key aspects of the envisioned mechanism, such as the dynamic redox couple between the initiator and photoredox catalyst, kinetics and thermodynamics of reversible chain end (de)activation, methods to improve initiator efficiency, solvent effects, and practical methods for molecular weight control via designer chain transfer agents are systematically investigated. Mechanistic insights are distinct from any other currently reported polymerization process, yet draw from photoredox catalyzed processes across small molecule and polymer synthesis.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.

该奖项将资助威斯康星大学麦迪逊分校化学系的安德鲁·J·博伊斯顿教授研究无金属开环歧化聚合。这项研究使精密塑料的合成成为可能，这些塑料用于车辆的轻量化，以提高能源效率，防弹冲击成分，甚至3D打印。在这项研究中，进行了系统的研究，以了解该反应是如何起作用的。此外，还研究了优化聚合条件以制备性能达到或超过规格的塑料所需的因素。这项研究为本科生和研究生提供合成聚合物化学方面的培训和教育，以及与陆军研究实验室的合作研究机会。外展活动的重点是在威斯康星大学麦迪逊分校为中学访客举办的讲习班，以及在教育者开放日上为当地高中增加对STEM的兴趣。本论文主要研究乙烯基醚引发的光氧化还原催化开环歧化聚合反应的机理。这项技术提供了使用金属基引发剂生产具有挑战性的聚合物类别的途径。系统地研究了引发剂与光氧化还原催化剂之间的动态氧化还原耦合、可逆链末端活化的动力学和热力学、提高引发剂效率的方法、溶剂效应以及通过设计链转移剂控制分子量的实用方法等关键方面。这一奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，认为值得支持。

项目成果

期刊论文数量（5）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

A highly efficient metal-free protocol for the synthesis of linear polydicyclopentadiene

DOI：
10.1039/d1py00191d
发表时间：
2021
期刊：
Polymer Chemistry
影响因子：
4.6
作者：
Xuejin Yang;Laura M. Murphy;F. Haque;Scott M. Grayson;Andrew J Boydston
通讯作者：
Xuejin Yang;Laura M. Murphy;F. Haque;Scott M. Grayson;Andrew J Boydston

Metal-Free Ring-Opening Metathesis Polymerization: From Concept to Creation

无金属开环复分解聚合：从概念到创造

DOI：
10.1021/acs.accounts.0c00427
发表时间：
2020
期刊：
Accounts of Chemical Research
影响因子：
18.3
作者：
Lu, Pengtao;Kensy, Victoria K.;Tritt, Rachel L.;Seidenkranz, Daniel T.;Boydston, Andrew J.
通讯作者：
Boydston, Andrew J.

An Ion‐Pairing Approach to Stereoselective Metal‐Free Ring‐Opening Metathesis Polymerization

立体选择性金属自由环开复分解聚合的离子配对方法

DOI：
10.1002/anie.202016393
发表时间：
2021
期刊：
Angewandte Chemie International Edition
影响因子：
0
作者：
Yang, Xuejin;Gitter, Sean R.;Roessler, Allison G.;Zimmerman, Paul M.;Boydston, Andrew J.
通讯作者：
Boydston, Andrew J.

C−H Functionalization and Allylic Amination for Post‐Polymerization Modification of Polynorbornenes

用于聚降冰片烯聚合后改性的 C–H 官能化和烯丙基胺化

DOI：
10.1002/anie.202303174
发表时间：
2023
期刊：
Angewandte Chemie International Edition
影响因子：
0
作者：
Gitter, Sean R.;Teh, Wei Pin;Yang, Xuejin;Dohoda, Alexander F.;Michael, Forrest E.;Boydston, Andrew J.
通讯作者：
Boydston, Andrew J.