Exploring Metal-Free Living Cationic Polymerizations via Reversible Addition-Fragmentation Chain Transfer

通过可逆加成-断裂链转移探索无金属活性阳离子聚合

• 批准号: 1808055
• 负责人: Wei You
• 金额: $ 40.87万
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-15 至 2022-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1808055&HistoricalAwards=false
• 关键词: Exploring; Metal; Free; Living; Cationic

Synthetic polymers (commonly known as plastics) are a mixture of different molecular "strings" having different lengths. While for many applications, such a mixture does not impact the physical properties of the polymer, some applications require polymers to have strings of the same length to attain specifically-desired polymer properties. The research group of Professor Wei You at the University of North Carolina Chapel Hill has discovered a new polymerization methodology for preparing polymers that have a narrow distribution of lengths. To further develop the methodology, this research seeks a better understanding of the polymerization process in order to achieve greater control of the lengths of such molecular strings. The research also seeks to broaden the applicability of the synthesis methods to a wide range of different polymers. Education, collaboration, and outreach are integral aspects of this project. Professor You actively recruits students of underrepresented groups into his research group. Graduate, undergraduate, and high school students receive training in cutting-edge small molecule and polymer synthetic methods, along with complex analytical techniques through engaging in this interdisciplinary research project. Professor You is actively involved in a number of outreach activities, including the UNC Science Expo (part of the North Carolina Science Festival). This event is UNC?s single largest science outreach event, attracting approximately 10,000 participants annually. In addition, Professor You has also designed short lectures on polymer solar cells for high school students and teachers brought as part of the Climate LEAP program.The classical living cationic polymerization achieves "living" characteristics via the equilibrium between the ionic (i.e., propagating chain end) and the covalent (i.e., resting chain end) species. In contrast, the controlled cationic polymerization recently discovered in Professor You's laboratory proceeds through an entirely new mechanism - a cationic chain transfer mechanism, analogous to that of the conventional Reversible Addition-Fragmentation Chain Transfer (RAFT) radical polymerization. This research explores and elucidates the mechanism of this new cationic polymerization process. The project investigates the mechanistic details of a new metal-free, protonic acid initiated and alcohol-mediated controlled cationic polymerization. The researchers expand this unique living cationic polymerization into polymerizing various electron-rich monomers, and unveiling the roles of the applied photocatalysts in the controlled cationic RAFT polymerization.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.

合成聚合物（通常称为塑料）是具有不同长度的不同分子“串”的混合物。虽然对于许多应用，这样的混合物不影响聚合物的物理性质，但是一些应用要求聚合物具有相同长度的串以获得特别期望的聚合物性质。北卡罗来纳州查佩尔山大学魏佑教授的研究小组发现了一种新的聚合方法，用于制备具有窄长度分布的聚合物。为了进一步发展的方法，本研究旨在更好地了解聚合过程，以实现更大的控制这样的分子串的长度。 该研究还寻求扩大合成方法对各种不同聚合物的适用性。教育、合作和推广是这个项目的组成部分。尤教授积极招募弱势群体的学生加入他的研究小组。 研究生，本科生和高中生通过参与这个跨学科的研究项目，接受尖端小分子和聚合物合成方法沿着复杂分析技术的培训。尤教授积极参与多项外展活动，包括科学博览会（北卡罗来纳州科学节的一部分）。 这件事，是？这是世界上最大的科学推广活动，每年吸引约10，000名参与者。此外，作为气候LEAP项目的一部分，尤教授还为高中生和教师设计了关于聚合物太阳能电池的简短讲座。经典的活性阳离子聚合通过离子（即，增长链端）和共价键（即，静止链末端）物种。 相比之下，最近在尤教授的实验室中发现的受控阳离子聚合通过一种全新的机制进行-阳离子链转移机制，类似于传统的可逆加成-断裂链转移（RAFT）自由基聚合。本研究探讨并阐明了这种新的阳离子聚合工艺的机理。 该项目研究了一种新的无金属，质子酸引发和醇介导的受控阳离子聚合的机理细节。 研究人员将这种独特的活性阳离子聚合扩展到聚合各种富电子单体，并揭示了应用的光催化剂在受控阳离子RAFT聚合中的作用。该奖项反映了NSF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，被认为值得支持。

项目成果

Importance of Nucleophilicity of Chain-Transfer Agents for Controlled Cationic Degenerative Chain-Transfer Polymerization

• DOI: 10.1021/acs.macromol.0c00290
• 发表时间: 2020-05
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Parker T. Boeck;Joji Tanaka;Shubin Liu;W. You