Sulfenyl Chloride Electrophilic Addition to Olefinic Monomers: A New Step-Growth Polymerization Reaction to Prepare Optical Polymers

亚磺酰氯与烯烃单体的亲电加成：一种制备光学聚合物的新的逐步增长聚合反应

• 批准号: 2201155
• 负责人: Jeffrey Pyun
• 金额: $ 55万
• 依托单位: University of Arizona
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-06-01 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2201155&HistoricalAwards=false
• 关键词: Sulfenyl; Chloride; Electrophilic; Addition; Olefinic

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor Jeffrey Pyun and Professor Robert Norwood from the University of Arizona will develop novel approaches to the chemical synthesis of optical polymers. Synthetic polymers, the main constituent of plastics, are ubiquitous in our everyday life. Through the design and synthetic control of the chemical structures of polymers, polymer properties can be tailored for use in a wide range of applications. This research project focuses on the investigation of chemical processes that will enable controlled polymerization of sulfide units into polymeric materials, which has significant potential to afford high refractive index, highly transparent optical plastics for use in consumer eye-ware, stretchable optical fiber and electro-optic devices. Currently, the industrial production of plastic optical lenses requires the use of high-cost sulfur-containing monomers. The Pyun and Norwood team aims to address this limitation by developing novel synthetic approaches that employ low-cost monomers as an alternative feedstock for high-volume manufacturing of next generation optical polymers. Graduate and undergraduate students, including women and underrepresented minorities, will receive interdisciplinary research training on synthetic polymer chemistry, polymer processing, optical physics, materials characterization, and device integration. In addition, Prof. Pyun and Prof. Norwood will expand a remote-research learning program to engage non-Chemistry and non-Optical Science majors in independent research activities. Specifically, the research team will develop a new step-growth polymerization process based on the electrophilic addition of sulfenyl chlorides to olefinic monomers. The synthesis of polyhalodisulfide materials and halogen free polydisulfides will be explored. The new science of the project will focus on the fundamental polymerization chemistry required to afford homopolymers, segmented block copolymers, thermoplastics and thermosets. Monomer reactivity will be studied to determine polymerization mechanisms and kinetics. The structural factors that influence the optical properties as well as the chemical and thermal stabilities of the polymers will be examined.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.

在化学系大分子、超分子和纳米化学项目的支持下，亚利桑那大学的Jeffrey Pyun教授和Robert Norwood教授将开发化学合成光学聚合物的新方法。合成聚合物是塑料的主要成分，在我们的日常生活中无处不在。通过设计和合成控制聚合物的化学结构，可以为广泛的应用量身定制聚合物的性能。该研究项目的重点是研究使硫化物单元能够控制聚合成聚合物材料的化学过程，这种聚合物材料具有巨大的潜力，可以提供高折射率、高透明度的光学塑料，用于消费眼镜、可伸缩光纤和电光设备。目前，塑料光学镜片的工业化生产需要使用高成本的含硫单体。皮恩和诺伍德团队的目标是通过开发新的合成方法来解决这一限制，这些方法使用低成本单体作为大批量制造下一代光学聚合物的替代原料。研究生和本科生，包括女性和代表性不足的少数族裔，将接受关于合成聚合物化学、聚合物加工、光学物理、材料表征和设备集成的跨学科研究培训。此外，潘教授和诺伍德教授将扩大远程研究学习计划，让非化学和非光学科学专业的学生参与独立的研究活动。具体地说，研究小组将开发一种新的阶梯生长聚合工艺，该工艺基于亚磺酰氯与烯烃单体的亲电加成。将探索多卤代二硫化物材料和无卤代聚二硫化物的合成。该项目的新科学将专注于生产均聚物、嵌段嵌段共聚物、热塑性塑料和热固性材料所需的基础聚合化学。将研究单体的反应性，以确定聚合机理和动力学。将研究影响聚合物光学性能以及化学和热稳定性的结构因素。该奖项反映了NSF的法定使命，并已通过使用基金会的智力优势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

Sulfenyl Chlorides: An Alternative Monomer Feedstock from Elemental Sulfur for Polymer Synthesis

• DOI: 10.1021/jacs.2c10317
• 发表时间: 2022-12-07
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Kang, Kyung-Seok;Olikagu, Chisom;Pyun, Jeffrey
• 通讯作者: Pyun, Jeffrey