CAREER: CAS: Copolymerization of Vinyl Monomers with Isocyanides for Degradable Polymers

职业：CAS：乙烯基单体与异氰化物共聚制备可降解聚合物

基本信息

批准号：
2337228
负责人：
Erin Stache
金额：
$ 75万
依托单位：
Princeton University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2023
资助国家：
美国
起止时间：
2023-07-01 至 2028-01-31
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2337228&HistoricalAwards=false
关键词：
CAREER CAS Copolymerization Vinyl Monomers

项目摘要

With the support of the Macromolecular, Supramolecular, and Nanochemistry program in the Division of Chemistry, Erin Stache of Cornell University is developing degradable polymers from monomers that are building blocks commonly found in commodity plastics. Polymerization processes will be designed to incorporate degradable functionality along the main polymer backbone. This polymer chain is designed to incorporate functionalities that allow for chain cleavage in the presence of light, rendering the commodity polymers photodegradable. The research team will also investigate the mechanistic and kinetic features of the developed polymerizations to understand further and optimize the reaction conditions and expand the monomer types that can be used in these processes. From the sustainability point of view, the design principles associated with this project have the potential to provide a promising and viable solution to the current challenges related to the widespread usage of non-degradable commodity plastics. The education and outreach activities will focus on educating the public across age demographics on the nature of the recycling industry and the science behind polymers and their structure. Additionally, training workshops will be developed to encourage the public to make an impact in their household and community. The efforts to further bring plastics knowledge prowess to general society will be enhanced through social media outreach using various platforms.This project will focus on developing controlled polymerization of isocyanides and vinyl monomers to install degradable functionality into the backbone of commodity polymers. In the first objective, kinetic and mechanistic aspects of cobalt-mediated radical copolymerization of isocyanides and acrylates will be systematically investigated. Strong emphasis will be placed on understanding (a) cross-propagation of activated acrylates with isocyanides to form imidoyl radicals and (b) intermolecular addition of the imidoyl radical to acrylates prior to alpha- or beta-scission that could result in the chain termination and/or transfer. The second objective will study the properties of isocyanide/acrylate copolymers, hydrolysis to afford the corresponding poly(acrylates-co-ketones), backbone elaboration, and degradation behavior of isocyanide and ketone copolymers. Lastly, the ambiphilic nature of isocyanides in a cationic copolymerization of vinyl monomers to access new copolymers will be exploited. Investigation of the mechanistic aspects of copolymerization of isocyanides with vinyl monomers could lead to a development of new and more versatile controlled radical polymerization methods. Additionally, this research has the potential to offer a facile route to a novel class of degradable polymers and to provide important insight into the percentage of imine or ketone functionality incorporation needed to both allow for photodegradation upon appropriate exposure and yet otherwise maintain desirable polymer 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.

在化学系高分子、超分子和纳米化学项目的支持下，康奈尔大学的 Erin Stache 正在利用单体开发可降解聚合物，这些单体是商品塑料中常见的构建单元。聚合过程将被设计为沿着聚合物主链结合可降解的功能。该聚合物链的设计融入了允许在光存在下链断裂的功能，从而使商品聚合物可光降解。研究团队还将研究所开发的聚合反应的机理和动力学特征，以进一步了解和优化反应条件，并扩展可用于这些过程的单体类型。从可持续性的角度来看，与该项目相关的设计原则有可能为当前与不可降解商品塑料广泛使用相关的挑战提供有前途且可行的解决方案。教育和外展活动将侧重于教育各年龄段的公众了解回收行业的性质以及聚合物及其结构背后的科学。此外，还将举办培训研讨会，以鼓励公众对其家庭和社区产生影响。将通过使用各种平台的社交媒体宣传，进一步加强将塑料知识力量进一步推向普通社会的努力。该项目将重点开发异氰化物和乙烯基单体的受控聚合，以将可降解功能安装到商品聚合物的主干中。在第一个目标中，将系统地研究钴介导的异氰化物和丙烯酸酯自由基共聚的动力学和机理。重点将放在理解（a）活化丙烯酸酯与异氰化物的交叉传播以形成亚氨酰基自由基和（b）在α-或β-断裂之前亚胺酰基自由基与丙烯酸酯的分子间加成，这可能导致链终止和/或转移。第二个目标将研究异氰化物/丙烯酸酯共聚物的性质、水解以提供相应的聚（丙烯酸酯-共聚-酮）、主链精制以及异氰化物和酮共聚物的降解行为。最后，将利用乙烯基单体的阳离子共聚中异氰化物的两亲性质来获得新的共聚物。对异氰化物与乙烯基单体共聚机理的研究可能会导致开发新的、更通用的受控自由基聚合方法。此外，这项研究有可能为一类新型可降解聚合物提供一条简便的途径，并提供对亚胺或酮官能团掺入百分比的重要见解，以允许在适当曝光下进行光降解，同时保持所需的聚合物性能。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。