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

• 批准号: 2237784
• 负责人: Erin Stache
• 金额: $ 75万
• 依托单位: Cornell 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: 2023-02-01 至 2023-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2237784&HistoricalAwards=false
• 关键词: CAREER; CAS; Copolymerization; Vinyl; Monomers

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.

在化学系的大分子，超分子和纳米化学计划的支持下，康奈尔大学的艾琳·斯塔奇（Erin Stache）正在开发来自商品塑料中通常发现的基础的单体的可降解聚合物。聚合过程将设计为沿主要聚合物主链融合可降解的功能。该聚合物链的设计旨在结合在光照下允许链裂解的功能，从而使商品聚合物可光降解。研究团队还将研究开发的聚合物的机械和动力学特征，以进一步了解和优化反应条件并扩展可在这些过程中使用的单体类型。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与广泛使用不可降解的商品塑料相关的当前挑战提供有希望且可行的解决方案。教育和宣传活动将着重于跨年龄人口统计学的公众教育回收行业的性质以及聚合物及其结构背后的科学。此外，将开发培训研讨会，以鼓励公众对其家庭和社区产生影响。通过社交媒体宣传将使用各种平台来增强塑料知识能力的努力。本项目将着重于开发异氰酸酯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支柱中。在第一个目标中，将系统地研究异氰化物和丙烯酸酯的钴介导的自由基共聚的动力学和机械方面。强烈的重点将放在（a）激活丙烯酸酯与异氰酸酯的交叉传播中形成咪二酰基自由基，（b）分子间添加咪二酰基在α-或β-算法之前对丙烯酸酯的丙烯酸酯的添加，这可能导致链终止和/或转移。第二个目标将研究异氰酸酯/丙烯酸酯共聚物的特性，水解，以提供相应的聚（丙烯酸酯 - 旋酮），骨架阐明以及异氰酸酯和酮共聚物的降解行为。最后，将利用异氰酸酯在乙烯基单体的阳离子共聚中的抗胆汁性质，以获取新的共聚物。研究异氰化物与乙烯基单体共聚的机械方面可能导致新的，更广泛的受控自由基聚合方法的发展。此外，这项研究有可能为一类新颖的可降解聚合物提供便利的途径，并为允许在适当暴露时允许光降解所需的imine或酮功能纳入百分比提供重要的见解，而另外则保持了理想的聚合物特性。这一奖项反映了NSF的法定任务和综述的依据，这是通过评估的范围，并且具有范围的依据。