David J. Lundberg, Kwangwook Ko, Landon J. Kilgallon and Jeremiah A. Johnson*,
{"title":"定义涉及可裂解共聚单体添加剂的共聚反应的反应性-解构性关系","authors":"David J. Lundberg, Kwangwook Ko, Landon J. Kilgallon and Jeremiah A. Johnson*, ","doi":"10.1021/acsmacrolett.4c00106","DOIUrl":null,"url":null,"abstract":"<p >The incorporation of cleavable comonomers as additives into polymers can imbue traditional polymers with controlled deconstructability and expanded end-of-life options. The efficiency with which cleavable comonomer additives (CCAs) can enable deconstruction is sensitive to their local distribution within a copolymer backbone, which is dictated by their copolymerization behavior. While qualitative heuristics exist that describe deconstructability, comprehensive quantitative connections between CCA loadings, reactivity ratios, polymerization mechanisms, and deconstruction reactions on the deconstruction efficiency of copolymers containing CCAs have not been established. Here, we broadly define these relationships using stochastic simulations characterizing various polymerization mechanisms (e.g., coltrolled/living, free-radical, and reversible ring-opening polymerizations), reactivity ratio pairs (spanning 2 orders of magnitude between 0.01 and 100), CCA loadings (2.5% to 20%), and deconstruction reactions (e.g., comonomer sequence-dependent deconstruction behavior). We show general agreement between simulated and experimentally observed deconstruction fragment sizes from the literature, demonstrating the predictive power of the methods used herein. These results will guide the development of more efficient CCAs and inform the formulation of deconstructable materials.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives\",\"authors\":\"David J. Lundberg, Kwangwook Ko, Landon J. Kilgallon and Jeremiah A. Johnson*, \",\"doi\":\"10.1021/acsmacrolett.4c00106\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The incorporation of cleavable comonomers as additives into polymers can imbue traditional polymers with controlled deconstructability and expanded end-of-life options. The efficiency with which cleavable comonomer additives (CCAs) can enable deconstruction is sensitive to their local distribution within a copolymer backbone, which is dictated by their copolymerization behavior. While qualitative heuristics exist that describe deconstructability, comprehensive quantitative connections between CCA loadings, reactivity ratios, polymerization mechanisms, and deconstruction reactions on the deconstruction efficiency of copolymers containing CCAs have not been established. Here, we broadly define these relationships using stochastic simulations characterizing various polymerization mechanisms (e.g., coltrolled/living, free-radical, and reversible ring-opening polymerizations), reactivity ratio pairs (spanning 2 orders of magnitude between 0.01 and 100), CCA loadings (2.5% to 20%), and deconstruction reactions (e.g., comonomer sequence-dependent deconstruction behavior). We show general agreement between simulated and experimentally observed deconstruction fragment sizes from the literature, demonstrating the predictive power of the methods used herein. These results will guide the development of more efficient CCAs and inform the formulation of deconstructable materials.</p>\",\"PeriodicalId\":18,\"journal\":{\"name\":\"ACS Macro Letters\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-04-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Macro Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsmacrolett.4c00106\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Macro Letters","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsmacrolett.4c00106","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
摘要
将可裂解共聚单体作为添加剂加入聚合物中,可使传统聚合物具有可控的解构性,并扩大其报废选择范围。可裂解共聚单体添加剂(CCA)的解构效率对其在共聚物骨架中的局部分布非常敏感,而共聚行为决定了这种分布。虽然已有定性的启发式方法来描述可解构性,但 CCA 的负载量、反应率、聚合机理和解构反应对含有 CCA 的共聚物的解构效率的全面定量联系尚未建立。在此,我们利用随机模拟对各种聚合机理(如受控/活化、自由基和可逆开环聚合)、反应率对(跨越 0.01 到 100 之间的 2 个数量级)、CCA 用量(2.5% 到 20%)和解构反应(如依赖于共聚单体序列的解构行为)进行了描述,从而大致确定了这些关系。我们显示模拟结果与文献中实验观察到的解构片段大小基本一致,证明了本文所用方法的预测能力。这些结果将为开发更高效的 CCA 提供指导,并为可解构材料的配方提供信息。
Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives
The incorporation of cleavable comonomers as additives into polymers can imbue traditional polymers with controlled deconstructability and expanded end-of-life options. The efficiency with which cleavable comonomer additives (CCAs) can enable deconstruction is sensitive to their local distribution within a copolymer backbone, which is dictated by their copolymerization behavior. While qualitative heuristics exist that describe deconstructability, comprehensive quantitative connections between CCA loadings, reactivity ratios, polymerization mechanisms, and deconstruction reactions on the deconstruction efficiency of copolymers containing CCAs have not been established. Here, we broadly define these relationships using stochastic simulations characterizing various polymerization mechanisms (e.g., coltrolled/living, free-radical, and reversible ring-opening polymerizations), reactivity ratio pairs (spanning 2 orders of magnitude between 0.01 and 100), CCA loadings (2.5% to 20%), and deconstruction reactions (e.g., comonomer sequence-dependent deconstruction behavior). We show general agreement between simulated and experimentally observed deconstruction fragment sizes from the literature, demonstrating the predictive power of the methods used herein. These results will guide the development of more efficient CCAs and inform the formulation of deconstructable materials.
期刊介绍:
ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science.
With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.