David J. Lundberg, Kwangwook Ko, Landon J. Kilgallon and Jeremiah A. Johnson*,
{"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}
引用次数: 0
Abstract
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.