Cargando…
Carbodiimide Ring-Opening Metathesis Polymerization
[Image: see text] Controlled incorporation of nitrogen into macromolecular skeletons is a long-standing challenge whose resolution would enable the preparation of soft materials with the scalability of man-made plastics and functionality of Nature’s proteins. Nylons and polyurethanes notwithstanding...
Autores principales: | , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10311665/ https://www.ncbi.nlm.nih.gov/pubmed/37396860 http://dx.doi.org/10.1021/acscentsci.3c00032 |
_version_ | 1785066788868849664 |
---|---|
author | Johnson, J. Drake Kaplan, Samuel W. Toth, Jozsef Wang, Zian Maw, Mitchell Sheiko, Sergei S. Zhukhovitskiy, Aleksandr V. |
author_facet | Johnson, J. Drake Kaplan, Samuel W. Toth, Jozsef Wang, Zian Maw, Mitchell Sheiko, Sergei S. Zhukhovitskiy, Aleksandr V. |
author_sort | Johnson, J. Drake |
collection | PubMed |
description | [Image: see text] Controlled incorporation of nitrogen into macromolecular skeletons is a long-standing challenge whose resolution would enable the preparation of soft materials with the scalability of man-made plastics and functionality of Nature’s proteins. Nylons and polyurethanes notwithstanding, nitrogen-rich polymer backbones remain scarce, and their synthesis typically lacks precision. Here we report a strategy that begins to address this limitation founded on a mechanistic discovery: ring-opening metathesis polymerization (ROMP) of carbodiimides followed by carbodiimide derivatization. An iridium guanidinate complex was found to initiate and catalyze ROMP of N-aryl and N-alkyl cyclic carbodiimides. Nucleophilic addition to the resulting polycarbodiimides enabled the preparation of polyureas, polythioureas, and polyguanidinates with varied architectures. This work advances the foundations of metathesis chemistry and opens the door to systematic investigations of structure-folding-property relationships in nitrogen-rich macromolecules. |
format | Online Article Text |
id | pubmed-10311665 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-103116652023-07-01 Carbodiimide Ring-Opening Metathesis Polymerization Johnson, J. Drake Kaplan, Samuel W. Toth, Jozsef Wang, Zian Maw, Mitchell Sheiko, Sergei S. Zhukhovitskiy, Aleksandr V. ACS Cent Sci [Image: see text] Controlled incorporation of nitrogen into macromolecular skeletons is a long-standing challenge whose resolution would enable the preparation of soft materials with the scalability of man-made plastics and functionality of Nature’s proteins. Nylons and polyurethanes notwithstanding, nitrogen-rich polymer backbones remain scarce, and their synthesis typically lacks precision. Here we report a strategy that begins to address this limitation founded on a mechanistic discovery: ring-opening metathesis polymerization (ROMP) of carbodiimides followed by carbodiimide derivatization. An iridium guanidinate complex was found to initiate and catalyze ROMP of N-aryl and N-alkyl cyclic carbodiimides. Nucleophilic addition to the resulting polycarbodiimides enabled the preparation of polyureas, polythioureas, and polyguanidinates with varied architectures. This work advances the foundations of metathesis chemistry and opens the door to systematic investigations of structure-folding-property relationships in nitrogen-rich macromolecules. American Chemical Society 2023-05-11 /pmc/articles/PMC10311665/ /pubmed/37396860 http://dx.doi.org/10.1021/acscentsci.3c00032 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Johnson, J. Drake Kaplan, Samuel W. Toth, Jozsef Wang, Zian Maw, Mitchell Sheiko, Sergei S. Zhukhovitskiy, Aleksandr V. Carbodiimide Ring-Opening Metathesis Polymerization |
title | Carbodiimide
Ring-Opening Metathesis Polymerization |
title_full | Carbodiimide
Ring-Opening Metathesis Polymerization |
title_fullStr | Carbodiimide
Ring-Opening Metathesis Polymerization |
title_full_unstemmed | Carbodiimide
Ring-Opening Metathesis Polymerization |
title_short | Carbodiimide
Ring-Opening Metathesis Polymerization |
title_sort | carbodiimide
ring-opening metathesis polymerization |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10311665/ https://www.ncbi.nlm.nih.gov/pubmed/37396860 http://dx.doi.org/10.1021/acscentsci.3c00032 |
work_keys_str_mv | AT johnsonjdrake carbodiimideringopeningmetathesispolymerization AT kaplansamuelw carbodiimideringopeningmetathesispolymerization AT tothjozsef carbodiimideringopeningmetathesispolymerization AT wangzian carbodiimideringopeningmetathesispolymerization AT mawmitchell carbodiimideringopeningmetathesispolymerization AT sheikosergeis carbodiimideringopeningmetathesispolymerization AT zhukhovitskiyaleksandrv carbodiimideringopeningmetathesispolymerization |