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Toward ultimate control of radical polymerization
- Herein, an approach via combination of confined porous textures and reversible deactivation radical polymerization techniques is proposed to advance synthetic polymer chemistry, i.e., a connection of metal-organic frameworks (MOFs) and activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). Zn-2(benzene-1,4-dicarboxylate)2(1,4-diazabicyclo[2.2.2]-octane) [Zn-2(bdc)(2)(dabco)] is utilized as a reaction environment for polymerization of various methacrylate monomers (methyl, ethyl, benzyl, and isobornyl methacrylate) in a confined nanochannel, resulting in polymers with control over dispersity, end functionalities, and tacticity with respect to distinct molecular size. To refine and reconsolidate the compartmentation effect on polymer regularity, initiator-functionalized Zn MOF was synthesized via cocrystallization with an initiator-functionalized ligand, 2-(2-bromo-2-methylpropanamido)-1,4-benzenedicarboxylate (Brbdc), in different ratios (10%, 20%, and 50%). Through the embedded initiator,Herein, an approach via combination of confined porous textures and reversible deactivation radical polymerization techniques is proposed to advance synthetic polymer chemistry, i.e., a connection of metal-organic frameworks (MOFs) and activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). Zn-2(benzene-1,4-dicarboxylate)2(1,4-diazabicyclo[2.2.2]-octane) [Zn-2(bdc)(2)(dabco)] is utilized as a reaction environment for polymerization of various methacrylate monomers (methyl, ethyl, benzyl, and isobornyl methacrylate) in a confined nanochannel, resulting in polymers with control over dispersity, end functionalities, and tacticity with respect to distinct molecular size. To refine and reconsolidate the compartmentation effect on polymer regularity, initiator-functionalized Zn MOF was synthesized via cocrystallization with an initiator-functionalized ligand, 2-(2-bromo-2-methylpropanamido)-1,4-benzenedicarboxylate (Brbdc), in different ratios (10%, 20%, and 50%). Through the embedded initiator, surface-initiated ARGET ATRP was directly initiated from the walls of the nanochannels. The obtained polymers had a high molecular weight up to 392 000. Moreover, a significant improvement in end-group functionality and stereocontrol was observed, entailing polymers with obvious increments in isotacticity. The results highlight a combination of MOFs and ATRP that is a promising and universal methodology to prepare various polymers with high molecular weight exhibiting well-defined uniformity in chain length and microstructure as well as the preserved chain-end functionality.…
Author details: | Hui-Chun LeeORCiD, Jongkook HwangORCiD, Uwe SchildeORCiDGND, Markus AntoniettiORCiDGND, Krzysztof MatyjaszewskiORCiD, Bernhard V. K. J. SchmidtORCiDGND |
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DOI: | https://doi.org/10.1021/acs.chemmater.8b00546 |
ISSN: | 0897-4756 |
ISSN: | 1520-5002 |
Title of parent work (English): | Chemistry of materials : a publication of the American Chemical Society |
Subtitle (English): | functionalized metal-organic frameworks as a robust environment for Metal-Catalyzed Polymerizations |
Publisher: | American Chemical Society |
Place of publishing: | Washington |
Publication type: | Article |
Language: | English |
Date of first publication: | 2018/05/08 |
Publication year: | 2018 |
Release date: | 2021/12/01 |
Volume: | 30 |
Issue: | 9 |
Number of pages: | 12 |
First page: | 2983 |
Last Page: | 2994 |
Funding institution: | German Academic Exchange Service (DAAD)Deutscher Akademischer Austausch Dienst (DAAD); Max Planck SocietyMax Planck Society |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
DDC classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Peer review: | Referiert |