Synergizing Visible Light-Mediated Cationic and Radical PET RAFT Through Electron-Rich Dithiobenzoates
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F25%3A10497892" target="_blank" >RIV/00216208:11310/25:10497892 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=dr2_B8NVzc" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=dr2_B8NVzc</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.macromol.4c03060" target="_blank" >10.1021/acs.macromol.4c03060</a>
Alternative languages
Result language
angličtina
Original language name
Synergizing Visible Light-Mediated Cationic and Radical PET RAFT Through Electron-Rich Dithiobenzoates
Original language description
In this work, we developed a novel electron-rich dithiobenzoate chain transfer agent (CTA) with excellent control for both cationic and radical photoelectron/energy transfer-reversible addition-fragmentation chain transfer (PET RAFT) polymerizations. The 2,4-dimethoxydithiobenzoate-based CTA enables the optimized stabilization of chain transfer intermediates, outperforming trithiocarbonates in the control of cationic RAFT polymerizations and dithiocarbamates in radical RAFT polymerizations of more active monomers. The excellent control of cationic PET RAFT polymerization offered by this novel CTA was demonstrated by the blue-light-mediated synthesis of poly(isobutyl vinyl ether) of various chain lengths with sub-1.2 dispersities. Furthermore, to highlight its benefit over previously reported dithiocarbamate and trithiocarbonate CTAs, this new CTA was employed for the one-pot synthesis of poly(isobutyl vinyl ether)-block-poly(methyl acrylate) diblock copolymers. The prepared CTA-terminated poly(isobutyl vinyl ether) was chain-extended by methyl acrylate via red-light-mediated radical RAFT polymerization, which afforded a diblock copolymer with a dispersity of 1.26, which significantly surpassed the dispersities achieved with analogous trithiocarbonates. The radical polymerization step uses a zinc tetraphenylporphyrin photocatalyst to achieve complete wavelength orthogonality, with a tris(4-methoxyphenyl)pyrylium photocatalyst used for the cationic polymerization step. The optimized electron-rich dithiobenzoate can then be used as a universal agent in the synthesis of advanced copolymers involving radical-cationic RAFT crossover polymerization steps.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10404 - Polymer science
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Macromolecules
ISSN
0024-9297
e-ISSN
1520-5835
Volume of the periodical
58
Issue of the periodical within the volume
4
Country of publishing house
US - UNITED STATES
Number of pages
9
Pages from-to
2085-2093
UT code for WoS article
001419533100001
EID of the result in the Scopus database
2-s2.0-85217531458