Postpolymerization modification of poly(2-isopropenyl-2-oxazoline) with thiols: scope and solvent effects
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F25%3A00617579" target="_blank" >RIV/61389013:_____/25:00617579 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.macromol.5c00046" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.macromol.5c00046</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.macromol.5c00046" target="_blank" >10.1021/acs.macromol.5c00046</a>
Alternative languages
Result language
angličtina
Original language name
Postpolymerization modification of poly(2-isopropenyl-2-oxazoline) with thiols: scope and solvent effects
Original language description
Poly(2-isopropenyl-2-oxazoline) (PIPOx) has emerged as a unique postpolymerization modification platform. However, only the relatively slow PIPOx reactions with carboxylic acids are currently routinely exploited. Here, we provide the first comprehensive investigation into PIPOx reactivity with different aliphatic and aromatic thiols. We revealed that these reactions are dramatically accelerated in water, affording high degrees of modification (DM) faster and/or under milder reaction conditions than in organic solvents. This was particularly important for the generally less-reactive aliphatic thiols, where we demonstrated high DM values for the first time. Aromatic thiols were found to be comparatively more reactive, with reactivity differences ascribed largely to the thiol acidity governed by substitution effects. Besides enhancing the reaction rate, the aqueous medium also greatly simplified product isolation in many cases. Furthermore, a precise stoichiometric control over DM, enabling precision tailoring of (co)polymer composition, was manifested for model thiols. Finally, we exemplified how thiol reactions can be used for the rapid and clean incorporation of a range of useful functionalities into the parent polymer, imparting important functional properties or creating reactive sites for further polymer modifications, including cross-coupling and para-fluoro-thiol click reactions. Our findings extend significantly the PIPOx-based postpolymerization modification platform.
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
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
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
10
Pages from-to
2125-2134
UT code for WoS article
001415226000001
EID of the result in the Scopus database
2-s2.0-85217246288