Volltext-Downloads (blau) und Frontdoor-Views (grau)

Amine-containing block copolymers for efficient catalyst-free hydroamination and preparation of functional metallopolymers

  • Cobaltocenium-containing polymers, an emerging class of materials, have historically been challenging to prepare due to their chemical robustness. In this work, we introduce a novel and highly efficient method for their preparation based on methacrylate-containing block copolymers (BCPs), allowing segment-selective introduction of functional moieties. The catalyst-free and quantitative hydroamination reaction we introduce has proven successful for the post-modification of amine-containing polymers with cobaltocenium. To demonstrate the versatility of this method, we successfully synthesized a series of BCPs consisting of polystyrene and a 5 to 20 wt% poly(tert-butyl aminoethyl methacrylate) (PtBAEMA) segment by living anionic polymerization. The selective functionalization with ethynyl-cobaltocenium hexafluorophosphate results in adjustable 5 to 40 wt% cobaltocenium units in the polymer as part of the PtBAEMA block segment. The success was monitored by IR spectroscopy, and the quantitative incorporation of the cobaltocenium moiety was verified by 1H NMR, UV-Vis spectroscopy, and TGA. DSC proved the block-selective cobaltocenium introduction by an additional glass transition temperature at 154 °C, and the strong microphase separation character of the amphiphilic BCPs leads to lamellar structures in the bulk state, as proven by TEM investigations. Finally, the water contact angle on polymer films is compared, showing polarity inversion and tunability upon conversion of hydrophilic amine to hydrophobic cobaltocenium hexafluorophosphate moieties. This successful synthesis and characterization of cobaltocenium-containing BCPs not only paves the way for a new class of metallopolymers but also offers functionalization possibilities for a variety of other responsive moieties, providing access to functional BCPs.
Metadaten
Document Type:Article
Author:Till RittnerORCiD, Kinza GhulamORCiD, Marcus KochORCiD, Markus GalleiORCiD
URN:urn:nbn:de:bsz:291:415-10104
DOI:https://doi.org/10.1039/d4py00780h
ISSN:1759-9962
Parent Title (English):Polymer Chemistry
Volume:15
Issue:35
First Page:3519
Last Page:3528
Language:English
Year of first Publication:2024
Release Date:2024/09/19
Impact:4.1 (2023)
Funding Information:European Union through the European Regional Development Fund (EFRE) and the State of Saarland, Germany, in the SWIMEMSYS project.
Scientific Units:Physical Analytics
Journals:Polymer Chemistry
DDC classes:500 Naturwissenschaften und Mathematik / 540 Chemie
Open Access:Open Access
Signature:INM 2024/090
Licence (German):License LogoCreative Commons - CC BY - Namensnennung 4.0 International