Utilization of 4-(trifluoromethyl)benzenesulfonates as Counter Ions Tunes the Initiator Efficiency of Sophisticated Initiators for the Preparation of Well-Defined poly(2-oxazoline)s

Title data

Engel, Nora ; Dirauf, Michael ; Seupel, Susanne ; Leiske, Meike N. ; Schubert, Stephanie ; Schubert, Ulrich S.:
Utilization of 4-(trifluoromethyl)benzenesulfonates as Counter Ions Tunes the Initiator Efficiency of Sophisticated Initiators for the Preparation of Well-Defined poly(2-oxazoline)s.
In: Macromolecular Rapid Communications. Vol. 40 (2019) Issue 12 . - 1900094.
ISSN 1521-3927
DOI: https://doi.org/10.1002/marc.201900094

Official URL:

Abstract in another language

During the last decades, poly(2-oxazoline)s (POx) have gained increased interest due to their versatility. In particular, cationic ring-opening polymerization (CROP) enables the synthesis of well-defined polymers bearing quantitative α- and ω-functionalities. In contrast to small initiating groups, the introduction of more sophisticated, respectively demanding groups remains challenging. To fulfill this challenge, the initiator should comply with one major requirement in order to yield well-defined polymers: a fast and complete initiation. The straight forward two-step synthesis of a novel initiator containing a 4-(trifluoromethyl)benzenesulfonate (fluorylate, TosCF3) counter-ion is herein presented to accomplish the introduction of a sophisticated functional 3-(2-(2-ethoxy)ethoxy)ethoxy)prop-1-ene (TEG) initiating group. Kinetic studies are conducted in acetonitrile and chlorobenzene using the hydrophilic 2-ethyl-2-oxazoline (EtOx) as well as the hydrophobic 2-octyl-2-oxazoline (OctOx) as monomers to examine the influences of the solvent as well as the different monomers. In particular, the initiator efficiency is determined by 1H and 19F nuclear magnetic resonance spectroscopy and compared to the corresponding tosylate (TEGTos) and triflate (TEGTf). It is shown that the fluorylate combines the stability of the tosylate and an enhanced propagation rate comparable to the triflate.

Further data

Item Type:	Article in a journal
Refereed:	Yes
Keywords:	2-oxazoline; cationic ring-opening polymerization; functional initiators; polymerization kinetics
Institutions of the University:	Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry Faculties Faculties > Faculty of Biology, Chemistry and Earth Sciences Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Junior Professor Sustainable and Functional Polymer Systems > Junior Professor Sustainable and Functional Polymer Systems - Juniorprof. Dr. Meike Leiske Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Junior Professor Sustainable and Functional Polymer Systems
Result of work at the UBT:	No
DDC Subjects:	500 Science > 540 Chemistry
Date Deposited:	18 Jan 2023 14:42
Last Modified:	13 Feb 2024 08:37
URI:	https://eref.uni-bayreuth.de/id/eprint/73445