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Deglmann, Peter ; Machleit, Sara ; Gallizioli, Cesare ; Rupf, Susanne M. ; Plajer, Alex:
Lithium catalysed sequence selective ring opening terpolymerisation : a mechanistic study.
In: Catalysis Science & Technology.
Bd. 13
(2023)
Heft 10
.
- S. 2937-2945.
ISSN 2044-4761
DOI: https://doi.org/10.1039/D3CY00301A
Abstract
The catalytic construction of well-defined materials from mixtures of building blocks is an important challenge in sustainable catalysis. In this regard, we have recently reported a new type of selective ring-opening terpolymerisation (ROTERP), in which three monomers (A, B, C) are selectively enchained into a (ABA′C)n sequence, but the reasons behind this unusual selectivity remained unanswered. In this study, we present a detailed investigation into the full ROTERP mechanism based on the reactivity of model intermediates, computational studies investigating >100 possible intermediates and transition states and reaction kinetics. Experimental verification of the intermediate speciation, the primary insertion steps and the side-reactions lets us show that although most insertions and side-reactions are thermodynamically viable, kinetic selection processes at the propagating chain end determine the sequence selectivity. Computational studies elucidate the special role and speciation of the lithium catalyst which during the catalytic cycle involves mono-metallic, bi-metallic and charge separated transition states comprising both coordinative activation of incoming monomers and functional groups of the polymer backbone adjacent to the propagating chain. Our study not only deciphers the mechanism of a rare selective terpolymerisation but also helps answering open questions relevant to ring-opening copolymerisation (ROCOP) and alkali-metal catalysis in general, thus guiding the design of future polymerisation catalysis for degradable materials.
Weitere Angaben
| Publikationsform: | Artikel in einer Zeitschrift |
|---|---|
| Begutachteter Beitrag: | Ja |
| Institutionen der Universität: | Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Lehrstuhl Makromolekulare Chemie I |
| Titel an der UBT entstanden: | Nein |
| Themengebiete aus DDC: | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Eingestellt am: | 19 Mär 2024 10:29 |
| Letzte Änderung: | 19 Mär 2024 10:29 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/88939 |