Please use this identifier to cite or link to this item:
http://doi.org/10.25358/openscience-9533
Authors: | Hahn, Christoph Rauschenbach, Moritz Frey, Holger |
Title: | Merging styrene and diene structures to a cyclic diene : anionic polymerization of 1-vinylcyclohexene (VCH) |
Online publication date: | 12-Sep-2023 |
Year of first publication: | 2023 |
Language: | english |
Abstract: | We report the first anionic polymerization of 1-vinylcyclohexene (VCH). This structure may be considered as an intermediate between dienes and styrene. The polymerization of this cyclic 1,2-disubstituted 1,3-diene proceeded quantitatively in cyclohexane at 25 °C with sec-butyllithium as an initiator. The obtained polymers have well-controlled molecular weights in the range of 5 to 142 kg mol−1, controlled by the molar ratio of monomer and initiator, with narrow molecular weight distributions (Đ<1.07–1.20). In situ 1H NMR kinetic characterization revealed a weak gradient structure for the copolymers of styrene and VCH, (rSty=2.55, rVCH=0.39). P(VCH) obtained in cyclohexane with sec-BuLi as an initiator showed both 1,4- and 3,4-incorporation mode (ratio: 64 : 36). It was demonstrated that the microstructure of the resulting P(VCH) can be altered by the addition of a modifier (THF), resulting in increasing 3,4-microstructure (up to 78 %) and elevated glass-transition temperature up to 89 °C. Thus, the monomer VCH polymerizes carbanionically like a diene, however leading to rigid polymers with high glass transition temperature, which provides interesting options for combination with other dienes to well-defined polymer architectures and materials. |
DDC: | 540 Chemie 540 Chemistry and allied sciences |
Institution: | Johannes Gutenberg-Universität Mainz |
Department: | FB 09 Chemie, Pharmazie u. Geowissensch. |
Place: | Mainz |
ROR: | https://ror.org/023b0x485 |
DOI: | http://doi.org/10.25358/openscience-9533 |
Version: | Published version |
Publication type: | Zeitschriftenaufsatz |
License: | CC BY |
Information on rights of use: | https://creativecommons.org/licenses/by/4.0/ |
Journal: | Angewandte Chemie : international edition 62 28 |
Pages or article number: | e202302907 |
Publisher: | Wiley-VCH |
Publisher place: | Weinheim |
Issue date: | 2023 |
ISSN: | 1521-3773 |
Publisher DOI: | 10.1002/anie.202302907 |
Appears in collections: | DFG-491381577-H |
Files in This Item:
File | Description | Size | Format | ||
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![]() | merging_styrene_and_diene_str-20230904112630528.pdf | 2.26 MB | Adobe PDF | View/Open |