Eintrag in der Universitätsbibliographie der TU Chemnitz
Volltext zugänglich unter
URN: urn:nbn:de:bsz:ch1-qucosa2-829323
Raisch, Maximilian
Sommer, Michael (Prof. Dr.) ; Göstl, Robert (Dr.) (Gutachter)
Mechanochromic Donor-Acceptor Torsional Springs Based on ortho-Substituted Diphenyldiketopyrrolopyrrole
Mechanochrome Donor-Akzeptor Torsionsfedern basierend auf ortho-substituiertem Diphenyldiketopyrrolopyrrol
Kurzfassung in englisch
Mechanochromic polymers are force-sensitive materials that change their color as a response to mechanical stimuli. This visualization of forces can be used to further optimize polymer-based materials by understanding microscopic force transduction or to display fatigue of material. Most mechanochromic systems rely on bond cleavage, so they can only distinguish between “on” and “off” state without any further correlation of the applied force with the optical signal. Although reversibility to the initial state is possible for most of these systems, it often demands time or input of energy making them rather unsuitable for sensing forces in real-time.In this work, the development and application of mechanochromic donor (D)-acceptor (A) torsional springs is presented as a new concept for mechanochromic materials. The mechanically induced planarization of D and A leads to a continuous red-shift of both absorption and emission color. A suitable DA-system is found in ortho-substituted diphenyldiketopyrrolopyrrole (o-DPP) having the large torsional angle required for the equilibrium geometry and therefore showing blue-shifted optical spectra compared to reference compounds with a smaller torsional angle. The covalent incorporation into tough poly(meta,meta,para-phenylene) (PmmpP) by Suzuki polycondensation enables sufficient force transduction to the DA spring during uniaxial elongation of thin-film specimens. The detected mechanochromic response correlates with the applied stress and shows full reversibility upon stress release. Theoretical experiments based on density functional theory (DFT) confirm the experimental results and offer a detailed explanation of the molecular deformations responsible for the optical shift. In addition, the application as stress sensor was tested investigating the molecular force transduction in glassy PmmpP as a function of the number average molecular weight (Mn) by blending o-DPP-PmmpP probe chains of varying Mn with pristine PmmpP. The distinct mechanochromic response for entangled and non-entangled probe chains, respectively, allows the extraction of the critical molar mass (Mc) that is required for entanglements to become effective. The resulting value for the entanglement molar mass Me ≈ 1/2 Mc is in excellent agreement with the value determined by rheology.
| Universität: | Technische Universität Chemnitz | |
| Institut: | Professur Polymerchemie | |
| Fakultät: | Fakultät für Naturwissenschaften | |
| Dokumentart: | Dissertation | |
| Betreuer: | Sommer, Michael (Prof. Dr.) | |
| URL/URN: | https://nbn-resolving.org/urn:nbn:de:bsz:ch1-qucosa2-829323 | |
| SWD-Schlagwörter: | Mechanochemie , Kreuzkupplungsreaktion , Polyphenyle | |
| Freie Schlagwörter (Englisch): | mechanochromic polymer , torsional spring , donor-acceptor , real-time stress sensor , diketopyrrolopyrrole , glassy polyphenylene , force probe | |
| DDC-Sachgruppe: | 547.7 | |
| Sprache: | englisch | |
| Tag der mündlichen Prüfung | 16.12.2022 |
