Khan, I.; Uddin, M. H.; Alshali, S.; Alqurashi, E.; Alyoubi, S.; Walters, N. Functionalized Hairy Nanoparticles for Reversible Thermoplastic Elastomeric Networks. Preprints2024, 2024092260. https://doi.org/10.20944/preprints202409.2260.v1
APA Style
Khan, I., Uddin, M. H., Alshali, S., Alqurashi, E., Alyoubi, S., & Walters, N. (2024). Functionalized Hairy Nanoparticles for Reversible Thermoplastic Elastomeric Networks. Preprints. https://doi.org/10.20944/preprints202409.2260.v1
Chicago/Turabian Style
Khan, I., Saber Alyoubi and Natalia Walters. 2024 "Functionalized Hairy Nanoparticles for Reversible Thermoplastic Elastomeric Networks" Preprints. https://doi.org/10.20944/preprints202409.2260.v1
Abstract
Polymers synthesized with end-of-life consideration allow for recovery and reprocessing. ”Living-anionic polymerization (LAP)” and hydrosilylation reaction were utilized to synthesize hair-end furan functionalized hairy nanoparticles (HNPs) with hard polystyrene (PS) core and soft polydimethylsiloxane (PDMS) via a one-pot approach. The synthesis was carried out by first preparing the living core through cross-linking styrene with divinylbenzene using sec-butyl lithium, followed by the addition of the hexamethylcyclotrisiloxane (D3) monomer to the living core. The living polymer was terminated by dimethylchlorosilane to obtain the HNPs with Si-H functional end groups. The furan functionalization was carried out by the hydrosilylation reaction between Si-H of the functionalized HNP and 2-vinyl furan. Additionally, furan functionalized polystyrene (PS) and polydimethylsiloxane (PDMS) were also synthesized by LAP. 1H NMR and ATR-IR spectra confirm the successful synthesis of the target polymers. Differential scanning calorimetry shows two glass transition temperatures indicative of a poly(dimethylsiloxane) soft phase and a poly(styrene) hard phase, suggesting that the HNPs are microphase separated. The furan functionalized HNPs form thermo-reversible networks upon cross-linking with bismaleimide (BMI) via a Diels−Alder coupling reaction. The kinetics of the forward Diels–Alder reaction between the functionalized polymer and BMI were studied at three different temperatures: 50 °, 60 °, and 70 °C by UV-Vis spectroscopy. The activation energy for the furan functionalized HNPs reaction with the bismaleimide was lower compared to the furan functionalized polystyrene and poly(dimethylsiloxane) linear polymers. The crosslinked polymer network formed from the Diels−Alder forward reaction dissociates at around 140 °–154 °C, and the HNPs are recovered. The recovered HNPs can be re-crosslinked at 50 °C. The results suggest that furan functionalized HNPs are promising building blocks for preparing thermo-reversible elastomeric networks.
Keywords
Living Anionic Polymerization (LAP); Thermoplastic Elastomer; Diels-Alder Reaction (DA); Glass Transition Temperature (Tg); Dynamic Covalent Bond; Kinetics
Subject
Chemistry and Materials Science, Polymers and Plastics
Copyright:
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
