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Miktoarm Star Copolymers Prepared by Transformation from Enhanced Spin Capturing Polymerization to Nitroxide-Mediated Polymerization (ESCP-Ŧ-NMP) toward Nanomaterials

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Department of Chemical Engineering, i-Center for Advanced Science and Technology (iCAST), National Chung Hsing University, Taichung 40227, Taiwan
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Industrial Technology Research Institute, Chutung, Hsinchu 31057, Taiwan
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Research Center for Functional Materials, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Ibaraki, Japan
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Department of Fundamental Science and Physical Education, Faculty of Science at Sriracha, Kasetsart University, Chonburi 20230, Thailand
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Department of Materials Science and Engineering, National Chung Hsing University, Taichung 40227, Taiwan
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Department of Environmental Engineering, Innovation and Development Center of Sustainable Agriculture, Research Center of Sustainable Energy and Nanotechnology, iCAST, National Chung Hsing University, Taichung 40227, Taiwan
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Authors to whom correspondence should be addressed.
Academic Editor: Ayae Sugawara-Narutaki
Nanomaterials 2021, 11(9), 2392; https://doi.org/10.3390/nano11092392
Received: 10 August 2021 / Revised: 4 September 2021 / Accepted: 10 September 2021 / Published: 14 September 2021
Reversible-deactivation radical polymerization (RDRP) serves as a powerful tool nowadays for the preparations of unique linear and non-linear macromolecules. In this study, enhanced spin capturing polymerizations (ESCPs) of styrene (St) and tert-butyl acrylate (tBA) monomers were, respectively, conducted in the presence of difunctional (1Z,1′Z)-1,1′-(1,4-phenylene) bis (N-tert-butylmethanimine oxide) (PBBN) nitrone. Four-arm (PSt)4 and (PtBA)4 star macroinitiators (MIs) can be afforded. By correspondingly switching the second monomer (i.e., tBA and St), miktoarm star copolymers (μ-stars) of (PSt)2-μ-(PtBA-b-PSt)2 and (PtBA)2-μ-(PSt-b-PtBA)2) were thus obtained. We further conducted hydrolysis of the PtBA segments to PAA (i.e., poly(acrylic acid)) in μ-stars to afford amphiphilic μ-stars of (PSt)2-μ-(PAA-b-PSt)2 and (PAA)2-μ-(PSt-b-PAA)2. We investigated each polymerization step and characterized the obtained two sets of “sequence-isomeric” μ-stars by FT-IR, 1H NMR, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). Interestingly, we identified their physical property differences in the case of amphiphilic μ-stars by water contact angle (WCA) and atomic force microscopy (AFM) measurements. We thus proposed two microstructures caused by the difference of polymer chain sequences. Through this polymerization transformation (Ŧ) approach (i.e., ESCP-Ŧ-NMP), we demonstrated an interesting and facile strategy for the preparations of μ-stars with adjustable/switchable interior and exterior polymer structures toward the preparations of various nanomaterials. View Full-Text
Keywords: ESCP; NMP; miktoarm star copolymers; polystyrene; poly(tert-butyl acrylate) ESCP; NMP; miktoarm star copolymers; polystyrene; poly(tert-butyl acrylate)
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MDPI and ACS Style

Lin, T.-Y.; Tu, C.-W.; Aimi, J.; Huang, Y.-W.; Jamnongkan, T.; Hsueh, H.-Y.; Lin, K.-Y.A.; Huang, C.-F. Miktoarm Star Copolymers Prepared by Transformation from Enhanced Spin Capturing Polymerization to Nitroxide-Mediated Polymerization (ESCP-Ŧ-NMP) toward Nanomaterials. Nanomaterials 2021, 11, 2392. https://doi.org/10.3390/nano11092392

AMA Style

Lin T-Y, Tu C-W, Aimi J, Huang Y-W, Jamnongkan T, Hsueh H-Y, Lin K-YA, Huang C-F. Miktoarm Star Copolymers Prepared by Transformation from Enhanced Spin Capturing Polymerization to Nitroxide-Mediated Polymerization (ESCP-Ŧ-NMP) toward Nanomaterials. Nanomaterials. 2021; 11(9):2392. https://doi.org/10.3390/nano11092392

Chicago/Turabian Style

Lin, Tzu-Yao, Cheng-Wei Tu, Junko Aimi, Yu-Wen Huang, Tongsai Jamnongkan, Han-Yu Hsueh, Kun-Yi A. Lin, and Chih-Feng Huang. 2021. "Miktoarm Star Copolymers Prepared by Transformation from Enhanced Spin Capturing Polymerization to Nitroxide-Mediated Polymerization (ESCP-Ŧ-NMP) toward Nanomaterials" Nanomaterials 11, no. 9: 2392. https://doi.org/10.3390/nano11092392

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