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High-Refractive-Index Polysiloxanes Containing Naphthyl and Phenanthrenyl Groups and Their Thermally Cross-Linked Resins
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    High-Refractive-Index Polysiloxanes Containing Naphthyl and Phenanthrenyl Groups and Their Thermally Cross-Linked Resins
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    Macromolecules

    Cite this: Macromolecules 2022, 55, 11, 4675–4691
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    https://doi.org/10.1021/acs.macromol.2c00265
    Published May 19, 2022
    Copyright © 2022 The Authors. Published by American Chemical Society

    Abstract

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    High-refractive-index polysiloxanes containing naphthyl, phenanthrenyl, phenyl, and methyl groups have been synthesized using a polycondensation reaction starting from substituted di- and trialkoxysilanes. The obtained polymers comprised linear siloxane and partially cross-linked silsesquioxane units and showed optical transparencies of up to 99% at a thickness around 120 μm and high refractive indices of up to 1.622. The polymeric structures contained stabilized silanol groups that were further cross-linked at increased temperatures of 200 °C resulting in the formation of hybrid inorganic–organic resins. These typical thermal treatments at 200 °C for 72 h kept the transparencies as high as 98% and slightly lowered the RIs to values up to 1.610. A detailed structure evaluation of the resulting systems showed, depending on the size of the polycyclic aromatic substituent, excimer formation, which is based on weak interactions of the aromatic groups in the polymeric material. After thermal consolidation, glass-transition temperatures of the cross-linked systems were in the range of 18–74 °C depending on the composition. Thermal stabilities of the final resins reached higher values than commonly used siloxane resins up to 470 °C. The final materials are potential resins for high-temperature optical applications.

    Copyright © 2022 The Authors. Published by American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.2c00265.

    • Spectroscopic data, elemental analysis, and RI measurements of dialkoxysilanes; spectroscopic, SEC, and MALDI-TOF data; DOC calculations; PXRD; and RI measurements of polysiloxanes (PDF)

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    This article is cited by 11 publications.

    1. Svenja Pohl, Markus Gallei, Guido Kickelbick. Impact of Size and Substitution Isomerism in Polycyclic Aromatic-Substituted Trialkoxysilanes on the Formation of Softenable Polysilsesquioxanes. Macromolecules 2025, 58 (3) , 1298-1313. https://doi.org/10.1021/acs.macromol.4c02737
    2. Elias C. J. Gießelmann, Stefan Engel, Svenja Pohl, Max Briesenick, Lukas P. Rüthing, Cedric Kloos, Aylin Koldemir, Lars Schumacher, Joshua Wiethölter, Jörn Schmedt auf der Günne, Guido Kickelbick, Oliver Janka. Rapid Synthesis of a Green Emitting Phosphor by Sulfidation of Intermetallic EuAl2 and its Use in a Hybrid Material. Chemistry of Materials 2025, 37 (1) , 97-108. https://doi.org/10.1021/acs.chemmater.4c02093
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    4. Sheng Wang, Xiaohong Li, Yingfeng Tu. A reflection on ‘Side-chain fullerene polyesters: a new class of high refractive index polymers’. Materials Horizons 2025, 12 (1) , 15-19. https://doi.org/10.1039/D4MH90124J
    5. L. C. Klein, Andrei Jitianu. Hybrid organic-inorganic gels that are melting gels. Journal of Sol-Gel Science and Technology 2025, 113 (1) , 30-38. https://doi.org/10.1007/s10971-024-06524-4
    6. Jan‐Falk Kannengießer, Bernd Morgenstern, Oliver Janka, Guido Kickelbick. Oligo‐Condensation Reactions of Silanediols with Conservation of Solid‐State‐Structural Features.. Chemistry – A European Journal 2024, 30 (16) https://doi.org/10.1002/chem.202303343
    7. Ankit Mishra, Pankaj Rajak, Ayu Irie, Shogo Fukushima, Rajiv K. Kalia, Aiichiro Nakano, Ken-ichi Nomura, Fuyuki Shimojo, Priya Vashishta. High-throughput computation and machine learning of refractive index of polymers. Applied Physics Letters 2023, 123 (12) https://doi.org/10.1063/5.0161198
    8. Svenja Pohl, Guido Kickelbick. Influence of alkyl groups on the formation of softenable polysilsesquioxanes. Journal of Sol-Gel Science and Technology 2023, 107 (2) , 329-346. https://doi.org/10.1007/s10971-023-06126-6
    9. Qihua Wu, Weixian Zhang, Wen Shao, Yong Pei, Jiajia Wang. Partially Bio-Based and fluorinated polysiloxane with high transparency and low dielectric constant. European Polymer Journal 2023, 194 , 112136. https://doi.org/10.1016/j.eurpolymj.2023.112136
    10. Yujin Jeon, Jisung Choi, Donghwa Seo, Soon Hwa Jung, Jeewoo Lim. Low birefringence and low dispersion aliphatic thermosets with a high and tunable refractive index. Polymer Chemistry 2023, 14 (10) , 1117-1123. https://doi.org/10.1039/D2PY01327D
    11. Cedric P. Ambulo, Kyle J. Carothers, Ashford T. Hollis, Hannah N. Limburg, Lirong Sun, Carl J. Thrasher, Michael E. McConney, Nicholas P. Godman. Photo‐Crosslinkable Inorganic/Organic Sulfur Polymers. Macromolecular Rapid Communications 2023, 44 (5) https://doi.org/10.1002/marc.202200798

    Macromolecules

    Cite this: Macromolecules 2022, 55, 11, 4675–4691
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.2c00265
    Published May 19, 2022
    Copyright © 2022 The Authors. Published by American Chemical Society

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