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Effects of Hydride Transfer Ring-Opening Reaction on B(C6F5)3 Catalyzed Polymerization of D4H Cyclosiloxane and Dialkoxysilanes toward Thermally Stable Silsesquioxane–Siloxane Hybrid Materials

Cite this: Macromolecules 2022, 55, 22, 10134–10144
Publication Date (Web):October 24, 2022
https://doi.org/10.1021/acs.macromol.2c00948
Copyright © 2022 American Chemical Society

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    Abstract

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    The Piers–Rubinsztajn (PR) reaction catalyzed by a metal-free B(C6F5)3 catalyst was reported as efficient in synthesizing novel polysiloxanes through polycondensation of dialkoxylsilanes and dihydrosiloxane monomers at room temperature. This study is aimed at developing new cyclosiloxane polymers having no hydrocarbon linker in the main chain via an equimolar PR reaction between tetrafunctional eight-membered cyclosiloxanes (TMCS) having the four reactive silyl hydrides (Si–H) at the Si vertices and bifunctional dialkoxylsilanes. The final polymers were targeted with the remaining Si–H group at the Si vertices of the TMCS repeating units for post-functionalization, good solubility in typical organic solvents for post-processing, and a stable ring structure in TMCS for outstanding macromolecular flexibility. However, hydride transfer ring-opening polymerization (HTRP) of TMCS was reported in the B(C6F5)3-catalyzed reaction system, which invariably causes uncontrollable gelation. Suppression of HTRP succeeded via control of total monomer concentration and reaction time reduction, thereby obtaining post-processable and post-functionalizable liquid cyclosiloxane prepolymers. Thermal curing of the prepolymers through self-cross-linking of the remaining reactive Si–H groups gave rise to free-standing films with excellent thermal stability exceeding 600 °C and a low dielectric constant. The functional versatility of the Si–H groups produces promising prepolymers for creating various functional materials.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.2c00948.

    • NMR spectra of monomers and polymers; residual Si–H analysis; photographs; FT-IR spectra analysis; DSC data; schematic of pencil hardness test; and surface wettability (PDF)

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    Cited By

    This article is cited by 3 publications.

    1. Naoki Yoshida, Kenta Yamamoto, Huie Zhu, Masaya Mitsuishi. Metal-Free Synthesis of Cross-Linkable Poly(silyl ether)s Using Cyclosiloxanes. ACS Applied Polymer Materials 2024, Article ASAP.
    2. Chongwen Yu, Tianhao Li, Xiao Hu, Ming Liu, Qing Huang, Liu He, Yujie Song. Anchoring Effect of Hyperbranched Carborane in Highly Cross-Linked Cyclosiloxane Networks toward High-Performance Polymers. Macromolecules 2023, 56 (12) , 4738-4747. https://doi.org/10.1021/acs.macromol.3c00286
    3. Manmian Chen, Huie Zhu, Masaya Mitsuishi. Nanosheets Based on Hard 2-Ureido-4[1H]-pyrimidone Units and Soft Cyclosiloxane Units as Membrane Materials. ACS Applied Nano Materials 2023, 6 (7) , 5653-5663. https://doi.org/10.1021/acsanm.3c00108