A Non-Hydrolytic Sol–Gel Route to Organic-Inorganic Hybrid Polymers: Linearly Expanded Silica and Silsesquioxanes

Abstract

Condensation reactions of chlorosilanes (SiCl4 and CH3SiCl3) and bis(trimethylsilyl)ethers of rigid, quasi-linear diols (CH3)3SiO–AR–OSi(CH3)3 (AR = 4,4′-biphenylene (1) and 2,6-naphthylene (2)), with release of (CH3)3SiCl as a volatile byproduct, afforded novel hybrid materials that feature Si–O–C bridges. The precursors 1 and 2 were characterized using FTIR and multinuclear (1H, 13C, 29Si) NMR spectroscopy as well as single-crystal X-ray diffraction analysis in case of 2. Pyridine-catalyzed and non-catalyzed transformations were performed in THF at room temperature and at 60 °C. In most cases, soluble oligomers were obtained. The progress of these transsilylations was monitored in solution with 29Si NMR spectroscopy. Pyridine-catalyzed reactions with CH3SiCl3 proceeded until complete substitution of all chlorine atoms; however, no gelation or precipitation was found. In case of pyridine-catalyzed reactions of 1 and 2 with SiCl4, a Sol–Gel transition was observed. Ageing and syneresis yielded xerogels 1A and 2A, which exhibited large linear shrinkage of 57–59% and consequently low BET surface area of 10 m2⋅g−1. The xerogels were analyzed using powder-XRD, solid state 29Si NMR and FTIR spectroscopy, SEM/EDX, elemental analysis, and thermal gravimetric analysis. The SiCl4-derived amorphous xerogels consist of hydrolytically sensitive three-dimensional networks of SiO4-units linked by the arylene groups. The non-hydrolytic approach to hybrid materials may be applied to other silylated precursors, if the reactivity of the corresponding chlorine compound is sufficient.

Keywords

• inorganic/organic networks
• non-aqueous gels
• arylene bridged
• chlorosilanes
• pyridine
• ²⁹Si solid state NMR