Preparation and utilization of poly(methacryloylsilatrane) as a salt‐dissociation enhancer in PEO‐based polymer electrolytes

Abstract

Polymers containing silatrane units were prepared by the free radical polymerization of methacryloylsilatrane (MPS), and their conductivities were evaluated. We confirmed that MPS can be polymerized without excessive decomposition of the silatrane units by the radical polymerization initiated by azobisisobutyronitrile. The chemical structure of the polymerized MPS (pMPS) was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy. The pMPS formed a homogeneous complex with lithium trifluoromethyl sulfonate (LiOTf), although the obtained pMPS/LiOTf complex did not show conductivity. The negligible conductivity was caused by the high glass transition temperature (Tg) of the pMPS matrix, which exceeded 70°C. The pMPS was subsequently utilized as a salt‐dissociation enhancer for the poly(ethylene oxide)‐based polymer electrolyte. MPS was copolymerized with poly[methacryloyl oligo(ethylene oxide)] (pMEO) by free radical polymerization. When the pMEO incorporated a small amount of MPS units (i.e. lower than 15 mol%), the elevation in Tg was not observed, and the conductivity markedly improved. Among the series of copolymers and when compared with pristine pMEO, the copolymer containing 6.3% of MPS units had the maximum conductivity (3.1 × 10−4 S cm−1 at 80°C). The Vogel–Fulcher–Tammann fitting parameters showed that the conductivity was improved by the increase in the number of carrier ions. The enhancement in salt dissociation was presumably due to the homogeneous incorporation of polar MPS units. However, when the MPS unit content exceeded 15 mol%, the conductivity was lowered because of the increase in Tg. Copyright © 2013 John Wiley & Sons, Ltd.

Solvent-Free and Efficient Synthesis of Silatranes via an Organocatalytic Protocol under Mild Conditions

“…A simple transesterification mechanism involving only acid–base interactions between DBU and the substrates enabled a high reaction rate and excellent selectivity. A full conversion rate was achieved for each of 19 silatrane derivatives ( 3a – 3s ) without the necessity to remove the generated alcohol under reduced pressure or using the Dean–Stark apparatus, which was common practice. − Furthermore, all products were spectroscopically pure after washing with hexane without any additional purification step such as vacuum distillation, sublimation, recrystallization, or reprecipitation. In view of above, the developed reaction protocol is highly energy-efficient, sustainable, time-saving, and readily scalable, as indicated by a very high EcoScale score, losing only 10 penalty points from the hydrocarbon solvent safety in the case of most derivatives .…”

Silatrane-Containing Polymethacrylates

“…К сожалению, в настоящее время практически отсутствуют публикации, посвященные силатрансодержащим полимерам, а в немногих имеющихся публикациях по данной тематике [6][7][8] не рассматривается биологическая активность полученных макромолекул. В то же время можно ожидать, что введение силатранового фрагмента в полимеры позволит получить новые био-логически активные полимерные системы, а исследование взаимосвязи свойств этих систем и особенностей строения полимеров сделает возможным получение макромолекулярных систем с заданными физико-химическими и биоактивными свойствами.…”

Biodegradable and Biocompatible Silatrane Polymers

“…There are practically no publications on the biological activity of silatrane-containing polymers. The few articles devoted to polymer silatranes [23][24][25][26][27] concern only the synthesis and study of the physical properties of these macromolecules. As far as we know, there is practically no literature on the surface of bioactive properties of silatrane-containing polymers.…”