# Hydrosilylation vs. Piers–Rubinsztajn: Synthetic Routes to Chemically Cross-Linked Hybrid Phosphazene-Siloxane 3D-Structures

**Authors:** Andrey S. Esin, Anna I. Chernysheva, Ekaterina A. Yurasova, Ekaterina A. Karpova, Vyacheslav V. Shutov, Igor S. Sirotin, Mikhail A. Soldatov, Mikhail V. Gorlov, Oleg A. Raitman

PMC · DOI: 10.3390/polym17141967 · 2025-07-17

## TL;DR

This paper explores two chemical reactions for creating cross-linked hybrid materials with potential uses in biomedical and battery applications.

## Contribution

The study demonstrates that hydrosilylation is more effective than Piers–Rubinsztajn for making phosphazene-siloxane materials.

## Key findings

- Piers–Rubinsztajn reaction fails due to catalyst deactivation by nitrogen atoms in phosphazene chains.
- Hydrosilylation successfully produced cross-linked hybrid materials with eugenoxy and guaiacoxy groups.
- Rheological and thermal properties of the materials were analyzed for potential applications.

## Abstract

Exploration of new ways for the direct preparation of cross-linked structures is a significant problem in terms of materials for biomedical applications, lithium batteries electrolytes, toughening of thermosets (epoxy, benzoxazine, etc.) with interpenetrating polymer network, etc. The possibility to utilize hydrosilylation and Piers–Rubinsztajn reactions to obtain cross-linked model phosphazene compounds containing eugenoxy and guaiacoxy groups has been studied. It was shown that Piers–Rubinsztajn reaction cannot be used to prepare phosphazene-based tailored polymer matrix due to the catalyst deactivation by nitrogen atoms of main chain units. Utilizing the hydrosilylation reaction, a series of cross-linked materials were obtained, and their properties were studied by NMR spectroscopy, FTIR, DSC, and TGA. Rheological characterizations of the prepared tailored matrices were conducted. This work showed a perspective of using eugenoxy functional groups for the preparation of three-dimensional hybrid phosphazene/siloxane-based materials for various applications.

## Full-text entities

- **Chemicals:** lithium (MESH:D008094), nitrogen (MESH:D009584), epoxy (MESH:D004853), polymer (MESH:D011108), Phosphazene (-), Siloxane (MESH:D012833), benzoxazine (MESH:D048588)

## Figures

7 figures with captions in the complete paper: https://tomesphere.com/paper/PMC12297966/full.md

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Source: https://tomesphere.com/paper/PMC12297966