# Synthesis and Characterization of Imidazolium-Based Ionenes

## TL;DR

This paper describes the synthesis and characterization of imidazolium-based ionenes, focusing on their thermal and hygroscopic properties influenced by anion and cation structures.

## Contribution

The study introduces a method to tailor ionene properties by varying anions and cations in the polymer backbone.

## Key findings

- Polymers with glass transition temperatures ranging from 30 °C to 131 °C were synthesized.
- Thermal stability varied between 170 °C and 385 °C depending on anion and cation structures.
- Anion-exchange reactions successfully replaced halides with four other counter-anions.

## Abstract

Owing to multiple non-covalent interactions, ionic groups impart unique chemical and physical properties into polymers including ion conductivity/mobility, permeation, and intrinsic healability. Ionenes contain ionic groups in their polymer backbone, which offer great versatility in polymer design. Herein, selected aliphatic and aromatic imidazoles were synthesized, which were used as monomeric building blocks for the preparation of thermoplastic ionenes by following a Sn2 step growth reaction across organic halides. The structure and molecular weight of the polymers was characterized by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) techniques. Once polymerized, anion-exchange reactions were carried out to replace the halides with four other counter-anions. Subsequently, the effect of the nature of the anion and the cation on the polymers’ thermal and hygroscopic properties was studied in detail by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and FTIR spectroscopy. Depending on the chemical structures of the polymeric cations and the related anions, tailored polymers with a glass transition temperature (Tg) in the range of 30 °C to 131 °C and a thermal stability varying between 170 °C and 385 °C were obtained.