Synthesis and Evaluation of Cellulose-Based, 1,2,3-Triazolium-Functionalized Polymerized Ionic Liquids: Thermal Transitions, Ionic Conductivities, and Morphological Properties

Authors

Rose J. Miller, Murray State University
Vanessa M. Smith, Murray State University
Stacey A. Love, Rutgers University - Camden
Sarah M. Byron, Murray State University
David Salas-de la Cruz, Rutgers University - Camden
Kevin M. Miller, Murray State UniversityFollow

Document Type

Peer Reviewed/Refereed Publication

Publication Date

1-15-2021

Publication Title

ACS Applied Polymer Materials

Department

Chemistry

College/School

Jesse D. Jones College of Science, Engineering and Technology

Abstract

A series of 1,2,3-triazolium-functionalized cellulose derivatives were prepared using an azide–alkyne “click” cyclization strategy, followed by quaternization. As cellulose represents an inexpensive and sustainable biomacromolecule, the ability to functionalize the backbone with an ionic liquid and generate conductive materials is of great interest. Here, three different counteranions ([Br], [OTf], and [NTf2]) were employed to explore the interplay between thermal, conductive, and morphological properties using a diverse set of techniques including nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray scattering, and dielectric relaxation spectroscopy (DRS). Functionalization of native cellulose resulted in the observation of a Tg, the values of which were inversely related to the size of the counteranion. Morphological analysis of the derivatives indicated that the materials were amorphous in nature, showing a clear nanophase separation dependent on the type of anion. By simply quaternizing the 1,2,3-triazole ring to produce the corresponding ionic moiety, the ionic conductivity of the material was increased by ∼6 orders of magnitude at higher temperatures as compared to the native samples. Ionic conductivity was observed to have an Arrhenius (linear) behavior and was enhanced up to 4 orders of magnitude upon exposure to humidity. The results provided evidence to suggest that the thermal and ionic conductivity properties are dependent on anion basicity and hydration.

Comments

This is an accepted manuscript of a paper published by the American Chemical Society in ACS Applied Polymer Materials, available at https://doi.org/10.1021/acsapm.0c01327

Recommended Citation

Miller, R. J., Smith, V. M., Love, S. A., Byron, S. M., la Cruz, D. S. D., & Miller, K. M. (2021). Synthesis and Evaluation of Cellulose-Based, 1, 2, 3-Triazolium-Functionalized Polymerized Ionic Liquids: Thermal Transitions, Ionic Conductivities, and Morphological Properties. ACS Applied Polymer Materials, 3(2), 1097-1106.