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Covalently Crosslinked 1,2,3-Triazolium-Containing Polyester Networks: Thermal, Mechanical, and Conductive

Clayton A Tracy1, Abagail M Adler1, Anh Nguyen1

  • 1Department of Chemistry, Murray State University, 1201 Jesse D. Jones Hall, Murray, Kentucky 42071, United States.

ACS Omega
|August 29, 2019
PubMed
Summary

New polymer networks with 1,2,3-triazolium ionic liquid groups were synthesized. These covalently crosslinked poly(ionic liquid) networks show tunable thermal, mechanical, and conductive properties, with conductivities up to 10^-6 S/cm.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Ionic Liquids

Background:

  • Ionic liquids (ILs) are salts with low melting points, offering unique properties like high conductivity and thermal stability.
  • Developing solid-state ionic conductors is crucial for applications in batteries, sensors, and actuators.
  • Polymerized ionic liquids (PILs) combine the processability of polymers with the functionality of ILs.

Purpose of the Study:

  • To synthesize novel covalently crosslinked 1,2,3-triazolium poly(ionic liquid) (TPIL) networks.
  • To investigate the structure-property relationships of TPILs concerning counteranion type and crosslink density.
  • To evaluate the thermal, mechanical, and ionic conductive properties of the synthesized TPIL networks.

Main Methods:

  • Azide-alkyne "click" cyclization was employed to create polymerizable acetoacetate monomers with 1,2,3-triazolium moieties.
  • Monomers were polymerized via base-catalyzed Michael addition to form covalently crosslinked TPIL networks.
  • Dielectric relaxation spectroscopy was used to determine ionic conductivities and analyze temperature-dependent behavior.

Main Results:

  • TPIL networks with various counteranions ([Br], [NO3], [BF4], [OTf], [NTf2]) and crosslink densities were successfully synthesized.
  • Ionic conductivities ranged from 10^-6 to 10^-9 S/cm at 30 °C and 30% relative humidity.
  • Conductivity showed dependence on the polymer's glass transition temperature, influenced by counteranion Lewis acidity/basicity and anion size.

Conclusions:

  • Covalently crosslinked TPIL networks offer a promising platform for solid-state ionic conductors.
  • Synthetic control over counteranion and crosslink density allows for tuning of material properties.
  • The study provides insights into the factors governing ionic conductivity in highly crosslinked poly(ionic liquid) systems.