Molecular Design of Polymerized Ionic Liquids
- Author(s): Sanoja, Gabriel Eduardo
- Advisor(s): Segalman, Rachel A
- Balsara, Nitash P
- et al.
Polymerized ionic liquids are an emerging class of functional materials with ionic liquid moieties covalently attached to a polymer backbone. As such, they synergistically combine the structural hierarchy of polymers with the versatile physicochemical properties of ionic liquids. Unlike other ion-containing polymers that are typically constrained to high glass transition temperatures, polymerized ionic liquids can exhibit low glass transition temperatures due to weak electrostatic interactions even at high charge fractions. Promising applications relevant to electrochemical energy conversion and CO2 capture and sequestration have been demonstrated for polymerized ionic liquids, but a molecular design strategy that allows for elucidation of their structure-property relationships is yet to be developed.
A combination of anionic polymerization, click chemistry, and ion metathesis allows for fine and independent control over polymer properties including the number of repeat units, fraction of ionic liquid moieties, composition, and architecture. This strategy has been exploited to elucidate the effect of lamellar domain spacing on the ionic conductivity of block copolymers based on hydrated protic polymerized ionic liquids. The conductivity relationship demonstrated in this study suggests that a mechanically robust material can be designed without compromising its ability to transport ions.
The vast set of ion pair combinations in polymerized liquids provides a unique opportunity to develop functional materials where properties can be controlled with subtle changes in molecular structure via ion metathesis. We illustrate the case of a polymerized ionic liquid that combines the low toxicity and macromolecular dimensions of poly(ethylene glycol) with the magnetic functionality of ion pairs containing iron(III). This material can yield novel theranostic agents with controlled residence time within the human body, and paramagnetic functionality to enhance 1H nuclei relaxation rate required for medical imaging.
Finally, the molecular design strategy is expanded to incorporate ion pairs based on metal-ligand coordination bonds between cations and imidazole moieties tethered to the polymer backbone. This illustrates a general approach for using chelating polymers with appropriate metal-ligand interactions to design high conductivity and tunable modulus polymer electrolytes