Designing Imidazolium Poly(amide-amide) and Poly(amide-imide) Ionenes and Their Interactions with Mono- and Tris(imidazolium) Ionic Liquids.

Kathryn E O’Harra,Irshad Kammakakam,Emily M Devriese,Jason E Bara,Danielle M Noll,Gala Solis,Enrique M Jackson

doi:10.3390/polym12061254

Kathryn E O’Harra, Irshad Kammakakam + Show 5 more

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https://doi.org/10.3390/polym12061254

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Journal: Polymers	Publication Date: May 30, 2020
Citations: 7	License type: CC BY 4.0

Affiliation: University of Alabama, Marshall Space Flight Center

Abstract

Here we introduce the synthesis and thermal properties of a series of sophisticated imidazolium ionenes with alternating amide-amide or amide-imide backbone functionality, and investigate the structural effects of mono(imidazolium) and unprecedented tris(imidazolium) ionic liquids (ILs) in these ionenes. The new set of poly(amide-amide) (PAA) and poly(amide-imide) (PAI) ionenes represent the intersection of conventional high-performance polymers with the ionene archetype–presenting polymers with alternating functional and ionic elements precisely sequenced along the backbone. The effects of polymer composition on the thermal properties and morphology were analyzed. Five distinct polymer backbones were synthesized and combined with a stoichiometric equivalent of the IL 1-benzyl-3-methylimidazolium bistriflimide ([Bnmim][Tf2N]), which were studied to probe the self-assembly, structuring, and contributions of intermolecular forces when IL is added. Furthermore, three polyamide (PA) or polyimide (PI) ionenes with simpler xylyl linkages were interfaced with [Bnmim][Tf2N] as well as a novel amide-linked tris(imidazolium) IL, to demonstrate the structural changes imparted by the inclusion of functional, ionic additives dispersed within the ionene matrix. This work highlights the possibilities for utilizing concepts from small molecules which exhibit supramolecular self-assembly to guide creative design and manipulate the structuring of ionenes.

Highlights

Ionic polymers present versatile structural and functional possibilities, vast options for ionic or ionizable groups and respective counterion types, and utility in diverse applications
We have demonstrated the suitability of imidazolium expansive possibilities of imidazolium ionenes, shifting toward more “high-performance”
We have successfully synthesized new PAA and PAI imidazolium ionenes, with alternating amide and imide functionality, demonstrating the amenability and modularity of this route to produce sophisticated, copolymer-like ionenes with precisely spaced features. These amide-linked ionenes demonstrate the possibility of large, complex repeat unit design using only A-A + B-B monomers while retaining processability

Summary

Introduction

Ionic polymers present versatile structural and functional possibilities, vast options for ionic or ionizable groups and respective counterion types, and utility in diverse applications. The classification of polyelectrolytes, ionomers, and ionenes distinguish the concentration and location of charged groups and further support innumerable structural possibilities within ionic polymer design (Figure 1). There have been abundant research efforts in recent decades dedicated to the design and applications surrounding polyelectrolytes and ionomers which contain charged features pendant to the main chain, highlighted in several reviews [1,2,3,4,5,6]. Polymers 2020, 12, x FOR PEER REVIEW limitless tunability structurally through manipulation of features including the chemical structure of features including the chemical structure of the ionic group, paired counterion, charge density, and the ionic group, paired counterion, charge density, and proximity to the possibly functional main chain.

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