RAFT synthesis of ABA triblock copolymers as ionic liquid-containing electroactive membranes

Tianyu Wu, Dong Wang, Mingqiang Zhang, James R. Heflin, Robert B. Moore, Timothy Edward Long

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

2-(Dimethylamino)ethyl acrylate (DMAEA) imparts versatile functionality to poly[Sty-b-(nBA-co-DMAEA)-b-Sty] ABA triblock copolymers. A controlled synthetic strategy minimized chain transfer reactions and enabled the preparation of high-molecular-weight ABA triblock copolymers with relatively narrow PDIs between 1.39 and 1.44 using reversible addition-fragmentation chain transfer (RAFT) polymerization. The presence of tertiary amine functionality and their zwitterionic derivatives in the central blocks of the triblock copolymers afforded tunable polarity toward ionic liquids. Gravimetric measurements determined the swelling capacity of the triblock copolymers for ionic liquids (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIm TfO) and 1-ethyl-3-methylimidazolium ethylsulfate (EMIm ES). A correlation of differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and small-angle X-ray scattering (SAXS) results revealed the impact of ionic liquid incorporation on the thermal transitions, thermomechanical properties, and morphologies of the triblock copolymers. IL-containing membranes of DMAEA-derived triblock copolymers and EMIm TfO exhibited desirable rubbery plateau moduli of ∼100 MPa and electromechanical actuation to a 4 V electrical stimulus. Maintaining the mechanical ductility of polymer matrices while increasing their ion-conductivity is paramount for future electroactive devices.

Original languageEnglish
Pages (from-to)6552-6559
Number of pages8
JournalACS Applied Materials and Interfaces
Volume4
Issue number12
DOIs
Publication statusPublished - 2012 Dec 26
Externally publishedYes

Fingerprint

Ionic Liquids
Ionic liquids
Block copolymers
Membranes
Dynamic mechanical analysis
X ray scattering
Polymer matrix
Amines
Swelling
Ductility
Differential scanning calorimetry
Molecular weight
Polymerization
Ions
Derivatives
2-(dimethylamino ethyl)acrylate

Keywords

  • acrylate
  • actuator
  • block copolymer
  • ionic liquid
  • membrane
  • SAXS

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

RAFT synthesis of ABA triblock copolymers as ionic liquid-containing electroactive membranes. / Wu, Tianyu; Wang, Dong; Zhang, Mingqiang; Heflin, James R.; Moore, Robert B.; Long, Timothy Edward.

In: ACS Applied Materials and Interfaces, Vol. 4, No. 12, 26.12.2012, p. 6552-6559.

Research output: Contribution to journalArticle

Wu, Tianyu ; Wang, Dong ; Zhang, Mingqiang ; Heflin, James R. ; Moore, Robert B. ; Long, Timothy Edward. / RAFT synthesis of ABA triblock copolymers as ionic liquid-containing electroactive membranes. In: ACS Applied Materials and Interfaces. 2012 ; Vol. 4, No. 12. pp. 6552-6559.
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N2 - 2-(Dimethylamino)ethyl acrylate (DMAEA) imparts versatile functionality to poly[Sty-b-(nBA-co-DMAEA)-b-Sty] ABA triblock copolymers. A controlled synthetic strategy minimized chain transfer reactions and enabled the preparation of high-molecular-weight ABA triblock copolymers with relatively narrow PDIs between 1.39 and 1.44 using reversible addition-fragmentation chain transfer (RAFT) polymerization. The presence of tertiary amine functionality and their zwitterionic derivatives in the central blocks of the triblock copolymers afforded tunable polarity toward ionic liquids. Gravimetric measurements determined the swelling capacity of the triblock copolymers for ionic liquids (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIm TfO) and 1-ethyl-3-methylimidazolium ethylsulfate (EMIm ES). A correlation of differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and small-angle X-ray scattering (SAXS) results revealed the impact of ionic liquid incorporation on the thermal transitions, thermomechanical properties, and morphologies of the triblock copolymers. IL-containing membranes of DMAEA-derived triblock copolymers and EMIm TfO exhibited desirable rubbery plateau moduli of ∼100 MPa and electromechanical actuation to a 4 V electrical stimulus. Maintaining the mechanical ductility of polymer matrices while increasing their ion-conductivity is paramount for future electroactive devices.

AB - 2-(Dimethylamino)ethyl acrylate (DMAEA) imparts versatile functionality to poly[Sty-b-(nBA-co-DMAEA)-b-Sty] ABA triblock copolymers. A controlled synthetic strategy minimized chain transfer reactions and enabled the preparation of high-molecular-weight ABA triblock copolymers with relatively narrow PDIs between 1.39 and 1.44 using reversible addition-fragmentation chain transfer (RAFT) polymerization. The presence of tertiary amine functionality and their zwitterionic derivatives in the central blocks of the triblock copolymers afforded tunable polarity toward ionic liquids. Gravimetric measurements determined the swelling capacity of the triblock copolymers for ionic liquids (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIm TfO) and 1-ethyl-3-methylimidazolium ethylsulfate (EMIm ES). A correlation of differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and small-angle X-ray scattering (SAXS) results revealed the impact of ionic liquid incorporation on the thermal transitions, thermomechanical properties, and morphologies of the triblock copolymers. IL-containing membranes of DMAEA-derived triblock copolymers and EMIm TfO exhibited desirable rubbery plateau moduli of ∼100 MPa and electromechanical actuation to a 4 V electrical stimulus. Maintaining the mechanical ductility of polymer matrices while increasing their ion-conductivity is paramount for future electroactive devices.

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