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Covalent Incorporation of Ionic Liquid into Ion‐Conductive Networks via Thiol–Ene Photopolymerization
Author(s) -
Tibbits Andrew C.,
Yan Yushan S.,
Kloxin Christopher J.
Publication year - 2017
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201700113
Subject(s) - photopolymer , cationic polymerization , ionic conductivity , polymer chemistry , ionic liquid , glass transition , ionic bonding , ene reaction , monomer , polymer , polymerization , bromide , materials science , conductivity , ion , chemistry , organic chemistry , electrolyte , electrode , catalysis
Ene‐functionalized ionic liquids with a range of different cationic groups and counteranions react stoichiometrically within a tetrathiol‐divinyl ether formulation within 20 minutes to form thiol–ene polymers with measurable ionic conductivities via a photoinitiated polymerization and crosslinking reaction. Dynamic mechanical analysis indicates that these networks are more spatially heterogeneous and possess higher glass transition temperatures ( T g ) compared with thiol–ene formulations without charge. While tuning the molar content of ionic liquid monomer is one method for adjusting the crosslink and charge densities of the thiol–ene polymeric ionic liquid networks, the presence of cation–anion interactions also plays a critical role in dictating the thermomechanical and conductive properties. Particularly, while cationic structure effects are not significant on the polymer properties, the use of a weakly coordinating hydrophobic anion (bistriflimide) instead of bromide‐based networks results in an apparent decrease in hydrated ion conductivity (7.4 to 1.5 mS cm −1 ) and T g (−9.6 to −17.8 °C).