Polymer, Vol.78, 42-50, 2015
Photo-healable ion gel with improved mechanical properties using a tetra-arm diblock copolymer containing azobenzene groups
Photo-healable ion gels with improved mechanical properties are demonstrated using a tetra-arm diblock copolymer (A(B)(4)) containing azobenzene groups. Physical ion gels were prepared by self-assembly of A(B)(4) in a hydrophobic ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim]PF6), where A block is the ionic liquid-compatible tetra-PEG, and B block is the thermo-/ photo-responsive random copolymer of 4-phenylazophenyl methacrylate and N-isopropylacrylamide (P(NIPAm-r-AzoMA)). The A(B)(4) ion gels have a higher modulus and fewer network defects than the triblock copolymer (A(B)(2)) ion gel (A block is PEG; B block is P(NIPAm-r-AzoMA)). Self-standing A(B)(4) ion gels were obtained at a lower polymer concentration than A(B)(2) ion gels in [C(4)mim]PF6. The A(B)(4)/[C(4)mim]PF6 and A(B)(2)/[C(4)mim]PF6 binary systems exhibit low-temperature gel-states and high-temperature sol-states. The gel-to-sol transition temperature also depends on the photo-isomerization state of the azobenzene moiety in the polymers. It is confirmed that photo-induced sol -gel transition is reversible at a suitable temperature. Photo-healable ion gels are demonstrated using the photo-induced reversible sol-gel transition, where damaged regions are UV-light-irradiated to induce the gel-to-sol transition then visible-light-irradiated to heal the gels by the sol-to-gel transition. Remarkable photo-healing efficiency in terms of the mechanical properties is realized by this procedure. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords:Block copolymer;Ionic liquid;Ion gel;Upper critical solution temperature;Photochromism;Photo-healable material