Photochromic and photomechanical ionene elastomer containing poly(tetrahydrofuran) segments and viologen units

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Abstract
Elastomeric polymer consisting of poly(oxytetramethylene) segments and viologen units (PTV) was synthesized by the reaction of dicationic living poly(tetrahydrofuran) with 4,4′‐bipyridine at −70°C. The chloride or bromide ion was introduced as the counter anion into the viologen groups of PTV by the treatment of the reaction mixture with aqueous sodium chloride or bromide, respectively. The solid film of PTV having chloride inon showed photochromism, i.e., color change by light irradiation, via photoreduction of the violegen groups. In contrast. PTV of bromide counter anion required a small amount of poly(N‐vinyl‐2‐pyrrolidone) to undergo the photochromic reaction. The irradiation of light also affected the stress relaxation of the polymers, namely PTV showed photomechanical behavior. This phenomenon is considered to be induced by the decrease of total number of ionic charges of PTV by photo‐reduction of the viologen groups followed by the change of a state of ionic clustering in the polymer matrix.