Abstract
ABSTRACTPhotochromic dyes have restricted use in rigid polycarbonates because of slow coloration and decoloration kinetics. In this study, it is shown that the decoloration kinetics of two photochromic dyes can be controlled by tuning the chain stiffness and free volume of the host matrix. The introduction of flexible moieties in rigid BPA‐based polycarbonate chain accelerates the decoloration of these dyes whereas a rigid co‐monomer delays the decoloration kinetics. Although Tg might be used as a parameter to improve photochromism in polymer matrices, dynamic mechanical analysis demonstrates that the decoloration kinetics of the dyes in host polymer matrices having similar Tg depends primarily on the secondary relaxations and, thus, on the polymer architecture. The effect of the co‐monomer type on the characteristic ratio is also discussed underlining the potential relationship between the free volume and chain stiffness. These results open the possibility to develop transparent or semitransparent photochromic materials based on tailor‐made co‐polycarbonates. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1593–1601
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