Photochromic Polymer Conjugates: The Importance of Macromolecular Architecture in Controlling Switching Speed within a Polymer Matrix

Naphthopyran-poly(n-butyl acrylate) conjugates with different geometries were assembled using ATRP. First, within a rigid lens matrix, all investigation of the photochromic behavior of various poly(n-butyl acrylate), p(n-BA), homopolymers showed that midplacement of a single dye moiety, made possible using a Y-branching difunctional photochromic initiator, gave superior fade kinetics per chain length of conjugated polymer compared to end-functionalized homopolymers. Furthermore, having the dye pendant from the chain opposed to directly within the chain was also found to be advantageous. Fading kinetics became faster when chain length was increased, except in the case of linear random copolymers made by copolymerization of n-butyl acrylate with a naphthopyran acrylate. A gradient copolymer made with a nonphotochromic difunctional initiator and a naphthopyran methacrylate displayed Superior kinetics. Films consisting or ABA triblock copolymers, incorporating the photochromic in the middle of a sort p(n-BA) section, gave slower switching speeds compared to lens samples, with responses that were highly tunable and dependent on the amount of soft section inhabited by the photochromic moiety.