Norbornenyl-based amphiphilic ABA-triblock azobenzene copolymers: Synthesis, photoresponsive and self-assembly properties

A series of well-defined ABA-triblock copolymers P(NB-PtBA)x-b-P(NB-PFP)y-b-P(NB-PtBA)x were synthesized by living ring-opening metathesis polymerization (ROMP) of norbornenyl-poly(tert-butyl acrylate) (NB-PtBA), norbornenyl-pentafluorophenyl (NB-PFP) and NB-PtBA in a sequential manner by the use of Grubbs’ third generation catalyst (G3). The corresponding amphiphilic ABA-triblock azobenzene copolymers P(NB-PAA)x-b-P(NB-Azo)y-b-P(NB-PAA)x were obtained in high yields after subsequent post-polymerization modifications, including the reaction of active esters with amine-functionalized azobenzene to introduce the azobenzene unit, and the hydrolysis reaction to remove the tert-butyl groups. Under alternating UV and visible light illumination, the light response behaviors of the polymers were demonstrated by UV–Vis spectroscopy, and the reversible changes were observed as a result of the reversible trans-cis photoisomerization of azobenzene mesogens. These amphiphilic copolymers can also spontaneously self-assemble into spherical nanoparticles in an aqueous medium, and the hydrodynamic diameter increases as the hydrophobic NB-Azo content increases. [Display omitted] •A series of norbornenyl-based amphiphilic ABA-triblock azobenzene copolymers was synthesized via living ROMP and typically post-polymerization modifications.•The photoresponsive and self-assembly behavior of the polymers were investigated in details.•This synthetic strategy can be applied to synthesis various multiblock copolymers with well-defined architectures.