Photooptical Properties of Polymethacrylates Having Cyanoazobenzene‐Containing Side Groups with Lateral Methyl Substituents and Different Spacer Length

New photochromic polymethacrylates with different spacer length having azobenzene side groups and lateral methyl substituents were synthesized. The phase behavior of polymethacrylates and their photooptical properties were studied and compared with unsubstituted analogues. It is shown that an introduction of lateral methyl substituents results in almost complete suppression of liquid crystalline (LC) phase formation and strong decrease of photoinduced dichroism values. It is found that rates of the photoinduced E‐Z isomerization and back thermal Z‐E isomerization are almost independent on spacer lengths. Due to the presence of lateral substituents, the photoinduced azobenzene Z‐form shows remarkable long lifetime, and back thermal conversion at room temperature takes more than 10 days. Specific peculiarities of the photoorientation process in polymer films under the polarized UV and visible light action were studied and their mechanism is suggested. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1337–1342