Photolysis-induced micellization of a poly(4-tert-butoxystyrene)-block-polystyrene diblock copolymer

A novel micellization induced by photolysis was attained using a poly(4-tert-butoxystyrene)-block-polystyrene diblock copolymer (PBSt-b-PSt). BSt-b-PSt showed no self-assembly in dichloromethane and existed as isolated copolymers. Dynamic light scattering demonstrated that the copolymer produced spherical micelles in dichloromethane by the irradiation with a high-pressure mercury lamp in the presence of photoacid generators, such as bis(alkylphenyl)iodonium hexafluorophosphate (BAI), diphenyliodonium hexafluorophosphate (DPI), and triphenylsulfonium triflate (TPS). The irradiation time to promote the micellization increased in the order of BAI < DPI < TPS, depending on the UV absorption intensity of the photoacid generators. The efficiency to promote the micellization was also dependent on the block length of the copolymer. Under an identical PBSt block length, the copolymer with the shorter PSt block length more easily formed micelles. The ¹H NMR analysis confirmed that the PBSt-b-PSt copolymer was converted into poly(4-vinyl phenol)-block-PSt, resulting in micelles by self-assembly.