Atom-transfer radical homo- and copolymerization of carbazole-substituted styrene and perfluorostyrene

Atom-transfer radical polymerization of 9-(4-vinyl-phenyl)carbazole (M1) and 9-(2,3,5,6-tetrafluoro-4-vinyl-phenyl)carbazole (M2) has been investigated using CuCl/N,N,N',N '',N ''-pentamethyldiethylenetriamine as catalyst and ethyl 2-bromoisobutyrate as an initiator. The polymerization of the monomers proceeded in a living fashion affording polymers with controlled molecular weight (M-n = 5000 g mol(-1) to 32000 g mol(-1)) and relatively low polydispersity (D = 1.2-1.5). The kinetic investigations showed that M2 polymerized at the faster rate as compared to M1. Block copolymers were successfully prepared starting from the polymerization of more reactive M2 followed by addition of M1. The same initiating system also induced living radical copolymerization of these monomers giving random copolymers. Usage of tetrafunctional initiator pentaerythritol tetrakis(2-bromoisobutyrate) in conjunction with CuCl/N,N,N',N '',N ''-pentamethyldiethylenetriamine as catalyst allowed to synthesize star-shaped linear and random copolymers from M1 and M2 with controlled molecular weight (up to M-n = 25000 g mol(-1)) and low polydispersity (D < 1.5). The thermal, photophysical and electrochemical properties of the synthesized linear and star-shaped polymers and copolymers were estimated. It was shown that photophysical properties of copolymers can be tuned by changing the copolymer composition.