Effect of substituted groups on the living anionic polymerization of 2-vinylcarbazole derivatives

To study the effect of the substituents in the N-position of the carbazole on anionic polymerization, 2-vinylcarbazole derivatives of 9-butyl-2-vinylcarbazole (NBu2VCz), 9-phenyl-2-vinylcarbazole (NPh2VCz), and 9-(pyridin-2-yl)-2-vinylcarbazole (NPy2VCz) were synthesized. The anionic polymerization of NBu2VCz and NPh2VCz using s-BuLi was performed at −78 °C with a 100% yield, but the polymerization of NBu2VCz showed a broader molecular weight distribution (Mw/Mn = 1.23) than NPh2VCz (Mw/Mn = 1.11). The anionic polymerization of NPy2VCz using s-BuLi and DPM-K had a yield below 5%. In particular, the living anionic polymerization of NPh2VCz with s-BuLi/styrene ([s-BuLi/St]0 = 0.33) shows a narrower Mw/Mn. The block copolymerization of NPh2VCz with styrene, α-methylstyrene (α-MeSt), and 2-vinylpyridine (2VP) was achieved successfully. The resulting block copolymers of PNPh2VCz-b-P2VP with fPNPh2VCz = 17.7, 34.6, 48.1, 62.4, and 82.9 were synthesized for investigation of living characteristics.