Controlled Synthesis of Poly(N-ethyl-3-vinylcarbazole) and Block Copolymers via RAFT Polymerization

Abstract

Poly (N-ethyl-3-vinylcarbazole), in which the carbazole unit is directly bound to the polymer main chain, has been synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. The homopolymers with controlled molecular weights and low polydispersities (Mw/Mn ) 1.15-1.29) were obtained by the polymerization of N-ethyl-3-vinylcarbazole (E3VC) with 2,2′-azobis(isobutyronitrile) (AIBN) as an initiator in the presence of benzyl 1-pyrrolecarbodithioate as a chain transfer agent (CTA). Good control of the polymerization was confirmed by the linear first-order kinetic plot, linear increase in the molecular weight with the conversion, and the linear relationship between the molecular weight and the monomer/CTA molar ratio. Successful chain extension from dithiocarbamate-terminated poly(E3VC) was also observed. Well-defined block copolymers with poly(E3VC) segment have been synthesized using the dithiocarbamate-terminated polystyrene as a macro-CTA. The resulting polymers, poly(E3VC) and polystyrene-b-poly(E3VC), absorbed light in the range from 300 to 380 nm and exhibited excimer emission at 454 nm with blue fluorescence. These polymers showed thermal stability above 350°C under nitrogen.

Living Radical Polymerization by the RAFT Process—A First Update

“…[106] 71* [97] NVP [97] 72* [97] NVP [97] (S) [98] 70b* R = CH 3 AA/EAA [120] (EAA) [120] BA/EAA [120] DMA/EAA [120] DMAEA/EAA [120] VAc [121] 73 [56] NVP [56] VAc [56] 74* [106] VAc [106] 75a* S [122] A See footnotes A,B of Table 1. [123] 77* NVP [124] 78 [54] S [54] 78a R = CH 3 78b R = Ph [55] S [55] 80 [55] S [55] 81 [55] S [55] [55] S [55] 83 [55] S [55] 84 [55] (S) [55] [55] (S) [55] 86 [125] BA MA/MAA [126] A See footnotes A,B of Table 1. [47] S [40,47] 88* (MA [96] S [96] ) 89* MMA [127] A See footnotes A,B of Table 1.…”

Controlled RAFT Polymerization of N‐Vinylphthalimide and its Hydrazinolysis to Poly(vinyl amine)

“…These xanthate-type CTAs were finally purified by column chromatography on silica (silica gel 60, spherical, particle size ¼ 63-210 mm, Kanto Chemical) with hexane/ethyl acetate (10:1 vol.-%) as the eluent. Benzyl 1-pyrrolecarbodithioate (CTA 6) [50,51] and benzyl dithiobenzoate (CTA 7) [52,53] were synthesized according to the procedures reported previously. CTA 6 was finally purified by column chromatography on silica with n-hexane/ethyl acetate (10:1) as the eluent.…”

Synthesis of Amphiphilic and Double‐Hydrophilic Block Copolymers Containing Poly(vinyl amine) Segments by RAFT Polymerization of N‐Vinylphthalimide

“…Syntheses of O-ethyl-S-(1-ethoxycarbonyl) ethyldithiocarbonate (CTA 1) [23,39] and benzyl 1-pyrrolecarbodithioate (CTA 2) [36,40] were carried out according to previously reported procedures. These CTAs were then purified by column chromatography on silica with the eluents n-hexane/ethyl acetate (10:1 vol.-%) for CTA 1 and n-hexane for CTA 2.…”