Anionic polymerization of N‐ethyl‐2‐vinylcarbazole and N‐ethyl‐3‐vinylcarbazole

Abstract

SynopsisThe polymerization of N-ethyl-2-vinylcarbazole and N-ethyl-3-vinylcarbazole by an anionic mechanism has been demonstrated. Polymerization reactions were monitored by ultraviolet/visible spectroscopy and Am, ,and e values for the propagating carbanions determined. The 2-vinyl monomer exhibits all the features of a standard "living" polymer; the carbanion is stable at ambient temperatures and high molecular weight, Bn -lo6, narrow distribution polymers and block copolymers with styrene have been prepared. The carbanion from the 3-vinyl monomer is much less stable and a clean polymerization can only be conducted a t temperatures below -6OOC.A comparison of the anionic polymerization characteristics of the N-, 2, and 3-vinyl carbazole monomer series is presented. 1133

Structure–properties relationship of carbazole and fluorene hybrid trimers: experimental and theoretical approaches

“…23,24 The samples for the measurements were prepared by drop casting of solutions of the compounds in THF onto a polyester film with Al layer. 25 Materials 4-Bromo-2 0 -nitrobiphenyl, 26 2-bromocarbazole, 26 2-bromo-9-ethylcarbazole, 27 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9-ethylcarbazole, 4,4 0 -dibromo-2-nitrobiphenyl, 16 2,7-dibromocarbazole, 16 2,7-dibromo-9-(2-ethylhexyl)carbazole, 16 2-bromo-9,9-diethylfluorene, 28 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-diethylfluorene, 28 2,7-dibromo-9,9-di(2-ethylhexyl)fluorene, 29 2,7-dibromo-9,9-dihexylfluorene 30 were prepared according to published procedures.…”

“…The starting compounds 2,7-dibromo-9,9-di(2-ethylhexyl)fluorene (1), 2,7-dibromo-9-(2-ethylhexyl)carbazole (2), 2,7-dibromo-9,9dihexylfluorene (3), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9ethylcarbazole (4) and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)-9,9-diethylfluorene (5) were synthesized according to the published procedures. [26][27][28][29][30] Pd-catalyzed Suzuki coupling reactions of dibromo compounds and arylboronates were accomplished by adding a catalytic amount of bulky tri-tert-butylphosphine as a promoter to afford the target compound with a carbazole core (FCF) as well as the compounds with a fluorene core (CFC, FFF) in good yields (Scheme 1). 1 H and 13 C NMR, mass spectrometries and elemental analysis confirmed the chemical structures of the compounds.…”

Precise Synthesis of Functional Block Copolymers by Living Anionic Polymerization of Vinyl Monomers Bearing Nitrogen Atoms in the Side Chain

“…The anionic polymerization of styrene derivatives bearing carbazole moieties, such as N ‐ethyl‐2‐vinylcarbazole ( N E2VCz) and N ‐ethyl‐3‐vinylcarbazole ( N E3VCz), which are positional isomers, was first conducted by Limburg and coworkers . The two isomers behaved differently.…”

“…The conducted by Limburg and coworkers. [41] The two isomers behaved differently. While the polymerization of NE2VCz showed living characteristics and was facile, that of NE3VCz was not accomplished due to the low stability of the carbanion.…”

Chemical modification of poly(N‐vinylcarbazole). II. Some properties of poly(N‐vinylcarbazole‐3,6‐diphthalimide)

“…These results are somewhat consistent with the observations of Limburg and Seanor (15,16) that the photoconductivity of pure PNVC is enhanced significantly in the N-vinylcarbazole -N-vinylphthalimide copolymer system. It has been suggested (15)(16)(17) that the enhancement in the photocurrent in this copolymer is due to absorption in the charge transfer (CT) band extended well into the visible wavelength. A similar explanation appears to be feasible also for the polymer P(NVC-DPI) whose CT complexes are likely to be formed between the pendant carbazole rings and the phthalimide groups.…”