Polymerization of N-vinylcarbazole

A detailed study of the polymerization of N-vinylcarbazole by tetranitromethane has provided strong evidence that in this system the reaction is propagated by a very small concentration of carbonium ions [25]. 

This idea was put forward first by Scott, Miller and Labes [57] for the polymerization of N-vinylcarbazole by organic electron-acceptors. It was then applied to initiation by the tropylium and other ions [52,58] by reducible metal ions but with emphasis on a possible radical reaction [59] and by sodium chloroaurate in which Au(III) is reduced (see also Section 4.5) [60]. Then Plesch suggested [6] an application of the idea of catalysis by metal halides generally, giving as an example, the following hypothetical scheme ... 

Another mode of termination by monomer, which has been suggested for the polymerization of N-vinylcarbazole, is formation of a quaternary ammonium ion from the growing cation and the monomer [25] which is essentially the same as reaction (XIa). 

Notable work in the area of photopolymerizations of donor monomers initiated by acceptor initiators was done by Shirota [5-7] in his study of polymerization of N-vinylcarbazole (VCZ) and by Hayashi and Irie [8] on the polymerization of a-methylstyrene (a-MSt). The initiation mechanism was proposed to proceed via the charge-transfer complex between VCZ (or a-MSt) and the acceptor, which then yields two kinds of ion-radicals D and A ... 

This in no way detracts from the proved ability of the cyclohepta-trienyl cation to oxidize reactive amines, and consequently there is always doubt as to the true nature of the reaction mechanism when tropylium ion initiates polymerization of N-vinylcarbazole. We have made a detailed kinetic study of this polymerization (34), using an adiabatic calorimetric technique. Some typical data are shown in Table VII. Initiation is instantaneous and complete, there is no termination, and kp is evaluated readily as 4.6 X 10+5M-1 sec. 1 at 0°C. with Ea = 6 kcal./mole. By comparing data for the ion pair dissociation constant of C7HT"SbCl 6 (Table I) with the catalyst concentrations employed (Table VII) it is apparent that free tropylium ions are the dominant initiating speices. It... 

Fullerene (1) has also been used as an initiator of the polymerization of vinyl monomers. The [60]fullerene-initiated polymerization of N-vinylcarbazole (64) under microwave irradiation conditions has been reported [67]. The main advan-... 

Suspension Polymerization of N-Vinylcarbazole Using Hydrolyzed Poly (vinyl... 

Polymerization of N-Vinylcarbazole Using Aqueous Perchloric Acid. 190... 

Spange, S. Graser, A. Huwe, A. Kremer. F. Tintemann, C. Behrens, P. Cationic host-guest polymerization of N-vinylcarbazole and vinyl ethers in MCM-41, MCM-48. and nanoporous glasses. Chem. Eur. J. 2001, 7. 3722-3728. 

There are very few reports available on the living cationic polymerization of N-vinylcarbazol, one of the most reactive monomers for cationic polymerization. Living polymerization of N-vinylcarbazol was reported in toluene or CH2CI2 solvent system using only HI [93] and I2 as initiator in CH2CI2 and CH2CI2/CCU 1/1 (v/v)... 

PVK carbon nanotube composites have been prepared by the electrochemical polymerization of N-vinylcarbazole in LiC104/acetonitrile solutions [22]. 

Tsubokawa N, Yoshihara T. Carbon whisker as an initiator of cationic polymerization of N-vinylcarbazole and A-vinyl-2-pyrrolidone. Polym J (Tokyo) 1991 23 177-83. 

Since the discovery of photoconductivity in poly(N-vinylcarbazole) (PVK) [1,2] a variety of polymers with carbazole groups have been synthesized and their photophysical properties have been investigated. The main topic of this article is the synthesis of photoconductive polymers, so minor attention is given to their photophysical properties. PVK (2b) can be synthesized by free-radical, cationic, or charge-transfer initiated polymerization of N-vinylcarbazole (2a). A detailed description of the PVK synthesis is given in Chapter 2 of this handbook. 

Sawamoto M, Fujimori J, Higashimura T. Living cationic polymerization of N-vinylcarbazole initiated by hydrogen iodide. Macromolecules 1987 20 916-920. 

There are very few reports available on the living cationic polymerization of N-vinylcarbazole, one of the most reactive monomer for cationic polymerization. Living polymerization... 

---