Some aspects of the polymerization of N‐vinylcarbazole by grignard reagents

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Abstract
The polymerization of N‐vinylcarbazole (NVC) initiated by PhMgBr in benzene was studied at 32°C. Rp is second order with respect to PhMgBr concentration but increases with NVC concentration (up to 0.06 M) and falls thereafter. Rp and Pn are depressed by the addition of thiophene and water. Modifiers such as benzaldehyde, butanone, and ethylene glycol practically inhibit the polymerization. Carbon tetrachloride and carbon dioxide, when passed through the NVC solution first, enhance the Rp and Pn increases with increasing PhMgBr and NVC concentrations, respectively. Rp increases with temperature, but Pn shows a maxium at a certain temperature. A cationic mechanism has been proposed where the polymerization is initiated by RMg+ cations produced from the ionization of PhMgBr by the Ashby and Smith mechanism.