Polymerization of N‐vinylcarbazole was studied systematically using electroinitiation with several quaternary ammonium salts as electrolytes in methylene chloride solution. Polymer was obtained only when the following electrolytes were used: tetraethylammonium perchlorate, tetrabutylammonium perchlorate, and tetrabutylammonium fluoroborate. Polymeric products of molecular weight 104–105 were formed in the anodic compartment of a divided cell. IR and 13C‐NMR spectra showed that the structures of the polymers were similar to those produced by conventional cationic polymerization, which suggests a similar mechanism for the resulting anodic product.

Fluorescence spectra of poly(indene) (PIN) and poly(acenaphthylene) (PAN) samples of molecular weight ranging from 1.8 x 103 to 2.9 x 106 were measured in dilute solution at different temperatures (2,10, 25, and 40 °C). The fluorescence ratio (Ie/Im) of PIN decreases upon increasing the chain molecular weight and becomes zero for chains of about 500 monomeric units. By contrast, the fluorescence ratio of PAN increases with molecular weight. The temperature dependence is also different for both polymers: in the range of temperatures studied here, PIN is in the high-temperature limit and PAN is in the low-temperature limit. These results are interpreted in terms of the number of chain self-contact points in the equilibrium conformation and also taking into account segmental diffusion. Monte Carlo simulation results of the number of self-contact points in Gaussian chains of different length are also presented.

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SynopsisCopolymers of styrene and vinyl acetate were synthesized electrochemically. The reaction system was composed of methylene chloride as the solvent, and a quaternary ammonium salt as the electrolyte. The reactions were run in a divided cell and the influence of current strength, reaction time, and temperature on the yield, molecular weight, and chemical composition of the resulting copolymers was investigated. It was found that the polymer chains were composed mainly of styrene units.