Electroinitiated polymerization of styrene in dimethylsulphate

✍ Scribed by G. Pistoia; B. Scrosati

• Publisher: Elsevier Science
• Year: 1974
• Tongue: English
• Weight: 373 KB
• Volume: 10
• Category: Article
• ISSN: 0014-3057
• DOI: 10.1016/0014-3057(74)90094-9

✦ Synopsis

The electroinitiated polymerization of styrene in tetrabutylammonium perchlorate-dimethylsulphate solutions has been investigated. Polystyrene of low molecular weight is formed cationically through a direct monomer oxidation to the radical cation. Kinetic as well as mechanistic considerations for this system are made difficult by a number of factors: (a) the polymer is to a large extent insoluble in dimethylsulphate; (b) side reactions of both monomer and polymer tend to decrease the yields and therefore the calculated kp values; (c) the supporting electrolyte concentration tends to affect the ionic equilibria in solution, so again influencing the kp values.

A polymer degradation, found for polystyrene in LiClO4-propylene carbonate solutions, was again noted and attributed to the effect of the current on the polymer covering the anode. The polymerization has no true termination, the only chain-stopping reactions being those giving rise to chain transfer.