Electron transfer polymerization

Thiem,and Klafike, W. Synthesis of Deoxy Oligosaccharides. 154, 285-332 (1990). Timpe, H.-J. Photoinduced Electron Transfer Polymerization. 156, 167-198 (1990). 

Timpe H-J (1990) Photoinduced Electron Transfer Polymerization. 155 167-198 TobeY (1994) Strained [n]Cyclophanes. 172 1-40 Tolentino H, see Fontaine A (1989) 151 179-203... 

The polymerization systems discussed in this article are those in which polymerizing monomer is directly involved in the electron transferring pair, which enables the production of ion-radical on monomer. At the moment we are able to induce photosensitized ionic polymerization only in limited instances. When the charge transfer polymerization is discussed, strict distinction between radical and ionic mechanisms is impossible. As shown in Fig. 2, the difference between ion and radical and that between molecule and ion-radical is only a matter of one electron. Thermal electron transfer polymerization is demonstrated for many polymerization systems. The combination of photochemistry and electron transfer polymerization is very promising and may open up a new field in photopolymers. 

On the basis of the polarographic studies, the direct electron transfer polymerizations of the monomers, of which half-wave potentials could be measured, were conducted keeping the potential at a level where the monomer alone was reduced and the electrolyte was not affected. During the electrolysis of a-methyl-styrene, for example, the red color of the carbanion was observed around the cathode, but dissipacted and vanished quickly. Only low polymers were found in the cathodic compartment, but no polymer in the anolyte. In the polymerization of other monomers almost identical results were obtained. From the fact that tri-n-butyl-amine was detected in the catholyte and analysis of the end group of polymers obtained, two possible termination steps were postulated ... 

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