Microstructure Studies by Degradation of Polysulfides

In Vol. I (Adv. Polymer Sci. 37) we have discussed the mechanism of polymerization of thiiranes relative to polymer microstructure. The microstructure influences the properties of the polymers e.g. linear polyethyleneimine is crystalline (mp = 59 °C), whereas the branched one is amorphous. 

Proportions of these isomers were correlated with the microstructure of the starting polymers. This was proved by degradation studies of the optically active poly(ds-DMT) the higher the optical activity, the higher the corresponding ratios (I/II and III/IV). 

Recently Aliev et al. 70) have discussed the formation of alkenes in the polymerization of thiiranes and the degradation of the corresponding polymers. A modified mechanism was proposed, assuming that the thiiranium sulfur atom is subject to nucleophilic attack by soft bases 71 72)  

Goethals, E. J. Polymeric Amines and Ammonium Salts , Pergamon Press, Oxford 1980 

Oxonium Ions in Organic Chemistry, Verlag Chemie, Weinheim 1971 

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