INCLUSION POLYMERIZATION IN PERHYDROTRIPHENYLENE STUDIED BY ELECTRON-SPIN-RESONANCE SPECTROSCOPY - GROWING CHAIN STRUCTURE AND CONFORMATION OF METHYLSUBSTITUTED POLYBUTADIENES

Inclusion polymerization of diene monomers promoted by gamma rays and performed in perhydrotriphenylene was studied by ESR techniques. During polymerization of butadiene, 1,3-pentadiene, isoprene, 2,3-dimethylbutadiene, 2-methylpentadiene, and 2,4-hexadiene, spectra attributable to allyl-type radicals were collected. It was demonstrated they actually represent the propagating radicals and they do not vary over a long period of time. They are not temperature dependent in the range minus 150 degree / plus 60 degree C, apart from the radical of polybutadiene, suggesting that the included methyl-substituted polybutadienes are conformationally fixed. When the two opposite insertions of monomers 1,4 and 4,1 are distinguishable, the radicals bearing the higher number of methyl groups at the ends of allyl system prevail.