Thermal polymerization and electronic spectra of vinylpyridine-zinc acetat system

Thermal rate of polymerization of 4-vinylpyridine (4-VP) was found to increase greatly in the presence of zinc acetate. The occurrence of radical polymerization was confirmed by studying the effects of additives (2.2-diphenyl-1-picrylhydrazyI (DPPH), air and water). Using zinc acetate as catalyst in THF, the order of thermal rate was 4-VP > MVP > 2-VP (no polymerization). It was concluded that the enhancement of the rate of thermal polymerization was not only due to the increase of propagation rate but also due to the thermal production of radicals by the interaction between monomer and metal salts. The influence of zinc salts on the electronic state of vinylpyridines was studied by electronic spectroscopy. The π→π^* transition band of 4-VP was observed to shift towards lower energy by complexing the monomer. The amounts of shift of 2-metlyl-5-vinylpyridine (MVP) and 2-vinylpyridine (2VP) were much smaller than those of the 4-VP-complexes. These spectral data were discussed on the basis of the electornic interction of metal ion with ligand as well as the steric effect in complex formation, and were correlated to the thermal polymerizabilities of complexed vinylpyridines.