| Abstract: | By irradiation with gamma rays styrene was grafted onto hydrochloric acid lignin. When the graft polymers were subjected to nitrobenzene oxidation, the vanillin yields indicated two kinds of reaction occurring in the grafting. Polystyrene branches were separated from the graft polymers, and their M?n were determined osmometrically. At grafting ratios of up to 100 the vanillin yields diminished proportionately with increasing grafting, and the M?n of the branches, 5000, was unchanged. At grafting ratios of more than 100 the vanillin yields were constant, independent of the ratios, but the M?n values of the branches increased with grafting. Paper chromatography of the aromatic acids obtained by oxidation of methylated lignin and the graft polymer indicated that isohemipic and metahemipic acids were more abundant in the acid fraction of the graft polymer than in the lignin itself. A qualitative mass analysis of the gaseous products evolving from the irradiated lignin showed the presence of hydrogen molecules only. Gamma-ray radiation brought about no change in the yields of vanillin. It was therefore concluded that radiation grafting on lignin at grafting ratios of less than 100 proceeded through the addition of the styrene polymer radicals to the aromatic nuclei of the lignin and that then branches propagated from the aliphatic part of the lignin, where C? H bond scission had been caused by the irradiation. The grafting sites of lignin would be C-5 and C-6 of the guaiacyl nucleus and, probably the β and γ carbon atoms of the aliphatic side chain of the lignin. |
