Formation, characterization, and chemical reactions of free radicals in lignin

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Virginia Polytechnic Institute and State University


Free radicals are produced in lignin during mechanical treatment and irradiation with light of various wavelengths.

During mechanical treatment, the lignin macromolecule is degraded severely as revealed by ESR and viscosity measurements. Several types of mechano-radicals are produced in lignin during the mechanical process. Among these the phenoxy radicals are rather stable, where carbon-radicals are labile at ambient conditions. Transient mechano-radicals reacted readily with oxygen molecules to produce peroxy radicals even at 77°K, but they decayed rapidly at ambient temperature.

Photodegradation of lignin was observed when macromolecule was irradiated with light of λ<3500 Å as revealed by ESR, viscosity, and weight loss. Phenoxy radicals are the predominant intermediates in the photoirradiated lignin as shown by ESR studies. Elimination of side chains of lignin phenyl propane units took effect in α-carbonyl group bearing molecules. By contrast, β aryl ether substituents adjacent to α-carbonyl groups caused ether cleavage under identical conditions of photoirradiation. This is attributed to energy transferred from excited α-carbonyl groups to the ether bonds. The α-carbonyl groups also functioned as photosensitizers accelerating photochemical reactions of lignin.

Termination and decomposition reactions of mechano-radicals and photoinduced free radicals in lignin ultimately lead to the formation of para- and ortho-quinones, carbonyl groups, and double bonds which cause the color of lignin.

These potential choromophoric groups can be partially removed from lignin by using ultraviolet light of λ> 4000 Å; and they can be completely removed by irradiation of lignin in the presence of dioxane-water with light of λ>3500 Å. Experimental findings suggest chat chromophoric groups in lignin were being trapped or blocked by dioxanyl radicals resulting in brightening. However, the photoreduced lignin-adduct suffered color reversion. This adverse effect can be prevented by using 2-hydroxy-4-methoxy-benzophenone as a photostabilizer.

The feasibility of applying photoreduction techniques to high- yield pulps was demonstrated. However, optimal experimental conditions for photoreduction of lignin in high-yield pulps have not been established yet.