Formation and behavior of mechanoradicals in pulp cellulose

The mechanical degradation of pulp cellulose fiber was studied at ambient temperature and at 77°K. ESR findings reveal that mechanical degradation occurs via free‐radical routes. Three types of mechanoradicals contributing singlet, doublet, and triplet ESR signals are identified. The singlet signals are derived from the alkoxy radicals at C4positions as a consequence of the cleavage of glucosidic bonds, the radical pairs generated at C1positions contributing the doublet signals. Triplet signals are derived from the C2and C3positions due to the cleavage of C2and C3bonds. Of these radicals, alkoxy radicals are the most stable at ambient temperature. Carbon radicals are capable of interacting rapidly with oxygen molecules to produce peroxy radical intermediates, where alkoxy radicals are inert toward oxygen molecules. ESR study also reveals that cellulose mechanoradicals are capable of initiating vinyl polymerization. MMA propagating radicals are identified when the monomers are in contact with cellulose mechanoradicals. The ability of mechanoradicals to initiate graft copolymerization from cellulose fiber is discussed.