Radical formation on TMP fibers and related lignin chemical changes

Oxidation of TMP fibers was compared at 298 K with molecular oxygen, in the presence of either [Co(salen)] in methanol or [Co(sulphosalen)] in water. Electron paramagnetic resonance (EPR) spectroscopy made it possible to reveal and quantify the formation of phenoxy cobalt radicals in the former case and of phenoxy radicals in the latter. These radicals reached the same concentration after 60 min from the onset of reaction. Fiber integrity was more preserved after oxidation in water than in methanol, as assessed by heteronuclear single quantum coherence - nuclear magnetic resonance (2D-HSQC-NMR) spectroscopy, nuclear magnetic resonance spectroscopy of carbon (13C-NMR), and Gel Permeation Chromatography (GPC). These results suggest that efficient radical formation on fibers can be achieved also with water-soluble catalysts. Thus, it is proposed that treatment with molecular oxygen in the presence of [Co(sulphosalen)] in water represents a promising way to approach an environmentally sustainable radicalization of fibers, without heavy modification of the lignin structure.