v98-060.chp:Corel VENTURA

This paper describes our efforts focused at defining the formation of diphenylmethane moieties in lignin during conventional kraft and soda pulping conditions. This objective was realized by confirming, initially, the assignment of a P NMR signal as being due exclusively to the presence of phosphitylated diphenylmethane (DPM) phenolic hydroxyl groups. More specifically, softwood milled wood lignin (Picea mariana) was subjected to kraft pulping conditions in the presence and absence of varying amounts of formaldehyde. After quantitative recovery of the lignin, the P NMR spectra were recorded and the spectra revealed selective signal growth in the region confined between 142.8 and 144.3 ppm, in accordance with previous model compound work and detailed calculations based on the Hammett principles. To further substantiate our conclusions we also carried out two series of isothermal (120°C) kraft and soda pulping experiments followed by quantitative determinations of the DPM moieties, and correlated our findings with the differences in chemistry known to occur between the two processes. Finally, diphenylmethane phenolic moieties were determined in isolated residual lignins from two western hemlock kraft pulp samples produced via an EMCC mill protocol and a laboratory batch digester, respectively. These structures prevailed amongst the condensed phenolic units of the conventional pulp, providing additional evidence to support the fact that modern modified pulping technologies beneficially alter the structure of residual kraft lignin.