Mercerization of cellulose. II. Alkali–cellulose intermediates and a possible mercerization mechanism

Abstract Continued study of the five crystalline Na–celluloses, previously shown to occur as intermediates during the mercerization of cellulose and exhibiting two types of crystallographic fiber repeats, further indicates that they fall into three classes based on their unit cells and NaOH contents. In one class are Na–celluloses I and III, both containing up to 34% NaOH; in the second class are Na–celluloses IIA and IIB, marked by ca.15 Å fiber repeat and containing up to 65% NaOH; and in the third class is Na–cellulose IV which is likely to be a hydrated form of cellulose II. Na–cellulose I was found to be the common first alkali–cellulose structure produced in the NaOH treatment of both cellulose I and cellulose II. Further study of this conversion step suggested a mercerization mechanism in which the alkali begins the conversion of cellulose to Na–cellulose I in the amorphous parts of the fiber. The conversion of the parallel‐chain cellulose I structure to an antiparallel one is likely to occur already in this first step.