synopsisThe reactions of a variety of activated vinyl compounds with cotton cellulose fabric containing quaternary ammonium hydroxide substituents were explored. Each reaction, catalyzed by the basic groups in the cellulose, was followed to or near the point of leveling off. The results are analyzed and discussed in terms of accessibility of the cellulosic compositions and in terms of the efficiency of the quaternary ammonium substituents as catalysts for the addition reactions. Estimates of relative forward rate constants (ky) and equilibrium constants (K) for the reactions were made. The values of k, for reactions of the vinyl compounds with the quaternary ammonium celluloses show a relative order which is similar to that for the reactions of the vinyl compounds with simple alcohols. Evidence is presented to indicate that, in some cases, the addition of vinyl compounds is accompanied by anionic-catalyzed graft polymerization.
INTRODUCTIONThe addition of cellulosic hydroxyl groups to reagents containing activated double bonds is of considerable interest in the chemical modification and crosslinking of Catalysis of reactions of cellulose by special groups that are built into the cellulosic structure offers possibilities for conducting reactions without the necessity for conventional (external) catalysts and for achieving reactions and results which are not possible via conventional catalysi~.~.~In connection with the investigation of thermally reversible crosslinking reactions in cotton cellulose, the reactions of cellulosic hydroxyl groups with activated vinyl compound have taken on a new interest, particularly in cellulosic compositions in which basic catalyst groups are built into the polymeric structure for in situ catalysis. [6][7][8] This paper reports the results of an exploration of reactions of cotton cellulose containing quaternary ammonium base substitutents with a variety of activated vinyl compounds. Relative kinetic and equilibrium data are reported and compared to published results from conventional reactions with external catalysts.