Ring-opening polymerization of decamethylcyclopentasiloxane initiated by a superbase: Kinetics and rheology

The use of phosphazene bases in combination with water was proved to be efficient in order to obtain polysiloxane polymers from cyclic monomers. Only a few minutes are necessary to obtain polymer chains with a monomer concentration of 5% at the equilibrium. For that purpose the space which is between a rheometer's plates is the most convenient device to monitor this reaction concerning a chemical and viscoelastic point of view. Therefore, here is proposed a chemo-rheology study that leads in the same time to the chemical kinetics equations and to the variation of the viscoelastic functions during the polymerization. In this way different catalysts are used and their efficiencies are compared as a function of their “basicity tank”. Whatever the experimental conditions involved are, viscosity versus polymer concentration or conversion shows a master curve for catalysts suitable to be used under extrusive conditions. Thus, only a few experiments are needed in order to develop a model which can be used to foresee the variation of the viscosity during the reaction.