ANIONIC-POLYMERIZATION OF OCTAMETHYLCYCLOTETRASILOXANE IN AQUEOUS EMULSION .1. PRELIMINARY-RESULTS AND KINETIC-STUDY

The synthesis of poly(dimethylsiloxane) (PDMS) by anionic polymerization of octamethylcyclotetrasiloxane (D4) in aqueous emulsion using an emulsifying agent acting also as initiator (benzyldimethyldodecylammonium hydroxide) is described. Stable emulsions of alpha,omega-dihydroxy PDMS with an easily controlled molar mass (up to 15 0000), a low polydispersity index and high yields were obtained. The amount of cyclics formed (essentially D4 to D7) is lower than that observed in bulk. Kinetics analysis and computerized simulations are in good agreement with a reaction scheme involving simultaneous polyaddition/polycondensation processes. At high monomer consumption, polycondensation predominates leading to a broadening of the molecular weight distribution (MWD). The apparent rate constants of initiation, propagation and condensation at various temperatures and the corresponding activation energies were determined.