Abstract The first part of this series is devoted to the preparation of vinyl functionalized multiblock silicones by the process of anionic ring opening polymerization in miniemulsion. The advantage of working in dispersed media is that different scales of reactivities are found between one-chain reactions, taking place at the interface (propagation, backbiting), and two-chain reactions, located in the bulk of the particles (polycondensation and intermolecular redistribution). First, homopolymerizations of octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (D4 V) were carried out and compared, focusing specifically on the rates of polymerization, backbiting and polycondensation processes. Copolymerization of D4 with D4 V then gave insight into the extent of mixed cycles’ formation and particularly how to avoid these. On this basis, recipes were carefully selected so that homopolymerization and scarce co-polycondensation and redistribution progress at the expense of backbiting reactions and thus multiblock copolymers are formed, the microstructure of which was confirmed with 29Si NMR.
