Synthesis of branched polystyrenes via cationic polymerisation

Branched polystyrenes have been prepared rapidly (within 15 min) and in good yields (40-99%) in dichloromethane solution at 0 °C via cationic copolymerisation of styrene (St) with divinylbenzene (DVB) using SnCl₄ as the initiator. All reaction components were deliberately used as supplied to evaluate whether such a simple approach could provide a facile synthesis of branched polymers and this has proved to be the case. The only additional experimental precaution was to avoid condensation of atmospheric moisture during the reactions. No additional chain regulating species was required to avoid crosslinking providing the St/DVB mole feed ratio was ?100/5. The intrinsic chain transfer to monomer reaction seems to be sufficient to reduce the length of the primary polymer chains and hence inhibit crosslinking and gelation in the case of the above mole feed ratios. The branching architecture of the products has been evaluated by ¹H NMR and MALS-SEC analyses.