Abstract: The polystyrene (PS) was synthesized via reversible addition fragmentation chain transfer (RAFT) radical polymerization using azobisisobutryonitrile (AIBN) as the initiator, (S, S)′-bis (α, α)′-dimethyl-α″-acetic acid) (trithiocarbionate) (BDAAT) as the chain transfer agent (CTA). In addition, the polystyrene (PS) was synthesized by traditional radical bulk polymerization. Under the high humidity and nitrogen conditions, the microporous films were prepared by water drop templated method using polystyrene (PS) and polyethylene glycol (PEG) as materials of the membranes respectively. The mechanism of the formation of PS honeycomb microporous films was discussed. Moreover, the influence of the polymerization manner, the solution concentration, and the volatility of solvents on the structure of the microporous films were also studied. The results showed that the morphology of microporous films was affected by the end group of linear polymer, hydrophilic matter and so on. The diameter of film pore decreased obviously with the increasing of the polymer concentration.

Key words: RAFT, microporous films, PS, water drop templated method