Dramatic Morphology Control in the Fabrication of Porous Polymer Films

Abstract Highly ordered, porous honeycomb films are prepared by the breath‐figure (BF) technique using dendron‐functionalized star polymers as precursors. By changing the nature of the dendritic end groups, dramatically different porous morphologies can be produced. Three series of star polymers are prepared with both the size of the 2,2‐bis(methoxy)propionic acid (bis‐MPA)‐based dendron end group and the dendron functionality being varied. Star polymers end‐functionalized with acetonide‐protected dendrons (generations 1 to 4) are initially prepared and the acetonide groups subsequently deprotected to yield hydroxyl‐functionalized star polymers. Modification of these hydroxyl groups with pentadecafluorooctanoyl chloride yields a third series of functionalized star polymers. The resulting star polymers have surface groups with very different polarity and by utilizing these star polymers to form honeycomb films by the BF technique, the morphology produced is dramatically different. The star polymers with amphiphilic character afford interconnected porous morphologies with multiple layers of pores. The star polymers with pentadecafluorooctanoyl end groups show highly ordered monolayers of pores with extremely thin walls and represent a new porous morphology that has previously not been reported. The ability to prepare libraries of different dendronized star polymers has given further insights into the BF technique and allows the final porous morphology to be controllably tuned utilizing the functional chain ends and generation number of the dendronized star polymers.