Using a polyelectrolyte to fabricate porous polyimide nanoparticles with crater‐like pores

We have used the reprecipitation method and subsequent two‐step imidization to fabricate highly porous polyimide (PI) nanoparticles possessing crater‐like surface pores (depths, diameters: tens of nanometers) from poly(amic acid) (PAA) derivatives in the presence of poly(sodium‐4‐styrenesulfonate) (PSS) as a polyelectrolytic porogen. The porous structures arose presumably through segregative microphase separation of PAA and PSS (i.e. repulsion between PAA and PSS in the presence of a common solvent) and subsequent removal of PSS. The addition of this strong polyelectrolyte improved the degree of porosity of the resulting PI nanoparticles and allowed controllable release of the porogen. The resulting porous PI nanoparticles exhibited a high thermal stability (5% weight loss at temperature 450°C). This technique is suitable for the preparation of novel low‐k materials and their surface‐related applications.