Fabrication of robust micro-patterned polymeric films via static breath-figure process and vulcanization

Here, we present the preparation of thermally stable and solvent resistant micro-patterned polymeric films via static breath-figure process and sequent vulcanization, with a commercially available triblock polymer, polystyrene-b-polyisoprene-b-polystyrene (SIS). The vulcanized honeycomb structured SIS films became self-supported and resistant to a wide range of organic solvents and thermally stable up to 350°C for 2h, an increase of more than 300K as compared to the uncross-linked films. This superior robustness could be attributed to the high degree of polyisoprene cross-linking. The versatility of the methodology was demonstrated by applying to another commercially available triblock polymer, polystyrene-b-polybutadiene-b-polystyrene (SBS). Particularly, hydroxy groups were introduced into SBS by hydroboration. The functionalized two-dimensional micro-patterns feasible for site-directed grafting were created by the hydroxyl-containing polymers. In addition, the fixed microporous structures could be replicated to fabricate textured positive PDMS stamps. This simple technique offers new prospects in the field of micro-patterns, soft lithography and templates.