Site-selective Hyper-crosslinking Enabled Solvent-Resistant Isoporous Membrane with Customizable Pore Characteristics and On-demand Sieving

Isoporous block copolymer membranes with high porosity and narrow pore size distribution have been viewed as ideal membrane platforms for precise separation of similarly sized particles or solutes. However, tailored made fabrication of solvent-resistant isoporous membranes with switchable pores and rigid pores for customizable sieving have been rarely reported. Herein, we show that site-selective hyper-crosslinking is effective and robust to prepare such membranes from polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP). The selective crosslinking in PS domains endow the membrane with excellent solvent resistance and structural stability. Since not participated in the crosslinking reaction, the P4VP brushes located in pore walls endow the crosslinked membranes with adaptive pore size, switchable permeance and tunable rejections that vary with Hansen solubility parameter of solvents. Moreover, by a facile while complete etching the P4VP from pores, the switchable performance is removed and resultant membranes show rigid pore characteristics and constant rejections that are well described by the Hagen-Poiseuille's equation. Crosslinked membranes with either switchable pores or rigid-likes pores exhibit superior long-term stability (30 days) in harsh solvents. This work presents a top-down method to construct highly stable isoporous membranes with both switchable and rigid pore characteristics from the same block copolymer, which will shed the light on precisely tailoring the pore size and pore rigidity for crosslinked isoporous membranes that will not only enable the tailored sieving but also the modelling of solvent flowing behaviours in nanopores.