PDMS with Tunable Side Group Mobility and Its Highly Permeable Membrane for Removal of Aromatic Compounds

Abstract Polydimethylsiloxane (PDMS), as the benchmark of organophilic membrane materials, still faces challenges for removal of aromatic compounds due to the undesirable transport channels. In this work, we propose to reconstruct the PDMS conformation with tunable side group mobility by introducing phenyl as rigid molecular spacer to relieve steric hindrance of large‐sized aromatic molecules; meanwhile, polymer segments are loosely stacked to provide additional degrees of freedom as increasing the permeant size. Moreover, the reconstructed PDMS is engineered into the composite membrane with prevention of condensation of aromatic compounds in the substrate pores. The resulting thin‐film composite membrane achieved one order of magnitude higher flux (11.8 kg m −2 h −1 ) with an equivalent separation factor (12.3) compared with the state‐of‐the‐art membranes for aromatic removal. The permeant‐customized membrane molecular and microstructure designing strategy opens a new avenue to develop membranes for specific separation targets.