Summary: This paper focuses on the addition of tert‐butylcalix[4]arene (CA) to cross‐linked poly(dimethylsiloxane) (PDMS) membranes derived from poly(dimethylsiloxane) di(methyl methacrylate) macromonomer (PDMSDMMA) and various divinyl cross‐linker compounds, on the pervaporation characteristics for the removal of dilute benzene from an aqueous solution. When an aqueous solution of 0.05 wt.‐% benzene was permeated through the cross‐linked PDMSDMMA membranes containing CA they showed high benzene/water selectivity and permeability. Both the benzene/water selectivity and permeability of the membranes were enhanced by increasing both the divinyl compound cross‐linker content and the amount of CA, and were significantly influenced by the type of divinyl compound. Addition of CA to PDMSDMMA membranes cross‐linked with divinylperfluorohexane (DVF) showed the best pervaporation performance. The normalized permeation rate, benzene/water separation factor, and pervaporation separation index of these membranes were 1.86 × 10−5 kg · m/(m2 · h), 5 027, and 9 350, respectively. The pervaporation characteristics of the cross‐linked PDMSDMMA membranes containing CA were studied with respect to their chemical and physical structure. Furthermore, the mechanism of the selective permeation of benzene over water through these membranes was investigated.
