A versatile route to modify polyethersulfone membranes by chemical reduction of aryldiazonium salts

Abstract

Ultrafiltration polyethersulfone membranes were modified covalently by chemical reduction of aryl diazonium salts. Functionalizations were performed with four aryl diazonium salts bearing different functional groups (4-benzyltriphenylphosphonium diazonium, 4-nitrophenyl diazonium, 4-benzonitrile diazonium and 4-phenylacetic acid diazonium) so as to demonstrate the versatility of the method. The efficiency of the different functionalizations was checked with various characterization techniques. Attenuated total reflectance–Fourier transform infra red spectroscopy revealed the presence of 4-nitrophenyl, 4-benzonitrile and 4-phenylacetic acid groups at the surface of the different modified membranes but no characteristic vibration band was detected on the surface of the membrane modified with 4-benzyltriphenylphosphonium diazonium. The presence of 4-benzyltriphenylphosphonium, however, could be demonstrated by both Energy Dispersive X-ray spectroscopy (detection of the Kα ray of phosphorous at 2.015 keV) and streaming current measurements (shift of the membrane isoelectric point). Finally, dead-end filtration of an antibiotic (tylosin) was carried out with the unmodified membrane and the membrane modified by 4-benzyltriphenyl-phosphonium diazonium. Experiments revealed that the transport properties of the grafted membrane were significantly modified, with a significant increase in rejection mainly due to electrostatic repulsions between the surface of the modified membrane and tylosin.