A tertiary
polyamide membrane was synthesized using N,N′-dimethyl-m-phenylenediamine.
The durability of this membrane to chlorination by hypochlorite treatment
followed by sodium hydroxide treatment was examined, and then deterioration
mechanisms were proposed. The tertiary polyamide membrane demonstrated
better durability to free chlorine than a conventional secondary polyamide
one; however, the former was deteriorated by hypochlorite for 24 h
at 2000 ppm of free chlorine below pH 7.5. The salt rejection and
permeation performance of the membrane were almost unchanged, and
the least chlorination of the active layer occurred during hypochlorite
treatment at pH 10. These results indicated that hypochlorous acid
rather than hypochlorite ion was the free chlorine species that induced
membrane deterioration. The deterioration became severe as chlorination
progressed, resulting in collapse of the active layer below pH 7.5.
Chlorination and hydrolysis of the model tertiary amide N-methylbenzanilide and Fourier transfer infrared spectroscopy of
a deteriorated membrane showed that chlorination of the tertiary polyamide
occurred via direct chlorination of the benzene bound to the amidic
nitrogen. Silver ion probing of the deteriorated membrane revealed
that amide bond scission occurred in the active layer, which might
be related to the electron deficiency of the amidic nitrogen caused
by chlorination of its benzene ring.