Polysulfones tethered with benzimidazole

Benzimidazole units have been grafted onto a polysulfone (PSU) backbone via long alkyl thio-ether chains using a two-step procedure. In the first step, lithiated PSU was reacted with 10-undecenoyl chloride to graft PSU with undecenoyl side chains. The second step involved a free-radical thiol-ene coupling reaction between the CC bonds of the pendant undecenoyl chains and 2-(2-benzimidazolyl)ethanethiol. In this reaction, all the CC bonds were converted into thio-ether linkages without any detectable structural degradation, as confirmed by ¹H NMR spectroscopy and size-exclusion chromatography. The procedure constitutes a convenient and general pathway to attach functional or mesogenic groups to PSU via long flexible spacers. Thermogravimetry showed that the benzimidazole-functionalized polymers were stable up to 250 °C under nitrogen atmosphere, and that the first degradation step was attributed to the cleavage of the thio-ether bond. While the grafting of the undecenoyl side chains was found to significantly decrease the glass transition temperature (T_g), the subsequent tethering of the benzimidazole only slightly increased the T_g of the grafted PSU backbone. The concentration of benzimidazole was probably too low for the formation of a percolating benzimidazole domain. This explains the quite modest proton conductivity measured under completely dry conditions, e.g. 34 nS/cm at 180 °C for a polymer functionalized with 1.7 benzimidazole units per repeating unit of PSU.