The correlation of sulfonation reaction kinetics with the degree of sulfonation (DS) and its effects on microstructure and morphology of electrospun fibers for the membrane of fuel cells

Abstract

Sulfonation is among the frequently used surface modification methods to endow new surface properties on polymer fibers. Direct sulfonation is the simplest chemical modification via incorporation of sulfonate functional groups onto fibers' surfaces at ordinary conditions. However, the process of functionalization compromises other properties of the electrospun membrane due to the extent of sulfonation reaction that occurred. This study was carried out to determine the effects on microstructure and morphology of crosslinked electrospun polybenzoxazine (PBz) fibers by correlating the reaction kinetics using a specific reaction parameter with the degree of sulfonation (DS). The kinetics of sulfonation reaction for PBz fibers is an electrophilic-based, first-type substitution mechanism where only one sulfonic acid (–SO₃H) group is attached to each of the repeating units in the aromatic structure of PBz under ordinary conditions. From a previous study, the rate of change of ion exchange capacity (IEC) was derived as a logarithmic correlation that increased rapidly for some time and became constant. This study employed the derived empirical relationship based on reaction kinetics to correlate the degree of sulfonation (DS) with IEC at varying reaction time. DS was calculated as 55%, 66% and 77%, for 3, 6 and 24 h, respectively. The maximum IEC of 2.71 with the corresponding DS of 100% was obtained theoretically but since sulfonation reaction kinetics at ordinary conditions proceeds at slower phase, it can only attain 86% DS with maximum IEC of 2.44 at a calculated time of 48 h. Sulfonation was confirmed by the functional groups present in the structural composition of PBz fibers using ATR-FTIR which were quantified based on the absorbance in the IR spectra showing an increased peak height with increased reaction time for the first 6 h. Morphological analyses using SEM images revealed an increase in fiber diameter with increased sulfonation time. In addition, the higher reaction time showed the effects of longer acid exposure which compromised the fibers' structural integrity with the presence of broken fibers and defects on fibers' surfaces after 24 h. The electrospun PBz fibers sulfonated for 6 h achieved the highest IEC value with DS of 66% which was enough to attain the balance of degree of sulfonation with electrochemical and morphological properties.