N-substitution of polybenzimidazoles: Synthesis and evaluation of physical properties

Series of N-substituted polybenzimidazoles (PBI) were synthesized using selective alkyl groups with varying bulk and flexibility, viz., methyl, n-butyl, methylene trimethylsilane and 4-tert-butylbenzyl. PBI-I based on 3,3′-diaminobenzidine (DAB) and isophthalic acid and PBI-BuI based on DAB and 5-tert-butyl isophthalic acid were chosen for N-substitution. Structural characterizations of substituted polymers by FT-IR and 1H NMR revealed elimination of hydrogen bonding. Evaluation of their physical properties revealed that N-substitution rendered better solvent solubility in common organic solvents, more open polymer matrix, but reduced thermal properties in comparison to their respective parent PBI. 4-tert-butylbenzyl, methylene trimethylsilane or n-butyl group substituted polymers were soluble even in chlorinated solvents (CHCl3 and TCE). Substantial variations in gas permeability of inert gases, He and Ar and attractive PHe/PAr selectivity, especially after methyl group substitution depicted potential of these materials for gas separation.

Graphical abstractPolybenzimidazole (PBI) is known for its excellent thermo-chemical stability but poor solvent solubility and low gas permeability. We report structural modifications of two promising PBIs by N-substitution with alkyl groups of varying bulk and flexibility. These modification improved solvents solubility and inert gas permeability considerably, depicting promises of this approach.Figure optionsDownload full-size imageDownload as PowerPoint slide