Surface area and pore structure properties of urethane-based copolymers containing β-cyclodextrin

The surface area and pore structure characteristics were investigated for a series of aliphatic- and aromatic-based polyurethane (PU) copolymers containing a macromolecular porogen (β-cyclodextrin). The bi-functional diisocyanates used as crosslinker units were: 1,6-hexamethylene, 4,4'-dicyclohexylmethane, 4,4'-diphenylmethane, 1,4-phenylene, and 1,5-naphthalene diisocyanate, respectively. The macromolecular porogen content was controlled by fixing the composition of β-CD and varying the co-monomer mole ratio from unity to larger integer values. Nitrogen adsorption results reveal that copolymer materials with variable mole ratios (β-CD: crosslinker) from 1:1 to 1:3 displayed relatively low BET surface areas (SA∼10(1) m(2)/g) and mesopore diameters (∼16-29 nm). In contrast, a dye adsorption method in aqueous solution with p-nitrophenol (PNP) at pH=4.60 and 295 K provided estimates of the surface area (1.5-6.2×10(2) m(2)/g) for the corresponding copolymer materials. Variation of the copolymer SA was attributed to the type of diisocyanate crosslinker and its relative mole ratio. The differences in the estimated SA values from porosimetry and the UV-Vis dye adsorption method for these nanoporous copolymers were attributed to the role of solvent as evidenced by swelling of the copolymer framework in aqueous solution and the respective temperature conditions.