Effect of vapor phase ethylenediamine crosslinking of matrimid on alcohol vapor sorption and diffusion

This work examines the sorption, diffusion, and polymer relaxation behavior for water and C1‐C7 alcohol vapors at 30 °C in ethylenediamine vapor‐phase crosslinked Matrimid. Ethylenediamine is sufficiently volatile that crosslinking can occur by exposing the polymeric film to saturated vapor, in contrast to more conventional means of dissolving the crosslinker in a solvent and immersing the polymeric film in the solution. The vapor‐phase exposure method avoids the use of additional solvent and undesired solvent‐induced swelling. Sorption isotherms demonstrate that water and C1‐C5 alcohols do not appreciably differ for unmodified and crosslinked Matrimid; however, an approximate 90% reduction in sorption was determined for hexanol and heptanol. A minor impact on diffusion coefficients for water, methanol, and ethanol was observed, while those of propanol and butanol were reduced over an order of magnitude. Relaxation kinetics were similarly unchanged for water and C1‐C3 alcohols, while being significantly reduced for butanol and higher alcohols. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44771.