The solubility of CO 2 and CH 4 in five polyimides was measured at 35.0°C and at pressures up to 10 atm (147 psia). The concentration of the penetrant gases dissolved in the polymers can be represented satisfactorily as a function of penetrant pressure by the “dual‐mode sorption” model. The solubility coefficients for CO 2 and CH 4 , S(CO 2 ) and S(CH 4 ), increase in the polyimide order: The magnitude of the solubility coefficients appears to depend primarily on the intermolecular forces between the penetrant gases and the polymers. The values of these coefficients are greater for the polyimides with larger mean interchain spacings, but no one‐to‐one correspondence appears to exist in this respect. The lower solubility of CO 2 in PMDA‐4,4'‐ m ‐APPS compared with that in the 6FDA polyimides may be due to the lower “excess” free volume of the former polymer. The ratio S (CO 2 )/S (CH 4 ) varies relatively little for a variety of PMDA and 6FDA polyimides.
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Hirose et al. (1991) studied this question.
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