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EFFECT OF BASIC SUBSTITUENTS ON GAS SORPTION AND PERMEATION IN POLYSULFONE

机译:碱性取代基对聚砜中气体吸收和渗透的影响

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The gas permeability, diffusivity, and solubility of a series of polysulfones bearing basic aryl substituents were determined at 35 degrees C and pressures up to 20 atm. Gas permeability and diffusivity values of the aryl-substituted polysulfones were markedly lower than those of unmodified polysulfone. These effects were ascribed to decreased fractional free volume and increased restriction to sub-T-g torsional motion in the substituted polymers. Polysulfone bearing benzylic amine substituents exhibited higher CO2 solubility and CO2/CH4 solubility selectivity than polysulfone, presumably due to favorable interactions between acidic CO2 molecules and basic-CH2-NH(2)groups. CO2 diffusivity in polysulfone bearing benzylic amine substituents is lower than expected based on free volume considerations, suggesting that interactions between CO2 and benzylic amine moieties may be strong enough to impede CO2 mobility in the modified polymer. These results are consistent with infrared spectroscopy data which suggest that the benzylic amino groups undergo reversible reaction with CO2 to form carbamate moieties. [References: 54]
机译:在35摄氏度和最高20 atm的压力下测定了一系列带有碱性芳基取代基的聚砜的气体渗透率,扩散率和溶解度。芳基取代的聚砜的气体渗透率和扩散率值明显低于未改性的聚砜。这些作用归因于减少的自由体积分数和对取代的聚合物中亚T-g扭转运动的限制增加。带有苄胺取代基的聚砜显示出比聚砜更高的CO2溶解度和CO2 / CH4溶解度选择性,这大概是由于酸性CO2分子与碱性CH2-NH(2)基团之间的良好相互作用所致。基于自由体积的考虑,带有苄胺取代基的聚砜中的CO2扩散率低于预期,这表明CO2和苄胺部分之间的相互作用可能足够强,从而阻碍了改性聚合物中的CO2迁移率。这些结果与红外光谱数据一致,红外数据表明苄基氨基与CO 2发生可逆反应以形成氨基甲酸酯部分。 [参考:54]

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