POLYMER SWELLING .9. SORPTION OF 1-CHLOROALKANES BY POLY(STYRENE-CO-DIVINYLBENZENE)

The relative swelling power, Cn, and adsorptivity, αn, with respect to poly(styrene-co-divinylbenzene) were established for the first 12 liquids in the homologous series Cl(CH2)nH. The results obtained thereby were compared with those obtained earlier for two analogous series in which the substituent in the 1-position is phenyl or iodo. These results confirm that the molecular nature of the absorption process is given better by αn than by Cn, which is the product of αn and the molar volume of the sorbed liquid. They also confirm that αn is determined by three parameters: the inherent dynamic packing efficiency, α0, when steric hindrance owing to (CHn)nH is not a factor; the incremental decrease in packing efficiency, A, per added methylene group owing to the corresponding increase in molecular bulkiness; and the added steric hindrance factor to adsorption, B, caused by self-association in such molecules when n > 6. Relationships that correlate log αn with the corresponding Hildebrand solubility parameter, δn, were established, and the significance of such correlations is discussed. © 1990 American Chemical Society.