Polymer Swelling.XXIII.Molecular Structure-Affinity Correlation Studies Involving Poly(styrene-co-divinylbenzene) Exposed to Acyclic Olefinic Liquids

摘要

The adsorption parameters (#alpha#) of 45 olefinic liquids with respect to poly-(styrene-co-divinylbenzene) were established gravimetrically in the usual way. Those for the structures that comprise R_aR_bC=CR_cR_d, where each R is H or an alkyl group,can be fitted to log #alpha#_f=log #alpha#_i-D_s(N_f-N_i)relationships, where N_i and N_f are the initial and final number of mass units in the subseries of the above general molecular structure (GMS). The constant #alpha#_i reflects the number of methyl groups in lieu of H atoms and their positional relationship to each other on the double bond,whereas the constant D_s reflects the unit change in log #alpha#_i caused by incrementation of a (CH_2)_nR substituent from n=1 to its allowable limit while the rest of the molecular structure is kept constant. The results observed thereby confirm that these adsorption phenomena involve a liaison between the pendent phenyl groups of the sorbent polymer and the double bond of the sorbate liquid. The adsorption data accumulated in these studies show that in the cases of olefinic liquids carrying other kinds of functional groups, such as aromatic or ether groups, the adsorption preference usually favors the other functionality, leaving the olefinic group in the "nonadsorbed" portion of the adsorbed molecule where it can exert a positive influence on adsorptivity due to dynamic associative interactions with the mobile sorbed molecules of its own kind.