Swelling Ratios and Rates of Sulfonation of Solvent Modified Copolymers of Styrene Cross-Linked with Pure m-and Pure p-Divinylbenzene

Solvent-modified (toluene) copolymers have been prepared from styrene cross-linked with commercial divinylbenzene, m-divinylbenzene, and p-divinylbenzene at divinyl monomer contents of 16 mole % and 32 mole % at FM = 0.50. The resultant copolymers have been characterized by swelling-ratio determinations and rates of sulfonation at 60 and 80°C. The solvent-modified 16 mole % cross-linked copolymers sulfonated at rates slightly greater than those characterizing the 8 mole % cross-linked copolymers prepared in the absence of diluent. The order of decreasing sulfonation rates for both the conventional 8 mole % cross-linked systems and for the solvent-modified 16 mole % cross-linked copolymers is commercial divinylbenzene/styrene, p-divinylbenzene/styrene, m-divinylbenzene styrene. The 32 mole % cross-linked systems exhibit a different order of decreasing sulfonation rates: commercial divinylbenzene/styrene, m-divinylbenzene/styrene, p-divinylbenzene/styrene. The swelling ratios of the 32 mole % solvent-modified copolymers were comparable to those of the conventional 8 mole % cross-linked systems.