Enzyme–Analogue Built Polymers. IX. Polymers with Mercapto Groups of Definite Cooperativity

By copolymerization of bis(p‐vinylbenzyl)disulfide (1) with crosslinking monomers and subsequent reduction of the disulfide bond with diborane, polymers with two closely positioned mercapto groups were prepared. Under comparable conditions polymers with randomly distributed mercapto groups were obtained from (p‐vinylbenzyl)thioacetate (2). The degree of cooperativity of the mercapto groups in polymers of (1) as well as the degree of site separation in polymers of (2) were determined quantitatively by oxidation with I2. The percentage of reoxidation by I2 to disulfide depends on degree of crosslinking of polymer, the concentration of mercapto groups, the degree of swelling and the reoxidation temperature. From these data valuable information on the arrangement of functional groups as well as on polymer structure was obtained.