Structural characterization of vulcanizates. Part II. Use of triphenylphosphine to determine the structures of sulfur linkages in unaccelerated natural rubber–sulfur vulcanizate networks

Abstract

Treatment of unaccelerated natural rubber–sulfur vulcanizate networks with triphenylphosphine in benzene at 80°C. effects the removal of part of the combined sulfur, the proportion removed decreasing with increasing cure time. This partial desulfurization of the network is attributed, on the basis of the mode of interaction of simple organic di- and polysulfides with triphenylphosphine, to the conversion of polysulfide linkages in the network into either mono- or disulfide groups. Knowledge of the amount of sulfur removed by the reagent, and of the chemical degree of crosslinking and combined sulfur content of the untreated networks permits the following semiquantitative conclusions to be reached concerning the structures of the sulfur linkages in the networks: (1) long polysulfidic crosslinks (S11 to S12) are initially formed, which on continued cure progressively decrease in length to a limiting value of S2 to S4; and (2) a very high proportion to the combined sulfur (ca. 77% for short cure times, increasing to ca. 95% on extended cure) is present in cyclic monosulfide groups situated along the polyisoprene chains.