Abstract
Deep insight into the chemistry of vulcanization, its kinetics, and network structures have been provided by the elucidation of reactions of mono and diolefins with sulfur and accelerators, primarily at NRPRA, and the kinetic measurements of transformation of vulcanizing agents with 1,5-polyenes by Scheele and co-workers at the Kautschuk Institute der Technischen Hochschule, Hannover. It is now established that both accelerated and unaccelerated vulcanization of 1,5-polyenes with sulfur begins with formation of polysulfide crosslinks. As sulfur disappearance and formation of polysulfide proceed, secondary reactions participate increasingly. These involve a series of transformations of the crosslinks originally formed. This leads to a continual change in chain length of crosslinks, in their chemical constitution, and in structural features of the polymer. Figure 1 shows schematically the results of sulfur vulcanization. Crosslinks consist of mono, di, or polysulfide structures, depending on vulcanization time and temperature. As polysulfide bonds disappear, the polymer is modified by the appearance of monosulfidic ring structures and conjugated double bonds in the chain. Secondary reactions may change the crosslink density of the vulcanizate. There are three possibilities: shortening of the crosslink chain length can proceed (a) without change in, (b) with decreasing, or (c) with increasing, crosslink density. Which occurs must be determined for each system. For each polymer the density of crosslinking, its chemical structure, and the extent of polymer modification determine physical, chemical, and technological properties of the vulcanizate.