ิ
ิulphur [12] or peroxides [13] formulations, which require
many assisting reagents in addition to the cross-linker, can be
employed to cure ENR. Sulphur reacts preferentially with the
double bonds rather than with the epoxide groups. However,
vulcanization by sulphur is more effective than in the case of NR.
Model molecules showed that this effect was associated to two
main causes. First, epoxide groups contiguous to double bonds
might have an activator role. Second, sulphur reaction with double
bonds is a radical addition mechanism, which is slowed down by
side reactions between adjacent double bonds. Since epoxidized NR
contains some isolated double bonds, this effect is reduced [12].
Sulphur vulcanizates of ENR show poor ageing, because thermal
decomposition of oxidized sulphides delivers acids which, over
time, catalyze ring opening reactions with the formation of ether
cross-links, and a subsequent increase in the stiffness of the
vulcanizates [12].