Stress relaxation in styrene-butadiene-styrene block copolymers containing unattached linear polybutadiene and styrene-butadiene diblocks

Stress relaxation has been studied in networks of styrene-butadiene-styrene triblock copolymers with spherical styrene domain structure containing 0.10 weight fraction of unattached linear polybutadiene (M_w = 389,000) or styrene-butadiene diblocks with very long butadiene segments (M = 225,000 or 510,000). The stretch ratio (uniaxial extension) was usually 1.15 and the temperature ranged from ?20 to +20°C. The contribution of the linear polybutadiene species to relaxation was essentially the same in two triblock networks with very different butadiene block lengths, as expected if the configurational rearrangements are dominated by reptation. In the diblock-triblock mixtures, in which the diblock butadiene segments are free at one end but anchored at the other and therefore incapable of reptation, there was no contribution to relaxation from the dangling butadiene segments of the diblock component; this would be expected if there are no relaxation mechanisms alternative to reptation for these very long semiattached species within the experimental time scale.