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Blends of multicyclic and linear polymers under biaxial elongational flowwere analyzed using coarse-grained molecular dynamics simulations. Themulticyclic/linear blends displayed overshoot in the normal stress differenceat the start-up of biaxial elongational flow. This overshoot was steeper formulticyclic/linear blends than for our previously reported monocyclic/linearblends [T. Murashima, K. Hagita, and T. Kawakatsu, Macromolecules, 2021, 54,7210]. Investigation of the origin of the overshoot in the multicyclic/linearblends revealed a different mechanism than that previously observed in ourmonocyclic/linear blends. Specifically, a "topological transition" mechanismcomprising a morphological change from the open- to closed-ring state wasobserved in the multicyclic chains, but not in the monocyclic chains. Thistopological transition drastically changes the stress of the rings. Althoughthe topological transition was also observed in asymmetric-multicyclic/linearblends, no stress overshoot appeared, owing to the asymmetry in the multicyclicchains. Therefore, we hypothesized that the structural symmetry in multicyclicchains is indispensable for overshoot behavior to occur. We determined that thetopological transition in multicyclic chains with structural symmetry inducesstress-overshoot behavior in multicyclic/linear blends under biaxialelongational flow.

macromolecules

Topological transition in multicyclic chains with structural symmetry  inducing stress-overshoot phenomena in multicyclic/linear blends under  biaxial elongational flow