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The process of polymer condensation, i.e. the formation of bonds betweenreactive end-groups, is ubiquitous in both industry and biology. Here we studygeneric systems undergoing polymer condensation in competition withcyclisation. Using a generalised Smoluchowski theory, molecular dynamicssimulations and experiments using DNA and T4 ligase, we find that this systemdisplays a transition, from a regime with finite-length chains at infinite timeand dominated by rings to one dominated by linear polymers that grow in time.Finally, we show that fluids prepared close to the transition may haveprofoundly different compositions and rheology at large condensation times.

Runaway Transition in Irreversible Polymer Condensation with Cyclisation