Tailoring the Chain Entanglement by Nitrogen Bubble-Assisted Polymerization

The reduction in the entangled state of the nascent ultrahigh-molecular-weight polyethylene (UHMWPE) is of fundamental importance to enhance its processability and mechanical properties. However, it remains a challenge to retard the formation of entanglements during polymerization above 60 °C because the chain propagation rate is notably higher than the chain crystallization rate. Herein, we present a feasible method for synthesizing the weakly entangled polyethylene via nitrogen microbubble-assisted polymerization. The mass transfer of ethylene inside the growing polyethylene particles is found to dominate the chain propagation process, which is influenced by the nitrogen bubble size. The contact/interval time (10–3 s) between the microbubbles and the particles, observed by a high-speed camera, appears several orders less than the chain propagation time. Consequently, such frequent contact/separation instantly blocks/recovers the reactant transfer on the solvent–particle interphase, causing an intermittent “dormancy effect” to retard the chain propagation and facilitate the chain crystallization. Therefore, the less entangled polyethylene is synthesized at a relatively high activity.