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.