Low-entangled UHMWPE melt: analytical model and computer simulations

In this work we developed a theoretical model to describe the polymerization of very long macromolecules with simultaneous precipitation. As a reference system for our model we consider UHMWPE polymerization process, via homogeneous catalysis and with molecular weight above ${10}^6$ monomers. We derived time dependency of the entanglement length in the system, and assessed how polymerization rate and fraction of initiators affects this dependency. We show that decrease of the fraction of initiators leads to increase of the average entanglement length in the melt after complete polymerization. The results are supported by computer simulations and in principle could be applied to the wide set of polymerized materials, both crystallized and amorphous.