Network formation and gelation in Telechelic star polymers

TL;DR

This study uses explicit Coulomb charges in simulations to analyze gelation in telechelic star polymers, revealing how dipole interactions lead to network formation and influence elastic properties.

Contribution

It introduces a bead-spring model with explicit charges to better predict gelation and structural organization in telechelic star polymers, avoiding effective potential approximations.

Findings

Dipole aggregation forms interconnected networks.

Network formation depends on dipole charge magnitude.

Structural organization varies with dipole charge and arm fraction.

Abstract

We investigate the efficiency of gelation and network formation in telechelic star polymer melt, where the tips of polymer arms are dipoles while rest of the monomers are uncharged. Our work is motivated by the experimental observations [A.Kulkarni et.al, Macromolecules, {\bf 48}, 6580 (2015)], in which rheological studies of telechelic star polymers of poly-(L-actide), a bio-degradable polymer, showed a drastic increase in elastic properties (up to $2000$ times) compared to corresponding star polymers without the telechelic arm ends. In contrast to previous studies, we avoid using effective attractive Lennard Jones potentials or dipolar potentials to model telechelic interactions. Instead we use explicit Coulomb positive and negative charges at the tip of polymer-arms of our bead-spring model of star polymers. By our simulations we show that the dipoles at the tip of star arms aggregate together to form clusters of dipoles. Each cluster has contribution from several stars, and in turn each star contributes to several clusters. Thus the entire polymer melt forms a connected network. Network forming tendencies decrease with decrease of the value of the effective charge constituting the dipole: this can be experimentally realized by choosing a different ionomer for the star tip. We systematically varied the value of dipole charges, the fraction of star-arms with dipoles at the tip and the length of the arms. The choice of explicit charges in our calculations enables us to make better quantitative predictions about the onset of gelation, moreover we get qualitatively distinct results about structural organization of dipoles within a dipole-cluster.