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Updated: Jan 23, 2026

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
Published on: September 26, 2016
Influence of Branching on the Configurational and Dynamical Properties of Entangled Polymer Melts
Alexandros Chremos1, Jack F Douglas2
1Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA. alexandros.chremos@nist.gov.
Abstract:
We probe the influence of branching on the configurational, packing, and density correlation function properties of polymer melts of linear and star polymers, with emphasis on molecular masses larger than the entanglement molecular mass of linear chains. In particular, we calculate the conformational properties of these polymers, such as the hydrodynamic radius R h , packing length p, pair correlation function g ( r ) , and polymer center of mass self-diffusion coefficient, D, with the use of coarse-grained molecular dynamics simulations. Our simulation results reproduce the phenomenology of simulated linear and branched polymers, and we attempt to understand our observations based on a combination of hydrodynamic and thermodynamic modeling. We introduce a model of "entanglement" phenomenon in high molecular mass polymers that assumes polymers can viewed in a coarse-grained sense as "soft" particles and, correspondingly, we model the emergence of heterogeneous dynamics in polymeric glass-forming liquids to occur in a fashion similar to glass-forming liquids in which the molecules have soft repulsive interactions. Based on this novel perspective of polymer melt dynamics, we propose a functional form for D that can describe our simulation results for both star and linear polymers, covering both the unentangled to entangled polymer melt regimes.
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