Results
Title

Experimentally Calibrated Random Walk of Branched Polymers: A Pragmatic Approach.

Authors

Hosemann, Benjamin; Drache, Marco; Beuermann, Sabine

Abstract

In order to control the branching behavior of polymers, the comparison of experimental and simulated data is important. The utilization of a nonlattice, self-avoiding necklace-bead random walk simulator is reported, which allows for the calculation of radii of gyration rg of polymer molecules with branched structures. The focus is on sensitivity toward short-chain branches, long-chain branches (LCBs), and the copolymer composition. Using only two parameters-the size of monomer beads and the minimum angle between three subsequent beads-a fast and reliable parameter fit procedure based on experimental data is described. The procedure is exemplarily shown for copolymers of vinylidene fluoride and hexafluoropropene (HFP) with HFP contents in the copolymer of at most 0.3 and is easily transferable to other polymers that may be analyzed by size-exclusion chromatography/multiangle laser light scattering close to θ conditions. Applying the Zimm-Stockmayer equation to simulated rg data allows for comparing the 'effective' number of LCBs with the number of LCBs given by kinetic simulations. A tool for better estimation of rate coefficients associated with the formation of short- and long-chain branches is provided.

Subjects

RANDOM walks; BRANCHED polymers; COPOLYMERS; DIFLUOROETHYLENE; CHROMATOGRAPHIC analysis

Publication

Macromolecular Theory & Simulations, 2016, Vol 25, Issue 6, p508

ISSN

1022-1344

Publication type

Academic Journal

DOI

10.1002/mats.201600067