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Experimentally Calibrated Random Walk of Branched Polymers: A Pragmatic Approach
Author(s) -
Hosemann Benjamin,
Drache Marco,
Beuermann Sabine
Publication year - 2016
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.201600067
Subject(s) - branching (polymer chemistry) , copolymer , polymer , gyration , radius of gyration , multiangle light scattering , monomer , materials science , random walk , polymer chemistry , scattering , light scattering , mathematics , physics , optics , statistics , geometry , composite material
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 r g 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 r g 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.