Simulation of GPC-Distribution Coefficients of Linear and Star-Shaped Molecules in Spherical Pores: Comparison of Simulation and Experiment

Abstract

Computer simulations of star-branched and linear polymers in spherical pores were performed in order to estimate their GPC-distribution coefficients. Based on these simulations, correction factors can be estimated, that allow correcting for the underestimation of the molecular weight of branched polymers if evaluated using a calibration curve based on linear standards.The results of the computer simulations were compared with experimental results of GPC-light scattering experiments of star polymers having of defined arm-numbers and arm-molecular weights. Good qualitative and quantitative agreement was found between experimental and simulated correction factors.The simulations were used additionally to elucidate the structure of coupling peaks in ATRP with multifunctional initiators. The elution volumes of these peaks were in good agreement with an expected dumbbell topology that would arise from arm-arm coupling of different stars.The authors would like to express their gratitude to Prof. A. Hirao, Tokyo Institute of Technology and PSS Polymer Standards Service GmbH, Mainz for supplying samples.