Simulation as a Tool for Feasibility Studies about PIP-SEC Experiments

Macromolecular Theory and SimulationsVolume 10, Issue 4 p. 262-274 Full Paper Simulation as a Tool for Feasibility Studies about PIP-SEC Experiments Markus Busch, Markus BuschSearch for more papers by this author Markus Busch, Markus BuschSearch for more papers by this author First published: 26 April 2001 https://doi.org/10.1002/1521-3919(20010401)10:4<262::AID-MATS262>3.0.CO;2-2Citations: 22AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Abstract Advanced homo- and copolymerization models have been used to perform a feasibility study on the potential of pulse-initiated polymerization (PIP) experiments for ethene (co)polymerizations. An application of PIP experiments directly to the ethene homo-polymerization appears not as a very promising strategy to derive the homo-propagation rate coefficient kp of ethene. This failure can be attributed to the special characteristics of high temperature size exclusion chromatographs, being required to determine the molecular weight distribution (MWD) of polyethylene. PI copolymerizations appear as an interesting alternative to provide access to the homo-propagation rate coefficient of ethene. Most advantageous in this strategy is the fact that even a simple convergence contemplation (using a variation in monomer composition) yields the ethene homo-propagation rate coefficient kp. Simply aiming at this coefficient, there is no necessity of knowing the detailed kinetic parameters of the copolymerization. In a further part, the extended kinetic information being available about branching processes in ethene polymerizations was used to test for the potential influence of a slower propagation rate of secondary macroradicals on the PIP structure in MWDs. Even at the significant level of branching present in ethene homopolymerizations still a PIP structure inside the MWD remains observable, assuming retardation up to an extend of almost two orders of magnitude. In order to perform these studies a kinetic model was designed explicitly accounting for the formation of secondary macroradicals by transfer. The kinetic information about branching being available in literature was adopted toward this scheme. Citing Literature Volume10, Issue4April 2001Pages 262-274 RelatedInformation