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Issue 24, 2016
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Diffusion of single molecular and macromolecular probes during the free radical bulk polymerization of MMA – towards a better understanding of the Trommsdorff effect on a molecular level

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Abstract

Free radical bulk polymerizations exhibit complex kinetics due to the viscosity increase during the polymerization process. Especially the termination rate constant can be strongly influenced by the mobility of polymer chains in the polymerization mixture. As a consequence an autoacceleration period, the so-called Trommsdorff effect, can be observed often. In order to investigate this behaviour on a nanoscopic scale, we directly visualized the mobility of molecules and macromolecules in polymerizing MMA solutions using a combination of highly sensitive fluorescence correlation spectroscopy and widefield fluorescence microscopy. For this purpose, rather monodisperse PMMA chains were synthesized by RAFT polymerization and fluorescence-labelled with perylenediimide derivatives. The behaviour of the different fluorescent probes could be related to their size and flexibility. Our studies show that diffusional heterogeneities must be accounted for when modeling bulk polymerization.

Graphical abstract: Diffusion of single molecular and macromolecular probes during the free radical bulk polymerization of MMA – towards a better understanding of the Trommsdorff effect on a molecular level

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Publication details

The article was received on 03 Apr 2016, accepted on 23 May 2016 and first published on 24 May 2016


Article type: Paper
DOI: 10.1039/C6PY00590J
Citation: Polym. Chem., 2016,7, 4100-4105
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    Diffusion of single molecular and macromolecular probes during the free radical bulk polymerization of MMA – towards a better understanding of the Trommsdorff effect on a molecular level

    J. M. Nölle, S. Primpke, K. Müllen, P. Vana and D. Wöll, Polym. Chem., 2016, 7, 4100
    DOI: 10.1039/C6PY00590J

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