Issue 9, 2012
From the journal:

Polymer Chemistry

Single molecule diffusion and its heterogeneity during the bulk radical polymerization of styrene and methyl methacrylate†

Beate Stempfle,a   Maren Dill,a   Martin J. Winterhalder,a   Klaus Müllenb  and  Dominik Wöll*ac  

* Corresponding authors

a Faculty of Chemistry, University of Konstanz, Universitätsstrasse 10, 78464 Konstanz, Germany

b Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany

c Zukunftskolleg, University of Konstanz, Universitätsstrasse 10, 78464 Konstanz, Germany
E-mail: dominik.woell@uni-konstanz.de
Tel: +49 7531 88 2024

Abstract

The diffusion of perylene diimide dye molecules of clearly distinct size was observed during the thermally initiated polymerization of styrene and methyl methacrylate (MMA) at room temperature. A combination of fluorescence correlation spectroscopy and widefield fluorescence microscopy allowed us to cover the entire conversion range from free diffusion in the monomer solution to immobilization in the produced polymer glass. The evolution of diffusion coefficients differs significantly in both systems. The diffusion coefficient of both dyes decreases clearly more rapidly during the polymerization of MMA, i.e. at the same conversion, diffusion coefficients in the polymerizing MMA solution are clearly lower compared to the polymerizing styrene solution. Extrapolation of the diffusion of the dyes to the diffusion of polymer chains can explain the more pronounced Trommsdorff effect during the polymerization of MMA. In contrast to other methods, single molecule fluorescence microscopy allows for a direct visualization of heterogeneities in single molecule motion. Our measurements point to the fact that the reason for the distinct behaviour of both polymerization systems lies in structural heterogeneities evolving in the PMMA/MMA system already at rather low conversion. In contrast, during the polymerization of styrene, only minor heterogeneities were observed.

Graphical abstract: Single molecule diffusion and its heterogeneity during the bulk radical polymerization of styrene and methyl methacrylate

About
Cited by
Related
Download options Please wait...

Supplementary files

Article information

DOI
https://doi.org/10.1039/C2PY20268A
Article type
Paper
Submitted
26 Apr 2012
Accepted
14 Jun 2012
First published
15 Jun 2012

Polym. Chem., 2012,3, 2456-2463

Permissions

Request permissions

Single molecule diffusion and its heterogeneity during the bulk radical polymerization of styrene and methyl methacrylate

B. Stempfle, M. Dill, M. J. Winterhalder, K. Müllen and D. Wöll, Polym. Chem., 2012, 3, 2456 DOI: 10.1039/C2PY20268A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements