The influence of a potential diffusion control on the outcome of modular polymer-polymer click conjugations

Preuss, C. M. & Barner-Kowollik, C. (2011) The influence of a potential diffusion control on the outcome of modular polymer-polymer click conjugations. Macromolecular Theory and Simulations, 20(8).

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Abstract

The only reliable factors for assessing if a polymer-polymer click conjugation is successful are an assessment of the number average M̄n of the resulting molecular weight distribution (MWD) and the shape of the number, respectively, concentration distribution as was demonstrated earlier. The present contribution explores if a potential chain length dependence (CLD) of the conjugation reaction-caused by a potential diffusion control-can affect the outcome of the polymer-polymer click ligation process. The CLD of the click rate coefficient, Ki,j click was implemented via a geometric mean approximation for chain length dependent termination, employing α-values from 1.0 to 0.2. The number averages M̄n and weight averages M̄w (and thus the PDIs) of the initial distributions were varied widely to explore under which conditions CLD effects have the largest impact. The present study clearly demonstrates that-if diffusion effects and thus a CLD of Ki,j click-play a role in polymer-polymer ligation, the MWDs generated through conjugation display a marked conversion dependence, i.e., M click n with the maximum Mclick n being reached at quantitative conversions. While the M̄n reached at quantitative conversions coincides with the M̄n obtained under CL-independent conditions, the final M̄w of both the CLD and non-CLD differs significantly. While the present theoretical study cannot replace the actual experiment, it unambiguously demonstrates that polymer-polymer click conjugations can be influenced by CLD effects. Given the larger α-values for smaller chain length, broad distributions in the range up to approximately 3 000 Da are especially affected. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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6 citations in Web of Science®
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ID Code: 99279
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :6
Export Date: 5 September 2016
CODEN: MTHSE
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, Geb. 11.23, 76128 Karlsruhe, Germany; email: christopher.barner-kowollik@kit.edu
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Keywords: chain length dependence, click conjugation, diffusion control, Actual experiments, Chain length dependent terminations, Chain-length dependence, Click rates, Concentration distributions, Diffusion effects, Geometric mean, Number average, Theoretical study, Diffusion, Molecular weight distribution, Polymers, Chain length
DOI: 10.1002/mats.201100033
ISSN: 10221344
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 05 Oct 2016 04:19

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