Nitroxide-Mediated Polymerization of Methyl Methacrylate Using an SG1-Based Alkoxyamine: How the Penultimate Effect Could Lead to Uncontrolled and Unliving Polymerization
✍ Scribed by Yohann Guillaneuf; Didier Gigmes; Sylvain R. A. Marque; Paul Tordo; Denis Bertin
- Publisher
- John Wiley and Sons
- Year
- 2006
- Tongue
- English
- Weight
- 194 KB
- Volume
- 207
- Category
- Article
- ISSN
- 1022-1352
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✦ Synopsis
Abstract
Summary: The nitroxide‐mediated polymerization (NMP) of MMA initiated with a new crowded SG1‐based alkoxyamine was performed. Contrary to the results expected after a kinetic analysis (Fischer's diagram), the polymerization of MMA at 45 °C with SG1 showed only partial control and livingness during the first 15% of conversion. Simulations using PREDICI highlighted that the kinetic rate constants currently in use had not been correctly estimated and that a strong penultimate effect drastically increased the equilibrium constant K (7 × 10^−7^), preventing a well‐controlled polymerization. Experimental determination of the k~c~ value (1.4 × 10^4^ L · mol^−1^ · s^−1^) confirmed a strong penultimate effect on the recombination reaction, whereas for the dissociation reaction this effect is lower (k~d~ = 10^−2^ · s^−1^).
Nitroxide‐mediated polymerization of MMA at 45 °C initiated with a new crowded SG1‐based alkoxyamine.
magnified imageNitroxide‐mediated polymerization of MMA at 45 °C initiated with a new crowded SG1‐based alkoxyamine.