## Abstract **Summary:** We present the first __ab initio__ simulation of a reversible addition fragmentation chain transfer (RAFT) polymerization. Using __ab initio__ molecular orbital theory, we calculate the equilibrium constants for the first eight addition–fragmentation steps in the cyanoisopr
A Mechanistic Interpretation of Initialization Processes in RAFT-Mediated Polymerization
✍ Scribed by James B. McLeary; Matthew P. Tonge; Bert Klumperman
- Book ID
- 102492556
- Publisher
- John Wiley and Sons
- Year
- 2006
- Tongue
- English
- Weight
- 231 KB
- Volume
- 27
- Category
- Article
- ISSN
- 1022-1336
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✦ Synopsis
Abstract
Summary: The presence of strong chain length selectivity behavior during initialization in the RAFT process is an experimental observation. The mechanistic underpinning of the observation is, however, open to interpretation. The rates and concentration profiles for the cyanoisopropyl‐dithiobenzoate‐mediated polymerization of styrene at 70 °C can be relatively well reproduced by either the slow fragmentation or intermediate radical termination models. The use of modeling that provides a fit to the data is an important tool, but should be considered as additional evidence in support of experimental data rather than as experimental evidence in and of itself.
Comparison of the time dependencies of the concentrations of AD, AMD, and AM~2~D by PREDICI modeling for the cyanoisopropyl‐mediated polymerization of styrene at 70 °C generated by the IRT model (lines) versus experimental data.
magnified imageComparison of the time dependencies of the concentrations of AD, AMD, and AM~2~D by PREDICI modeling for the cyanoisopropyl‐mediated polymerization of styrene at 70 °C generated by the IRT model (lines) versus experimental data.
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