**Acknowledgement**

MLC gratefully acknowledges generous allocations of time on the National Facility of the National Computational Infrastructure, support from the Australian Research Council (ARC) under its Centres of Excellence program, and an ARC Future Fellowship. EC gratefully acknowledges financial support from the Russian Foundation for Basic Research (project 11-03-00640).

### **7. References**

Ah Toy, A., Vana, P., Davis, T. P. & Barner-Kowollik, C. (2004). Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of Methyl Acrylate: Detailed Structural Investigation via Coupled Size Exclusion Chromatography−Electrospray Ionization Mass Spectrometry (SEC−ESI-MS), *Macromolecules*, *vol.* 37 (No. 3), pp. 744– 751

Barner-Kowollik, C., Coote, M. L., Davis, T. P. et al. (2003). The reversible additionfragmentation chain transfer process and the strength and limitations of modeling: comment on the "Magnitude of the fragmentation rate coefficient. *Journal of Polymer Science, Part A: Polymer Chemistry, vol.* 41 (No. 18), pp. 2828–2832

432 Nitroxides – Theory, Experiment and Applications

standard polymerization conditions.

Ching Yeh Lin and Michelle L. Coote

**Author details** 

**Acknowledgement** 

(project 11-03-00640).

**7. References** 

magnitude at least; in particular cases the error could be appreciably higher. This is one of the reasons why we use extensively the photolysis of MNP: for this reaction there is a reliable value of rate coefficient of tert-butyl radical spin trapping. The other challenge is that, in estimating kinetic constants, one also has to assume that other reaction channels are not significant. The generally good agreement with theoretical calculations suggests that these assumptions are likely to be reasonable most of the time, though the unusual results for BB are also a warning that these assumptions need to be continually re-evaluated for each new system studied. Nonetheless, it has to be stressed that the presence of the spin trap, by outcompeting most side reactions, does greatly minimize the impact of kinetic assumptions on the accuracy of the kinetic results, particularly when compared with

The spin trap technique therefore has much to offer the radical polymer field. For instance, the application of the spin traps has helped to solve a number of problems in complexradical polymerization and copolymerization (Golubev et al., 1978). They have also helped to address controversies related to spontaneous initiation and unusual inhibition of some polymerization systems (Zaremski et al., 1999). We hope that the results presented in this work will encourage the further development and application of these techniques for RAFT

MLC gratefully acknowledges generous allocations of time on the National Facility of the National Computational Infrastructure, support from the Australian Research Council (ARC) under its Centres of Excellence program, and an ARC Future Fellowship. EC gratefully acknowledges financial support from the Russian Foundation for Basic Research

Ah Toy, A., Vana, P., Davis, T. P. & Barner-Kowollik, C. (2004). Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of Methyl Acrylate: Detailed Structural Investigation via Coupled Size Exclusion Chromatography−Electrospray

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