Nitroxide-mediated living radical polymerization: Determination of the rate coefficient for alkoxyamine C-O bond homolysis by quantitative ESR

Macromolecules

Volumn 32, Issue 25, 1999, Pages 8269-8276

  Bon, Stefan A F ^a,b   Chambard, Grégory ^a   German, Anton L ^a  

^a EINDHOVEN UNIVERSITY OF TECHNOLOGY   (Netherlands)

^b UNIVERSITY OF WARWICK   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; CHEMICAL BONDS; GEL PERMEATION CHROMATOGRAPHY; NITROGEN OXIDES; POLYSTYRENES; REACTION KINETICS; TOLUENE;

ALKOXYAMINE; HOMOLYSIS; LIVING RADICAL POLYMERIZATION;

FREE RADICAL POLYMERIZATION;

EID: 0033334322     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma990771r     Document Type: Article

References (31)

1. Kovtun, G. A.; Aleksandrov, A. L.; Golubev, V. A. Izv. Akad. Nauk SSSR, Ser. Khim. 1973, 2197.
2. Howard, J. A.; Tait, J. C. J. Org. Chem. 1978, 43, 4279.
3. Ingold, K. U. In Free Radicals; Kochi, J. K., Ed.; Wiley: New York, 1973; Vol. 1, Chapter 2.
4. Solomon, D. H.; Rizzardo, E.; Caciolo, P. Eur. Pat. Appl. 135280, 1985; Chem. Abstr. 1985, 102, 221335q.
5. Solomon, D. H.; Rizzardo, E.; Caciolo, P. Eur. Pat. Appl. 135280, 1985; Chem. Abstr. 1985, 102, 221335q.
6. Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K. Macromolecules 1993, 26, 2987.
7. Skene, W. G.; Belt, S. T.; Connolly, T. J.; Hahn, P.; Scaiano, J. C. Macromolecules 1998, 31, 9103.
8. Grattan, D. W.; Carlsson, D. J.; Howard, J. A.; Wiles, D. M. Can. J. Chem. 1979, 57, 2834.
9. t is within experimental error), can be used but should be interpreted with care.
10. (a) Goto, A.; Terauchi, T.; Fukuda, T.; Miyamoto, T. Macromol. Rapid Commun. 1997, 18, 673.
11. (b) Fukuda, T.; Goto, A. Macromol. Rapid Commun. 1997, 18, 682.
12. It is known that nitroxides are able to readily abstract hydrogen atoms under photochemical conditions. The hydrogen atom is abstracted by the photoexcited nitroxyl group in the n → π* excited state ((a) Keana, J. F. W.; Dinerstein, R. J.; Baitis, F. J. Org. Chem. 1971, 36, 209.
13. (b) Call, L.; Ullman, E. Tetrahedron Lett. 1973, 961). Thermal hydrogen atom abstraction, as has been observed, is known to be possible at elevated temperatures for conventional nitroxides, such as TEMPO 1 and derivatives thereof
14. ((c) Wasserman, A. M.; Buchachenko, A. L. Izv. Akad. Nauk SSSR, Ser. Khim. 1967, 1947.
15. (d) Hill, D. J. T.; O'Donnel, J. H.; O'Sullivan, P. W. Prog. Polym. Sci. 1982, 8, 215.
16. (e) Connolly, T. J.; Scaiano, J. C. Tetrahedron Lett. 1997, 38, 1133). Nitroxides with electron-withdrawing substituents are much more reactive toward hydrogen atom abstraction and addition reactions to vinyl groups, e.g., N,N-bis(trifluoromethyl)amine-N-oxyl.
17. (f) Banks, R. E.; Haszeldine, R. N.; Stevenson, M. J. J. Chem. Soc. C 1966, 901.
18. (g) Banks, R. E.; Choudhury, D. R.; Haszeldine, R. N. J. Chem. Soc., Perkin Trans. 1 1973, 1092.
19. (h) Banks, R. E.; Birchall, J. M.; Brown, A. K.; Haszeldine, R. N.; Moss, F. J. Chem. Soc., Perkin Trans. 1 1975, 2033.
20. (i) Malatesta, V.; Ingold, K. U. J. Am. Chem. Soc. 1981, 103, 3094.
21. (j) Doba, T.; Ingold, K. U. J. Am. Chem. Soc. 1984, 106, 3958.
22. Van Herk, A. M. J. Chem. Educ. 1995, 72, 138.
23. It is known that purging a liquid sample with helium is more efficient in the removal of oxygen than purging with argon.
24. E.g.: Moad, G.; Rizzardo, E.; Solomon, D. H. Macromolecules 1982, 15, 909.
25. The authors are aware that the reactions of oxygen and compounds thereof are an oversimplification of reality. For example, a possible (induced) decomposition of the peroxide is not taken into account (see e.g. for the reaction of acyl peroxides with TEMPO: Moad, G.; Rizzardo, E.; Solomon, D. H. Tetrahedron Lett. 1981, 22, 1165).
26. IUPAC Solubility Data Series; Battino, R., Ed.; Pergamon Press: New York, 1981; Vol. 7.
27. Sueoka, K. Bull. Chem. Soc. Jpn. 1994, 67, 978.
28. Bartlett, P. D.; Benzing, E. P.; Pincock, R. E. J. Am. Chem. Soc. 1960, 82, 1762.
29. Rosantzev, E. G.; Hazzard, B. J.; Ulirch, H. Free Nitroxyl Radicals; Plenum Press: New York, 1970.
30. Czoch, R. Appl. Magn. Reson. 1996, 10, 293.
31. NAG Library Mark 5, Numerical Algorithms Group, Oxford.