Abstract

Various alkoxyamine initiators for nitroxide mediated radical polymerization (NMRP) were prepared in high yields by a simple substitution reaction of nitroxide anions with benzyl bromide. The required nitroxide anions were easily generated by treating either nitroxide free radicals or hydroxy amine with an alkali metal such as sodium or potassium in THF. This method is both practical and efficient, since the ionic conditions prevent other side reactions from occurring, such as the self-coupling or oligomerization reactions that are observed in the case of radical trapping conditions. To demonstrate the utility of the resulting alkoxyamine initiators, end- and telechelic-alkoxyamine PEG macroinitiators derived from the alkoxyamines were synthesized by a simple chemical modification, and used for the preparation of PEG-b-PS and PS-b-PEG-b-PS block copolymers by NMRP.

주제어

#nitroxide mediated radical polymerization (NMRP)   #alkoxyamine initiator   #polystyrene-b-poly(ethylene oxide) block copolymer  

참고문헌 (28)

1. M. K. Georges, R. P. N. Veregin, P. M. Kazmaier, and G. K. Hamer, Macromolecules, 26, 2987 (1993) 
2. J. Pyun and K. Matyjaszewski, Chem. Mater., 13, 3436 (2001) 
3. R. Matsuno, K. Yamamoto, H. Otsuka, and A. Takahara, Macromolecules, 37, 2203 (2004) 
4. S. M. Lindner and M. Thelakkat, Macromolecules, 37, 8832 (2004) 
5. L. Andruzzi, W. Senaratne, A. Hexemer, C. K. Ober, and E. J. Kramer, Polym. Mater. Sci. Eng., 88, 604 (2003) 
6. C. J. Hawker and J. L. Hedrick, Macromolecules, 28, 2993 (1995) 
7. D. E. Bergbreiter and B. Walchuk, Macromolecules, 31, 6380 (1998) 
8. T. Krause, W. D. Habicher, M. Messerschmidt, and B. I. Voit, Design. Monom. Polym., 7, 391 (2004) 
9. J. E. Anderson, D. Casarini, J. E. T. Corrie, and L. Lunazzi, J. Chem. Soc., Perkin Trans., 2, 1299 (1993) 
10. K. Sill and T. Emrick, Chem. Mater., 16, 1240 (2004) 
11. R. B. Grubbs, J. K. Wegrzyn, and Q. Xia, Chem. Comm., 80 (2005) 
12. C. J. Hawker, J. Am. Chem. Soc., 116, 11185 (1994) 
13. M. K. Georges, R. P. N. Veregin, G. K. Hamer, and P. M. Kazmaier, Macromol. Symp., 88, 89 (1994) 
14. I. Q. Li, B. A. Howell, R. A. Koster, and D. B. Priddy, Macromolecules, 29, 8554 (1996) 
15. W. Xu, X. Zhu, Z. Cheng, J. Chen, and J. Lu, Macromol. Res., 12, 32 (2004) 
16. A. J. Convertine, N. Ayres, C. W. Scales, A. B. Lowe, and C. L. McCormick, Biomacromolecules, 5, 1177 (2004) 
17. E. Yoshida, T. Ishizone, A. Hirao, S. Nakahama, T. Takata, and T. Endo, Macromolecules, 27, 3119 (1994) 
18. M. K. Georges, R. P. N. Veregin, P. M. Kazmaier, and G. K. Hamer, Polym. Prepr., 35, 582 (1994) 
19. J. M. Catala, F. Buble, and S. O. Hammouch, Macromolecules, 28, 8441 (1995) 
20. J. Chiefari, Y. K. Chong, F. Ercole, J. Krstina, J. Jeffery, T. P. T. Le, R. T. A. Mayadunne, G. F. Meijs, C. L. Moad, G. Moad, E. Rizzardo, and S. H. Thang, Macromolecules, 31, 5559 (1998) 
21. Y. Chen, W. Wang, W. Yu, Z. Yuan, E.-T. Kang, K.-G. Neoh, B. Krauter, and A. Greiner, Adv. Funct. Mater., 14, 471 (2004) 
22. J.-S. Wang and K. Matyjaszewski, J. Am. Chem. Soc., 117, 5614 (1995) 
23. D. Benoit, V. Chaplinski, R. Braslau, and C. J. Hawker, J. Am. Chem. Soc., 121, 3904 (1999) 
24. A. Cowell and A. K. Stille, J. Am. Chem. Soc., 102, 4193 (1980) 
25. J.-S. Wang and K. Matyjaszewski, Macromolecules, 28, 7901 (1995) 
26. T. von Werne and T. E. Patten, J. Am. Chem. Soc., 121, 7409 (1999) 
27. U. Stalmach, B. De Boer, A. D. Post, P. F. Van Hutten, and G. Hadziioannou, Angew. Chem. Int. Ed., 40, 428 (2001) 
28. C. J. Hawker, G. G. Barclay, A. Orellana, J. Dao, and W. Devonport, Macromolecules, 29, 5245 (1996) 

이 논문을 인용한 문헌 (0)

1. 이 논문을 인용한 문헌 없음