Article

 

Controlled Synthesis of Block Copolymers containing N–isopropylacrylamide by Reversible Addition–Fragmentation Chain–Transfer (RAFT) Polymerization

 

Alejandro Vega–Rios and Angel Licea–Claveríe^*

 

Centro de Graduados e Investigación, Instituto Tecnológico de Tijuana, A.P. 1166, 22414 Tijuana, B.C., México. *e–mail: aliceac@tectijuana.mx.

 

Received June 14, 2010.
Accepted November 8, 2010.

 

Abstract

Synthesis of diblock copolymers of N–isopropylacrylamide with n–hexyl acrylate, styrene, methyl methacrylate and 2–hydroxyethyl methacrylate, were carried out by using a sequential "living" polymerization method in the presence of chain transfer agent (CTA) 4–Cyano–4–(phenylcarbonothioylthio)pentanoic acid. The block copo–lymer composition and molecular weight could be well controlled while maintaining a narrow molecular weight distribution. The block copolymers were characterized by ¹H NMR, GPC with MALLS detection and DSC. The molar ratio CTA/Initiator rather than the sequence of monomer addition is the key parameter for achieving the desired materials. We report the first synthesis of poly(HEMA)–b–poly(NIPAAm) with a polydispersity index (IPD) of 1.20 by RAFT.

Keywords: Block Copolymer, RAFT, poly(NIPAAm), poly(MMA), poly(HEMA), poly(St).

 

Resumen

La síntesis de copolímeros en dibloques de N–isopropila–crilamida con acrilato de n–hexilo, estireno metacrilato de metilo y metacrilato de 2–hidroxietilo, se llevó a cabo mediante polimerización viviente secuencial en presencia del agente de transferencia de cadena (CTA) ácido 4–ciano–4–[fenilcarbonotioiltio] pentanoico. La composición y peso molecular de los copolímeros en bloques se pudo controlar manteniendo un índice de polidispersidad bajo. Los copolímeros en bloque se caracterizaron por ¹H RMN, GPC con MALLS y por DSC. La relación CTA/Iniciador resultó ser más relevante que la secuencia de adición de monómeros para lograr los materiales deseados. Se reporta por primera vez la síntesis de poli(HEMA)–b–poli(NIPAAm) con un índice de polidispersidad de 1.20 por RAFT.

Palabras clave: Copolímeros en bloques, RAFT, poli(NIPAAm), poli(MMA), poli(HEMA), poli(St).

 

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Acknowledgements

This investigation was supported by a grants of CONACYT No SEP2006–60792 and DGEST No. 947–08–P. We thank A. Ochoa and I. Rivero for performing NMR analysis and U. Pérez and F. Soto for some synthetic work.

 

References

1. Sebenik, A. Prog. Polym. Sci. 1998, 23, 875–917.         [ Links ]

2. Szwarc, M. Nature 1956, 178, 1168–1169.         [ Links ]

3. Lowe, B. A., McCormick, L. C., Prog. Polym. Sci. 2007, 32, 283–351.         [ Links ]

4. Chiefari, J.; Chong, Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T.P.T.; Mayadunne, R. T. A.; Meijs, G. F.; Moad, C. L.; Moad, G.; Rizzardo, E.; Thang, S. H. Macromolecules 1998, 31, 5559–5562.         [ Links ]

5. Feldermann, A.; Ah Toy, A.; Phan, H.; Stenzel, H. M.; Davis, T. P.; Barner–Kowollik, C. Polymer 2004, 45, 3997–4007.         [ Links ]

6. McLeary, B. J.; Tonge, P. M.; Klumperman, B. Macromol. Rapid Commun. 2006, 27, 1233–1240.         [ Links ]

7. Moad, G.; Rizzardo, E.; Thang, S. H., Material Matters 2010, 5, 2–5.         [ Links ]

8. Moad, G.; Rizzardo, E.; Thang, S. H., Aust. J. Chem. 2005, 58, 379–410.         [ Links ]

9. Moad, G.; Anderson, A. G.; Ercole, F.; Johnson, C. H. J.; Krstina, J.; Moad, C. L.; Rizzardo, E.; Spurling, T. H.; Thang, S. H. in Matyjaszewski, K. (Ed.) ACS Symp. Ser. Vol. 685: Controlled Radical Polymerization. American Chemical Society, Washington 1998, 332–360.         [ Links ]

10. Chong, Y. K.; Tam, P. T. L.; Moad, G.; Rizzardo, E.; Thang, H. S. Macromol. 1999, 32, 2071–2074.         [ Links ]

11. Schild, H. G. Prog. Polym. Sci. 1992, 17, 163–249.         [ Links ]

12. Rzaev, Z. M. O.; Dinçer, S.; Pişkin, E. Prog. Polym. Sci. 2007, 32, 534–595.         [ Links ]

13. York, W. A.; Kirkland, E. S.; McCormick, L. C. Adv. Drug Delivery Rev., 2008, 60, 1018–1036.         [ Links ]

14. Matyjaszewski, K.; Davis, T. P.: Eds. Handbook of Radical Polymerization, Wiley–Interscience; Hoboken 2002, 199.         [ Links ]

15. Ganachaud, F.; Balic, R.; Monteiro, M. J.; Gilbert, R. G. Macromolecules 2000, 33, 8589–8596.         [ Links ]

16. Costioli, M. D.; Berdat, D.; Freitag, R.; André, J.; Müller, A. H. E. Macromolecules 2005, 38, 3630–3637.         [ Links ]

17. Brandrup, J.; Immergut, E. H.; Grulke, E. A. Eds. Polymer Handbook Fourth Ed., John Wiley & Sons: New York 1999, p II–80.         [ Links ]

18. Tang, T.; Castelleto, V.; Parras, P.; Hamley I. W.; King, S. M.; Roy, D.; Perrier, S.; Hoogenboom, R.; Schubert, U. S. Macromol. Chem. Phys. 2006, 207, 1718–1726.         [ Links ]

19. Cortez–Lemus, N.; Salgado–Rodriguez, R.; Licea–Claverie, A. J. Polym. Sci. A: Polym. Chem. 2010, 48, 3033–3051.         [ Links ]

20. Pfukwa, R.; Pound, G.; Klumperman, B. Polym. Prep. (Amer. Chem. Soc, Div. Polym. Chem.) 2008, 49, 117–118.         [ Links ]

21. Nuopponen, M.; Ojala, J.; Tenhu, H. Polymer 2004, 45, 3643–3650.         [ Links ]

22. Brandrup, J.; Immergut, E. H.; Grulke, E. A. Eds. Polymer Handbook Fourth Ed., John Wiley & Sons: New York 1999, Chapter VI.         [ Links ]

23. Mitsukami, Y.; Donovan, S. M.; Lowe, B. A.; McCormick, L. C. Macromolecules 2001, 34, 2248–2256.         [ Links ]

24. Thang, H. S.; Chong, B. Y. K.; Mayadunne, T. A. R.; Moad, G.; Rizzardo, E. Tetrahedron Lett. 1999, 40, 2435–2438.         [ Links ]

25. Brandrup, J.; Immergut, E.H.; Grulke, E.A. Eds. Polymer Handbook Fourth Ed., John Wiley & Sons: New York 1999, Chapter VII.         [ Links ]

26. Salgado–Rodriguez, R.; Licea–Clavene, A.; Arndt, K. F. Eur. Polym. J. 2004, 40, 1931–1940.         [ Links ]

27. Weda, P.; Trzebicka, B.; Dworak, A.; Tsvetanov, C. B. Polymer 2008, 49, 1467–1474.         [ Links ]