FeCp(CO)2I: A phosphine-free half-metallocene-type iron(II) catalyst for living radical polymerization of styrène

Macromolecules

Volumn 32, Issue 20, 1999, Pages 6877-6880

  Kotani, Yuzo ^a   Kamigaito, Masami ^a   Sawamoto, Mitsuo ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; FREE RADICAL POLYMERIZATION; INITIATORS (CHEMICAL); IRON COMPOUNDS; METALLORGANIC POLYMERS; MOLECULAR WEIGHT DISTRIBUTION;

LIVING RADICAL POLYMERIZATION; METALLOCENE;

POLYSTYRENES;

EID: 0032595875     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma9906130     Document Type: Article

References (35)

1. This work was presented in part at the 48th Annual Meeting of the Society of Polymer Science, Kyoto, Japan, May 1999; paper IPdOSO: Kotani, Y.; Kamigaito, M.; Sawamoto, M. Polym. Prepr. Jpn. 1999, 48 (2), 135.
2. For recent reviews on living radical polymerizations, see: (a) Georges, M. K; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K. Trends Polym. Sci. 1994, 2, 66.
3. (b) Davis, T. P.; Kukulj, D.; Haddleton, D. M.; Maloney, D. R. Trends Polym. Sci. 1995,3, 365.
4. Malmström, E. E.; Hawker, C. J. Macromol. Chem. Phys. 1998, 199, 823.
5. Sawamoto, M.; Kamigaito, M. Trends Polym. Sci. 1996, 4, 371.
6. (e) Colombani, D. Prog. Polym. Sci. 1997, 22, 1649.
7. (f) Controlled Radical Polymerization; Matyjaszewski, K., Ed.; ACS Symposium Series 685; American Chemical Society: Wash-ington, DC, 1998.
8. (g) Sawamoto, M.; Kamigaito, M. In Synthesis of Polymers (Materials Science and Technology Series); Schlüter, A.-D., Ed.; Wiley-VCH: Weinheim, Germany, 1999; Chapter 6.
9. Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T. Macromolecules 1995, 28, 1721.
10. Ando, T.; Kato, M.; Kamigaito, M.; Sawamoto, M. Macromolecules 1996, 29, 1070.
11. Ando, T.; Kamigaito, M.; Sawamoto, M. Tetrahedron 1997, 53, 15445.
12. Nishikawa, T.; Ando, T.; Kamigaito, M.; Sawamoto, M. Macromolecules 1997, 30, 2244.
13. Wang, J.-S.; Matyjaszewski, K. J. Am, Chem. Soc. 1995,117, 5614.
14. Wang, J.-S.; Matyjaszewski, K. Macromolecules 1995, 28, 7901.
15. Patten, T. E.; Xia, J.; Abernathy, T.; Matyjaszewski, K. Science 1996, 272, 866.
16. Percée, V.; Barboiu, B. Macromolecules 1995, 28, 7970.
17. Percée, V.; Barboiu, B.; Kim, H.-J. J. Am. Chem. Soc. 1998, 720, 305.
18. Haddleton, D. M.; Jasieczek, C. B.; Hannon, M. J.; Shooter, A. J. Macromolecules 1997, 30, 2190.
19. Ando, T.; Kamigaito, M.; Sawamoto, M. Macromolecules 1997, 30, 4507.
20. Matyjaszewski, K; Wei, M.; Xia, J.; McDermott, N. E. Macromolecules 1997, 30, 8161.
21. Granel, C.; Dubois, Ph.; Jerome, R.; Teyssié, Ph. Macromolecules 1996, 29, 8576.
22. Uegaki, H.; Kotani, Y.; Kamigaito, M.; Sawamoto, M. Macromolecules 1997, 30, 2249.
23. Uegaki, H.; Kotani, Y.; Kamigaito, M.; Sawamoto, M. Macromolecules 1998, 31, 6756.
24. Percée, V.; Barboiu, B.; Neumann, A.; Ronda, J. C.; Zhao, M. Macromolecules 1996, 29, 3665.
25. Moineau, G.; Granel, C.; Dubois, Ph.; Jérôme, R.; Teyssié, Ph. Macromolecules 1998, 31, 542.
26. Lecomte, Ph.; Draiper, I.; Dubois, Ph.; Teyssié, Ph.; Jérôme, R. Macromolecules 1997, 30, 7631.
27. Kotani, Y.; Kamigaito, M.; Sawamoto, M. Macromolecules 1999, 32, 2420.
28. Takahashi, H.; Ando, T.; Kamigaito, M.; Sawamoto, M. Macromolecules 1999, 32, 3820.
29. Elzinga, J.; Hogeveen, H. J. Org. Chem. 1980, 45, 3957.
30. Davis, R.; Durrant, J. L. A.; Khazal, N. M. S.; Bitterwolf, T. E. J. Organomet. Chem. 1990, 386, 229.
31. Ida H.; Sawamoto, M. Polym. Prepr. Jpn. 1998,47 (2), 149.
32. Uegaki, H.; Kamigaito, M.; Sawamoto, M. J. Polym. Sci., Part A: Polym. Chem. 1999, 37, 3003.
33. The polymerization was carried out under dry nitrogen in baked glass tubes equipped with a three-way stopcock or in baked and sealed glass tubes. All reagents were used after ordinary purifications, the metal complexes were handled in a glovebox under dry and oxygen-free argon, and the toluene solvent was bubbled with dry nitrogen for more than 15 min immediately before use. A typical example with FeCp(CO)2l in conjunction with 1 and Ti(Oi-Pr).i is given below. Styrène (2.20 mL), tetralin (0.660 mL), and solutions of 1 (887 mM in toluene; 0.216 mL) and Ti(Oi-Pr)4 (0.0945 mL) were added into FeCptCO)^! (29.2 mg) sequentially in this order at room temperature under dry nitrogen; the total volume of the reaction mixture was thus 3.20 mL. Immediately after mixing, aliquots (0.4 mL each) of the solution were injected into baked glass tubes, which were then sealed and placed in an oil bath kept at 80 °C. In predetermined intervals, the polymerization was terminated by cooling the reaction mixtures to -78 °C. Monomer conversion was determined from the concentration of residual monomer measured by gas chromatography with tetralin as an internal standard. The quenched reaction solutions were diluted with toluene (ca. 10 mL) and vigorously shaken with an absorbent [KYOWAAD-2000G-7 (Mgo.7Alo.sOi.is); Kyowa Chemical Industry Co., Ltd.] (ca. 5 g) to remove the metal-containing residues. After the absorbent was separated by filtration (Whatman 113V), the filtrate was washed with water and evaporated to dryness to give the products, which were subsequently vacuum-dried overnight.
34. 1H NMR analysis were fractionated by preparative SEC (column: Shodex K-2002).
35. Onishi, I.; Baek, K-Y.; Kotani, Y; Kamigaito, M.; Sawamoto, M. Polym. Prepr. Jpn. 1999, 48 (2), 136.