Macromolecular Research, Vol.15, No.1, 31-38, February, 2007
Titanium Complexes: A Possible Catalyst for Controlled Radical Polymerization
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Pentamethylcyclopentadienyltitanium trichloride, bis(cyclopentadienyl)titanium dichloride (Cp2TiCl2), and bis(pentamethylcyclopentadienyl)titanium dichloride were used in the polymerization of styrene without the aid of Group I-III cocatalysts. The properties of the resulting polymer indicated that polymerization was more controlled than in thermal polymerization. The kinetic studies indicated that a lower level of termination is present and that the polymer chain can be extended by adding an additional monomer. To elucidate the mechanism of polymerization, a series of experiments was performed. All results supported the involvement of a radical mechanism in the polymerization using Cp2TiCl2. The possibility of atom transfer radical polymerization (ATRP) mechanism was investigated by isolating the intermediate species. We could confirm the activation step from the reaction of 1-PECl with Cp2TiCl by detecting the coupling product of the generated active radicals. However, the reversible deactivation reaction competes with other side reactions, and it detection was difficult with our model system.
Keywords:titanium complexes;catalyst;controlled radical polymerization;atom transfer radical polymerization
- Herman DF, Nelson WK, J. Am. Chem. Soc., 75, 3877 (1953)
- Nesmeyanov AN, Nogina OV, Freidlina RK, Dokl. Akad. Nauk SSSR, 95, 813 (1954)
- Inoue S, Tsuruta T, Furukawa J, Makromol. Chem., 49, 13 (1961)
- Wang JS, Matyjaszewski K, J. Am. Chem. Soc., 117(20), 5614 (1995)
- Haddleton DM, Jackson SG, Bon SAF, J. Am. Chem. Soc., 122(7), 1542 (2000)
- Percec V, Asandei AD, Asgarzadeh F, Bera TK, Barboiu B, J. Polym. Sci. A: Polym. Chem., 38(20), 3839 (2000)
- Brar AS, Kaur S, J. Polym. Sci. A: Polym. Chem., 43(23), 5906 (2005)
- Kato M, Kamigaito M, Sawamoto M, Higashimura T, Macromolecules, 28(5), 1721 (1995)
- Hong SC, Shin KE, Noh SK, Lyoo WS, Macromol. Res., 13(5), 391 (2005)
- Bielawski CW, Louie J, Grubbs RH, J. Am. Chem. Soc., 122(51), 12872 (2000)
- Drozdzak R, Allaert B, Ledoux N, Dragutan I, Dragutan V, Verpoort F, Adv. Synth. Catal., 347, 1721 (2005)
- Ando T, Kamigaito M, Sawamoto M, Macromolecules, 30(16), 4507 (1997)
- Matyjaszewski K, Wei ML, Xia JH, McDermott NE, Macromolecules, 30(26), 8161 (1997)
- Louie J, Grubbs RH, Chem. Commun., 1479 (2000)
- O'Reilly RK, Gibson VC, White AJP, Williams DJ, Polyhedron, 23, 2921 (2004)
- Shaver MP, Allan LEN, Rzepa HS, Gibson VC, Angew. Chem.-Int. Edit., 45, 1241 (2006)
- Granel C, Dubois P, Jerome R, Teyssie P, Macromolecules, 29(27), 8576 (1996)
- Uegaki H, Kotani Y, Kamigaito M, Sawamoto M, Macromolecules, 31(20), 6756 (1998)
- Duquesne E, Habimana J, Degee P, Dubois P, Macromol. Chem. Phys., 207, 1116 (2006)
- Lecomte P, Drapier I, Dubois P, Teyssie P, Jerome R, Macromolecules, 30(24), 7631 (1997)
- Weiser MS, Mulhaupt R, J. Polym. Sci. A: Polym. Chem., 43(17), 3804 (2005)
- Percec V, Barboiu B, Neumann A, Ronda JC, Zhao MY, Macromolecules, 29(10), 3665 (1996)
- Moineau G, Granel C, Dubois P, Jerome R, Teyssie P, Macromolecules, 31(2), 542 (1998)
- Kotani Y, Kamigaito M, Sawamoto M, Macromolecules, 32(8), 2420 (1999)
- Komiya S, Chigira T, Suzuki T, Hirano M, Chem. Lett., 347 (1999)
- Brandts JAM, van de Geijn P, van Faassen EE, Boersma J, van Koten G, J. Org. Chem., 584, 246 (1999)
- Unpublished result
- Landini D, Rolla F, J. Org. Chem., 45, 3527 (1980)
- Matyjaszewski K, Woodworth BE, Zhang X, Gaynor SG, Metzner Z, Macromolecules, 31(17), 5955 (1998)
- Pangborn AB, Giardello MA, Grubbs RH, Rosen RK, Timmers FJ, Organometallics, 15, 1518 (1996)
- Li I, Howell BA, Matyjaszewski K, Shigemoto T, Smith PB, Priddy DB, Macromolecules, 28(19), 6692 (1995)
- Matyjaszewski K, Davis K, Patten T, Wei M, Tetrahedron, 53, 15321 (1997)