Abstract
This contribution reports on the recent advances in living olefin polymerization catalysis and block copolymer formation made by fluorinated bis(phenoxy-imine)Ti complexes (fluorinated Ti-FI catalysts), which were discovered by Mitsui Chemicals. Fluorinated Ti-FI catalysts are capable of mediating thermally robust living ethylene and highly stereoselective living propylene polymerization. This highly controlled living nature has made it possible to synthesize a wide variety of monodisperse polymers, functionalized polymers and block copolymers from ethylene, propylene, higher α-olefins, cyclic olefins and styrene. The living FI polymers possess unique and often previously inaccessible microstructures, and some of the FI polymers were revealed to display unique morphologies and useful material properties. Therefore, the discovery and development of the fluorinated Ti-FI catalysts has not only made a significant impact on living olefin polymerization catalysis but has also given industry opportunities to make unique polyolefin-based materials for the benefit of the world at large.
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M. Szwarc, J. Polym. Sci., Part A: Polym. Chem., 36, IX (1998).
Y. Doi, M. Takada, and T. Keii, Bull. Chem. Soc. Jpn., 52, 1802 (1979).
Y. Doi, S. Ueki, and T. Keii, Macromolecules, 12, 814 (1979).
Y. Doi, S. Ueki, and T. Keii, Makromol. Chem., 180, 1359 (1979).
Y. Doi and T. Keii, Adv. Polym. Sci., 73/74, 201 (1986).
Y. Doi, N. Tokuhiro, and K. Soga, Makromol. Chem., Makromol. Chem. Phys., 190, 643 (1989).
For review: a) H. H. Brintzinger, D. Fisher, R. Mülhaupt, B. Rieger, and R. M. Waymouth, Angew. Chem., Int. Ed., 34, 1143 (1995).
M. Bochmann, J. Chem. Soc., Dalton Trans., 255 (1996).
A. L. McKnight and R. M. Waymouth, Chem. Rev., 98, 2587 (1998).
G. J. P. Britovsek, V. C. Gibson, and D. F. Wass, Angew. Chem., Int. Ed., 38, 428 (1999).
S. D. Ittel, L. K. Johnson, and M. Brookhart, Chem. Rev., 100, 1169 (2000).
Z. Hou and Y. Wakatsuki, Coord. Chem. Rev., 231, 1 (2002).
H. Hagen, J. Boersma, and G. van Koten, Chem. Soc. Rev., 31, 357 (2002).
S. Gambarotta, Coord. Chem. Rev., 237, 229 (2003).
V. C. Gibson and S. K. Spitzmesser, Chem. Rev., 103, 283 (2003).
Y. Suzuki, H. Terao, and T. Fujita, Bull. Chem. Soc. Jpn., 76, 1493 (2003).
J. Gromada, J.-F. Carpentier, and A. Mortreux, Coord. Chem. Rev., 248, 397 (2004).
D. W. Stephan, Organometallics, 24, 2548 (2005).
W. Wang, T. Tanaka, M. Tsubota, M. Fujiki, S. Yamanaka, and K. Nomura, Adv. Synth. Catal., 347, 433 (2005).
P. D. Bolton and P. Mountford, Adv. Synth. Catal., 347, 355 (2005).
H. Yasuda, M. Furo, H. Yamamoto, A. Nakamura, S. Miyake, and N. Kibino, Macromolecules, 25, 5115 (1992).
K. Mashima, S. Fujikawa, and A. Nakamura, J. Am. Chem. Soc., 115, 10990 (1993).
M. Brookhart, J. M. DeSimone, B. E. Grant, and M. J. Tanner, Macromolecules, 28, 5378 (1995).
J. D. Scollard and D. H. McConville, J. Am. Chem. Soc., 118, 10008 (1996).
C. M. Killian, D. J. Tempel, L. K. Johnson, and M. Brookhart, J. Am. Chem. Soc., 118, 11664 (1996).
R. Baumann, W. M. Davis, and R. R. Schrock, J. Am. Chem. Soc., 119, 3830 (1997).
Y. M. Jeon, S. J. Park, J. Heo, and K. Kim, Organometallics, 17, 3161 (1998).
H. Hagihara, T. Shiono, and T. Ikeda, Macromolecules, 31, 3184 (1998).
Y. Fukui, M. Murata, and K. Soga, Macromol. Rapid Commun., 20, 637 (1999).
K. C. Jayaratne and L. R. Sita, J. Am. Chem. Soc., 122, 958 (2000).
E. Y. Tshuva, I. Goldberg, and M. Kol, J. Am. Chem. Soc., 122, 10706 (2000).
Z. Hou, Y. Zhang, H. Tezuka, P. Xie, O. Tardif, T. Koizumi, H. Yamazaki, and Y. Wakatsuki, J. Am. Chem. Soc., 122, 10533 (2000).
T. Matsugi, S. Matsui, S. Kojoh, Y. Takagi, Y. Inoue, T. Fujita, and N. Kashiwa, Macromolecules, 35, 4880 (2002).
J. C. Jansen, R. Mendichi, M. C. Sacchi, and I. Tritto, Macromol. Chem. Phys., 204, 522 (2003).
X. F. Li, K. Dai, W. P. Ye, L. Pan, and Y. S. Li, Organometallics, 23, 1223 (2004).
V. Busico, R. Cipullo, N. Friederichs, S. Ronca, and M. Togrou, Macromolecules, 36, 3806 (2003).
S. Bambirra, D. van Leusen, A. Meetsma, B. Hessen, and J. H. Teuben, Chem. Commun., 522 (2003).
Y. Yoshida, J. Mohri, S. Ishii, M. Mitani, J. Saito, S. Matsui, H. Makio, T. Nakano, H. Tanaka, M. Onda, Y. Yamamoto, A. Mizuno, and T. Fujita, J. Am. Chem. Soc., 126, 12023 (2004).
H. Zhang and K. Nomura, J. Am. Chem. Soc., 127, 9364 (2005).
Y. Yoshida, S. Matsui, and T. Fujita, J. Organomet. Chem., 690, 4382 (2005).
A. E. Cherian, J. M. Rose, E. B. Lobkovsky, and G. W. Coates, J. Am. Chem. Soc., 127, 13770 (2005).
X. Li, J. Baldamus, and Z. Hou, Angew. Chem., Int. Ed., 44, 962 (2005).
Z. Cai, M. Shigemasa, Y. Nakayama, and T. Shiono, Macromolecules, 39, 6321 (2006).
For recent reviews, see: a) G. W. Coates, P. D. Hustad, and S. Reinartz, Angew. Chem., Int. Ed., 41, 2236 (2002).
B. Liu, H. Matsuoka, and M. Terano, Macromol. Rapid Commun., 22, 1 (2001).
For living olefin polymerization with phenoxy-based catalysts, see: ref. 3j.
For a basic patent on FI catalysts, see: T. Fujita, Y. Tohi, M. Mitani, S. Matsui, J. Saito, M. Nitabaru, K. Sugi, H. Makio, and T. Tsutsui, Eur. Patent 0874005, 1998 (filed in April 1997).
For reviews: a) S. Matsui and T. Fujita, Catal. Today, 66, 63 (2001).
H. Makio, N. Kashiwa, and T. Fujita, Adv. Synth. Catal., 344, 477 (2002).
N. Matsukawa, S. Ishii, R. Furuyama, J. Saito, M. Mitani, H. Makio, H. Tanaka, and T. Fujita, e-polymers, 2003, no. 021 (http://www.e-Polymers.org).
M. Mitani, J. Saito, S. Ishii, Y. Nakayama, H. Makio, N. Matsukawa, S. Matsui, J. Mohri, R. Furuyama, H. Terao, H. Bando, H. Tanaka, and T. Fujita, Chem. Rec., 4, 137 (2004).
Y. Nakayama, H. Bando, Y. Sonobe, and T. Fujita, Bull. Chem. Soc. Jpn., 77, 617 (2004).
K. Michiue, S. Matsui, Y. Yoshida, and T. Fujita, Recent Res. Dev. Chem., 2, 191 (2004).
H. Makio and T. Fujita, Bull. Chem. Soc. Jpn., 78, 52 (2005).
Y. Nakayama, J. Saito, H. Bando, and T. Fujita, Chem. Eur. J., 12, 7546 (2006).
S. Matsui, Y. Tohi, M. Mitani, J. Saito, H. Makio, H. Tanaka, M. Nitabaru, T. Nakano, and T. Fujita, Chem. Lett., 28, 1065 (1999).
J. Saito, M. Mitani, S. Matsui, N. Kashiwa, and T. Fujita, Macromol. Rapid Commun., 21, 1333 (2000).
N. Matsukawa, S. Matsui, M. Mitani, J. Saito, K. Tsuru, N. Kashiwa, and T. Fujita, J. Mol. Catal. A: Chem., 169, 99 (2001).
S. Matsui, M. Mitani, J. Saito, Y. Tohi, H. Makio, N. Matsukawa, Y. Takagi, K. Tsuru, M. Nitabaru, T. Nakano, H. Tanaka, N. Kashiwa, and T. Fujita, J. Am. Chem. Soc., 123, 6847 (2001).
S. Ishii, J. Saito, M. Mitani, J. Mohri, N. Matsukawa, Y. Tohi, S. Matsui, N. Kashiwa, and T. Fujita, J. Mol. Catal. A: Chem., 179, 11 (2002).
S. Ishii, J. Saito, S. Matsuura, Y. Suzuki, R. Furuyama, M. Mitani, T. Nakano, N. Kashiwa, and T. Fujita, Macromol. Rapid Commun., 23, 693 (2002).
R. Furuyama, J. Saito, S. Ishii, M. Mitani, S. Matsui, Y. Tohi, H. Makio, N. Matsukawa, H. Tanaka, and T. Fujita, J. Mol. Catal. A: Chem., 200, 31 (2003).
Y. Nakayama, H. Bando, Y. Sonobe, H. Kaneko, N. Kashiwa, and T. Fujita, J. Catal., 215, 171 (2003).
For a basic patent on living ethylene and propylene polymerization and block copolymer formation with Ti-FI catalysts, see: M. Mitani, Y. Yoshida, J. Mohri, K. Tsuru, S. Ishii, S. Kojoh, T. Matsugi, J. Saito, N. Matsukawa, S. Matsui, T. Nakano, H. Tanaka, N. Kashiwa, and T. Fujita, WO Patent 01/55231 A1, 2001 (filed in January 2000). For a patent on modified Ti-FI catalysts relating to the basic patent, see: G. W. Coates, J. Tian, and P. D. Hustad, US Patent 6562930, 2003 (filed in September 2001).
For reviews: a) M. Mitani, T. Nakano, and T. Fujita, Chem. Eur. J., 9, 2396 (2003).
R. Furuyama, J. Saito, S. Ishii, H. Makio, M. Mitani, H. Tanaka, and T. Fujita, J. Organomet. Chem., 690, 4398 (2005).
J. Saito, M. Mitani, J. Mohri, Y. Yoshida, S. Matsui, S. Ishii, S. Kojoh, N. Kashiwa, and T. Fujita, Angew. Chem., Int. Ed., 40, 2918 (2001).
J. Saito, M. Mitani, J. Mohri, S. Ishii, Y. Yoshida, T. Matsugi, S. Kojoh, N. Kashiwa, and T. Fujita, Chem. Lett., 30, 576 (2001).
J. Saito, M. Mitani, M. Onda, J. Mohri, S. Ishii, Y. Yoshida, T. Nakano, H. Tanaka, T. Matsugi, S. Kojoh, N. Kashiwa, and T. Fujita, Macromol. Rapid Commun., 22, 1072 (2001).
J. Tian, P. D. Hustad, and G. W. Coates, J. Am. Chem. Soc., 123, 5134 (2001).
M. Fujita and G. W. Coates, Macromolecules, 35, 9640 (2002).
J. Tian, P. D. Hustad, and G. W. Coates, J. Am. Chem. Soc., 124, 3614 (2002).
M. Lamberti, D. Pappalardo, A. Zambelli, and C. Pellecchia, Macromolecules, 35, 658 (2002).
M.-S. Weiser and R. Mülhaupt, Macromol. Symp., 236, 111 (2006).
For recent papers on FI catalysts and related complexes: a) M. Mazzeo, M. Strianese, M. Lamberti, I. Santoriello, and C. Pellecchia, Macromolecules, 39, 7812 (2006).
G. J. Clarkson, V. C. Gibson, P. K. Y. Goh, M. L. Hammond, P. D. Knight, P. Scott, T. M. Smit, A. J. P. White, and D. J. Williams, Dalton Trans., 5484 (2006).
D. J. Arriola, E. M. Carnahan, P. D. Hustad, R. L. Kuhlman, and T. T. Wenzel, Science, 312, 714 (2006).
J. Saito, Y. Suzuki, H. Makio, H. Tanaka, M. Onda, and T. Fujita, Macromolecules, 39, 4023 (2006).
J. Saito, Y. Tohi, S. Matsui, M. Mitani, and T. Fujita, Macromolecules, 38, 4955 (2005).
A. E. Cherian, E. B. Lobkovsky, and G. W. Coates, Macromolecules, 38, 6259 (2005).
M. Lamberti, M. Consolmagno, M. Mazzeo, and C. Pellecchia, Macromol. Rapid Commun., 26, 1866 (2005).
D. A. Pennington, S. J. Coles, M. B. Hursthouse, M. Bochmann, and S. J. Lancaster, Chem. Commun., 3150 (2005).
D. A. Pennington, W. Clegg, S. J. Coles, R. W. Harrington, M. B. Hursthouse, D. L. Hughes, M. E. Light, M. Schormann, M. Bochmann, and S. J. Lancaster, Dalton Trans., 561 (2005).
K. P. Bryliakov, E. A. Kravtsov, D. A. Pennington, S. J. Lancaster, M. Bochmann, H. H. Brintzinger, and E. P. Talsi, Organometallics, 24, 5660 (2005).
R. K. J. Bott, M. Hammond, P. N. Horton, S. J. Lancaster, M. Bochmann, and P. Scott, Dalton Trans., 3611 (2005).
H. Zhu, M. Wang, C. Ma, B. Li, C. Chen, and L. Sun, J. Organomet. Chem., 690, 3929 (2005).
C.-H. Qi, S.-B. Zhang, and J.-H. Sun, J. Organomet. Chem., 690, 3946 (2005).
M. Van Meurs, G. J. P. Britovsek, V. C. Gibson, and S. A. Cohen, J. Am. Chem. Soc., 127, 9913 (2005).
H. Terao, S. Ishii, J. Saito, S. Matsuura, M. Mitani, N. Nagai, H. Tanaka, and T. Fujita, Macromolecules, 39, 8584 (2006).
S. Reinartz, A. F. Mason, E. B. Lobkovsky, and G. W. Coates, Organometallics, 22, 2542 (2003).
Y. Suzuki, T. Oshiki, H. Tanaka, K. Takai, and T. Fujita, Chem. Lett., 34, 1458 (2005).
S. Ishii, R. Furuyama, N. Matsukawa, J. Saito, M. Mitani, H. Tanaka, and T. Fujita, Macromol. Rapid Commun., 24, 452 (2003).
Although, normally, fluorinated Zr-FI catalysts do not initiate living ethylene polymerization, a fluorinated Zr-FI catalyst 31 with iodines in ligand with MAO activation polymerizes ethylene in a quasi-living fashion (linear relationship between Mn and ethylene consumption) and produces ultra-high molecular weight PE with a narrow molecular weight distribution (Mn 2300000, Mw/Mn 1.12), see ref. 19e. This fact may open up new possibilities for fluorinated Zr-FI catalysts engaged in living olefin polymerization.
M. Mitani, J. Mohri, Y. Yoshida, J. Saito, S. Ishii, K. Tsuru, S. Matsui, R. Furuyama, T. Nakano, H. Tanaka, S. Kojoh, T. Matsugi, N. Kashiwa, and T. Fujita, J. Am. Chem. Soc., 124, 3327 (2002).
M.-S. Weiser, M. Wesolek, and R. Mülhaupt, J. Organomet. Chem., 691, 2945 (2006).
M.-S. Weiser, Y. Thomann, L.-C. Heinz, H. Pasch, and R. Mülhaupt, Polymer, 47, 4505 (2006).
M.-S. Weiser and R. Mülhaupt, Macromol. Rapid Commun., 27, 1009 (2006).
L.-C. Heinz, M.-S. Weiser, T. Macko, R. Mülhaupt, and H. Pasch, Int. J. Polym. Anal. Charact., 11, 47 (2006).
M.-S. Weiser, PhD thesis, Albert-Ludwigs-University Freiburg (Germany), 2006.
R. Furuyama, M. Mitani, J. Mohri, R. Mori, H. Tanaka, and T. Fujita, Macromolecules, 38, 1546 (2005).
Regarding the effect of the incorporation of F(s) and CF3(s) to Ti-FI catalysts on catalytic performance, Ishii and Fujita have revealed that Ti-FI catalysts having plural F(s) or CF3(s) in the phenyl group on the imine-N, in particular in the meta-positions, display extremely enhanced catalytic activity for ethylene polymerization, see ref. 8e; this effect has been confirmed for propylene polymerization using similar Ti-FI catalysts by Mason, Cherian and Coates, see ref. 13f and 25.
M. Mitani, R. Furuyama, J. Mohri, J. Saito, S. Ishii, H. Terao, N. Kashiwa, and T. Fujita, J. Am. Chem. Soc., 124, 7888 (2002).
M. Mitani, R. Furuyama, J. Mohri, J. Saito, S. Ishii, H. Terao, T. Nakano, H. Tanaka, and T. Fujita, J. Am. Chem. Soc., 125, 4293 (2003).
G. Milano, L. Cavallo, and G. Guerra, J. Am. Chem. Soc., 124, 13368 (2002).
X. Bei, D. C. Swenson, and R. F. Jordan, Organometallics, 16, 3282 (1997).
Y. Tohi, S. Matsui, H. Makio, M. Onda, and T. Fujita, Macromolecules, 36, 523 (2003).
Y. Tohi, T. Nakano, H. Makio, S. Matsui, T. Fujita, and T. Yamaguchi, Macromol. Chem. Phys., 205, 1179 (2004).
A. F. Mason, J. Tian, P. D. Hustad, E. B. Lobkovsky, and G. W. Coates, Isr. J. Chem., 42, 301 (2002).
J. Tian and G. W. Coates, Angew. Chem., Int. Ed., 39, 3626 (2000).
A. F. Mason and G. W. Coates, J. Am. Chem. Soc., 126, 10798 (2004).
Y. Nakayama, J. Saito, H. Bando, and T. Fujita, Macromol. Chem. Phys., 206, 1847 (2005).
D. Veghini, L. M. Henling, T. J. Burkhardt, and J. E. Bercaw, J. Am. Chem. Soc., 121, 564 (1999).
V. Busico, R. Cipullo, F. Cutillo, G. Talarico, and A. Razavi, Macromol. Chem. Phys., 204, 1269 (2003).
L. J. Irwin and S. A. Miller, J. Am. Chem. Soc., 127, 9972 (2005).
C. De Rosa, T. Circelli, F. Aurimma, R. T. Mathers, and G. W. Coates, Macromolecules, 37, 9034 (2004).
J. Saito, M. Onda, S. Matsui, M. Mitani, R. Furuyama, H. Tanaka, and T. Fujita, Macromol. Rapid Commun., 23, 1118 (2002).
A. V. Prasad, H. Makio, J. Saito, M. Onda, and T. Fujita, Chem. Lett., 33, 250 (2004).
A. F. Mason and G. W. Coates, J. Am. Chem. Soc., 126, 16326 (2004).
S. Ishii and T. Fujita, unpublished results.
S. Kojoh, T. Matsugi, J. Saito, M. Mitani, T. Fujita, and N. Kashiwa, Chem. Lett., 30, 822 (2001).
P. D. Hustad and G. W. Coates, J. Am. Chem. Soc., 124, 11578 (2002).
R. T. Mathers and G. W. Coates, Chem. Commun., 422 (2004).
H. Makio and T. Fujita, JP 2005-97588 (2005).
G. Talarico, V. Busico, and L. Cavallo, Organometallics, 23, 5989 (2004).
S. C. F. Kui, N. Zhu, and M. C. W. Chan, Angew. Chem., Int. Ed., 42, 1628 (2003).
M. C. W. Chan, S. C. F. Kui, J. M. Cole, G. J. McIntyre, S. Matsui, N. Zhu, and K.-H. Tam, Chem. Eur. J., 12, 2607 (2006).
Y. Suzuki, H. Tanaka, T. Oshiki, K. Takai, and T. Fujita, Chem. Asian J., 1, 878 (2006).
H. Makio and T. Fujita, Macromol. Symp., 213, 221 (2004).
H. Makio, T. Oshiki, K. Takai, and T. Fujita, Chem. Lett., 34, 1382 (2005).
M. Mitani, J. Mohri, R. Furuyama, S. Ishii, and T. Fujita, Chem. Lett., 32, 238 (2003).
J. Yoon, R. T. Mathers, G. W. Coates, and E. L. Thomas, Macromolecules, 39, 1913 (2006).
K. Michiue, M. Onda, M. Mitani, and T. Fujita, “Studies in Surface Science and Catalysis (Progress in Olefin Polymerization Catalysts and Polyolefin Materials),” Elsevier Scinece B. V., in press.
S. S. Ono, T. Matsugi, N. Matsukawa, S. Kojoh, T. Fujita, N. Kashiwa, and S. Yamamoto, Chem. Lett., 32, 1182 (2003).
J. Ruokolaine, R. Mezzenga, G. H. Fredrickson, E. J. Kramer, P. D. Hustad, and G. W. Coates, Macromolecules, 38, 851 (2005).
A. Radulescu, R. T. Mathers, G. W. Coates, D. Richter, and L. J. Fetters, Macromolecules, 37, 6962 (2004).
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Sakuma, A., Weiser, MS. & Fujita, T. Living Olefin Polymerization and Block Copolymer Formation with FI Catalysts. Polym J 39, 193–207 (2007). https://doi.org/10.1295/polymj.PJ2006152
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DOI: https://doi.org/10.1295/polymj.PJ2006152
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