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129 Syndiospecific living polymerization of propylene with fluorine-containing titanium Fl catalyst
515
Science and Technology in Catalysis 2002 Copyright 9 2003 by Kodansha Ltd.
129 Syndiospecific Living Polymerization of Propylene with Fluorine-Containing Tita n iu m FI Catalyst
Junji SAITO, Makoto MITANI, Mitsuhiko ONDA, Junich MOHRI, Seiich ISHII, Yasunori YOSHIDA, Rieko, FURUYAMA, Takashi NAKANO, Norio KASHIWA, Terunori FUJITA R & D Center, Mitsui Chemicals, Inc., 580-32 Nagaura, Sodegaura, Chiba, 299-0265, Japan
1.
Introduction
Recently, we have discovered new olefin polymerization catalysts based on group 4 transition metal complexes bearing two phenoxy-imine chelate ligands, named H Catalysts [ 1-4], as a result of ligand-oriented catalyst design research. H Catalysts display high catalytic performance for the polymerization of ethylene, ethylene-propylene, 1-hexene, etc. Further study has revealed that titanium FI Catalysts possessing fluorine atoms in the ligands proceed living polymerization of ethylene and/or propylene above room temperature [5-8]. In this paper, we would like to report the propylene polymerization behavior of four titanium FI Catalysts having fluorine atoms in the ligands.
2. R e s u l t s a n d d i s c u s s i o n Complexes 1 - 4, all of which behave R1 Complexes I as living ethylene polymerization catalysts above room temperature, were investigated for their potential as propylene polymerization catalysts. Polymerizations were conducted at 25 ~ under 0.6 MPa propylene pressure for 3 h using dried methylalumoxane (DMAO) Fig. 1. TitaniumFI Catalystshaving fluorine atom at variousposition as a cocatalyst. The results are collected in Table 1. Polymerization activities were increased from 0.53 to 15.3 kg/mmol-Ti.h with an increase in the number of fluorine atoms in the ligand o
Table 1 Propylene polymerizationresult with complex 1 - 4/DMAO "'End-' Complex Cat. DMAO Yield Activi~ 'j M n L'j Mw/Mn [gmoll |mmol] [mgl ...... lxl031 1 1 50 5.0 79 0.53 2.4,107 1.10, 14.9 2 2 50 5.0 465 3.10 4.6,87.4 1.06, 6.14 3 3 30 5.0 951 10.6 8.8,184 1.04, 4.19 4 4 10 2.5 460 15.3 73.8 1.10 ' conditions: 25 oC, toluene 380mL, propylene 0.6 Mpa pressure, polymerizationtime 3h [,1 [kg/mol-cat.h] ~ l M n values were determined by using polypropylene calibration.
'-
516 J. Saito et al. (Activity order 4 > 3 > 2 > 1). These results are probably ascribed to the electron-withdrawing nature of fluorine, resulting in a more electrophilic (a titanium center. Complexes 1 - 3 produced elastomer-like polypropylenes having no peak melting temperatures. GPC analyses revealed that produced polypropylenes have multimodal curves involving narrow polydispersity polypropylene (Fig. 2). These polypropylenes are produced by plural o~ kinds of active species. Since FI Catalysts possess two bidentate non-symmetric ligands, they have potentially five isomeric structures. Although complexes I - 3 / DMAO catalyst systems behave as single-site catalysts and produce polyethylenes @) having narrow polydispersities [6], these complexes may have plural kinds of active species for propylene polymerization, resulting in multimodal behavior. Alternatively, polymerization with complex 4 yielded, crystalline polypropylene (Tm 135 ~ M n = 73800, possessing an extremely narrow polydispersity, Mw/Mn 1 . 1 0 . Further Fig.2 GPC charts ofpolypropylenes with (a)complex 1, (b) 2, (c) 3 research on complex 4 / DMAO showed that M n values of the produced polymers linearly increased with polymerization time, meaning that the system proceeds living polymerization [7]. 13C NMR analysis (Table 1. Entry 4) revealed that the produced polypropylene was highly syndiotactic, rr 92.9%, which is one of the highest values among monodisperse polypropylenes ever known. ~3C NMR analysis also showed the isolated m-dyad errors(>l 0%) in the methyl pentad region, suggesting that syndiospecific polymerization proceeds via a chain-end controlled mechanism. Detailed investigations about active species of these catalyst systems are underway. In summary, the propylene polymerization behavior of four fluorine-containing titanium FI Catalysts has been introduced. FI Catalysts 1 - 3 produce multimodal polypropylenes whereas FI Catalyst 4 bearing perfluorophenyl group initiates room-temperature living propylene polymerization to form highly syndiotactic polypropylene.
3. References
[1] I". Fujita, Y. Tohi, M. Mitani, S. Matsui, J.Saito, M. Nitabaru, K.Sugi, H. Makio, and T. Tsutsui, patent, EP0874005 (1998) [2] S. Matsui, M. Mitani, J. Saito, Y. Tohi, H. Makio, N. Matsukawa, Y. Takagi, K. Tsuru, M. Nitabaru, T. Nakano, H. Tanaka, N. Kashiwa, T. Fujita, J. Am. Chem. Soc., 123 (2001) 6847. [3] J. Saito, M. Mitani, S. Matsui, N. Kashiwa, and T. Fujita, Macromol. Rapid, Commun. 21 (2000) 1333. [4] J. Saito, M.Mitani, S.Matsui, Y.Tohi, H.Makio, T.Nakano, H. Tanaka, N. Kashiwa, T.Fujita, Macromol. Chem. Phys. 203 (2002) 59. [5] J. Saito, M. Mitani, J. Mohri, Y. Yoshida, S. Matsui, S. Ishii, S. Kojoh, N. Kashiwa, 1". Fujita, Angew. Chem. Int. Ed. 40 (2001) 2918, [6] 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, T. Fujita, J. Am. Chem. Soc., 124 (2002) 3327 [7] J. Saito, M. Mitani, J. Mohri, S. Ishii, Y. Yoshida, T. Matsugi, S. Kojoh, N. Kashiwa, T. Fujita, Chem. Lett., 2001 P.576 [8] M. Mitani, R. Furuyama, J. Mohri, J. Saito, S. Ishii, H. Terao, N. Kashiwa, T. Fujita, J. Am. Chem. Sot., 124 (2002) 7888.
Science and Technology in Catalysis 2002 Copyright 9 2003 by Kodansha Ltd.
129 Syndiospecific Living Polymerization of Propylene with Fluorine-Containing Tita n iu m FI Catalyst
Junji SAITO, Makoto MITANI, Mitsuhiko ONDA, Junich MOHRI, Seiich ISHII, Yasunori YOSHIDA, Rieko, FURUYAMA, Takashi NAKANO, Norio KASHIWA, Terunori FUJITA R & D Center, Mitsui Chemicals, Inc., 580-32 Nagaura, Sodegaura, Chiba, 299-0265, Japan
1.
Introduction
Recently, we have discovered new olefin polymerization catalysts based on group 4 transition metal complexes bearing two phenoxy-imine chelate ligands, named H Catalysts [ 1-4], as a result of ligand-oriented catalyst design research. H Catalysts display high catalytic performance for the polymerization of ethylene, ethylene-propylene, 1-hexene, etc. Further study has revealed that titanium FI Catalysts possessing fluorine atoms in the ligands proceed living polymerization of ethylene and/or propylene above room temperature [5-8]. In this paper, we would like to report the propylene polymerization behavior of four titanium FI Catalysts having fluorine atoms in the ligands.
2. R e s u l t s a n d d i s c u s s i o n Complexes 1 - 4, all of which behave R1 Complexes I as living ethylene polymerization catalysts above room temperature, were investigated for their potential as propylene polymerization catalysts. Polymerizations were conducted at 25 ~ under 0.6 MPa propylene pressure for 3 h using dried methylalumoxane (DMAO) Fig. 1. TitaniumFI Catalystshaving fluorine atom at variousposition as a cocatalyst. The results are collected in Table 1. Polymerization activities were increased from 0.53 to 15.3 kg/mmol-Ti.h with an increase in the number of fluorine atoms in the ligand o
Table 1 Propylene polymerizationresult with complex 1 - 4/DMAO "'End-' Complex Cat. DMAO Yield Activi~ 'j M n L'j Mw/Mn [gmoll |mmol] [mgl ...... lxl031 1 1 50 5.0 79 0.53 2.4,107 1.10, 14.9 2 2 50 5.0 465 3.10 4.6,87.4 1.06, 6.14 3 3 30 5.0 951 10.6 8.8,184 1.04, 4.19 4 4 10 2.5 460 15.3 73.8 1.10 ' conditions: 25 oC, toluene 380mL, propylene 0.6 Mpa pressure, polymerizationtime 3h [,1 [kg/mol-cat.h] ~ l M n values were determined by using polypropylene calibration.
'-
516 J. Saito et al. (Activity order 4 > 3 > 2 > 1). These results are probably ascribed to the electron-withdrawing nature of fluorine, resulting in a more electrophilic (a titanium center. Complexes 1 - 3 produced elastomer-like polypropylenes having no peak melting temperatures. GPC analyses revealed that produced polypropylenes have multimodal curves involving narrow polydispersity polypropylene (Fig. 2). These polypropylenes are produced by plural o~ kinds of active species. Since FI Catalysts possess two bidentate non-symmetric ligands, they have potentially five isomeric structures. Although complexes I - 3 / DMAO catalyst systems behave as single-site catalysts and produce polyethylenes @) having narrow polydispersities [6], these complexes may have plural kinds of active species for propylene polymerization, resulting in multimodal behavior. Alternatively, polymerization with complex 4 yielded, crystalline polypropylene (Tm 135 ~ M n = 73800, possessing an extremely narrow polydispersity, Mw/Mn 1 . 1 0 . Further Fig.2 GPC charts ofpolypropylenes with (a)complex 1, (b) 2, (c) 3 research on complex 4 / DMAO showed that M n values of the produced polymers linearly increased with polymerization time, meaning that the system proceeds living polymerization [7]. 13C NMR analysis (Table 1. Entry 4) revealed that the produced polypropylene was highly syndiotactic, rr 92.9%, which is one of the highest values among monodisperse polypropylenes ever known. ~3C NMR analysis also showed the isolated m-dyad errors(>l 0%) in the methyl pentad region, suggesting that syndiospecific polymerization proceeds via a chain-end controlled mechanism. Detailed investigations about active species of these catalyst systems are underway. In summary, the propylene polymerization behavior of four fluorine-containing titanium FI Catalysts has been introduced. FI Catalysts 1 - 3 produce multimodal polypropylenes whereas FI Catalyst 4 bearing perfluorophenyl group initiates room-temperature living propylene polymerization to form highly syndiotactic polypropylene.
3. References
[1] I". Fujita, Y. Tohi, M. Mitani, S. Matsui, J.Saito, M. Nitabaru, K.Sugi, H. Makio, and T. Tsutsui, patent, EP0874005 (1998) [2] S. Matsui, M. Mitani, J. Saito, Y. Tohi, H. Makio, N. Matsukawa, Y. Takagi, K. Tsuru, M. Nitabaru, T. Nakano, H. Tanaka, N. Kashiwa, T. Fujita, J. Am. Chem. Soc., 123 (2001) 6847. [3] J. Saito, M. Mitani, S. Matsui, N. Kashiwa, and T. Fujita, Macromol. Rapid, Commun. 21 (2000) 1333. [4] J. Saito, M.Mitani, S.Matsui, Y.Tohi, H.Makio, T.Nakano, H. Tanaka, N. Kashiwa, T.Fujita, Macromol. Chem. Phys. 203 (2002) 59. [5] J. Saito, M. Mitani, J. Mohri, Y. Yoshida, S. Matsui, S. Ishii, S. Kojoh, N. Kashiwa, 1". Fujita, Angew. Chem. Int. Ed. 40 (2001) 2918, [6] 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, T. Fujita, J. Am. Chem. Soc., 124 (2002) 3327 [7] J. Saito, M. Mitani, J. Mohri, S. Ishii, Y. Yoshida, T. Matsugi, S. Kojoh, N. Kashiwa, T. Fujita, Chem. Lett., 2001 P.576 [8] M. Mitani, R. Furuyama, J. Mohri, J. Saito, S. Ishii, H. Terao, N. Kashiwa, T. Fujita, J. Am. Chem. Sot., 124 (2002) 7888.