Polymerization of propylene by a new generation of iron catalysts: Mechanisms of chain initiation, propagation, and termination

Macromolecules

Volumn 32, Issue 7, 1999, Pages 2120-2130

  Small, Brooke L ^a   Brookhart, Maurice ^a  

^a University of North Carolina at Chapel Hill   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CATALYSTS; IRON; MOLECULAR STRUCTURE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYMERIZATION;

CHAIN TRANSFER; ISOTACTICITY; LIGANDS; REGIOREGULARITY;

POLYPROPYLENES;

EID: 0033528618     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma981698s     Document Type: Article

References (99)

1. For recent reviews, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143.
2. (b) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255.
3. (c) Kaminsky, W.; Arndt, M. Adv. Polym. Sci. 1997, 127, 143.
4. (d) Möhring, P. C.; Coville, N. J. J. Organomet. Chem. 1994, 479, 1.
5. (e) Fink, G., Mülhaupt, R., Brintzinger, H. H., Eds. Ziegler Catalysts: Recent Scientific Innovations and Technological Improvement; Springer-Verlag: Berlin, 1995.
6. (a) Busico, V.; Cipullo, R.; Chadwick, J. C.; Modder, J. F.; Sudmejjer, O. Macromolecules 1994, 27, 7538.
7. (b) Asakura, T.; Nakayama, N.; Demura, M.; Asano, A. Macromolecules 1992, 25, 4876.
8. (c) Zambelli, A.; Tosi, C. Adv. Polym. Sci. 1974, 15, 31.
9. (d) Grassi, A.; Zambelli, A.; Resconi, L.; Albizzati, E.; Mazzocchi, R. Macromolecules 1988, 21, 617.
10. (e) Guerra, G.; Longo, P.; Corradini, P.; Resconi, L. J. Am. Chem. Soc. 1997, 119, 4394.
11. (f) Ewart, S. W.; Sarsfield, M. J.; Jeremic, D.; Tremblay, T. L.; Williams, E. F.; Baird, M. C. Organometallics 1998, 17, 1502.
12. (a) Spalek, W.; Küber, F.; Winter, A.; Rohrmann, J.; Bachmann, B.; Antberg, M.; Dolle, V.; Paulus, E. Organometallics 1994, 13, 954.
13. (b) Spalek, W.; Antberg, M.; Rohrmann, J.; Winter, A.; Bachmann, B.; Kiprof, P.; Behm, J.; Hermann, W. Angew. Chem., Int. Ed. Engl. 1992, 31, 1347.
14. (c)Resconi, L.; Jones, R. L.; Rheingold, A. L.; Yap, G. P. A. Organometallics 1996,15, 998.
15. (a) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217.
16. (b) Bruce, M. D.; Coates, G. W.; Hauptman, E.; Waymouth, R. M.; Ziller, J. W. J. Am. Chem. Soc. 1997, 119, 11174.
17. (c) Hauptman, E.; Waymouth, R. M.; Ziller, J. W. J. Am. Chem. Soc. 1993, 117, 11586.
18. (d) Mallin, D. T.; Rausch, M. D.; Lin, Y. G.; Dong, S.; Chien, J. C. W. J. Am. Chem. Soc. 1990, 112, 2030.
19. (e) Llinas, G. H.; Rausch, M. D.; Lin, G.-Y.; Winter, H. H.; Atwood, J. L.; Bott, S. G.; Chien, J. C. W. J. Am. Chem. Soc. 1991, 113, 8569.
20. (f) Golab, J. T. Chemtech 1998, 28, 17.
21. (a) Killian, C. M.; Tempel, D. T.; Johnson, L. K.; Brookhart, M. J. Am. Chem. Soc. 1996, 118, 11664.
22. (b) McClain, S. J.; McCord, E. F.; Johnson, L. K.; Ittel, S. D.; Nelson, L. T. J.; Arthur, S. D.; Halfhill, M. J.; Teasley, M. F.; Tempel, D. J.; Killian, C. M.; Brookhart, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1997, 38, 772.
23. (c) Nelson, L. T. J.; McCord, E. F.; Johnson, L. K.; McClain, S. J.; Ittel, S. D.; Killian, C. M.; Brookhart, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1997, 38, 133.
24. (d) Johnson, L. K.; Killian, C. M.; Arthur, S. D.; Feldman, J.; McCord, E. F.; McClain, S. J.; Kreutzer, K. A.; Bennett, A. M. A.; Coughlin, E. B.; Ittel, S. D.; Parthasarathy, A.; Tempel, D. J.; Brookhart, M. (DuPont/ UNC) World Patent Application 96/23010, 1996.
25. Britovsek, G. J. P.; Gibson, V. C.; Kimberley, B. S.; Maddox, P. J.; McTavish, S. J.; Solan, G. A.; White, A. J. P.; Williams, D. J. Chem. Commun. 1998, 849.
26. (a) Bennett, A. M. A. (DuPont) World Patent Application 98/ 27124, 1998.
27. (b) Small, B. L.; Brookhart, M.; Bennett, A. M. A. J. Am. Chem. Soc. 1998, 120, 4049.
28. Small, B. L.; Brookhart, M. J. Am. Chem. Soc. 1998, 120, 7143.
29. (a) Small, B. L.; Brookhart, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1998, 39, 213.
30. (b) Brookhart, M.; Small, B. L. (UNC) World Patent Application 98/30612, 1998.
31. MMAO is the same as MAO except for the substitution of 25% of the methyl groups with isobutyl groups. MMAO has the advantage of increased shelf life, but as is discussed in this paper, these isobutyl groups can affect the composition of the polymer end groups.
32. (a) Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 6414.
33. (b) Killian, C. M.; Johnson, L. K.; Brookhart, M. Organometallics 1997, 16, 2005.
34. (a) Peebles, L. H., Jr. Molecular Weight Distributions in Polymers; Wiley-Interscience: New York, 1971.
35. (b) Flory, P. J. Principles of Polymer Chemistry; Cornell University Press: Ithaca, N. Y., 1953.
36. Marks, T. J. Acc. Chem. Res. 1992, 25, 57.
37. (b) Resconi, L.; Piemontesi, P.; Fransiscono, G.; Abis, L.; Fiorani, T. J. Am. Chem. Soc. 1992, 114, 1025.
38. (c) Giardello, M. A.; Eisen, M. S.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 12144.
39. (d) Marques, M. V.; Nunes, P. C.; Tait, P. J. T.; Dias, A. E. J. Polym. Sci.; Part A 1993, 31, 219.
40. (e) Komiya, S.; Katoh, M.; Ikariya, T.; Grubbs, R. H.; Yamamoto, T.; Yamamoto, A. J. Organomet. Chem. 1984, 260, 115.
41. Ewen, J. A. J. Am. Chem. Soc. 1984, 106, 6355.
42. Bovey, F. A. J. Polym. Sci. 1960, 44, 173.
43. (a) Doi, Y.; Asakuru, T. Makromol. Chem. 1975, 176, 507.
44. (b) Sheldon, R. A.; Fueno, T.; Tsunstsugu; Kurukawa, J. J. Polym. Sci., Part B 1985, 3, 23.
45. (c) Xu, J.; Feng, L.; Yang, S. Macromolecules 1997, 30, 2539.
46. There are numerous examples in the literature of complexes whose stereospecific behavior changes with modifications in the reaction conditions. See refs 1 and 14.
47. (a) Wild, F. R. W. P.; Zsolani, L.; Huttner, G.; Brintzinger, H. H. J. Organomet. Chem. 1982, 232, 233.
48. (b) Wild, F. R. W. P.; Wasiucionek, M.; Huttner, G.; Brintzinger, H. H. J. Organomet. Chem. 1985, 288, 63.
49. (c) Kaminsky, W.; Külper, K.; Brintzinger, H. H.; Wild, F. R. W. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 507.
50. (a) Ewen, J. A.; Elder, M. J.; Jones, R. L.; Haspeslagh, L.; Atwood, J. L.; Bott, S. G.; Robinson, K. Makromol. Chem., Macromol. Symp. 1991, 48/49, 253.
51. (b) Ewen, J. A.; Haspeslagh, L.; Atwood, J. L.; Zang, H. J. Am. Chem. Soc. 1987, 109, 6544.
52. (c) Ewen, J. A.; Jones, R. L.; Razavi, A.; Ferrara, J. D. J. Am. Chem. Soc. 1988, 110, 6255.
53. Sinn, H.; Kaminsky, W. Adv. Organomet. Chem. 1980, 18, 99.
54. (b) Kaminsky, W.; Miri, M.; Sinn, H.; Woldt, R. Makromol. Chem., Rapid Commun. 1983, 4, 417.
55. (c) Soga, K.; Shiono, T.; Takemura, S.; Kaminsky, W. Makromol. Chem., Rapid Commun. 1987, 8, 305.
56. (a) Herzog, T. A.; Zubris, D. L.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 11988.
57. (b) Coughlin, E. B.; Bercaw, J. E. J. Am. Chem. Soc. 1992, 114, 7606.
58. (c) Bierwagen, E. P.; Bercaw, J. E.; Goddard, W. A. J. Am. Chem. Soc. 1994, 116, 1481.
59. (d) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045.
60. (a) Averbuj, C.; Tish, E.; Eisen, M. S. J. Am. Chem. Soc. 1998, 120, 8640.
61. (b) Volkis, V.; Shmulinson, M.; Averbuj, C.; Lisovskii, A.; Edelmann, F. T.; Eisen, M. S. Organometallics 1998, 3155, 5.
62. (c) Chen, Y.-X.; Metz, M. V.; Li, L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 6287, 7.
63. (d) Gauthier, W. J.; Collins, S. Macromolecules 1995, 28, 3779.
64. (e) van der Leek, Y.; Angermund, K.; Reffke, M.; Kleinschmidt, R.; Goretzki, R.; Fink, G. Chem. Eur. J. 1997, 3, 585.
65. 3; Z = 4; R = 0.044; GOF = 1.62.
66. (a) Tempel, D. J. Doctoral Dissertation, University of North Carolina at Chapel Hill, 1998.
67. (b) Svejda, S. A.; Brookhart, M. Unpublished results.
68. 3; Z = 4; R = 0.088; GOF = 4.90. Crystals of 6a were grown by allowing pentane to slowly diffuse into a solution of the complex in chlorobenzene.
69. We have found that exposure of the iron complexes to halogenated solvents results in greatly exaggerated magnetic susceptibility values and greatly reduced activities. These observations are consistent with free-radical reactions leading to the formation of Fe(III) species and catalytically inactive impurities.
70. -.
71. For leading references relating to a variety of migratory insertion processes and polymerization systems, see: (a) Tempel, D. J.; Brookhart, M. Organometallics 1998, 17, 2290.
72. (b) Lee, H.; Hascall, T.; Desrosiers, P. J.; Parkin, G. J. Am. Chem. Soc. 1998, 120, 5830.
73. (c) Brookhart, M.; Hauptman, E.; Lincoln, D. M. J. Am. Chem. Soc. 1992, 114, 10394.
74. (d) Brookhart, M.; Lincoln, D. M.; Volpe, A. F.; Schmidt, G. F. Organometallics 1989, 8, 1212.
75. (e) Green, M. L. H.; Sella, A.; Wong, L.-L. Organometallics 1992, 11, 2650.
76. (f) Mecking, S.; Johnson, L. K.; Wang, L.; Brookhart, M. J. Am. Chem. Soc. 1998, 120, 888.
77. (g) Rix, F. C.; Brookhart, M.; White, P. S. J. Am. Chem. Soc. 1996, 118, 2436.
78. (a) Cheng, H. N.; Smith, D. A. Macromolecules 1986, 19, 2065.
79. (b) Carvill, A.; Zetta, L.; Zannoni, G.; Sacchi, M. C. Macromolecules 1998, 31, 3783.
80. (a) Eshuis, J.; Tan, Y.; Teuben, J. H.; Renkema, J. J. Mol. Catal. 1990, 62, 277.
81. (b) Eshuis, J.; Tan, Y.; Meetsma, A.; Teuben, J. H. Organometallics 1992, 11, 362.
82. (c) Yang, X.; Stern, C. L.; Marks, T. J. Angew. Chem., Int. Ed. Engl. 1992, 31, 1375.
83. (d) Mise, T.; Kageyama, A.; Miya, S.; Yamazaki, H. Chem. Lett. 1991, 1525.
84. (e) Kesti, M.; Waymouth, R. M. J. Am. Chem. Soc. 1992, 114, 3565.
85. (f) Guo, Z.; Swenson, D.; Jordan, R. Organometallics 1994, 13, 1424.
86. (g) Hajela, S.; Bercaw, J. E. Organometallics 1994, 13, 1147.
87. (h) Yang, X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015.
88. 13C NMR chemical shift of 33.5 ppm.
89. 13C NMR alkyl substituent effects in branched hydrocarbons, see: Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Spectrometric Identification of Organic Compounds, 5th ed.; John Wiley & Sons: New York, 1991; Chapter 5.
90. Zambelli, A.; Locatelli, P.; Bajo, G.; Bovey, F. A. Macromolecules 1975, 8, 687.
91. Zambelli, A.; Locatelli, P.; Bajo, G. Macromolecules 1979, 12, 154.
92. Hayashi, T.; Inoue, Y.; Chûjô, R.; Asakura, T. Macromolecules 1988, 21, 2675.
93. β-H transfer to the incoming monomer to generate a new Fe-alkyl species, or to the metal to form an Fe-H species, are both possible routes for chain transfer. If β-H transfer to monomer occurs, it must occur in a primary (1,2) fashion (opposite the regiochemistry observed for propagation) to generate an Fe-propyl complex.
94. 2AlCl will polymerize propylene at -78 °C in a 2,1 fashion to generate syndiotactic polypropylene. These systems are not highly regioregular, and the polymer chains apparently do not terminate via β-H elimination to give unsaturated end groups suitable for NMR analysis. For example, see: (a) Doi, Y. Macromolecules 1979, 12, 248.
95. (b) Zambelli, A.; Allegra, G. Macromolecules 1980, 13, 42.
96. (c) Ammendola, P.; Shijing, X.; Grassi, A.; Zambelli, A. Gazz. Chim. Ital. 1988, 118, 769.
97. (d) Zambelli, A.; Léty, A.; Tosi, C.; Pasquon, I. Makromol. Chem. 1968, 115, 73.
98. (e) Zambelli, A.; Giongo, M. G.; Natta, G. Makromol. Chem. 1968, 112, 183.
99. Note added in proof. Analysis of polypropylene made from catalyst 1/methylalumoxane has recently been reported: Pellecchia, C.; Mazzeo, M.; Pappalardo, D. Macromol. Rapid Commun. 1998, 19, 651.