Living polymerization of α-olefins using Ni(II)-α-diimine catalysts. Synthesis of new block polymers based on α-olefins

Journal of the American Chemical Society

Volumn 118, Issue 46, 1996, Pages 11664-11665

  Killian, Christopher M ^a   Tempel, Daniel J ^a   Johnson, Lynda K ^a   Brookhart, Maurice ^a  

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

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CATALYSIS; POLYMERIZATION; REACTION ANALYSIS;

EID: 0029860908     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962516h     Document Type: Article

References (21)

1. (a) Odian, G. G. Principles of Polymerization, 3rd ed.; John Wiley & Sons, Inc.: New York, 1991.
2. (b) Webster, O. W. Science 1991, 251, 887.
3. For leading references, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143. (b) Giardello, M. A.; Eisen, M. S.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 12114-12129. (c) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045-1053. (d) Ewen, J. A.; Jones. R. L. J. Am. Chem. Soc. 1988, 110, 6255-6256. (e) Kaminsky, W.; Külper, K.; Brintzinger, H. H.; Wild, F. R. W. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 507-508. (f) Waymouth, R. M.; Coates, G. W. Science 1995, 267, 217. (g) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5868.
4. For leading references, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143. (b) Giardello, M. A.; Eisen, M. S.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 12114-12129. (c) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045-1053. (d) Ewen, J. A.; Jones. R. L. J. Am. Chem. Soc. 1988, 110, 6255-6256. (e) Kaminsky, W.; Külper, K.; Brintzinger, H. H.; Wild, F. R. W. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 507-508. (f) Waymouth, R. M.; Coates, G. W. Science 1995, 267, 217. (g) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5868.
5. For leading references, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143. (b) Giardello, M. A.; Eisen, M. S.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 12114-12129. (c) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045-1053. (d) Ewen, J. A.; Jones. R. L. J. Am. Chem. Soc. 1988, 110, 6255-6256. (e) Kaminsky, W.; Külper, K.; Brintzinger, H. H.; Wild, F. R. W. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 507-508. (f) Waymouth, R. M.; Coates, G. W. Science 1995, 267, 217. (g) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5868.
6. For leading references, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143. (b) Giardello, M. A.; Eisen, M. S.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 12114-12129. (c) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045-1053. (d) Ewen, J. A.; Jones. R. L. J. Am. Chem. Soc. 1988, 110, 6255-6256. (e) Kaminsky, W.; Külper, K.; Brintzinger, H. H.; Wild, F. R. W. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 507-508. (f) Waymouth, R. M.; Coates, G. W. Science 1995, 267, 217. (g) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5868.
7. For leading references, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143. (b) Giardello, M. A.; Eisen, M. S.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 12114-12129. (c) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045-1053. (d) Ewen, J. A.; Jones. R. L. J. Am. Chem. Soc. 1988, 110, 6255-6256. (e) Kaminsky, W.; Külper, K.; Brintzinger, H. H.; Wild, F. R. W. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 507-508. (f) Waymouth, R. M.; Coates, G. W. Science 1995, 267, 217. (g) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5868.
8. For leading references, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143. (b) Giardello, M. A.; Eisen, M. S.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 12114-12129. (c) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045-1053. (d) Ewen, J. A.; Jones. R. L. J. Am. Chem. Soc. 1988, 110, 6255-6256. (e) Kaminsky, W.; Külper, K.; Brintzinger, H. H.; Wild, F. R. W. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 507-508. (f) Waymouth, R. M.; Coates, G. W. Science 1995, 267, 217. (g) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5868.
9. For leading references, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143. (b) Giardello, M. A.; Eisen, M. S.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 12114-12129. (c) Mitchell, J. P.; Hajela, S.; Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 1045-1053. (d) Ewen, J. A.; Jones. R. L. J. Am. Chem. Soc. 1988, 110, 6255-6256. (e) Kaminsky, W.; Külper, K.; Brintzinger, H. H.; Wild, F. R. W. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 507-508. (f) Waymouth, R. M.; Coates, G. W. Science 1995, 267, 217. (g) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5868.
10. (a) Doi, Y.; Ueki, S.; Keii, T. Macromolecules 1979, 12, 814-819.
11. (b) Doi, Y.; Hizal, G.; Soga, K. Makromol. Chem. 1987, 188, 1273-1279 and references therein.
12. For examples of living polymerization of ethylene, see: (a) Brookhart, M.; DeSimone, J. M.; Grant, B. E.; Tanner, M. J. Macromolecules 1995, 28, 5378-5380 and references therein. (b) Mashima, K.; Fujikawa, S.; Urata, H.; Tanaka, Y.; Urata, H.; Oshiki, T.; Tanaka, E.; Nakamura, A. Organometallics 1995, 14, 2633-2640.
13. For examples of living polymerization of ethylene, see: (a) Brookhart, M.; DeSimone, J. M.; Grant, B. E.; Tanner, M. J. Macromolecules 1995, 28, 5378-5380 and references therein. (b) Mashima, K.; Fujikawa, S.; Urata, H.; Tanaka, Y.; Urata, H.; Oshiki, T.; Tanaka, E.; Nakamura, A. Organometallics 1995, 14, 2633-2640.
14. Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 6414-6415.
15. This work was reported in part at 211th National ACS Meeting New Orleans, LA; Inorganic Division, Abstr. 261.
16. MMAO is a modified methylaluminoxane activator containing 25% isobutyl aluminoxane.
17. For ethylene homopolymerization under these conditions chain transfer is significant. Polyethylene prepared at -20 °C using 1a has a MWD of 1.48, while polyethylene prepared at -40 °C has a MWD of 1.39.
18. Details of the microstructure of the poly(α-olefins) and the mechanism of α-olefin polymerization will be the subject of a future publication: S. J. McLain, E. McCord, M. Brookhart, D. J. Tempel, L. K. Johnson, C. M. Killian.
19. Exclusive 1,2-enchainment would result in polypropylene with 333 branches/1000 carbons, poly(1-hexene) with 167 branches/1000 carbons, and poly(1-octadecene) with 56 branches/1000 carbons.
20. g of polypropylene prepared from these catalysts ranges from -16 to -55 °C.
21. m (see Table 1).