Direct precise functional group introduction into polyolefins: Efficient incorporation of vinyltrialkylsilanes in ethylene copolymerizations by nonbridged half-titanocenes

Macromolecules

Volumn 41, Issue 23, 2008, Pages 8974-8976

  Nomura, Kotohiro ^a   Kakinuki, Kenichi ^a   Fujiki, Michiya ^a   Itagaki, Koji ^a  

^a NARA INSTITUTE OF SCIENCE AND TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

COORDINATION POLYMERIZATIONS; ETHYLENE COPOLYMERIZATIONS; SPECIFIC REACTIVITIES; TITANOCENES;

COORDINATION REACTIONS; ETHYLENE; FUNCTIONAL GROUPS; POLYMERS; POLYOLEFINS; TRANSITION METALS;

COPOLYMERIZATION;

EID: 64549105614     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma8020757     Document Type: Article

References (54)

1. For book and reviews, see: (a) Chung, T. C. Functionalization of Polyolefins; Academic Press: San Diego, CA, 2002.
2. (b) Boffa, L. S.; Novak, B. M. Chem. Rev. 2000, 100, 1479.
3. (c) Chung, T. C. Prog. Polym. Sci. 2002, 27, 39.
4. (d) Boaen, N. K.; Hillmyer, M. A. Chem. Soc. Rev. 2005, 34, 267.
5. (e) Nomura, K.; Kitiyanan, B. Curr. Org. Synth. 2008, 5, 217.
6. For recent examples for transition-metal-catalyzed coordination copolymerization with monomers containing polar functionalities, see: (a) Wendt, R. A.; Fink, G. Macromol. Chem. Phys. 2000, 201, 1365.
7. (b) Hakala, K.; Helaja, T.; Lofgren, B. J. Polym. Sci., Part A: Polym. Chem. 2000, 38, 1966.
8. (c) Hagihara, H.; Murata, M.; Uozumi, T. Macromol. Rapid Commun. 2001, 22, 353.
9. (d) Imuta, J.; Kashiwa, N.; Toda, Y. J. Am. Chem. Soc. 2002, 124, 1176.
10. (e) Hagihara, H.; Tsuchihara, K.; Takeuchi, K.; Murata, M.; Ozaki, H.; Shiono, T. J. Polym. Sci., Part A: Polym. Chem. 2004, 42, 52.
11. (f) Hagihara, H.; Tsuchihara, K.; Sugiyama, J.; Takeuchi, K.; Shiono, T. Macromolecules 2004, 37, 5145.
12. (g) Wendt, R. A.; Angermund, K.; Jensen, V.; Thiel, W.; Fink, G. Macromol. Chem. Phys. 2004, 205, 308.
13. (h) Inoue, Y.; Matsugi, T.; Kashiwa, N.; Matyjaszewski, K. Macromolecules 2004, 37, 3651.
14. Examples for late transition metal catalysts:(a) Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 6414.
15. (b) Mecking, S.; Johnson, L. K.; Wang, L.; Brookhart, M. J. Am. Chem. Soc. 1998, 120, 888.
16. (c) Younkin, T. R.; Connor, E. F.; Henderson, J. I.; Friedrich, S. K.; Grubbs, R. H.; Bansleben, D. A. Science 2000, 287, 460.
17. (d) Connor, E. F.; Younkin, T. R.; Henderson, J. I.; Hwang, S.; Grubbs, R. H.; Roberts, W. P.; Litzau, J. J. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 2842.
18. Selected examples (ATRP, nitroxide, RAFT, etc.):(a) Liu, S.; Elyashiv, S.; Sen, A. J. Am. Chem. Soc. 2001, 123, 12738.
19. (b) Tian, G.; Boone, H. W.; Novak, B. M. Macromolecules 2001, 34, 7656.
20. (c) Elyashiv-Barad, S.; Greinert, N.; Sen, A. Macromolecules 2002, 35, 7521.
21. (d) Venkatesh, R.; Klumperman, B. Macromolecules 2004, 37, 1226.
22. (e) Venkatesh, R.; Harrison, S.; Haddleton, D. M.; Klumperman, B. Macromolecules 2004, 37, 4406.
23. (f) Gu, B.; Liu, S.; Leber, J. D.; Sen, A. Macromolecules 2004, 37, 5142.
24. (g) Liu, S.; Gu, B.; Rowlands, H. A.; Sen, A. Macromolecules 2004, 37, 7924.
25. (h) Nagel, M.; Poli, D.; Sen, A. Macromolecules 2005, 38, 7262.
26. (i) Luo, R.; Sen, A. Macromolecules 2007, 40, 154.
27. (a) Stibrany, R. T.; Schulz, D. N.; Kacker, S.; Patil, A. O.; Baugh, L. S.; Rucker, S. P.; Zushma, S.; Berluche, E.; Sissano, J. A. Macromolecules 2003, 36, 8584.
28. (b) Baugh, L. S.; Sissano, J. A.; Kackier, S.; Berluche, E.; Stibrany, R. T.; Schulz, D. N.; Rucker, S. P. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 1817.
29. Controlled introduction of terminal olefin by copolymerization with 1,7-octadiene:Nomura, K.; Liu, J.; Fujiki, M.; Takemoto, A. J. Am. Chem. Soc. 2007, 129, 14170. Related references were cited therein.
30. For copolymerization with alkenyl silane, see:(a) Byun, D.-J.; Shin, S.-M.; Han, C. J.; Kim, S. Y. Polym. Bull. 1999, 43, 333.
31. w values in the resultant polymers decreased upon increasing the ATMS content(s) due to the subsequent β-hydrogen elimination after ATMS insertion.
32. Copolymerization with alkenylsilanes:(a) Amin, S. B.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 2938.
33. (b) Amin, S. B.; Marks, T. J. J. Am. Chem. Soc. 2006, 128, 4506.
34. Chain transfer by Si:(a) Fu, P.-F.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 10747.
35. (b) Koo, K.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 8791.
36. (c) Koo, K.; Fu, P.-F.; Marks, T. J. Macromolecules 1999, 32, 981.
37. For preparation of poly(vinylsilane)s, see:(a) Natta, G.; Mazzanti, G.; Long, P.; Bernardini, F. J. Polym. Sci. 1958, 31, 181.
38. (b) Carbonaro, A.; Greco, A.; Bassi, I. W. Eur. Polym. J. 1968, 4, 445.
39. (c) Itoh, M.; Iwata, K.; Kobayashi, M.; Takeuchi, R.; Kabeya, T. Macromolecules 1998, 31, 5609. Related references were cited therein.
40. 2Cl): Stoebenau, E. J., III; Jordan, R. J. J. Am. Chem. Soc. 2006, 128, 8162. No complexes were formed with VTMS and TBE.
41. For reported examples for insertion of vinyltrimethylsilane into cationic zirconium complexes, see:(a) Guram, A. S.; Jordan, R. F. Organometallics 1990, 9, 2190.
42. (b) Guram, A. S.; Jordan, R. F. Organometallics 1991, 10, 3470.
43. (c) Guram, A. S.; Jordan, R. F. J. Org. Chem. 1993, 58, 5595.
44. (d) Rodewald, S.; Jordan, R. F. J. Am. Chem. Soc. 1994, 116, 4491.
45. Review:Nomura, K.; Liu, J.; Padmanabhan, S.; Kitiyanan, B. J. Mol. Catal. A 2007, 267, 1.
46. For selected reports for ethylene copolymerizations, see:(a) Nomura, K.; Oya, K.; Komatsu, T.; Imanishi, Y. Macromolecules 2000, 33, 3187.
47. (b) Nomura, K.; Okumura, H.; Komatsu, T.; Naga, N. Macromolecules 2002, 35, 5388.
48. (c) Wang, W.; Fujiki, M.; Nomura, N. J. Am. Chem. Soc. 2005, 127, 4582.
49. (d) Zhang, H.; Nomura, K. J. Am. Chem. Soc. 2005, 127, 9364.
50. (e) Nomura, K.; Wang, W.; Fujiki, M.; Liu, J. Chem. Commun. 2006, 2659.
51. (f) Itagaki, K.; Fujiki, M.; Nomura, K. Macromolecules 2007, 40, 6489.
52. 13C NMR (dept) spectra of the copolymers are shown in the Supporting Information.
53. π-complex.
54. 3, which would explain the poor incorporation of the latter monomer (this should also affect the coordination energy). Recently, Prof. Bochmann (University of East Anglia, UK) suggested a possibility of 2,1-insertion rather than 1,2-insertion. Therefore, we will explore the details in the forthcoming full article. K.N. expresses his thanks to the reviewer and Prof. Bochmann for helpful comments.