화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.18, No.10, 967-973, October, 2010
DOI10.1007/s13233-010-1013-z  Export Citation
Deuterium labeling and mechanistic insights in the polymerization of propylene promoted by benzamidinate complexes
Victoria Volkis, Sinai Aharonovich, and Moris S. Eisen†
  • Schulich Faculty of Chemistry and Institute of Catalysis Science, Technology Haifa, Haifa, 32000, Israel
E-mail:
A new epimerization mechanism was introduced for the polymerization of propylene obtained by octahedral benzamidinate complexes. Deuterium labeling showed that deuterium is transferred from a methyne to a methylene position in the polymer inducing a stereoerror and an elastic material. In addition, two active species are formed during the polymerization of propylene promoted by the octahedral bis(benzamidinate) titanium dialkyl complexes.
Keywords:benzamidinate complexes;polypropylene;mechanistic insights
  1. See, for example: Li H, Marks TJ, Proc. Natl. Acad. Sci. U.S.A., 103, 5295 (2006) and references therein.
  2. Baugh LS, Canich JAM, Stereoselective Polymerization with Single-Site Catalysts, CRC Press, Boca Raton, Florida, 2007.
  3. Nayak PL, Popular Plastics & Packaging, 48, 86 (2003).
  4. Guo N, Stern CL, Marks TJ, J. Am. Chem. Soc., 130(7), 2246 (2008)
  5. Motta A, Fragala IL, Marks TJ, J. Am. Chem. Soc., 129(23), 7327 (2007)
  6. Wang B, Coord. Chem. Rev., 250, 242 (2006)
  7. Prashar S, Antinolo A, Otero A, Coord. Chem. Rev., 250, 133 (2006)
  8. Tritto I, Boggioni L, Ferro DR, Coord. Chem. Rev., 250, 212 (2006)
  9. Hotta A, Cochran E, Ruokolainen J, Khanna V, Fredrickson GH, Kramer EJ, Shin YW, Shimizu F, Cherian AE, Hustad PD, Rose JM, Coates GW, Proc. Natl. Acad. Sci. U.S.A., 103, 15327 (2006)
  10. Kaminsky W, Tran PD, Werner R, Macromol. Symp., 213, 101 (2004)
  11. Resconi L, Cavallo L, Fait A, Piemontesi F, Chem. Rev., 100(4), 1253 (2000)
  12. Rodriguez-Delgado A, Hannant MD, Lancaster SJ, Bochmann M, Macromol. Chem. Phys., 205, 334 (2004)
  13. Holden G, Thermoplastic elastomers, in Kirk-Othmer Encyclopedia of Chemical Technology, 5th Edition, 2007, vol. 24, p. 695.
  14. Bhowmick AK, Current Topics in Elastomers Research, CRC Press, Boca Raton, Florida, 2008, pp 101-164.
  15. De Rosa C, Auriemma F, Prog. Polym. Sci, 31, 145 (2006)
  16. Cobzaru C, Hild S, Boger A, Troll C, Rieger B, Coord. Chem. Rev., 250, 189 (2006)
  17. Edson JB, Wang ZG, Kramer EJ, Coates GW, J. Am. Chem. Soc., 130(14), 4968 (2008)
  18. Coates GW, Hustad PD, Reinartz S, Angew. Chem.-Int. Edit., 41, 2236 (2002)
  19. Busico V, Talarico G, Cipullo R, Macromol. Symp., 226, 1 (2005)
  20. Harney MB, Zhang Y, Sita LR, Angew. Chem.-Int. Edit., 45, 2400 (2006)
  21. Harney MB, Zhang Y, Sita LR, Angew. Chem.-Int. Edit., 45, 6140 (2006)
  22. Coates GW, Waymouth RM, Science, 267(5195), 217 (1995)
  23. Lin S, Waymouth RM, Acc. Chem. Res., 35, 765 (2002)
  24. Busico V, Cipullo R, Kretschmer WP, Talarico G, Vacatello M, Van Axel Castelli V, Angew. Chem.-Int. Edit., 41, 505 (2002)
  25. Busico V, Castelli VVA, Aprea P, Cipullo R, Segre A, Talarico G, Vacatello M, J. Am. Chem. Soc., 125(18), 5451 (2003)
  26. Veghini D, Henling LM, Burkhardt TJ, Bercaw JE, J. Am. Chem. Soc., 121(3), 564 (1999)
  27. Brandow CG, Mendiratta A, Bercaw JE, Organometallics, 20, 4253 (2001)
  28. Miller SA, Bercaw JE, Organometallics, 21, 934 (2002)
  29. Chen MC, Roberts JAS, Marks TJ, J. Am. Chem. Soc., 126(14), 4605 (2004)
  30. Keaton RJ, Sita LR, J. Am. Chem. Soc., 124(31), 9070 (2002)
  31. Sillars DR, Landis CR, J. Am. Chem. Soc., 125(33), 9894 (2003)
  32. Busico V, Cipullo R, J. Am. Chem. Soc., 116(20), 9329 (1994)
  33. Busico V, Caporaso L, Cipullo R, Landriani L, Angelini G, Margonelli A, Segre AL, J. Am. Chem. Soc., 118(8), 2105 (1996)
  34. Busico V, Cipullo R, Cutillo F, Vacatello M, Macromolecules, 35(2), 349 (2002)
  35. Resconi L, J. Mol. Catal. A-Chem., 146, 167 (1999)
  36. Moscardi G, Resconi L, Cavallo L, Organometallics, 20, 1918 (2001)
  37. Kukral J, Lehmus P, Klinga M, Markku RB, Eur. J. Inorg. Chem., 6, 1349 (2002)
  38. Gilchrist JH, Bercaw JE, J. Am. Chem. Soc., 118(48), 12021 (1996)
  39. Leclerc MK, Brintzinger HH, J. Am. Chem. Soc., 117(5), 1651 (1995)
  40. Yoder JC, Bercaw JE, J. Am. Chem. Soc., 124(11), 2548 (2002)
  41. Smolensky E, Eisen MS, J. Chem. Soc.-Dalton Trans., 5623 (2007)
  42. Volkis V, Averbuj C, Eisen MS, J. Organomet. Chem., 692, 1940 (2007)
  43. Bambirra S, Otten E, van Leusen D, Meetsma A, Hessen B, Zeit. Anorg. Allg. Chemie, 632, 1950 (2006)
  44. Volkis V, Rodensky M, Lisovskii A, Balazs Y, Eisen MS, Organometallics, 25, 4934 (2006)
  45. Volkis V, Tumanskii B, Eisen MS, Organometallics, 25, 2722 (2006)
  46. Volkis V, Lisovskii A, Tumanskii B, Shuster M, Eisen MS, Organometallics, 25, 2526 (2006)
  47. Volkis V, Nelkenbaum E, Lisovskii A, Hasson G, Semiat R, Kapon M, Botoshansky M, Eishen Y, Eisen MS, J. Am. Chem. Soc., 125(8), 2179 (2003)
  48. Volkis V, Schmulinson M, Shaviv E, Lisovskii A, Plat D, Kuhl O, Koch T, Hey-Hawkins E, Eisen MS, in Beyond Metallocenes; Next Generation Polymerization Catalysts, Patil AO, Hlatky GG, Eds., American Chemical Society Symposium Series, 857, 46 (2003).
  49. Busico V, Cipullo R, Cutillo F, Vacatello M, Macromolecules, 35(2), 349 (2002)
  50. Busico V, Caporaso L, Cipullo R, Landriani L, Angelini G, Margonelli A, Segre AL, J. Am. Chem. Soc., 118(8), 2105 (1996)
  51. Resconi L, J. Mol. Catal. A-Chem., 146, 167 (1999)
  52. Yoder JC, Bercaw JE, J. Am. Chem. Soc., 124(11), 2548 (2002)
  53. Volkis V, Smolensky E, Lisovskii A, Eisen MS, J. Polym. Sci. A: Polym. Chem., 43(19), 4505 (2005)
  54. Brown JM, Hughes GD, Inorg. Chim. Acta., 252, 229 (1996)