Marked Counteranion Effects on Single-Site Olefin Polymerization Processes. Correlations of Ion Pair Structure and Dynamics with Polymerization Activity, Chain Transfer, and Syndioselectivity

Journal of the American Chemical Society

Volumn 126, Issue 14, 2004, Pages 4605-4625

  Chen, Ming Chou ^a   Roberts, John A S ^a   Marks, Tobin J ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; MONOMERS; NEGATIVE IONS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYMERIZATION; PROPYLENE; X RAY DIFFRACTION;

COCATALYSTS; REORGANIZATION PATHWAYS;

OLEFINS;

1,3 DICHLOROBENZENE; ALKENE; MONOMER; PROPYLENE; SOLVENT; TOLUENE;

ARTICLE; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; DIASTEREOISOMER; DYNAMICS; EPIMERIZATION; MOLECULAR WEIGHT; NUCLEAR MAGNETIC RESONANCE; POLYMERIZATION; STEREOCHEMISTRY; TEMPERATURE; X RAY DIFFRACTION;

EID: 1842738507     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja036288k     Document Type: Article

References (134)

1. For recent reviews, see: (a) Pédeutour, J.-N.; Radhakrishnan, K.; Cramail, H.; Deffieux, A. Macromol. Rapid Commun. 2001, 22, 1095-1123.
2. (b) Chen, Y.-X.; Marks, T. J. Chem. Rev. 2000, 100 (4), 1391-1434.
3. (c) Gladysz, J. A., Ed. Chem. Rev. 2000, 100, 1167-1682.
4. (d) Marks, T. J.; Stevens, J. C., Eds. Top. Catal. 1999, 7, 1-208.
5. (e) Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. Angew. Chem., Int. Ed. Engl. 1999, 38, 428-447.
6. (f) Jordan, R. F.; Ed. J. Mol. Catal. 1998, 128, 1-337.
7. For recent cocatalyst studies, see: (a) Busico, V.; Cipullo, R.; Cutillo, F.; Vacatello, M.; Van Axel Castelli, V. Macromolecules 2003, 36, 4258-4261.
8. (b) Mohammed, M.; Nele, M.; Al-Humydi, A.; Xin, S.; Stapleton, R.; Collins, C. J. Am. Chem. Soc. 2003, 125, 7930-7941.
9. (c) Li, L.; Metz, M. V.; Li, H.; Chen, M.-C.; Marks, T. J. J. Am. Chem. Soc. 2002, 124, 12 725-12 741.
10. (d) Metz, M. V.; Schwartz, D. J.; Stern, C. L.; Marks, T. J.; Nickias, P. N. Organometallics 2002, 21, 4159-4168.
11. (e) Metz, M. V.; Sun, Y. M.; Stern, C. L.; Marks, T. J. Organometallics 2002, 21, 3691-3702.
12. (f) Wilmes, G. M.; Polse, J. L.; Waymouth, R. M. Macromolecules 2002, 35, 6766-6772.
13. (g) Lancaster, S. J.; Rodriguez, A.; Lara-Sanchez, A.; Hannant, M. D.; Walker, D. A.; Hughes, D. H.; Bochmann, M. Organometallics 2002, 21, 451-453.
14. (h) Rodriguez, G.; Brant, P. Organometallics 2001, 20, 2417-2420.
15. (i) Kaul, F. A. R.; Puchta, G. T.; Schneider, H.; Grosche, M.; Mihalios, D.; Herrmann, W. A. J. Organometallic Chem. 2001, 621, 177-183.
16. (j) Chen, Y.-X.; Kruper, W. J.; Roof G.; Wilson, D. R. J. Am. Chem. Soc. 2001, 123, 745-746.
17. (k) Zhou, J.; Lancaster, S. J.; Walker, D. A.; Beck, S.; Thornton-Pett, M.; Bochmann, M. J. Am. Chem. Soc. 2001, 123, 223-237.
18. (l) Kehr, G.; Roesmann, R.; Frohlich, R.; Holst, C.; Erker, G. Eur. I. Inorg. Chem. 2001, 535-538.
19. (m) Mager, M.; Becke, S.; Windisch, H.; Denninger, U. Angew. Chem., Int. Ed. Engl. 2001, 40, 1898-1902.
20. (n) Chase, P. A.; Piers, W. E.; Patrick, B. O.; J. Am. Chem. Soc. 2000, 122, 12 911-12 912.
21. (o) LaPointe, R. E.; Roof, G. R.; Abboud, K. A.; Klosin, J. J. Am. Chem. Soc. 2000, 122, 9560-9561.
22. (p) Sun, Y. M.; Metz, M. V.; Stern, C. L.; Marks, T. J. Organometallics 2000, 19, 1625-1627.
23. (q) Metz, M. V.; Schwartz, D. J.; Stern, C. L.; Nickias, P. N.; Marks, T. J. Angew. Chem., Int. Ed. Engl. 2000, 39, 1312-1316.
24. (a) Sinn, H.; Kaminsky, W. Adv. Organomet. Chem. 1980, 18, 99-149.
25. (b) Sinn, H.; Kaminsky, W.; Vollmer, H.-J.; Woldt, R. Angew. Chem., Int. Ed. Engl. 1980, 19, 390-392.
26. (a) Yang, X.; Stern, C. L.; Marks. T. J. J. Am. Chem. Soc. 1994, 116, 10 015-10 031.
27. (b) Yang, X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1991, 113, 3623-3625.
28. (c) Ewen, J. A.; Elder, M. J. Chem. Abstr. 1991, 115, 136 998g.
29. (a) Li, L.; Stern, C. L.; Marks, T. J. Organometallics 2000, 19, 3332-3337.
30. (b) Li, L.; Marks, T. J. Organometallics 1998, 17, 3996-4003.
31. (c) Chen, Y.-X.; Stern, C. L.; Yang, S.; Marks, T. J. J. Am. Chem. Soc. 1996, 118, 12 451-12 452.6.
32. (d) also see ref 2c,d.
33. (e) For a recent chelating borane review. see: Piers, W. E.; Irvine, G. J.; Williams, V. C. Eur. J. Inorg. Chem. 2000, 2131-2142.
34. (a) Chien, J. C. W.; Tsai, W.-M.; Rausch, M. D. J. Am. Chem. Soc. 1991, 113, 8570-8571.
35. (b) Yang, X.; Stern, C. L.; Marks, T. J. Organometallics 1991, 10, 840-842.
36. (c) Ewen, J. A.; Elder, M. J. Eur. Pat. Appl. 426637 1991; Chem. Abstr. 1991, 115, 136987c, 136988d.
37. For related fluorinated tetraarylborates, see: (a) Kaul, F. A. R.; Puchta, G. T.; Schneider, H.; Grosche, M.; Mihalios, D.; Herrmann, W. A. J. Organomet. Chem. 2001, 621, 184-189.
38. (b) also see refs 2g,h,k.
39. (c) Jia, L.; Yang, X.; Stern, C. L.; Marks, T. J. Organometallics 1997, 16, 842-857.
40. (d) Jia, L.; Yang, X.; Ishihara, A.; Marks, T. J. Organometallics 1995, 14, 3135-3137.
41. (a) Chen, Y.-X.; Metz, M. V.; Li, L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 6287-6305.
42. (b) Chen, Y. X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1997, 119, 2582-2583.
43. (c) Elder, M. J.; Ewen, J. A. Eur. Pat. Appl. EP 573, 403, 1993; Chem. Abstr. 1994, 121, 0207d.
44. (d) also see Ref. 2o.
45. (a) Razavi, A.; Thewalt, U. J. Organomet. Chem. 1993, 445, 111-114.
46. (b) Razavi, A.; Ferrara, J. J. Organomet. Chem. 1992, 435, 299-310.
47. Chen, M.-C.; Marks, T. J. J. Am. Chem. Soc. 2001, 123, 11 803-11 804.
48. (a) Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. in ref. 1c, pp 1253-1345.
49. (b) Coates, G. W. in ref 1c, pp 1223-1252.
50. (c) Veghini, D.; Henling, L. M.; Burkhardt, T. J.; Bercaw, J. E. J. Am. Chem. Soc. 1999, 121, 564-573.
51. (d) Ewen, J. A.; Jones, R. L.; Razavi, A.; Ferrara, J. D. J. Am. Chem. Soc. 1988, 110, 6255-6256.
52. (a) Beswick, C. L.; Marks, T. J. J. Am. Chem. Soc. 2000, 122, 10 358-10 370.
53. (b) Deck, P. A.; Beswick, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 1772-1784.
54. (c) Luo, L.; Marks, T. J. in ref 1d, pp 97-106.
55. (d) also see refs 7c and 8a.
56. (a) See ref 2a.
57. (b) Busico, V.; Cipullo, R. Prog. Polym. Sci. 2001, 26, 443-533.
58. (c) Farina, M.; Terragni, A. Makromol. Chem., Rapid Commun. 1993, 14, 791-798.
59. (d) Such techniques are reviewed in ref 11a.
60. Beck, S.; Lieber, S.; Schaper, F.; Geyer, A.; Brintzinger, H. H. J. J. Am. Chem. Soc. 2001, 123, 1483-1489.
61. Massey, A. G.; Park, A. J. J. Organomet. Chem. 1964, 2, 245-250.
62. (a) Busico, V.; Cipullo, R.; Monaco, G.; Vacatello, M. Macromolecules 1997, 30, 6251-6263.
63. (b) Pellecchia, C.; Pappalardo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158.
64. (c) Busico, V.; Cipullo, R.; Corradini, P.; Landriani, L.; Vacatello, M. ; Segre, A. L. Macromolecules 1995, 28, 1887.
65. (d) Miyatake, T.; Miaunuma, K.; Kakugo, M. Macromol. Symp. 1993, 66, 203.
66. (e) Kakugo, M.; Miyatake, T.; Miaunuma, K. Stud. Surf. Sci. Catal. 1990, 56, 517.
67. (f) Longo, P.; Grassi, A. Makromol. Chem. 1990, 191, 2387.
68. (g) Randall, J. C. J. Polym. Sci., Part B: Polym. Phys. 1975, 13, 889.
69. 6, has a maximum rate of propylene consumption of ∼0.015 mol/min (0.77/42* (75/60)), which should be lower at 20 °C because lower activity is observed at lower temperatures. Thus, propylene mass transfer effects should be negligible for all catalysts under the present conditions.
70. Macura, S.; Ernst, R. R. Mol. Phys. 1980, 41, 95-117.
71. Perrin, C. L.; Dwyer, T. J. Chem. Rev. 1990, 90, 935-967, and also see ref 14.
72. Rutledge, D. N., Ed. Signal Treatment and Signal Analysis in NMR; Elsevier Science: New York, 2003: Ch. 16.
73. (a) Sandstrom, J. Dynamic NMR Spectroscopy; Academic Press: New York, 1982; pp 77-92, and also see ref 4a.
74. 2 is line width at half-height of the exchange broadened peak in Hz. and W is the line width in the absence of exchange (the no-exchange limit, 0 °C for 7 and 23 °C for 10). The corresponding free energies of activation can also be derived using ΔAG‡ = - RT[In(k/T) + In(h/k)].
75. Budzelaar, P. H. M. gNMR v. 4.1.0; Adept Scientific plc, 1999
76. Strauss. S. H. Chem. Rev. 1993, 93, 927-942.
77. (a) Lanza, G.; Fragala, I. L.; Marks, T. J. Organometallics 2002, 21, 5594-5612.
78. (b) Lanza, G.; Fragala, I. L.; Marks, T. J. Organometallics 2001, 20, 4006-4017.
79. (c) Lanza, G.; Fragala, I. L.; Marks, T. J. J. Am. Chem. Soc. 2000, 122, 12 764-12 777.
80. NMR-scale reaction of 1 with MAO is not amenable to interpretation, thus will not be discussed here.
81. - were obtained, as reported previously, see ref 8a.
82. 2(Me)(t-Bu), ref 14.
83. -. Guzei, I. A.; Stockland, R. A.; Jordan, R. F. Acta Crystallogr., Sect. C (Cryst. Str. Comm.) 2000, C56, 635-636.
84. -, Beck, S.; Prosenc, M. H.; Brintzinger, H. H.; Goretzki, R.; Herfert, N.; Fink, G. J. Mol. Catal. A: Chem. 1996, 111, 67-79.
85. 3, ref. 4a, also see: Bochmann, M.; Lancaster, S. J.; Hursthouse, M. B.; Malik, K. M. A. Organometallics 1994, 13, 2235-2243.
86. -, ref. 4a.
87. (f) Average of the five complexes, F-J.
88. Zuccaccia, C.; Stahl, N. G.; Macchioni, A.; Chen, M.-C.; Roberts, J. A.; Marks, T. J. J. Am. Chem. Soc. 2004, 126, 1448-1464.
89. Line broadening is found to be independent of concentration over an 8-fold range for 7, arguing that an intramolecular exchange process is prevalent.
90. -1) as determined from EXSY data demonstrates that 0 °C is a suitable temperature to take as the zero-exchange limit for the purposes of line-shape analysis.
91. Signal overlap precludes use of other sets of signals for this determination.
92. -1. assuming total cancellation of NOE and exchange cross-peak intensity at these positions.
93. 4 as solvent reveal that in this more polar medium, the barrier to ion pair reorganization in 7 is lowered, whereas with 10 such a process is still undetectable.
94. For experiments using MAO (2) as cocatalyst, an Al:Zr ratio of 60: 1 is employed, to improve comparability with results collected using molecular cocatalysts. Control experiments in which the Al:Zr ratio is varied across a 30-fold range show no significant dependence of the pentad distribution on this ratio. These results are presented in Table 2 of the Supporting Information.
95. 1-symmetric catalysts, isotacticity sometimes increases with increasing polymerization temperature: (a) Kleinschmidt, R.; Reffke, M.; Fink, G. Macromol. Rapid Commun. 1999, 20, 284-288.
96. (b) Grisi, F.; Longo, P.; Zambelli, A.; Ewen, J. A. J. Mol. Catal. A: Chem. 1999, 140, 225-233.
97. 2-symmetric catalyst propylene polymerization temperature dependent study, see: Resconi, L.; Piemontesi, F.; Camurati, I.; Sudmeijer, O.; Nifant'ev, I. E.; Ivchenko, P. V.; Kuz'mina, G. K. J. Am. Chem. Soc. 1998, 120, 2308-2321.
98. See ref 11. Other proposed processes giving rise to m stereodefects are discussed below. See ref 2c.
99. An empirical model for the calculation of the solution-phase composition of propylene in toluene and isododecane under relavent conditions is presented in (a) Dariva, C.; Lovisi, H.; Santa Mariac, L. C.; Coutinho, F. M. B.; Oliveira, J. V.; Pinto, J. C. Can. J. Chem. Eng. 2003, 81, 147-152.
100. (b) also see ref 17.
101. s-symmetric catalysts, lower propylene concentrations correlate with lower product molecular weights and tacticities (mostly m stereodefects), ref 13c.
102. 1-symmetric catalysts: Kukral, J.; Lehmus, P.; Feifel, T.; Troll, C.; Rieger, B. Organometallics 2000, 19, 3767-3775.
103. 2-symmetric catalyst propylene concentration studies, see ref 17,
104. and also: (d) Busico, V.; Cipullo, R.; Cutillo, F.; Vacatello, M. Macromolecules 2002, 35, 349-354.
105. (e) Busico, V.; Brita, D.; Caporaso, L.; Cipullo, R.; Vacatello, M. Macromolecules 1997, 30, 3971-3977.
106. and (f) Resconi, L.; Fait, A.; Piemontesi, R.; Colonesi, M. Macromolecules 1995, 28, 6667-6676.
107. 2-symmetric catalyst propylene studies, there is debate in the literature as to the exact order of monomer in production of isotactic polypropylene. See refs 17, 38d-f. Ref 38d contains a model reconciling observed apparent propagation [propylene] dependences using a rigorous approach that holds propagation to be first-order in monomer.
108. Liu, Z.; Somsook, E.; White, C. B.; Rosaaen, K. A.; Landis, C. R. J. Am. Chem. Soc. 2001, 123, 11 193-11 207.
109. Sillars, D. R.; Landis, C. R. J. Am. Chem. Soc. 2003, 125, 9894-9895.
110. For general kinetic models, see: (a) Nele, M.; Mohammed, M.; Xin, S.; Collins, S.; Dias, M. L.; Pinto, J. C. Macromolecules 2001, 34, 3830-3841.
111. (b) Grisi, F.; Longo, P.; Zambelli, A.; Ewen, J. A. J. Mol. Catal. A: Chem. 1999, 140, 225.
112. (c) Ewen, J. A. J. Mol. Catal. A: Chem. 1998, 128, 103.
113. --based systems are to some degree stabilized in the presence of olefin, and extant literature finds catalyst activity during polymerization to be more or less constant: (a) Wester, T. S.; Johnsen, H.; Kittilsen, P.; Rytter, E. Makromol. Chem. Phys. 1998, 199, 1989-2004.
114. 3], see: (b) Liu, Z.; Somsook, E.; Landis, C. R. J. Am. Chem. Soc. 2001, 123, 2915-2916.
115. For relevant ethylene homopolymerization results using mononuclear and binuclear constrained geometry catalysts see: (c) Abramo, G. P.; Li, L.; Marks, T. J. J. Am. Chem. Soc. 2002, 124, 13 966-13 967, and also see ref 2c.
116. (d) Landis, C. R.; Rosaaen, K. A.; Sillars, D. R. J. Am. Chem. Soc. 2003, 125, 1710-1711.
117. For example, in NMR study of the freshly generated ion pairs, we observe systems 8 and 9 to undergo rapid decomposition (with 9 faster than 8), while 7 decomposes slowly and 10 exhibits comparatively high thermal stability.
118. p for Table 11.
119. mm) and insertion rates. The chain epimerization rates follow the ordering: 3 > 5 > 2 > 4 > 6. It is likely in any event that the various steps involved in chain epimerization are subject to anion-dependent steric and electronic influences in a complex manner.
120. (a) Propylene solubilities at 1 atm can be expected to vary somewhat with solvent. However. with 1,3-dichlorobenzene as solvent we observe that whereas activity (hence insertion rate) increases, so also does the rate of xmrx steric pentad formation, relative to insertion. On the basis of what we have demonstrated here from the propylene concentration study, we would expect the opposite, were the effect exclusively a concentration effect.
121. (b) Herfert, N.; Fink, G. Makromol. Chem. 1992, 193, 773-778.
122. (c) Coevoet, D.; Cramail, H.; Deffieux, A. Makromol. Chem. Phys. 1999, 200, 1208-1214.
123. 2-symmetric catalyst system, Forlini, F.; Tritto, L.; Locatelli, P.; Sacchi, M. C.; Piemontesi, F. Makromol. Chem. Phys. 2000, 201, 401-408.
124. (d) For CGC catalyst systems, see: Kleinschmidt, R.; Griebenow, Y.; Fink, G. J. Mol. Cotal. A-Chem. 2000, 157, 83-90.
125. (a) Stahl, N. G.; Zuccaccia, C.; Jensen, T. R.; Marks, T. J. J. Am. Chem. Soc. 2003, 125, 5256-5257.
126. (b) Stahl, N. G.; Marks, T. J.; Macchioni, A.; Zuccaccia, C. Presented in part at the 222nd ACS National Meeting, Chicago, IL, August 2001, Abstract INORG 407.
127. - is not assumed to be a solvent-separated or dissociated ion pair.
128. (a) Cossee, P. Tetrahedron Lett. 1960, 17, 12.
129. (b) Cossee, P. Tetrahedron Lett. 1960, 17, 17.
130. (c) Arlman, E. J.; Cossee, P. J. Catal. 1964, 3, 99. Cossee, P. J. Catal. 1964, 3, 80. Cossee, P.
131. (a) Beswick, C. L.; Marks, T. J. Organometallics 1999, 18, 2410-2412.
132. (b) Deck, P. A.; Beswick, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 12 167-12 167.
133. (c) and also see ref. 12.
134. Chen, M.-C.; Roberts, J. A. S.; Marks, T. J. Organometallics 2004, 23, 932-935.