The mechanism of the self-initiated thermal polymerization of styrene. Theoretical solution of a classic problem

Journal of the American Chemical Society

Volumn 127, Issue 4, 2005, Pages 1265-1277

  Khuong, Kelli S ^a   Jones, Walter H ^a   Pryor, William A ^b   Houk, K N ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b LOUISIANA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

FREE RADICAL POLYMERIZATION; INITIATORS (CHEMICAL); PROBABILITY DENSITY FUNCTION; THERMOANALYSIS;

FLORY MECHANISMS; HYDROGEN TRANSFER; MAYO MECHANISMS; MONORADICAL POLYMERIZATION; THERMAL POLYMERIZATION;

STYRENE;

CYCLOBUTANE DERIVATIVE; DIPHENYLCYCLOBUTANE; HYDROGEN; STYRENE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; DENSITY FUNCTIONAL THEORY; DIELS ALDER REACTION; MATHEMATICAL ANALYSIS; POLYMERIZATION; PROTON TRANSPORT; THERMODYNAMICS;

EID: 13644262206     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0448667     Document Type: Article

References (65)

1. Pryor, W. A. Radical Polymerizations. Free Radicals; McGraw-Hill: New York, 1966; pp 117-129, 237-239. Molecular weight is inversely proportional to square root of initiator concentration.
2. Rubens, L. C.; Boyer, R. F. The Polymerization of Styrene. In Styrene; Boundy, R. H., Boyer, R. F., Eds.; ACS Monograph 115; Reinhold: New York, 1952; pp 215-288.
3. An excellent review on the subject of spontaneous polymerization of styrene: Pryor, W. A.; Lasswell, L. D. Adv. Free-Radical Chem. 1975, 5, 27-99.
4. (a) Mayo, F. R. J. Am. Chem. Soc. 1968, 90, 1289-1295.
5. (b) Mayo, F. R. J. Am. Chem. Soc. 1953, 75, 6133-6141.
6. (a) Pryor, W. A. Petroleum Prepr. 1980, 25, 12-18.
7. (b) Pryor, W. A.; Coco, J. H.; Daly, W. H.; Houk, K. N. J. Am. Chem. Soc. 1974, 96, 5591-5593.
8. Flory, P. J. J. Am. Chem. Soc. 1937, 59, 241-253.
9. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
10. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
11. Guner, V.; Khuong, K. S.; Leach, A. G.; Lee, P.; Bartberger, M. D.; Houk, K. N. J. Phys. Chem. A 2003, 107, 11445-11459.
12. (a) Khuong, K. S.; Houk, K. N. J. Am. Chem. Soc. 2003, 125, 14867-14883.
13. (b) Suhrada, C. P.; Houk, K. N. J. Am. Chem. Soc. 2002, 124, 8796-8797.
14. (c) Nendel, M.; Sperling, D.; Wiest, O.; Houk, K. N. J. Org. Chem. 2000, 65, 3259-3268.
15. (d) Beno, B. R.; Wilsey, S.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 4816-4826.
16. (e) Houk, K. N.; Nendel, M.; Wiest, O.; Storer, J. W. J. Am. Chem. Soc. 1997, 19, 10545-10546.
17. (f) Houk, K. N.; Beno, B. R.; Nendel, M.; Black, K.; Yoo, H. Y.; Wilsey, S.; Lee, J. Theochem 1997, 398-399, 169-179.
18. Gräfenstein, J.; Hjerpe, A. M.; Kraka, E.; Cremer, D. J. Phys. Chem. A 2000, 104, 1748-1761.
19. Burke, K.; Perdew, J. P.; Wang, W. In Electronic Density Functional Theory: Recent Progress and New Directions; Dobsin, J. F., Vignale, G., Das, M. P., Eds.; Plenum: New York, 1998.
20. (a) Winkler, M.; Sander, W. J. Phys. Chem. A 2001, 105, 10422-10432.
21. (b) Staroverov, V. N.; Davidson, E. R. J. Am. Chem. Soc. 2000, 122, 7377-7385.
22. Brown, W. G. Makromol. Chem. 1969, 128, 130-136.
23. Dodson, R. M.; Zielske, A. G. J. Org. Chem. 1967, 32, 28-31.
24. Kurze, V. J.; Stein, D. J.; Šimák, P.; Kaiser, R. Angew. Makromol. Chem. 1970, 12, 25-41.
25. Kirchner, V. K.; Buchholz, K. Angew. Makromol. Chem. 1970, 13, 127-138.
26. Kirchner, K.; Riederle, K. Angew. Makromol. Chem. 1983, 111, 1-16.
27. Chong, Y. K.; Rizzardo, E.; Solomon, D. H. J. Am. Chem. Soc. 1983, 105, 7761-7762.
28. Moad, G.; Rizzardo, E.; Solomon, D. H. Polym. Bull. 1982, 6, 589-593.
29. Devonport, W.; Michalak, L.; Malmström, E.; Mate, M.; Kurdi, B.; Hawker, C. J.; Barclay, G. G.; Sinta, R. Macromolecules 1997, 30, 1929-1934.
30. Buzanowski, W. C.; Graham, J. D.; Priddy, D. B.; Shero, E. Polymer 1992, 33, 3055-3059.
31. (a) Pryor, W. A.; Henderson, R. W.; Patsiga, R. A.; Carroll, N. J. Am. Chem, Soc. 1966, 88, 1199-1205.
32. (b) Kirchner, K. Makromol. Chem. 1966, 96, 179-186.
33. (c) Kopecky, K. R.; Evani, S. Can. J. Chem. 1969, 47, 4049-4058.
34. (d) Henderson, R. W.; Pryor, W. A. Int. J. Chem. Kinet. 1972, 4, 325-330.
35. Hiatt, R. R.; Bartlett, P. D. J. Am. Chem. Soc. 1959, 81, 1149-1154.
36. (a) Kopecky, K. R.; Evani, S. Can. J. Chem. 1969, 47, 4041-4048.
37. (b) Kopecky, K. R.; Soler, J. Can. J. Chem. 1974, 52, 2111-2118.
38. Miranda, M. A.; Font-Sanchis, E.; Pérez-Prieto, J.; Scaiano, J. C. J. Org. Chem. 1999, 64, 7842-7845.
39. (a) Li, T.; Padia, A. B.; Hall, H. K., Jr. Macromolecules 1990, 23, 3899-3904.
40. (b) Kauffmann, H. F. Mackromol. Chem. 1979, 180, 2649-2663, 2665-2680, 2681-2693, 2695-2705.
41. Jones, G., II; Chow, V. L. J. Org. Chem. 1974, 39, 1447-1448.
42. Bamford, C. H.; Dewar, M. J. S. Proc. R. Soc. (London) 1948, AI92, 309-328.
43. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.9; Gaussian, Inc.: Pittsburgh, PA, 1998.
44. (a) Yamaguchi, K.; Jensen, F.; Dorigo, A.; Houk, K. N. Chem. Phys. Lett. 1988, 149, 537-542.
45. (b) Yamanaka, S.; Kawakami, T.; Nagao, H.; Yamaguchi, K. Chem. Phys. Lett. 1994, 231, 25-33.
46. Potential problems with spin projected DFT are discussed: Wittbrodt, J. M.; Schlegel, H. B. J. Chem. Phys. 1996, 105, 6574-6577.
47. (a) Kauffmann, H. F.; Olaj, O. F.; Breitenbach, J. W. Makromol. Chem. 1976, 177, 939-945.
48. (b) Olaj, O. F.; Kauffmann, J. F.; Breitenbach, J. W. Makromol. Chem. 1977, 178, 2707-2717. These two references report that time-dependent UV absorption of polymerizing styrene gives evidence for the formation of both the exo and the endo AH dimers. The authors conclude that the exo and endo isomers have different stationary concentrations.
49. Sears, T. J.; Johnson, P. M.; Jin, P.; Oatis, S. J. Chem. Phys. 1996, 104, 781-792.
50. Hybrid DFT methods include a portion of exact HF exchange which leads to larger instability because HF is always less stable than DFT. Also see ref 7 and ref 12b.
51. Leach, A. G.; Catak, S.; Houk, K. N. Chem. Eur. J. 2002, 8, 1290-1299.
52. Doubleday, C., Jr. J. Am. Chem. Soc. 1993, 115, 11968-11983.
53. Rule, J. D.; Wilson, S. R.; Moore, J. S. J. Am. Chem. Soc. 2003, 125, 12992-12993.
54. 1-n, where n is the order of the reaction. The density of styrene at 20°C is 0.9059 g/mL, equating to a concentration of 8.7 M. Boyer, R. F.; Keskkula, H.; Platt, A. E. Styrene Polymers. Encyclopedia of Polymer Science and Technology, Vol. 13; Wiley & Sons: New York, 1970; p 136.
55. Transition-state theory predicts that Diels-Alder adducts would compose less than 0.1% (B3LYP) or 1% (BPW91) of the total amount of dimers formed at 180°C.
56. Carpenter, B. K. J. Phys. Org. Chem. 2003, 16, 858-868 and references therein.
57. Contour energy surfaces were also generated with R and UBPW91. They show the same general features as the plots in Figures 6 and 7.
58. DA is -619.255546 au.
59. (a) Boyer, R. F.; Keskkula, H.; Platt, A. E. Styrene Polymers. In Encyclopedia of Polymer Science and Technology; Wiley & Sons: New York, 1970; 13, pp 173-175.
60. (b) Mayo, F. R. J. Am. Chem. Soc. 1943, 65, 2324-2329.
61. (a) Lebovits, A.; Teach, W. C. J. Polym. Sci. 1960, 47, 527-529.
62. (b) Louchex, C.; Benoit, H. Compt. Rend. 1960, 251, 382-384.
63. (c) Müller, K. F. Makromol. Chem. 1964, 79, 128-134.
64. Gregg, R. A.; Mayo, F. R. Discuss. Faraday Soc. 1947, 2, 328-337.
65. Pryor, W. A.; Coco, J. H. Macromolecules 1970, 3, 500-508.