Living cationic polymerization of vinyl ether with methanol/metal chloride initiating systems: Relationship between polymerization behavior and the nature of lewis acids

Macromolecules

Volumn 43, Issue 6, 2010, Pages 2739-2747

  Kanazawa, Arihiro ^a   Kanaoka, Shokyoku ^a   Aoshima, Sadahito ^a  

^a OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CENTRAL METALS; CHLORIDE ANIONS; CONTROLLED POLYMERIZATION; DORMANT SPECIES; ETHYL ACETATES; EXCHANGE REACTION; ISOBUTYL; LEWIS ACID; LIVING CATIONIC POLYMERIZATION; MALDI TOF MS; MATRIX-ASSISTED LASER DESORPTION IONIZATION; METAL CHLORIDES; METAL HALIDE; METHOXY GROUP; NMR ANALYSIS; POLYMERIZATION BEHAVIOR; PROPAGATION REACTION; PROTONIC ACID; RAPID EQUILIBRIUM; REACTION MIXTURE; TIME OF FLIGHT MASS SPECTROMETRY;

ACIDS; CHLORINE COMPOUNDS; DESORPTION; ESTERS; ETHERS; LIVING POLYMERIZATION; MASS SPECTROMETRY; METAL HALIDES; METHANOL; NEGATIVE IONS; POLYACRYLATES; POLYMERS;

CATIONIC POLYMERIZATION;

EID: 77951889802     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma902616j     Document Type: Article

References (44)

1. For reviews on living cationic polymerization, see: (a) Sawamoto, M. Prog. Polym. Sci 1991, 16, 111-172.
2. (b) Kennedy, J. P.; Ivan, B. Designed Polymers by Carbocationic Macromolecular Engineering: Theory and Practice; Hanser: New York, 1992.
3. (c) Matyjaszewski, K.; Sawamoto, M. In Cationic Polymerizations; Matyjaszewski, K., Ed.; Marcel Dekker; New York, 1996; Chapter 4.
4. (d) Kennedy, J. P. , J. Polym. Sci, Part A: Polym. Chem. 1999, 37, 2285-2293.
5. (e) Puskas, J. E.; Kaszas, G. Prog. Polym. Sci 2000, 25, 403-452.
6. (f) De, P.; Faust, R. In Macromolecular Engineering. Precise Synthesis, Materials Properties, Applications; Matyjaszewski, K., Gnanou, Y., Leibler, L., Eds.; Wiley-VCH GmbH & Co. KGaA: Weinheim, Germany, 2007; Chapter 3.
7. (g) Aoshima, S.; Yoshida, T.; Kanazawa, A.; Kanaoka, S., J. Polym. Sci, Part A: Polym. Chem. 2007, 45, 1801-1813.
8. Higashimura, T.; Miyamoto, M.; Sawamoto, M. Macromolecules 1985, 18, 611-616.
9. Aoshima, S.; Higashimura, T. Macromolecules 1989, 22, 1009-1013.
10. Kim, Y. H.; Heitz, T. Makromol. Chem., Rapid Commun. 1990, 11, 525-533.
11. Schappacher, M.; Deffieux, A. Macromolecules 1991, 24, 2140-2142.
12. Kamigaito, M.; Sawamoto, M.; Higashimura, T. Macromolecules 1991, 24, 3988-3992.
13. Kamigaito, M.; Sawamoto, M.; Higashimura, T. Macromolecules 1992, 25, 2587-2591.
14. Kanazawa, A.; Kanaoka, S.; Aoshima, S. Macromolecules 2009, 42, 3965-3972.
15. Kishimoto, Y.; Aoshima, S.; Higashimura, T. Macromolecules 1989, 22, 3877-3882.
16. Yoshida, T.; Tsujino, T.; Kanaoka, S.; Aoshima, S., J . Polym. Sci, Part A: Polym. Chem. 2005, 43,468-472.
17. Kanazawa, A.; Hirabaru, Y.; Kanaoka, S.; Aoshima, S., J. Polym. Sci, Part A: Polym. Chem. 2006, 44, 5795-5800.
18. Baaz, M.; Gutmann, V. In Friedel-Crafts and Related Reactions; Olah, G. A., Ed.; Interscience; New York, 1963; Vol. 1, Chapter 5.
19. Guo, Q.; Miyaji, T.; Hara, R.; Shen, B.; Takahashi, T. Tetrahedron 2002, 58, 7327-7334.
20. Masuda, T.; Yoshimura, T.; Fujimori, J.; Higashimura, T., J. Chem. Soc, Chem. Commun. 1987, 1805-1806.
21. Masuda, T.; Mishima, K.; Fujimori, J.; Nishida, M.; Muramatsu, H.; Higashimura, T. Macromolecules 1992, 25, 1401-1404.
22. In the following studies, sec- or ferf-alcohols are used as initiators which generate sec- or ferf-carbocation via the abstraction of the OH group for conventional or living cationic polymerization of isobutene or styrènes: (a) Nguyen, H. A.; Kennedy, J. P. Polym. Bull. 1981, 6, 47-54.
23. (b) Mishra, M. K.; Chen, C. C.; Kennedy, J. P. Polym. Bull. 1989, 22, 455-462.
24. (c) Chen, C. C.; Kaszas, G.; Puskas, J. E.; Kennedy, J. P. Polym. Bull. 1989, 22, 463-470.
25. (d) Kaszas, G.; Puskas, J. E.; Chen, C. C.; Kennedy, J. P. Polym. Bull. 1988, 20, 413-419.
26. (e) Satoh, K.; Kamigaito, M.; Sawamoto, M. Macromolecules 2000, 33, 5405-5410.
27. (f) Satoh, K.; Nakashima, J.; Kamigaito, M.; Sawamoto, M. Macromolecules 2001, 34, 396-401.
28. 2/ dimethyl sulfide initiating system, see: Nakatani, K.; Ouchi, M.; Sawamoto, M., J. Polym. Sci, Part A: Polym. Chem. 2009, 47, 4194-4201.
29. Higashimura, T.; Kamigaito, M.; Kato, M.; Hasebe, T.; Sawamoto, M. Macromolecules 1993, 26, 2670-2673.
30. Katayama, H.; Kitaguchi, H.; Kamigaito, M.; Sawamoto, M. , J. Polym. Sci, Part A: Polym. Chem. 2000, 38, 4023-4031.
31. n values (Table 2, entries 2-4) indicate the low efficiency of transfer reactions. This may stem from the moderate basicity (nucleophilicity) of methanol and/ or its much lower concentration than that of IBVE.
32. Denisov, N. T.; Shuvalova, N. I.; Shuvalov, V. F. Zh. Fiz. Khim. 1971, 45, 2796-2799.
33. Funk, H.; Schmeil, F.; Scholz, H. Z. Anorg. Allg. Chem. 1961, 310, 86-89.
34. Modec, B.; Brencic, J. Eur. J. Inorg. Chem. 2005, 1698-1709.
35. Limberg, C.; Parsons, S.; Downs, A. J.; Watkin, D. J., J. Chem. Soc, Dalton Trans. 1994, 1169-1174.
36. 5 into different forms moderated enough to induce living polymerization.
37. n = 1.13. The detailed results will be published in a near future.
38. n values and narrow MWDs.
39. These cases, which are limited to these two Lewis acids, suggest the effect of the sizes of the metals. Silicon and germanium are small atoms that can coordinate four relatively large chloride anions to form the bulky metal tetrachlorides. Thus, the ligand exchange reaction, which liberates one chloride anion to accept the smaller methoxy group, contributes to diminishing the bulkiness around the central metal. This results in an increase in Lewis acidity, which causes larger polymerization rates.
40. Since the product polymers have high molecular weights regardless of monomer conversion, it is believed that the activation energy of the production of the carbocation from the acetal by the catalyst is high and that the equilibrium between the dormant and active species is slow. Under such conditions, the carbocation is hard to produce but, once it is produced, reacts with a lot of monomer molecules to give high molecular weight polymers.
41. Bradley, D. C.; Halim, F. M. Abd-El; Wardlaw, W., J. Chem. Soc. 1950, 3450-3454.
42. Bradley, D. C.; Halim, F. M. Abd-El; Mehrotra, R. C.; Wardlaw, W., J. Chem. Soc. 1952, 4960-4963.
43. Perkins, P. G., J. Inorg. Nucl. Chem. 1966, 28, 2599-2602.
44. Ault, B. S.; Everhart, J. B., J. Phys. Chem. 1996, 100, 15726-15730.