Cationic polymerization of isobutyl vinyl ether using alcohols both as cationogen and catalyst-modifying reagent: Effect of lewis acids and alcohols on living nature

Journal of Polymer Science, Part A: Polymer Chemistry

Volumn 48, Issue 11, 2010, Pages 2509-2516

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

^a OSAKA UNIVERSITY   (Japan)

Author keywords

Alcohol; Cationic polymerization; Lewis acid; Living polymerization; Poly(vinyl ethers)

Indexed keywords

1 ,4-DIOXANE; ANHYDROUS ALCOHOLS; CALCIUM HYDRIDE; ETHYL ACETATES; ISO-PROPANOLS; ISOBUTYL; LEWIS ACID; LITHIUM ALUMINUM HYDRIDE; POLY(VINYL ETHERS); REDUCED PRESSURE; TERT BUTANOL; TRIMETHYLSILYL; VINYL ETHERS;

ACIDS; CALCIUM; CHLORINE; CHROMATOGRAPHIC ANALYSIS; ESTERS; ETHERS; GELS; LITHIUM; LIVING POLYMERIZATION; METHANE; METHANOL; MOLECULAR WEIGHT DISTRIBUTION; ORGANIC POLYMERS; POLYMERS; POLYSTYRENES;

CATIONIC POLYMERIZATION;

EID: 77952127436     PISSN: 0887624X     EISSN: 10990518     Source Type: Journal    
DOI: 10.1002/pola.24009     Document Type: Article

References (35)

1. Kaminsky, W. J Polym Sci Part A: Polym Chem 2004, 42, 3911-3921.
2. Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem Rev 2000, 100, 1169-1203.
3. Coates, G. W. Chem Rev 2000, 100, 1223-1252.
4. Matsugi, T.; Fujita, T. Chem Soc Rev 2008, 37, 1264-1277.
5. Kamigaito, M.; Ando, T.; Sawamoto, M. Chem Rev 2001, 101, 3689-3745.
6. Matyjaszewski, K.; Xia, J. Chem Rev 2001, 101, 2921-2990.
7. For reviews: (a) Sawamoto, M. Prog Polym Sci 1991, 16, 111-172;
8. (b) Kennedy, J. P.; Ivan, B. Designed Polymers by Carbocationic Macromolecular Engineering: Theory and Practice; Hanser: New York, 1992;
9. (c) Matyjaszewski, K.; Sawamoto, M. In Cationic Polymerizations; Matyjaszewski, K.; Ed.; Marcel Dekker: New York, 1996; Chapter 4;
10. (d) Kennedy, J. P. J Polym Sci Part A: Polym Chem 1999, 37, 2285-2293;
11. (e) Puskas, J. E.; Kaszas, G. Prog Polym Sci 2000, 25, 403-452;
12. (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, 2007; Chapter 3;
13. (g) Goethals, E. J.; Prez, F. D. Prog Polym Sci 2007, 32, 220-246;
14. (h) Aoshima, S.; Kanaoka, S. Chem Rev 2009, 109, 5245-5287.
15. Kanazawa, A.; Kanaoka, S.; Aoshima, S. Macromolecules 2009, 42, 3965-3972.
16. Kanazawa, A.; Kanaoka, S.; Aoshima, S. Macromolecules 2010, 43, 2739-2747.
17. 2/dimethyl sulfide initiating system, see: Nakatani, K.; Ouchi, M.; Sawamoto, M. J Polym Sci Part A: Polym Chem 2009, 47, 4194-4201.
18. Kamigaito, M.; Sawamoto, M.; Higashimura, T. Macromolecules 1995, 28, 5671-5675.
19. Katayama, H.; Kitaguchi, H.; Kamigaito, M.; Sawamoto, M. J Polym Sci Part A: Polym Chem 2000, 38, 4023-4031.
20. 1H NMR analyses (Supporting Information Fig. S2). The product polymers had proton α-ends derived from the scission between H and OtBu.
21. Mishra, M. K.; Chen, C. C.; Kennedy, J. P. Polym Bull 1989, 22, 455-462.
22. n values were similar (Supporting Information Fig. S3). The initiating species in these systems are considered to be protic impurities such as adventitious water (water is confirmed to function as a good cationogen with these metal chlorides).
23. 5 to MeOH, which give polymers with a single series of peaks, the chain-end only with carbon-chlorine bonds existed during the polymerization.
24. 4 (Supporting Information Rg. S4), which confirms the production of protic acids by the reaction between the two components.
25. 4, moderate amounts of the second peaks (mass value: +42) were present in the lower MW region, although almost only a single series of peaks corresponding to the structures with chain-ends derived from the quencher existed in the higher MW region.
26. 4 gave small amounts of two other kinds of peaks. The differences in value from the main peaks were about +30 and +68. Some reactions such as crosslinking may be involved by the surplus ethylene glycol, although the detailed mechanisms and structures were not clear.
27. 22,23 The difference is explained to be due to the solvation present in the former case. The gas phase order is attributed to the effect of the polarizability. Thus, the results obtained in this study may stem from the sum of various effects including these factors.
28. Bordwell, F. G. Acc Chem Res 1988, 21, 456-463.
29. Brauman, J. I.; Blair, L. K. J Am Chem Soc 1968, 90, 6561-6562.
30. Brauman, J. L; Blair, L K. J Am Chem Soc 1970, 92, 5986-5992.
31. 5 (5.0 or 10 mM/5.0 mM) combinations produced uncontrolled polymers with higher MW along with living polymers (Supporting Information Fig. S6). The results indicated that the Lewis acidity of the metal halides examined in this study was moderated for living polymerization by the effective interaction with a central metal, in addition to the tuning of the electron density of a central metal through the ligand exchange.
32. Bradley, D. C.; Chakravarti, B. N.; Wardlaw, W. J Chem Soc 1956, 4439-4442.
33. Bradley, D. C.; Mehrotra, R. C.; Wardlaw, W. J Chem Soc 1952, 4204-4209.
34. 5 may result from the coordination of the OtBu or the second oxo group.
35. 4(OMe) + HCl. The fast exchanges also support the highly efficient reactions generating protic species which function as cationogens for cationic polymerization.