Controlled/"living" radical polymerization of methyl methacrylate by atom transfer radical polymerization

Macromolecules

Volumn 30, Issue 7, 1997, Pages 2216-2218

  Grimaud, Thomas ^a   Matyjaszewski, Krzysztof ^a  

^a CARNEGIE MELLON UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST ACTIVITY; CATALYST DEACTIVATION; COMPLEXATION; FREE RADICAL POLYMERIZATION; INITIATORS (CHEMICAL); MOLECULAR WEIGHT; MONOMERS; REACTION KINETICS; SYNTHESIS (CHEMICAL);

ATOM TRANSFER RADICAL POLYMERIZATION; BIPYRIDINE LIGANDS; CONTROLLED RADICAL POLYMERIZATION; LIVING RADICAL POLYMERIZATION; POLYDISPERSITY;

POLYMETHYL METHACRYLATES;

EID: 0031557566     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma961796i     Document Type: Article

References (30)

1. Webster, O. Science 1991, 251, 887.
2. Szwarc, M. Carbanions, Living Polymers and Electron Transfer Processes; Interscience Publishers: New York, 1968.
3. Matyjaszewski, K. Cationic Polymerizations; Marcel Dekker: New York, 1996.
4. Webster, O. W.; Hertler, W. R.; Sogah, D. Y.; Farnham, W. B.; RajanBabu, T. V. J. Am. Chem. Soc. 1983, 105, 5706.
5. Solomon, D. H.; Rizzardo, E.; Cacioli, P. Eur. Pat. Appl. EP 135280, 1985.
6. Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K. Macromolecules 1993, 26, 2987.
7. Greszta, D.; Mardare, D.; Matyjaszewski, K. Macromolecules 1994, 27, 638.
8. Wayland, B. B.; Pszmik, G.; Mukerjee, S. L.; Fryd, M. J. Am. Chem. Soc. 1994, 116, 7943.
9. Wang, J. S.; Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117, 5614.
10. Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T. Macromolecules 1995, 28, 1721.
11. Patten, T. E.; Xia, J.; Abernathy, T.; Matyjaszewski, K. Science 1996, 272, 866.
12. Curran, D. P. Synthesis 1988, 489.
13. Bellus, D. Pure Appl. Chem. 1985, 57, 1827.
14. Kharasch, M. S.; Jensen, E. V.; Urry, W. H. Science 1944, 102, 128.
15. Wang, J. S.; Matyjaszewski, K. Macromolecules 1995, 28, 7901.
16. Gaynor, S. G.; Edelman, S. Z.; Matyjaszewski, K. Macromolecules 1996, 29, 1079.
17. Greszta, D.; Matyjaszewski, K. ACS Polym. Prepr. 1996, 37 (1), 569.
18. Nakagawa, Y.; Matyjaszewski, K. ACS Polym. Prepr. 1996, 37 (2), 270.
19. Ando, T.; Kato, M.; Kamigaito, M.; Sawamoto, M. Macromolecules 1996, 29, 1070.
20. 1H NMR: 8.55 ppm (d), 8.2 (d), 7.0 (d), 2.6 (d), 1.5-1.7 (m), 1-1.35 (m), 0.8 (t).
21. n < 30 000) under dry argon or in sealed tubes under vacuum for higher molecular weights. Methyl methacrylate was filtered through an alumina column and then dried over molecular sieves, degassed by argon bubbling, and stored under argon. Diphenyl ether was dried over molecular sieves, degassed and stored in the same way. Copper bromide was purified with glacial acetic acid and washed with pure ethanol, then stored under argon p-Toluenesulfonyl chloride was used as received. When using a Schlenk flask, all reagents were added except initiator, and the mixture was degassed three times by freeze-pump-thaw cycles. The mixture was heated sit reaction temperature (90 °C) until homogeneous (about 2 min) and then initiator was added. When using sealed tubes, a single solution (5 mL of MMA + 5 mL of DPE + catalyst and ligand) was prepared for all the tubes. Then 2 mL of the reaction mixture was distributed to each tube, initiator was added, and the reaction mixture was degassed three times before sealing under vacuum. The resulting polymer solutions were cooled down after sampling, dissolved in THF and analyzed by gas chromatography (residual concentration of monomer is determined with dodecane as an internal standard). Prior to injection on to the SEC, samples were passed through a neutral alumina column in order to remove catalyst. SEC calibration curves were calculated with polydnethyl methacrylate) standards from Polymer Laboratories.
22. Percec, V.; Barboiu, B. Macromolecules 1995, 28, 7970.
23. Percec, V.; Barboiu, B.; Neumann, A.; Ronda, J. C.; Zhao, M. Macromolecules 1996, 29, 3665.
24. 0 is the molecular weight of monomer and p is the conversion.
25. n = 1.13).
26. Buback, M.; Gilbert, R. G.; Hutchinson, R. A; Klumperman, B.; Kuchta, F.-D.; Manders, B. G., O'Driscoll, K. P.; Russell, G. T.; Schweer, J. Macromol. Chem. Phys. 1995, 196, 3267.
27. -1 respectively.
28. Buback, M.; Gilbert, R. G.; Ruseell, G. T.; Hill, J. T.; Moad, G.; O'Driscoll, K. F.; Shen, J.; Winnik, M. A. J. Polym. Sci., Polym. Chem. Ed. 1992, 30, 851.
29. Bengouh, W. I.; Fairservice, W. H. Trans. Faraday Soc. 1965, 61, 1206.
30. Beagouh, W. I.; Fairservice, W. H. Trans. Faraday Soc. 1971, 67, 414.