NMP of chloromethylsytrene with minimized PDI: The role of the initiator/nitroxide system and the meta isomer

Macromolecules

Volumn 44, Issue 9, 2011, Pages 3666-3669

  Bultz, Elijah ^a   Bender, Timothy P ^a  

^a UNIVERSITY OF TORONTO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ETHYL BENZOATE; META ISOMERS; NITROXIDE MEDIATED POLYMERIZATION; NITROXIDES; POLYDISPERSITY INDICES; TETRAMETHYL; UNIMOLECULAR INITIATORS;

POLYDISPERSITY;

EID: 79955668288     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma200058f     Document Type: Article

References (17)

1. Sata, T.; Yoshida, T.; Matsusaki, K. J. Membr. Sci. 1996, 120, 101-110
2. Gauthier, M.; Moeller, M. Macromolecules 1991, 24, 4548-4553
3. Monthéard, J. P.; Boinon, B.; Zerroukhi, A.; Cachard, A. Polymer 1992, 33, 3756-3758
4. Komber, H.; Georgi, U.; Voit, B. Macromolecules 2009, 42, 8307-8315
5. Cheng, C. J. Polym. Sci., Part A 2005, 43, 4754-4770
6. Kazmaier, P. M.; Daimon, K.; Georges, M. K.; Hamer, G. K.; Veregin, R. P. N. Macromolecules 1997, 30, 2228-2231
7. Weimer, M. W.; Fréchet, J. M. J.; Gitsov, I. J. Polym. Sci., Part A 1998, 36, 955-970
8. Komber, H.; Georgi, U.; Voit, B. Macromolecules 2009, 42, 8307-8315
9. Tsoukatos, T.; Pispas, S.; Hadjichristidis, N. Macromolecules 2000, 33, 9504-9511
10. See for example: Lin, C.; Gitsov, I. Macromolecules 2010, 43, 10017-10030
11. Xi, Y.; Chandramouleeswaran, S.; Xiaochao, Y.; Chae, K. K.; Vincent, M. R. Macromol. Rapid Commun. 2010, 31, 910-914
12. Georgi, U.; Erber, M.; Stadermann, J.; Abulikemu, M.; Komber, H.; Lederer, A.; Voit, B. J. Polym. Sci., Part A 2010, 48, 2224-2235
13. van der Veen, M. H.; de Boer, B.; Stalmach, U.; van de Wetering, K. I.; Hadziioannou, G. Macromolecules 2004, 37, 3673-3684
14. CMS is available in two different grades: the para isomer sold as "4-chloromethylstyrene" or a technical grade which has a 2:3 ratio of the para and meta isomers sold simply as "chloromethylstyrene", which we will refer to hereafter as 4CMS and tgCMS, respectively. See also Scheme 1.
15. In all polymerizations, the monomer(s) were purified by vacuum distillation immediately before use. Prior to all polymerizations the contents of the reaction vessel were sparged with nitrogen to removed dissolved oxygen, and during polymerization a constant positive pressure blanket of nitrogen was maintained. Samples were taken hourly for GPC and GC analysis until the polymerization was too viscous to stir. Additional experimental details are given in the Supporting Information.
16. Hawker, C. J. J. Am. Chem. Soc. 1994, 116, 11185-11186. The chemical structure of BST and a procedure for its synthesis are given in the Supporting Information
17. A recent study from Georges et al. has shown that for the polymerization of styrene under NMP conditions a rate enhancement is possible through the use of elevated temperatures while maintaining good control over the polymerization due to the use of an excess of TEMPO. The excess nitroxide is claimed to allow for a higher temperature to be employed while maintaining the equilibrium between TEMPO-capped alkoxyamine and active propagating radicals at a point whereby termination processes are minimized. See: Dollin, M.; Szkurhan, A. R.; Georges, M. K. J. Polym. Sci., Part A 2007, 45, 5487-5493