RAFT mediated polymerization of methyl methacrylate initiated by bergman cyclization: Access to high molecular weight narrow polydispersity polymers

Gerstel, P. & Barner-Kowollik, C. (2011) RAFT mediated polymerization of methyl methacrylate initiated by bergman cyclization: Access to high molecular weight narrow polydispersity polymers. Macromolecular Rapid Communications, 32(5).

View at publisher


The first RAFT mediated polymerization of methyl methacrylate initiated by diradicals derived from Bergman cyclization was performed employing 3,4-benzocyclodec-3-ene-1,5-diyne (BCDY) as diradical source and cyanoisopropyldithiobenzoate (CPDB) as RAFT agent. The polymerization was conducted in bulk at 80°C for 3h. The concentration of the enediyne was kept constant at 3.0× 10-2 mol ·L-1 and the RAFT agent concentration was varied between 0.0mol ·L-1 and 2.4× 10-1 mol ·L-1. A detailed ESI-MS analysis reveals the absence of intramolecular termination reactions (ring formation) in the RAFT mediated system, which usually makes diradicalic initiation unfavorable. The presence of polymeric chains propagating at both ends could be confirmed. The conversion of the RAFT mediated polymerization was up to more than two times higher than the RAFT free polymerization at identical conditions. Thus, polymers with narrow polydispersities (1.1 ≤ PDI ≤ 1.5) even at very high molecular weights (near 400000Da) were obtained within modest reaction times. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact and interest:

4 citations in Scopus
Search Google Scholar™
4 citations in Web of Science®

Citation counts are sourced monthly from Scopus and Web of Science® citation databases.

These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.

Citations counts from the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

ID Code: 99269
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :4
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76128 Karlsruhe, Germany; email: christopher.barner-kowollik@kit.edu
Chemicals/CAS: methacrylic acid methyl ester, 80-62-6; Methacrylates; Methylmethacrylate; Polymers
References: Moad, G., Barner-Kowollik, C., The Mechanism and Kinetics of the RAFT Process: Overview, Rates, Stabilities, Side Reactions, Product Spectrum and Outstanding Challenges (2008) Handbook of RAFT Polymerization, p. 51. , in:, 1st edition, C. Barner-Kowollik, Ed., Wiley-VCH, Weinheim, p. ff; Moad, G., Rizzardo, E., Thang, S.H., (2005) Aust. J. Chem., 58, p. 379; Moad, G., Rizzardo, E., Thang, S.H., (2006) Aust. J. Chem., 59, p. 669; Moad, G., Rizzardo, E., Thang, S.H., (2009) Aust. J. Chem., 62, p. 1402; Vana, P., Davis, T.P., Barner-Kowollik, C., (2002) Macromol. Theory Simul., 11, p. 823; Rzayev, J., Penelle, J., (2004) Angew. Chem., Int. Ed., 43, p. 1691; Zhang, Z., Zhu, X., Zhu, J., Cheng, C., (2006) Polymer, 47, p. 6970; Haward, R.N., (1950) Trans. Faraday Soc., 46, p. 204; Toplikar, E.G., Herman, M.S., Padias, A.B., Hall, H.K., Priddy, D.B., (1997) Polymer Bulletin, 39, p. 37; Rule, J.D., Wilson, S.R., Moore, J.S., (2003) J. Am. Soc., 125, p. 12992; Bergman, R.G., (1973) Acc. Chem. Res., 6, p. 25; Lee, M.D., Dunne, T.S., Siegel, M.M., Chang, C.C., Morton, G.O., Borders, D.B., (1987) J. Am. Chem Soc., 109, p. 3464; Sherer, E.C., Kirschner, K.N., Pickard, F.C., Rein, C., Feldgus, S., Shields, G.C., (2008) J. Phys. Chem. B, 112, p. 16917; Grissom, J.W., Gunawardena, G.U., Klingberg, D., Huang, D., (1996) Tetrahedron, 52, p. 6453; Kar, M., Basak, A., (2007) Chem. Rev., 107, p. 2861; Zeidan, T.A., Kovalenko, S.V., Manoharan, M., Alabugin, I.V., (2006) J. Org. Chem., 71, p. 962; Nicolaou, K.C., Zuccarello, G., Ogawa, Y., Schweiger, E.J., Kumazawa, T., (1988) J. Am. Chem. Soc., 110, p. 4866; Iida, K., Hirama, M., (1995) J. Am. Chem. Soc., 117, p. 8875; John, J.A., Tour, J.M., (1994) J. Am. Chem. Soc., 116, p. 5011; Bhongale, C.J., Yang, C., Hsu, C., (2006) Chem. Commun., p. 2274; Martin, S.J., (1998) J. Am. Chem. Soc., 120, p. 9078; Cheng, X., Ma, J., Zhi, J., Yang, X., Hu, A., (2010) Macromol., 43, p. 909; Rule, J.D., Moore, J.S., (2005) Macromol., 38, p. 7266; Thang, S.H., Chong, Y.K., Mayadunne, R.T.A., Moad, G., Rizzardo, E., (1999) Tetrahedron Lett., 40, p. 2435; Semmelhack, M.F., Nei, T., Foubelo, F., (1993) Tetrahedron Lett., 23, p. 3277; Semmelhack, M.F., Nei, T., Foubelo, F., (1994) J. Org. Chem., 59, p. 5038; Brandrup, I., Immergut, E., (2003) Polymer Handbook, , 4th edition, Wiley & Sons, New York; Johnston-Hall, G., Theis, A., Monteiro, M.J., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Macromol. Chem. Phys., 206, p. 2047
Keywords: bergmann cyclization, methyl methacrylate, RAFT, Bergman cyclization, Diradicals, Enediynes, High molecular weight, Identical conditions, Methyl methacrylates, Polymeric chain, RAFT agents, RAFT-mediated polymerization, Reaction time, Ring formation, Termination reactions, Acrylic monomers, Esters, Polydispersity, Polymerization, Polymers, Cyclization, methacrylic acid derivative, methacrylic acid methyl ester, polymer, chemical structure, chemistry, molecular weight, Methacrylates, Methylmethacrylate, Molecular Structure
DOI: 10.1002/marc.201000730
ISSN: 10221336
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 05 Oct 2016 03:16

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page