Controlled/living ring-closing cyclopolymerization of diallyldimethylammonium chloride via the reversible addition fragmentation chain transfer process

Assem, Y., Chaffey-Millar, H., Barner-Kowollik, C., Wegner, G., & Agarwal, S. (2007) Controlled/living ring-closing cyclopolymerization of diallyldimethylammonium chloride via the reversible addition fragmentation chain transfer process. Macromolecules, 40(11).

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For the first time, controlled/living free-radical polymerization of a cyclopolymerizing monomer, that is diallyldimethylammonium chloride (DADMAC), was achieved via reversible addition fragmentation chain transfer (RAFT) chemistry in the presence of both trithiocarbonate and xanthate RAFT/macromolecular design via the interchange of xanthate (MADIX) agents in aqueous solution at 60, 80, and 90 °C. The structural characterization of the polymers was achieved via nuclear magnetic resonance spectrometry, indicating that during the RAFT polymerization of DADMAC, identical to its equivalent conventional free radical polymerization, five-membered rings are formed almost exclusively. In the case of the trithiocarbonate agent, there was excellent agreement between the theoretical and experimental number average molecular weights, Mn, with narrow polydispersities (approaching polydispersity index (PDI) ≈ 1.10) being observed (2100 g mol-1 < Mn < 51 000 g mol-1). Chain extension was carried out by sequential batchwise addition of the monomer, confirming the living character of the system. However, the increase in Mn with respect to conversion was not linear in the case of the xanthate agent, yet the PDIs were as low as 1.12, indicating that control was achieved. The inclusion of NaCl into the reaction mixture reduces of the rate of polymerization for both RAFT agents. Such an observation supports the hypothesis that electrostatic repulsion is crucial to fragmentation of the primary propagating radicals from the adduct RAFT radical; that is, it appears that an electrostatic interaction is affecting the (chemical) RAFT equilibrium. © 2007 American Chemical Society.

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ID Code: 99140
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :35
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, University of New South WalesAustralia; email:
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Keywords: Electrostatics, Free radical polymerization, Macromolecules, Magnetic resonance spectroscopy, Monomers, Solutions, Cyclopolymerizing monomers, Diallyldimethylammonium chloride, Reversible addition fragmentation chain transfer (RAFT), Ring-closing cyclopolymerization, Ammonium compounds
DOI: 10.1021/ma0629079
ISSN: 00249297
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: 06 Oct 2016 03:00

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