Abstract
In the “cycloketyl radical mediated living polymerization” (CMP) process, a cycloketyl compound, [9,9′]bixanthenyl-9,9′diol (BIXAN) was ultilized as initiator and mediator. The cycloketyl (CK) radical was used as the dormant radical to achieve the increase of molecular weight. Herein, a series of cycloketyl thioketones were synthesised by Lawesson’s reagent by one step reaction with high yeild, and we found that, when a special cycloketyl thioketone compound, thioxanthene-9-thione (TXT), was added to a routine radical polymerization system, TXT could capture chain radical, and simultaneously formed an radical analogous to CK radical in structure, which could trigger the growth of polymer chains. This simple system was efficient to initiate the polymerization of methyl methacrylate (MMA) and in all cases the molecular weights increased with the increase of conversions. By the end-group analysis with 1H-NMR and MALDI-TOF MS, it was confirmed that the P-STXT radical was used to control the polymerization. The re-initiating reactions were achieved when PMMA was used as the macro-initiator.
This is a preview of subscription content, log in via an institution to check access.
References
Hawker, C. J.; Bosman, A. W.; Harth, E. New polymer synthesis by nitroxide mediated living radical polymerizations. Chem. Rev. 2001, 101, 3661–3688
Nicolas, J.; Guillaneuf, Y.; Lefay, C.; Bertin, D.; Gigmes, D.; Charleux, B. Nitroxide-mediated polymerization. Prog. Polym. Sci. 2013, 38, 63–235
Matyjaszewski, K. Atom transfer radical polymerization. Chem. Rev. 2001, 101, 2921–2990
Matyjaszewski, K.; Tsarevsky, N. V. Macromolecular, engineering by atom transfer radical polymerization. J. Am. Chem. Soc. 2014, 136, 6513–6533
Moad, G.; Rizzardo, E.; Thang. S. H. Radical additionfragmentation chemistry in polymer synthesis. Polymer 2008, 49, 1079–1131
Yagci, Y.; Tasdelen, M. A. Mechanistic transformations involving living and controlled/living polymerization methods. Prog. Polym. Sci. 2006, 31, 1133–1170
Magenau, A. J. D.; Strandwitz, N. C.; Matyjaszewski, K. Electrochemically mediated atom transfer radical polymerization. Science 2011, 332, 81–84
Zheng, X. F.; Yue, M.; Yang, P.; Li, Q.; Yang, W. T. Cycloketyl radical mediated living polymerization. Polym. Chem. 2012, 3, 1982–1986
Toy, A.; Chaffey-Millar, H.; Davis, T. P.; Stenzel, M. H.; Izgorodina, E. I.; Coote, M. L.; Barner-Kowollik, C. Thioketone spin traps as mediating agents for free radical polymerization processes. Chem. Commun. 2006, 8(8), 835–837
Junkers, T.; Stenzel, M. H.; Davis, T. P.; Barner-Kowollik, C. Controlling free-radical polymerization via a dormant radical species. Macromol. Rapid Commun. 2007, 28, 746–753
Gunzler, F.; Junkers, T.; Barner-Kowollik, C. Studying the mechanism of thioketone-mediated polymerization via electrospray ionization mass spectrometry. J. Polym. Sci., Part A: Polym. Chem. 2009, 47(7), 1864–1876
Junkers, T.; Delaittre, G.; Chapman, R.; Gunzler, F.; Chernikova, E.; Barner-Kowollik, C. Thioketone-mediated polymerization with dithiobenzoates: proof for the existence of stable radical intermediates in RAFT polymerization. Macromol. Rapid Commun. 2012, 33, 984–990
Varma, R. S.; Kumar, D. Microwave-accelerated solvent-free synthesis of thioketones, thiolactones, thioamides, thionoesters, and thioflavonoids. Org. Lett. 1999, 1, 697–700.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (Nos. 21404004, 51521062, 51221002, 51103009, and 51473015) and the Innovation and Promotion Project of Beijing University of Chemical Technology.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Yan, X., Wang, G., Zhang, LH. et al. Thioxanthene-9-thione Mediated MMA Polymerization. Chin J Polym Sci 36, 805–810 (2018). https://doi.org/10.1007/s10118-018-2140-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10118-018-2140-9