Abstract
n-Butyllithium-initiated ring-opening polymerization of ethylene oxide with potassium t-butoxide in the mixture of benzene and dimethyl sulfoxide (DMSO) at 35 °C yielded corresponding “living” polymeric alkoxide. The molecular weight was well controlled on the basis of stoichiometric balance. Quantitative chain-end functionalizations, such as the amination, the azidation, and the thiolation of polymeric alkoxide, were performed. The yields were almost quantitative (over 98 mol%). The resulting products were characterized by the combination of 1H NMR spectroscopy, UV/Visible spectroscopy, FTIR, MALDI-TOF MS analysis, and size exclusion chromatographic analysis.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Advances in lithium-ion batteries, B. Scrosati and W. Schalkwijk, Eds., Plenum, New York, 2002.
J.-M. Tarascon and M. Armand, Nature, 414, 359 (2001).
F. Croce, R. Curini, A. Martinelli, L. Persi, F. Ronci, B. Scrosati, and R. Caminiti, J. Phys. Chem. B, 103, 10632 (1999).
D. Swierczynski, A. Zalewska, and W. Wieczorek, Chem. Mater., 13, 1560 (2001).
H.-M. Xiong, D.-P. Liu, H. Zhang, and J.-S. Chen, J. Mater. Chem., 14, 2775 (2004).
J. M. Harris and R. B. Chess, Nat. Rev. Drug Discovery, 2, 214 (2003).
R. Duncan, Nat. Rev. Drug Discovery, 2, 347 (2003).
M. Sharpe, S. E. Easthope, G. M. Keating, and H. M. Lamb, Drugs, 62, 2089 (2002).
R. Satchi-Tainaro, R. Duncan, and C. M. Barnes, Adv. Polym. Sci., 193, 1 (2006).
J.-F. Lutz and A. Hoth, Macromolecules, 39, 893 (2006).
T.-L. Cheng, C.-M. Cheng, B.-M. Chen, S.-A. Tsao, K.-H. Chuang, S.-W. Hsiao, Y.-H. Lin, and S.-R. Roffler, Bioconjug. Chem., 16, 1225 (2005).
W. S. Shim, J. S. Lee, and D. S. Lee, Macromol. Res., 13, 344 (2005).
R. P. Quirk, Anionic Synthesis of Polymers with Functional Groups, in Comprehensive Polymer Science, S. L. Aggarwal and S. Russo, Eds., Pergamon Press, Oxford, 1992, Suppl. Vol., Chap. 5, pp 82–106.
R. P. Quirk and J. Kim, Macromonmers and Macroinitiators, in Ring-opening Polymerization; Mechanisms, Catalysis, Structure, Utility, D. J. Brunelle, Ed., Hanser, New York, 1993, Chap. 9, pp 263–293.
S. Slomkowski and A. Duda, Anionic Ring-Opening Polymerization, in Ring-opening Polymerization; Mechanisms, Catalysis, Structure, Utility, D. J. Brunelle, Ed., Hanser, New York, 1993, Chap. 3, pp 87–128.
H. L. Hsieh and R. P. Quirk, Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, New York, 1996, Chap. 24, pp 685–710.
D. H. Richards and M. Szwarc, Trans. Faraday Soc., 55, 1644 (1959).
L. E. St. Pierre and C. C. Price, J. Am. Chem. Soc., 78, 3432 (1956).
B. Esswein and M. Moller, Angew. Chem. Int. Ed. Engl., 35, 623 (1996).
R. P. Quirk, J. Kim, C. Kausch, and M. Chun, Polym. Int., 39, 3 (1996).
R. P. Quirk, J. Kim, K. Rodrigues, and W. L. Mattice, Makromol. Chem. Macromol. Symp., 42/43, 463 (1991).
J. Kim, S. Choi, K. M. Kim, D. H. Go, H. J. Jeon, J. Y. Lee, H. S. Park, C. H. Lee, and H. M. Park, Macromol. Res., 15, 337 (2007).
J. H. Maeng, D. H. Lee, K. H. Jung, Y. H. Bae, I.-S. Park, S. Jeong, S.; Y. S. Jeon, C.-K. Shim, W. Kim, J. Kim, J. Lee, Y.-M. Lee, J.-H. Kim, W. H. Kim, and S. S. Hong, Biomaterials, 31, 4995 (2010).
H. Gilman and F. K. Cartledge, J. Organomet. Chem., 2, 447 (1964).
C. C. Price and D. D. Carmelite, J. Am. Chem. Soc., 88, 4039 (1966).
C. E. H. Bawn, A. Ledwith, and N. McFarlane, Polymer, 10, 653 (1969).
S. Hiki and K. Kataoka, Bioconjug. Chem., 21, 248 (2010).
R. P. Quirk, T. Yoo, Y. Lee, J. Kim, and B. Lee, Adv. Polym. Sci., 153, 68 (2000).
H. J. Jeon, D. H. Go, S. Choi, K. M. Kim, J. Y. Lee, D. J. Choo, H.-O. Yoo, J. M. Kim, and J. Kim, Colloids Surf. A: Physicochem. Eng. Asp., 317, 496 (2008).
M. S. Thompson, T. P. Vadala, M. L. Vadala, Y. Lin, and J. S. Riffle, Polymer, 49, 345 (2008).
A.-L. Brocas, C. Mantzaridis, D. Tunc, and S. Carlotti, Prog. Polym. Sci., 38, 845 (2013).
M. A. Tasdelen, M. U. Kahveci, and Y. Yagci, Prog. Polym. Sci., 36, 455 (2011).
R. Mahou and C. Wandrey, Polymers, 4, 561 (2012).
L. E. Overman and E. M. O'Connor, J. Am. Chem. Soc., 98, 771 (1976).
R. E. Humphrey and J. M. Hawkins, Anal. Chem., 36, 1812 (1964).
V. Balachandran, T. Karthick, S. Perumal, and A. Nataraj, Ind. J. Pure Appl. Phys., 51, 178 (2013).
S. Yang, Y. Kim, H. C. Kim, A. B. Siddique, G. Youn, H. J. Kim, H. J. Park, J. Y. Lee, S. Kim, and J. Kim, Polym. Chem., DOI: 10.1039/c5py01444a (2015).
W. Siebourg, R. D. Lundberg, and R. W. Lenz, Macromolecules, 13, 1013 (1980).
P. N. D. Singh, S. M. Mandel, R. M. Robinson, Z. Zhu, R. Franz, B. S. Ault, and A. D. Gudmundsdottir, J. Org. Chem., 68, 7951 (2003).
I. V. Koval, Russ. Chem. Rev., 63, 735 (1994).
B. Li, M. Berliner, R. Buzon, C. K.-F. Chiu, S. T. Colgan, T. Kaneko, N. Keene, W. Kissel, T. Le, K. R. Leeman, B. Marquez, R. Morris, L. Newell, S. Wunderwald, M. Witt, J. Weaver, Z. Zhang, and Z. Zhang, J. Org. Chem., 71, 9045 (2006).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Kim, S.W., Siddique, A.B., An, J.W. et al. Quantitative ω-amination, ω-azidolysis, and ω-thiolation of poly(ethylene oxide)s through anionic mechanism. Macromol. Res. 24, 188–195 (2016). https://doi.org/10.1007/s13233-016-4023-7
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13233-016-4023-7