An Efficient Method for Synthesis of PEO-Based Macromonomer and Macroinitiator

Jungahn Kim; Song-yee Choi; Kyung Min Kim; Da Hyeon Go; Hee Jeong Jeon; Jae Yeol Lee; Hyeong Soo Park; Cheol Han Lee; Heung Mok Park

Macromolecular Research, Vol.15, No.4, 337-342, June, 2007

Jungahn Kim^†, Song-yee Choi, Kyung Min Kim, Da Hyeon Go, Hee Jeong Jeon, Jae Yeol Lee, Hyeong Soo Park¹, Cheol Han Lee¹, and Heung Mok Park¹

Research Institute of Basic Sciences and Department of Chemistry, Kyung Hee University, Seoul 130-701, Korea
¹Department of Chemical Engineering, Sogang University, Seoul 121-742, Korea

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The n-butyllithium-initiated ring-opening polymerization of ethylene oxide, in a mixture of benzene and dimethylsulfoxide (DMSO), between 25-45 ℃, with potassium tert-butoxide, is a useful and powerful method to control the molecular weight as well as achieve a quantitative chain-end functionalization yield of the resulting polymeric alkoxide via a one pot synthesis. The molecular weight of the product could be controlled by adjusting the ratio of grams of monomer to moles of initiators, such as n-butyllithium ([n-BuLi]) and potassium t-butoxide ([t-BuOK]). The yields for the macromonomer and -brominated poly(ethylene oxide) (PEO) were quantitative in relation to the chain-end functionalizations of the polymeric alkoxide formed. The resulting products were characterized by a combination of 1H-NMR spectroscopic and size exclusion chromatographic analyses.

Keywords:poly(ethylene oxide);molecular weight control;chain-end functionalizations;macromonomer;macroinitiator

[References]

Advances in lithium-ion batteries, B. Scrosati and W. Schalkwijk, Eds., Plenum, New York (2002)
Tarascon JM, Armand M, Nature, 414, 359 (2001)
Croce F, Curini R, Martinelli A, Persi L, Ronci F, Scrosati B, Caminiti R, J. Phys. Chem. B, 103(48), 10632 (1999)
Swierczynski D, Zalewska A, Wieczorek W, Chem. Mater., 13, 1560 (2001)
Xiong HM, Liu DP, Zhang H, Chen JS, J. Mater. Chem., 14, 2775 (2004)
Harris JM, Chess RB, Nature Rev. Drug Disc., 2, 214 (2003)
Duncan R, Nature Rev. Drug Disc., 2, 347 (2003)
Sharpe M, Easthope SE, Keating GM, Lamb HM, Drugs, 62, 2089 (2002)
Satchi-Tainaro R, Duncan R, Barnes CM, Adv. Polym. Sci., 193, 1 (2006)
Lutz JF, Hoth A, Macromolecules, 39(2), 893 (2006)
Cheng TL, Cheng CM, Chen BM, Tsao SA, Chuang KH, Hsiao SW, Lin YH, Roffler SR, Biconjugate Chem., 16, 1225 (2005)
Shim WS, Lee JS, Lee DS, Macromol. Res., 13(4), 344 (2005)
Quirk RP, Anionic synthesis of polymers with functional groups, in Comprehensive Polymer Science, S. L. Aggarwal and S. Russo, Eds., Pregamon Press, Seoul, 1992, Suppl. Figure. SEC results for polymers shown in Figure 3. Vol., Chap. 5, pp 82-106
Quirk RP, Kim J, Macromonmers and Macroinitiators, in Ring-opening Polymerization; Mechanisms, Catalysis, Structure, Utility, D. J. Brunelle, Ed., Hanser, New York, 1993, Chap. 9, pp 263-293
Slomkowski S, Duda A, 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
Hsieh HL, Quirk RP, Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, New York, 1996, Chap. 24, pp 685-710
Richards DH, Szwarc M, Trans. Faraday Soc., 55, 1644 (1959)
Pierre LE, Price CC, J. Am. Chem. Soc., 78, 3432 (1956)
Esswein B, Moller M, Angew. Chem.-Int. Edit. Engl., 35, 623 (1996)
Quirk RP, Kim J, Kausch C, Chun M, Polym. Int., 39, 3 (1996)
Quirk RP, Kim J, Rodrigues K, Mattice WL, Makromol. Chem. Macromol. Symp., 42/43, 463 (1991)
Morton M, Fetters LJ, Rubber Chem. Technol., 48, 359 (1975)
Stouffer JM, McCarthy TJ, Macromolecules, 21, 1204 (1988)
Gilman H, Cartledge FK, J. Organomet. Chem., 2, 447 (1964)
Napoli A, Tirelli N, Kilcher G, Hubbell JA, Macromolecules, 34(26), 8913 (2001)
Quirk RP, Ma JJ, J. Polym. Sci. A: Polym. Chem., 24, 2031 (1988)
Halaska V, Lochmann L, Lim D, Collect. Czech. Chem. Commun., 33, 3245 (1968)
Figueruelo JE, Worsfold DJ, Eur. Polym. J., 4, 439 (1968)
Schlosser M, J. Organomet. Chem., 8, 9 (1967)
Brandsma L, Verkruijsse H, Preparative Polar Organometallic Chemistry 1, Springer-Verlag, Berlin Heidelberg, 1987, Chap. II, p 41
Bawn CEH, Ledwith A, McFarlane N, Polymer, 10, 653 (1969)
Price CC, Carmelite DD, J. Am. Chem. Soc., 88, 4039 (1966)
Hsieh HL, Quirk RP, Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, New York, 1996, Chap. 4, pp 71-92

[Referenced By]

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[2] Tarascon JM, Armand M, Nature, 414, 359 (2001)

[3] Croce F, Curini R, Martinelli A, Persi L, Ronci F, Scrosati B, Caminiti R, J. Phys. Chem. B, 103(48), 10632 (1999)

[4] Swierczynski D, Zalewska A, Wieczorek W, Chem. Mater., 13, 1560 (2001)

[5] Xiong HM, Liu DP, Zhang H, Chen JS, J. Mater. Chem., 14, 2775 (2004)

[6] Harris JM, Chess RB, Nature Rev. Drug Disc., 2, 214 (2003)

[7] Duncan R, Nature Rev. Drug Disc., 2, 347 (2003)

[8] Sharpe M, Easthope SE, Keating GM, Lamb HM, Drugs, 62, 2089 (2002)

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[10] Lutz JF, Hoth A, Macromolecules, 39(2), 893 (2006)

[11] Cheng TL, Cheng CM, Chen BM, Tsao SA, Chuang KH, Hsiao SW, Lin YH, Roffler SR, Biconjugate Chem., 16, 1225 (2005)

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[13] Quirk RP, Anionic synthesis of polymers with functional groups, in Comprehensive Polymer Science, S. L. Aggarwal and S. Russo, Eds., Pregamon Press, Seoul, 1992, Suppl. Figure. SEC results for polymers shown in Figure 3. Vol., Chap. 5, pp 82-106

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[17] Richards DH, Szwarc M, Trans. Faraday Soc., 55, 1644 (1959)

[18] Pierre LE, Price CC, J. Am. Chem. Soc., 78, 3432 (1956)

[19] Esswein B, Moller M, Angew. Chem.-Int. Edit. Engl., 35, 623 (1996)

[20] Quirk RP, Kim J, Kausch C, Chun M, Polym. Int., 39, 3 (1996)

[21] Quirk RP, Kim J, Rodrigues K, Mattice WL, Makromol. Chem. Macromol. Symp., 42/43, 463 (1991)

[22] Morton M, Fetters LJ, Rubber Chem. Technol., 48, 359 (1975)

[23] Stouffer JM, McCarthy TJ, Macromolecules, 21, 1204 (1988)

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[25] Napoli A, Tirelli N, Kilcher G, Hubbell JA, Macromolecules, 34(26), 8913 (2001)

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[27] Halaska V, Lochmann L, Lim D, Collect. Czech. Chem. Commun., 33, 3245 (1968)

[28] Figueruelo JE, Worsfold DJ, Eur. Polym. J., 4, 439 (1968)

[29] Schlosser M, J. Organomet. Chem., 8, 9 (1967)

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[31] Bawn CEH, Ledwith A, McFarlane N, Polymer, 10, 653 (1969)

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[33] Hsieh HL, Quirk RP, Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, New York, 1996, Chap. 4, pp 71-92