A comparison of the cationic ring-opening polymerizations of 3-oxetanol and glycidol

A. Timothy Royappa; Mitra R. Vashi; Cholena L. Russo; Aaron C. Blackwell

Macromolecular Research, Vol.21, No.10, 1069-1074, October, 2013

DOI10.1007/s13233-013-1151-1 Export Citation

A comparison of the cationic ring-opening polymerizations of 3-oxetanol and glycidol

A. Timothy Royappa^†, Mitra R. Vashi, Cholena L. Russo, and Aaron C. Blackwell

Department of Chemistry, University of West Florida, 11000 University Parkway, Pensacola, FL, 32514, USA

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The technologically important polymers poly(3-oxetanol) and polyglycidol (sometimes referred to as polyglycerol) were both synthesized in high yield by a one-pot BF3-catalyzed cationic ring-opening polymerization of the respective monomers in dichloromethane at ambient temperature. The polymerization reactions and the resulting polymers were compared. The polymerization of 3-oxetanol was less exothermic than the polymerization of glycidol under identical reaction conditions, because of the lower ring strain in 3-oxetanol than in glycidol, confirmed by semi-empirical calculations. The resulting polymers were similar, i.e., they had similar Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) spectra, molecular weights, thermal properties and physical characteristics. However, the poly(3-oxetanol) had a higher ratio of secondary to primary alcohols than did polyglycidol.

Keywords:hyperbranched polymer;polyether-polyol;polyglycidol;poly(3-oxetanol);polyglycerol;cationic polymerization;ring-opening polymerization

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[2] Sunder A, Hanselmann R, Frey H, Mulhaupt R, Macromolecules, 32(13), 4240 (1999)

[3] Royappa AT, Dalal N, Giese MW, J. Appl. Polym. Sci., 82(9), 2290 (2001)

[4] Royappa AT, Vogt ML, Sharma V, J. Appl. Polym. Sci., 91(2), 1344 (2004)

[5] Frey H, Haag R, J. Biotechnol., 90, 257 (2002)

[6] Huang YC, Royappa AT, Tundel S, Tsukamoto K, Sharma V, J. Appl. Polym. Sci., 111(5), 2275 (2009)

[7] Yu XF, Liu ZH, Janzen J, Chafeeva I, Horte S, Chen W, Kainthan RK, Kizhakkedathu JN, Brooks DE, Nat. Mater., 11(5), 468 (2012)

[8] Kim SC, Oh TH, Kim DW, Lee CJ, Kang YK, Macromol. Res., 17(3), 141 (2009)

[9] Wojtowicz JA, Polak RJ, J. Org. Chem., 38, 2061 (1973)

[10] Vandenberg EJ, Mullis JC, Juvet RS, Miller T, Nieman RA, J. Polym. Sci. A: Polym. Chem., 27, 3113 (1989)

[11] Kubisa P, Penczek S, Prog. Polym. Sci, 24, 1409 (1999)

[12] Hawker CJ, Lee R, Frechet JMJ, J. Am. Chem. Soc., 113, 4583 (1991)

[13] Radke W, Litvinenko G, Muller AHE, Macromolecules, 31(2), 239 (1998)

[14] Caytan E, Remaud GS, Tenailleau E, Akoka S, Talanta, 71, 1016 (2007)

[15] Rempp P, Merrill EW, in Polymer Synthesis, 2nd ed., Huthig & Wepf, Heidelberg, 1991, p 157.