Ring-Opening Block Copolymerization of ε-Caprolactone with L-Lactide Catalyzed by N-Heterocyclic Carbenes: Synthesis, Characteristics, Mechanism

Lifang Zhang; Ning Li; Yan Wang; Jizhe Guo; Junfei Li

Macromolecular Research, Vol.22, No.6, 600-605, June, 2014

DOI10.1007/s13233-014-2092-z Export Citation

Ring-Opening Block Copolymerization of ε-Caprolactone with L-Lactide Catalyzed by N-Heterocyclic Carbenes: Synthesis, Characteristics, Mechanism

Lifang Zhang^†, Ning Li, Yan Wang^†, Jizhe Guo, and Junfei Li

Institute of Material Chemistry, Shanxi Normal University, Linfen, 041004, P. R. China

E-mail:,

Block aliphatic polyesters can be useful for medical and pharmaceutical applications. These materials can be prepared by sequential ring-opening polymerization reactions. In this work, a set of poly(ε-caprolactone)-poly(Llactide) aliphatic polyester AB diblock copolymers and poly(L-lactide)-poly(ε-caprolactone)-poly(L-lactide) aliphatic polyester ABA triblock copolymers were prepared by consecutive controlled ring-opening polymerizations. Ring-opening polymerization of ε-caprolactone in the presence of 1-isopropyl-3-(4-methoxyphenyl) imidazol-2-ylidene and ethylene glycol offered α ,ω-dihydroxyl-terminate poly(ε-caprolactone). An array of poly(L-lactide)-poly(ε-caprolactone)-poly(L-lactide) triblock copolymers with controlled molecular weights and narrow molecular weight distributions was synthesized using the telechelic poly(ε-caprolactone) samples as macroinitiators for the ring-opening polymerization of L-lactide. 1H NMR and 13C NMR spectral data of copolymers showed the chemical structures without random placement. Meanwhile, the spectral data also indicated that this polymerization mechanism was in agreement with the activated monomer mechanism.

Keywords:block copolymerization;ε-caprolactone;L-lactide;1-isopropyl-3-(4-methoxyphenyl) imidazol-2-ylidene.

[References]

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[2] Ghosh S, J. Chem. Res., 241 (2004)

[3] Penczek S, Cypryk M, Duda A, Kubisa P, Slomkowski S, Prog. Polym. Sci., 32, 247 (2007)

[4] Shen YQ, Zhu KJ, Shen ZQ, Yao KM, J. Polym. Sci. A: Polym. Chem., 34(9), 1799 (1996)

[5] Van Butsele K, Jerome R, Jerome C, Polymer, 48(26), 7431 (2007)

[6] Nomura N, Akita A, Ishii R, Mizuno M, J. Am. Chem. Soc., 132(6), 1750 (2010)

[7] Vanhoorne P, Dubois P, Jerome R, Teyssie P, Macromolecules, 25, 37 (1992)

[8] Bero M, Kasperczyk J, Macromol. Chem. Phys., 197, 3251 (1996)

[9] Kister G, Cassanas G, Bergounhon M, Hoarau D, Vert M, Polymer, 41(3), 925 (2000)

[10] Fay F, Renard E, Langlois V, Linossier I, Vallee-Rehel K, Eur. Polym. J., 43, 4800 (2007)

[11] Calandrelli L, Calarco A, Laurienzo P, Malinconico M, Petillo O, Peluso G, Biomacromolecules, 9(6), 1527 (2008)

[12] Pappalardo D, Annunziata L, Pellecchia C, Macromolecules, 42(16), 6056 (2009)

[13] Qian H, Bei J, Wang S, Polym. Degrad. Stab., 68, 423 (2000)

[14] Song CX, Feng XD, Macromolecules, 17, 2764 (1984)

[15] Huang MH, Li S, Coudane J, Vert M, Macromol. Chem. Phys., 204, 1994 (2003)

[16] Jeon O, Lee SH, Kim SH, Lee YM, Kim YH, Macromolecules, 36(15), 5585 (2003)

[17] Lahcini M, Castro PM, Kalmi M, Leskela M, Repo T, Organometallics, 23, 4547 (2004)

[18] Wang JL, Dong CM, Macromol. Chem. Phys., 207, 554 (2006)

[19] Zhao Z, Yang L, Hu Y, He Y, Wei J, Li S, Polym. Degrad. Stab., 92, 1769 (2007)

[20] Wei ZY, Liu L, Yu FY, Wang P, Qu C, Qi M, Polym. Bull., 61(4), 407 (2008)

[21] Jang HK, Kim BS, Macromol. Res., 21(4), 370 (2013)

[22] Zintl M, Molnar F, Urban T, Bernhart V, Preishuber-Pflugl P, Rieger B, Angew. Chem. Int. Ed., 47, 3458 (2008)

[23] Le Borgne A, Vincens V, Jouglard M, Spassky N, Macromol. Symp., 73, 37 (1993)

[24] Egami H, Katsuki T, J. Am. Chem. Soc., 129(29), 8940 (2007)

[25] Hutson GE, Dave AH, Rawal VH, Org. Lett., 9, 3869 (2007)

[26] Zamfir M, Patrickios CS, Montagne F, Abetz C, Abetz V, Oss-Ronen L, Talmon Y, J. Polym. Sci. A: Polym. Chem., 50(8), 1636 (2012)

[27] Hamou ASH, Djadoun S, Macromol. Symp., 303, 114 (2011)

[28] Connor EF, Nyce GW, Myers M, Mock A, Hedrick JL, J. Am. Chem. Soc., 124(6), 914 (2002)

[29] Nyce GW, Lamboy JA, Connor EF, Waymouth RM, Hedrick JL, Org. Lett, 4, 3587 (2002)

[30] Nyce GW, Glauser T, Connor EF, Mock A, Waymouth RM, Hedrick JL, J. Am. Chem. Soc., 125(10), 3046 (2003)

[31] Bonhote P, Dias AP, Papageorgiou N, Kalyanasundaram K, Gratzel M, Inorg. Chem., 35(5), 1168 (1996)

[32] Raynaud J, Gnanou Y, Taton D, Macromolecules, 42(16), 5996 (2009)

[33] Coulembier O, Lohmeijer BGG, Dove AP, Pratt RC, Mespouille L, Culkin DA, Benight SJ, Dubois P, Waymouth RM, Hedrick JL, Macromolecules, 39(17), 5617 (2006)