[en] The oxyanionic ring-opening polymerization of propylene oxide (PO) from an exogenous alcohol activated with benign (complexed) metal-alkali carboxylates is described. We demonstrate that the equimolar mixture of potassium acetate (KOAc) and 18-crown-6 ether (18C6) is the complex of choice for preparing poly(propylene oxide) (PPO) in a controlled manner. In the presence of 18C6/KOAc, hydrogen-bonded alcohols act as soft nucleophiles promoting the PO SN 2 process at room temperature and in solvent-free conditions while drastically limiting the occurrence of parasitic hydrogen abstraction generally observed during the anionic ROP of PO. The resulting PPO displays predictable and unprecedent molar masses (up to 20 kg.mol-1 ) with low dispersities (ƉM < 1.1), rendering the 18C6/KOAc complex the most performing activator for the oxyanionic polymerization of PO reported to date. Preliminary studies on the preparation of block and statistical copolyethers have also been reported.
Disciplines :
Chemistry
Author, co-author :
Fornaciari, Charlotte; Laboratory of Polymeric and Composite Materials (LPCM), Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons, Place du Parc, 20, Mons, 7000, Belgium ; Department of Chemistry, University of Pavia, Viale Taramelli, 10, Pavia, 27100, Italy
Pasini, Dario; Department of Chemistry, University of Pavia, Viale Taramelli, 10, Pavia, 27100, Italy
Coulembier, Olivier ; Université de Mons - UMONS > Faculté des Sciences > Service des Matériaux Polymères et Composites
Language :
English
Title :
Controlled oxyanionic polymerization of propylene oxide: unlocking the molecular-weight limitation by a soft nucleophilic catalysis.
a) J. Herzberger, K. Niederer, H. Pohlit, J. Seiwert, M. Worm, F. R. Wurm, H. Frey, Chem. Rev. 2016, 116, 2170;
b) R. Klein, F. R. Wurm, Macromol. Rapid Commun. 2015, 36, 1147.
a) G. Cendejas, C. A. Flores-Sandoval, N. Huitrón, R. Herrera, L. S. Zamudio-Rivera, H. I. Beltrán, F. Vázquez, J. Mol. Struct. 2008, 879, 40;
b) Z. Grobelny, M. Matlengiewicz, J. Jurek-Suliga, S. Golba, K. Skrzeczyna, Polym. Bull. 2018, 75, 1101.
a) L. E. S. Pierre, C. C. Price, J. Am. Chem. Soc. 1956, 78, 3432;
b) D. M. Simons, J. J. Verbanc, J. Polym. Sci. 1960, 44, 303.
G.-E. Yu, F. Heatley, C. Booth, T. G. Blease, J. Polym. Sci., Part A: Polym. Chem. 1994, 32, 1131.
S. Penczek, M. Cypryk, A. Duda, P. Kubisa, S. Slomkowski, Prog. Polym. Sci. 2007, 32, 247.
a) T. Aida, S. Inoue, Macromolecules 1981, 14, 1162;
b) T. Aida, R. Mizuta, Y. Yoshida, S. Inoue, Makromol. Chem. 1981, 182, 1073;
c) H. Sugimoto, C. Kawamura, M. Kuroki, T. Aida, S. Inoue, Macromolecules 1994, 27, 2013;
d) M. Akatsuka, T. Aida, S. Inoue, Macromolecules 1994, 27, 2820;
e) T. Aida, S. Inoue, Acc. Chem. Res. 1996, 29, 39;
f) W. Braune, J. Okuda, Angew. Chem., Int. Ed. 2003, 42, 64;
g) C. Billouard, S. Carlotti, P. Desbois, A. Deffieux, Macromolecules 2004, 37, 4038;
h) A. Deffieux, S. Carlotti, P. Desbois, Macromol. Symp. 2005, 229, 24;
i) S. Carlotti, P. Desbois, C. Billouard, A. Deffieux, Polym. Int. 2006, 55, 1126;
j) A. Labbé, S. Carlotti, C. Billouard, P. Desbois, A. Deffieux, Macromolecules 2007, 40, 7842;
k) M. Gervais, A. Labbé, S. Carlotti, A. Deffieux, Macromolecules 2009, 42, 2395;
l) Y. Chen, J. Shen, S. Liu, J. Zhao, Y. Wang, G. Zhang, Macromolecules 2018, 51, 8286;
m) J. Blankenburg, E. Kersten, K. Maciol, M. Wagner, S. Zarbakhsh, H. Frey, Polym. Chem. 2019, 10, 2863;
n) R. Matthes, C. Bapp, M. Wagner, S. Zarbakhsh, H. Frey, Macromolecules 2021, 54, 11228.
a) G. A. Gladkovskii, L. P. Golovina, G. F. Vedeneyeva, V. S. Lebedev, Polym. Sci. U.S.S.R. 1973, 15, 1370;
b) G. Gee, W. C. E. Higginson, K. J. Taylor, M. W. Trenholme, J. Chem. Soc. 1961, 4298.
a) M. Ionescu, I. Mihalache, V. Dumitru, F. Stoenescu, V. Ion, Rev. Chim. 1988, 39, 1060;
b) J. Ding, F. Heatley, C. Price, C. Booth, Eur. Polym. J. 1991, 27, 895;
c) Z. Grobelny, M. Matlengiewicz, J. Jurek, M. Michalak, D. Kwapulińska, A. Swinarew, E. Schab-Balcerzak, Eur. Polym. J. 2013, 49, 3277.
S. Naumann, A. W. Thomas, A. P. Dove, Angew. Chem., Int. Ed. 2015, 54, 9550.
a) P. M. Pihko, Angew. Chem., Int. Ed. 2004, 43, 2062;
b) P. R. Schreiner, Chem. Soc. Rev. 2003, 32, 289;
c) K. Tanaka, A. Mori, S. Inoue, J. Org. Chem. 1990, 55, 181;
d) E. J. Corey, M. J. Grogan, Org. Lett. 1999, 1, 157;
e) M. S. Sigman, E. N. Jacobsen, J. Am. Chem. Soc. 1998, 120, 4901;
f) Y. Huang, A. K. Unni, A. N. Thadani, V. H. Rawal, Nature 2003, 424, 146;
g) A. K. Unni, N. Takenaka, H. Yamamoto, V. H. Rawal, J. Am. Chem. Soc. 2005, 127, 1336;
h) N. T. Mcdougal, S. E. Schaus, J. Am. Chem. Soc. 2003, 125, 12094;
i) B. M. Nugent, R. A. Yoder, J. N. Johnston, J. Am. Chem. Soc. 2004, 126, 3418.
a) F. Ono, M. Hasegawa, S. Kanemasa, J. Tanaka, Tetrahedron Lett. 2008, 49, 5105;
b) Y. N. Bespalko, E. N. Shved, React. Kinet., Mech. Catal. 2019, 126, 903;
c) Z. Yan, Y. Hu, C. Du, J. Deng, K. Wang, G. Luo, J. Catal. 2020, 385, 44;
d) Z. Yan, Z. Ma, J. Deng, G. Luo, Chem. Eng. Sci. 2021, 242, 116746.
a) T. Saito, Y. Aizawa, T. Yamamoto, K. Tajima, T. Isono, T. Satoh, Macromolecules 2018, 51, 689;
b) K. Takojima, T. Saito, C. Vevert, V. Ladelta, P. Bilalis, J. Watanabe, S. Hatanaka, T. Konno, T. Yamamoto, K. Tajima, N. Hadjichristidis, T. Isono, T. Satoh, Polym. J. 2020, 52, 103.
a) S. Moins, C. Henoumont, Q. De Roover, S. Laurent, J. De Winter, O. Coulembier, Catal. Sci. Technol. 2021, 11, 4387;
b) Q. De Roover, T. Vucko, S. P. Vincent, J. De Winter, O. Coulembier, Catal. Sci. Technol. 2021, 11, 6048.
C. Ozen, T. Satoh, S. Maeda, J. Comput. Chem. 2020, 41, 2197.
P. Vermeeren, T. Hansen, P. Jansen, M. Swart, T. A. Hamlin, F. M. Bickelhaupt, Chem. - Eur. J. 2020, 26, 15538.
C.-M. Chen, X. Xu, H.-Y. Ji, B. Wang, L. Pan, Y. Luo, Y.-S. Li, Macromolecules 2021, 54, 713.
S. Foltran, R. Méreau, T. Tassaing, Phys. Chem. Chem. Phys. 2011, 13, 9209.
A. S. Goldmann, M. Glassner, A. J. Inglis, C. Barner-Kowollik, Macromol. Rapid Commun. 2013, 34, 810.
a) B. F. Lee, M. J. Kade, J. A. Chute, N. Gupta, L. M. Campos, G. H. Fredrickson, E. J. Kramer, N. A. Lynd, C. J. Hawker, J. Polym. Sci., Part A: Polym. Chem. 2011, 49, 4498;
b) K. P. Barteau, M. Wolffs, N. A. Lynd, G. H. Fredrickson, E. J. Kramer, C. J. Hawker, Macromolecules 2013, 46, 8988;
c) J. Lee, A. J. Mcgrath, C. J. Hawker, B.-S. Kim, ACS Macro Lett. 2016, 5, 1391;
d) Y. Hong, J.-M. Kim, H. Jung, K. Park, J. Hong, S.-H. Choi, B.-S. Kim, Biomacromolecules 2020, 21, 4913.
