Live Monitoring of Anionic Living Polymerizations by Electrospray-Ionization Mass Spectrometry.
carbanions
kinetics
mass spectrometry
polymerization
reactive intermediates
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
01 Mar 2023
01 Mar 2023
Historique:
received:
01
12
2022
pubmed:
4
1
2023
medline:
4
1
2023
entrez:
3
1
2023
Statut:
ppublish
Résumé
Anionic polymerizations are of exceptional practical importance, but difficult to analyze due to the high reactivity of the growing polymer chains. Here, we demonstrate that electrospray-ionization mass spectrometry (ESI-MS) permits direct observation of the active carbanionic intermediates formed in the anionic ring-opening polymerization of 1-cyanocyclopropanecarboxylate in tetrahydrofuran. This includes the identification of a side product, as well as real-time analysis of the polymerization reaction. From the mass spectra obtained, we can derive not only the mean molar mass and the polydispersity, but also the rate constants for the initiation and the individual propagation steps. The initiation proceeds significantly faster than the propagation steps. Accordingly, the examined reaction corresponds to a living polymerization, as we also confirmed by additional control experiments. Besides giving detailed insight into the reaction system probed here, we also expect the presented methodology to make possible the in-situ analysis of further anionic polymerizations.
Identifiants
pubmed: 36596722
doi: 10.1002/chem.202203762
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202203762Subventions
Organisme : Deutsche Forschungsgemeinschaft
ID : INST 186/1326-1 FUGG
Organisme : Niedersächsisches Ministerium für Wissenschaft und Kultur
ID : INST 186/1326-1 FUGG
Informations de copyright
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
Références
Y. Miura, J. Mater. Chem. B 2020, 8, 2010-2019;
D. T. Gentekos, R. J. Sifri, B. P. Fors, Nat. Rev. Mater. 2019, 4, 761-774.
O. W. Webster, Science 1991, 251, 887-893.
B. H. Stuart in Polymer Analysis, Wiley, Chichester, 2002;
S. D. Hanton, Chem. Rev. 2001, 101, 527-570;
J. U. Izunobi, C. L. Higginbotham, J. Chem. Educ. 2011, 88, 1098-1104.
I. A. Kaltashov, R. R. Abzalimov, J. Am. Soc. Mass Spectrom. 2008, 19, 1239-1246;
S. M. Hunt, M. M. Sheil, M. Belov, P. J. Derrick, Anal. Chem. 1998, 70, 1812-1822.
P. Chen, Angew. Chem. 2003, 115, 2938-2954;
Angew. Chem. Int. Ed. 2003, 42, 2832-2847;
L. S. Santos, J. O. Metzger, Angew. Chem. 2006, 118, 991-995;
Angew. Chem. Int. Ed. 2006, 45, 977-981.
F. Kreyenschmidt, N. F. Eisele, V. Hevelke, R. Rahrt, A.-K. Kreyenschmidt, K. Koszinowski, Angew. Chem. 2022, 134, e202210211;
Angew. Chem. Int. Ed. 2022, 61, e202210211.
For the use of ESI-MS for the in-situ analysis of neutral polymers charged by the coordination of Na+ ions, see:
J. J. Haven, J. Vanderbergh, T. Junkers, Chem. Commun. 2015, 51, 4611-4614;
P. H. M. Van Steenberge, J. Vandenbergh, M.-F. Reyniers, T. Junkers, D. R. D'hooge, G. B. Marin, Macromolecules 2017, 50, 2625-2636;
J. J. Haven, N. Zaquen, M. Rubens, T. Junkers, Macromol. React. Eng. 2017, 11, 1700016.
N. F. Eisele, K. Koszinowski, J. Org. Chem. 2021, 86, 3750-3757.
L. C. Kagumba, J. Penelle, Macromolecules 2005, 38, 4588-4594;
J. Penelle, H. Hérion, T. Xie, P. Gorissen, Macromol. Chem. Phys. 1998, 199, 1329-1336;
A. Benlahouès, B. Brissault, S. Boileau, J. Penelle, Macromol. Chem. Phys. 2018, 219, 1700463.
Z. L. Cheng, K. W. M. Siu, R. Guevremont, S. S. Berman, J. Am. Soc. Mass Spectrom. 1992, 3, 281-288;
J. L. Sterner, M. V. Johnston, G. R. Nicol, D. P. Ridge, J. Mass Spectrom. 1990, 35, 385-391.
J. Guittard, M. Tessier, J. C. Blais, G. Bolbach, L. Rozes, E. Maréchal, J. C. Tabet, J. Mass Spectrom. 1996, 31, 1409-1421.
T. Henriksen, R. K. Juhler, B. Svensmark, N. B. Cech, J. Am. Soc. Mass Spectrom. 2005, 16, 446-455.
K. L. Vikse, Z. Ahmadi, C. C. Manning, D. A. Harrington, J. S. McIndoe, Angew. Chem. 2011, 123, 8454-8456,
Angew. Chem. Int. Ed. 2011, 50, 8304-8306;
K. L. Vikse, Z. Ahmadi, J. S. McIndoe, Coord. Chem. Rev. 2014, 279, 96-114;
R. Theron, Y. Wu, L. P. E. Yunker, A. V. Hesketh, I. Pernik, A. S. Weller, J. S. McIndoe, ACS Catal. 2016, 6, 6911-6197;
R. G. Belli, Y. Wu, H. Ji, A. Joshi, L. P. E. Yunker, J. S. McIndoe, L. Rosenberg, Inorg. Chem. 2019, 58, 747-755.
L. Jašíková, M. Anania, S. Hybelbauerová, J. Roithová, J. Am. Chem. Soc. 2015, 137, 13647-13657;
J. Váňa, T. Terencio, V. Petrović, O. Tischler, Z. Novák, J. Roithová, Organometallics 2017, 36, 2072-2080.
K. Koszinowski, D. S. Stephenson, J. Org. Chem. 2018, 83, 14314-14322.
M. Itakura, K. Sato, M. A. Lusenkova, S. Matsuyama, K. Shimada, T. Saito, S. Kinugasa, J. Appl. Polym. Sci. 2004, 94, 1101-1106.
S. Hoops, S. Sahle, R. Gauges, C. Lee, J. Pahle, N. Simus, M. Singhal, L. Xu, P. Mendes, U. Kummer, Bioinformatics 2006, 22, 3067-3074.
S. Trimpin, D. E. Clemmer, Anal. Chem. 2008, 80, 9073-9083.
P. M. Jüstel, C. D. Pignot, A. R. Ofial, J. Org. Chem. 2021, 86, 5965-5972.
R. Lucius, R. Loos, H. Mayr, Angew. Chem. 2002, 114, 97-102;
Angew. Chem. Int. Ed. 2002, 41, 91-95.
A. Benlahouès, B. Brissault, S. Boileau, J. Penelle, Macromol. Chem. Phys. 2018, 219, 1700463.
T. Shimomura, J. Smid, M. Szwarc, J. Am. Chem. Soc. 1967, 89, 5743-5749.
G. T. Thomas, S. Donnecke, I. C. Chagunda, J. S. McIndoe, Chem. Methods 2022, 2, e202100068.