[en] Organometallic-mediated radical polymerization (OMRP) has seen a significant growth in the last years notably due to the development of new metal complexes, especially cobalt derivatives. Despite of this, none of the reported complexes offers optimal control for monomers with very different reactivity, which somewhat limits the synthesis of copolymers. In order to expand the scope of cobalt-mediated radical polymerization (CMRP), we investigated an in situ ligand exchange reaction for modulating the properties of the cobalt complex at the polymer chain-end and adjusting the C-Co bond strength involved in the control process. With the aim of improving the synthesis of poly(vinyl acetate)-b-poly(n-butyl acrylate) copolymers, bidentate acetylacetonate ligands, which impart high level of control to the polymerization of vinyl acetate (VAc), were replaced in situ at the PVAc-cobalt chain-end by tetradentate Salen type ligands that are more suited to acrylates.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Kermagoret, Anthony ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Christine ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Debuigne, Antoine ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization
Publication date :
January 2015
Journal title :
European Polymer Journal
ISSN :
0014-3057
eISSN :
1873-1945
Publisher :
Elsevier Science
Volume :
62
Pages :
312-321
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE] BELSPO - Politique scientifique fédérale [BE] ULg FSR - Université de Liège. Fonds spéciaux pour la recherche [BE]
Funding text :
The University of Liège in the frame of the “Fonds spéciaux pour la recherche - crédits de démarrage”
M. Ouchi, T. Terashima, and M. Sawamoto Transition metal-catalyzed living radical polymerization: toward perfection in catalysis and precision polymer synthesis Chem Rev 109 11 2009 4963 5050
S. Perrier, and P. Takolpuckdee Macromolecular design via reversible addition-fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization J Polym Sci, Part A: Polym Chem 43 22 2005 5347 5393
V. Sciannamea, R. Jérôme, and C. Detrembleur In-situ nitroxide-mediated radical polymerization (NMP) processes: their understanding and optimization Chem Rev 108 2008 1104 1126
S. Yamago Precision polymer synthesis by degenerative transfer controlled/living radical polymerization using organotellurium, organostibine, and organobismuthine chain-transfer agents Chem Rev 109 11 2009 5051 5068
M. Destarac On the critical role of RAFT agent design in reversible addition-fragmentation chain transfer (RAFT) polymerization Polym Rev 51 2 2011 163 187
A. Debuigne, M. Hurtgen, C. Detrembleur, C. Jérôme, C. Barner-Kowollik, and T. Junkers Interpolymer radical coupling: a toolbox complementary to controlled radical polymerization Prog Polym Sci 37 2012 1004 1030
G. Moad, E. Rizzardo, and S.H. Thang Living radical polymerization by the RAFT process - a third update Aust J Chem 65 8 2012 985 1076
J. Nicolas, Y. Guillaneuf, C. Lefay, D. Bertin, D. Gigmes, and B. Charleux Nitroxide-mediated polymerization Prog Polym Sci 38 1 2013 63 235
B.M. Rosen, and V. Percec Single-electron transfer and single-electron transfer degenerative chain transfer living radical polymerization Chem Rev 109 11 2009 5069 5119
F. di Lena, and K. Matyjaszewski Transition metal catalysts for controlled radical polymerization Prog Polym Sci 35 8 2010 959 1021
A. Debuigne, R. Poli, C. Jérôme, R. Jérôme, and C. Detrembleur Overview of cobalt-mediated radical polymerization: roots, state of the art and future prospects Prog Polym Sci 34 3 2009 211 239
K. Matyjaszewski Comparison and classification of controlled/living radical polymerizations ACS Symp Ser 768 2000 2 26
N.V. Tsarevsky Catalytic activity and performance of copper-based complexes mediating atom transfer radical polymerization Isr J Chem 52 3-4 2012 276 287
L. Bai, L. Zhang, Z. Cheng, and X. Zhu Activators generated by electron transfer for atom transfer radical polymerization: recent advances in catalyst and polymer chemistry Polym Chem 3 10 2012 2685 2697
N.V. Tsarevsky, and K. Matyjaszewski "Green" atom transfer radical polymerization: from process design to preparation of well-defined environmentally friendly polymeric materials Chem Rev 107 6 2007 2270 2299
M. Hurtgen, C. Detrembleur, C. Jérôme, and A. Debuigne Insight into organometallic-mediated radical polymerization Polym Rev 51 2011 188 213
R. Poli Relationship between one-electron transition-metal reactivity and radical polymerization processes Angew Chem Int Ed 45 31 2006 5058 5070
H. Tang, N. Arulsamy, M. Radosz, Y. Shen, N.V. Tsarevsky, and W.A. Braunecker Highly active copper-based catalyst for atom transfer radical polymerization J Am Chem Soc 128 50 2006 16277 16285
W. Tang, Y. Kwak, W. Braunecker, N.V. Tsarevsky, M.L. Coote, and K. Matyjaszewski Understanding atom transfer radical polymerization: effect of ligand and initiator structures on the equilibrium constants J Am Chem Soc 130 32 2008 10702 10713
K. Matyjaszewski Atom transfer radical polymerization (ATRP): current status and future perspectives Macromolecules 45 10 2012 4015 4039
R. Poli Radical coordination chemistry and its relevance to metal-mediated radical polymerization Eur J Inorg Chem 10 2011 1513 1530
G. Moineau, M. Minet, P. Dubois, P. Teyssié, T. Senninger, and R. Jérôme Controlled radical polymerization of (Meth)acrylates by ATRP with NiBr 2(PPh3)2 as catalyst Macromolecules 32 1 1999 27 35
Y.A. Kabachii, S.Y. Kochev, L.M. Bronstein, I.B. Blagodatskikh, and P.M. Valetsky Atom transfer radical polymerization with Ti(III) halides and alkoxides Polym Bull 50 4 2003 271 278
A.D. Asandei, and I.W. Moran TiCp2Cl-catalyzed living radical polymerization of styrene initiated by oxirane radical ring opening J Am Chem Soc 126 49 2004 15932 15933
E. Le Grognec, J. Claverie, and R. Poli Radical polymerization of styrene controlled by half-sandwich Mo(III)/Mo(IV) couples: all basic mechanisms are possible J Am Chem Soc 123 39 2001 9513 9524
F. Stoffelbach, R. Poli, and P. Richard Half-sandwich molybdenum(III) compounds containing diazadiene ligands and their use in the controlled radical polymerization of styrene J Organomet Chem 663 1-2 2002 269 276
W.A. Braunecker, W.C. Brown, B.C. Morelli, W. Tang, R. Poli, and K. Matyjaszewski Origin of activity in Cu-, Ru-, and Os-mediated radical polymerization Macromolecules 40 24 2007 8576 8585
W.A. Braunecker, Y. Itami, and K. Matyjaszewski Osmium-mediated radical polymerization Macromolecules 38 23 2005 9402 9404
M.-S. Weiser, and R. Muelhaupt Cobalt(II) octanoate and cobalt(II) perfluorooctanoate catalyzed atom transfer radical polymerization of styrene in toluene and fluorous media-a versatile route to catalyst recycling and oligomer formation J Polym Sci, Part A: Polym Chem 43 17 2005 3804 3813
Y. Kotani, M. Kamigaito, and M. Sawamoto Re(V)-mediated living radical polymerization of styrene:1 ReO2I(PPh3)2/R-I initiating systems Macromolecules 32 8 1999 2420 2424
K. Matyjaszewski, and J. Xia Atom transfer radical polymerization Chem Rev 101 2001 2921 2990
F. Simal, A. Demonceau, and A.F. Noels Highly efficient ruthenium-based catalytic systems for the controlled free-radical polymerization of vinyl monomers Angew Chem Int Ed 38 4 1999 538 540
L. Delaude, S. Delfosse, A. Richel, A. Demonceau, and A.F. Noels Tuning of ruthenium N-heterocyclic carbene catalysts for ATRP Chem Commun 13 2003 1526 1527
R. Drozdzak, B. Allaert, N. Ledoux, I. Dragutan, V. Dragutan, and F. Verpoort Ruthenium complexes bearing bidentate Schiff base ligands as efficient catalysts for organic and polymer syntheses Coord Chem Rev 249 24 2005 3055 3074
K. Matyjaszewski, S. Coca, S.G. Gaynor, M. Wei, and B.E. Woodworth Zerovalent metals in controlled/"living" radical polymerization Macromolecules 30 23 1997 7348 7350
J. Louie, and R.H. Grubbs Highly active iron imidazolylidene catalysts for atom transfer radical polymerization Chem Commun 16 2000 1479 1480
V.C. Gibson, R.K. O'Reilly, D.F. Wass, A.J.P. White, and D.J. Williams Polymerization of methyl methacrylate using four-coordinate (α-diimine)iron catalysts: atom transfer radical polymerization vs. catalytic chain transfer Macromolecules 36 8 2003 2591 2593
R.K. O'Reilly, V.C. Gibson, A.J.P. White, and D.J. Williams Design of highly active iron-based catalysts for atom transfer radical polymerization: tridentate salicylaldiminato ligands affording near ideal nernstian behavior J Am Chem Soc 125 28 2003 8450 8451
J.-S. Wang, and K. Matyjaszewski Controlled/"living" radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes J Am Chem Soc 117 20 1995 5614 5615
K. Matyjaszewski, T.E. Patten, and J. Xia Controlled/"living" radical polymerization. Kinetics of the homogeneous atom transfer radical polymerization of styrene J Am Chem Soc 119 4 1997 674 680
T.E. Patten, J. Xia, T. Abernathy, and K. Matyjaszewski Polymers with very low polydispersities from atom transfer radical polymerization Science 272 5263 1996 866 868
T.E. Patten, and K. Matyjaszewski Copper(I)-catalyzed atom transfer radical polymerization Acc Chem Res 32 10 1999 895 903
N. Ayres Atom transfer radical polymerization: a robust and versatile route for polymer synthesis Polym Rev 51 2 2011 138 162
B.B. Wayland, G. Poszmik, S.L. Mukerjee, and M. Fryd Living radical polymerization of acrylates by organocobalt porphyrin complexes J Am Chem Soc 116 17 1994 7943 7944
A. Debuigne, J.-R. Caille, and R. Jérôme Highly efficient cobalt-mediated radical polymerization of vinyl acetate Angew Chem Int Ed 44 2005 1101 1104
M.P. Greuel, L.D. Arvanitopoulos, and H.J. Harwood Cobaloxime photoinitiators for free radical polymerization 1995 University of Akron USA p. 18
T.P. Davis, D. Kukulj, D.M. Haddleton, and D.R. Maloney Cobalt-mediated free-radical polymerization of acrylic monomers Trends Polym Sci 3 11 1995 365 373
B.B. Wayland, C.-H. Peng, X. Fu, Z. Lu, and M. Fryd Degenerative transfer and reversible termination mechanisms for living radical polymerizations mediated by cobalt porphyrins Macromolecules 39 24 2006 8219 8222
C.-H. Peng, M. Fryd, and B.B. Wayland Organocobalt mediated radical polymerization of acrylic acid in water Macromolecules 40 19 2007 6814 6819
A. Debuigne, Y. Champouret, R. Jérôme, R. Poli, and C. Detrembleur Mechanistic insights into the cobalt-mediated radical polymerization (CMRP) of vinyl acetate with cobalt(III) adducts as initiators Chem - Eur J 14 13 2008 4046 4059
C.-S. Hsu, T.-Y. Yang, and C.-H. Peng Vinyl acetate living radical polymerization mediated by cobalt porphyrins: kinetic-mechanistic studies Polym Chem 5 12 2014 3867 3875
K.S.S. Kumar, Y. Gnanou, Y. Champouret, J.-C. Daran, and R. Poli Radical polymerization of vinyl acetate with bis(tetramethylheptanedionate)cobalt(II): coexistence of three different mechanisms Chem - Eur J 15 19 2009 4874 4885
K.M. Smith, W.S. McNeil, and A.S. Abd-El-Aziz Organometallic-mediated radical polymerization: developing well-defined complexes for reversible transition metalalkyl bond homolysis Macromol Chem Phys 211 1 2010 10 16
B.B. Wayland, L. Basickes, S. Mukerjee, M. Wei, and M. Fryd Living radical polymerization of acrylates initiated and controlled by organocobalt porphyrin complexes Macromolecules 30 26 1997 8109 8112
Z. Lu, M. Fryd, and B.B. Wayland New life for living radical polymerization mediated by cobalt(II) metalloradicals Macromolecules 37 8 2004 2686 2687
B.K. Langlotz, J.L. Fillol, J.H. Gross, H. Wadepohl, and L.H. Gade Living radical polymerization of acrylates mediated by 1,3-bis(2-pyridylimino)isoindolatocobalt(II) complexes: monitoring the chain growth at the metal Chem - Eur J 14 33 2008 10267 10279
A. Debuigne, J.-R. Caille, and R. Jérôme Synthesis of end-functional poly(vinyl acetate) by cobalt-mediated radical polymerization Macromolecules 38 13 2005 5452 5458
A.N. Morin, C. Detrembleur, C. Jérôme, T.P. De, R. Poli, and A. Debuigne Effect of head-to-head addition in vinyl acetate controlled radical polymerization: why Is Co(acac)2-mediated polymerization so much better? Macromolecules 46 11 2013 4303 4312
I. Allaoua, B.E. Goi, M.M. Obadia, A. Debuigne, C. Detrembleur, and E. Drockenmuller (Co)Polymerization of vinyl levulinate by cobalt-mediated radical polymerization and functionalization by ketoxime click chemistry Polym Chem 5 8 2014 2973 2979
C. Detrembleur, A. Debuigne, M. Hurtgen, C. Jérôme, J. Pinaud, and M. Fèvre Synthesis of 1-vinyl-3-ethylimidazolium-based ionic liquid (Co)polymers by cobalt-mediated radical polymerization Macromolecules 44 16 2011 6397 6404
A. Debuigne, N. Willet, R. Jérôme, and C. Detrembleur Amphiphilic poly(vinyl acetate)-b-poly(N-vinylpyrrolidone) and novel double hydrophilic poly(vinyl alcohol)-b-poly(N-vinylpyrrolidone) block copolymers prepared by cobalt-mediated radical polymerization Macromolecules 40 20 2007 7111 7118
M. Hurtgen, J. Liu, A. Debuigne, C. Jérôme, and C. Detrembleur Synthesis of thermo-responsive poly(N-vinylcaprolactam)-containing block copolymers by cobalt-mediated radical polymerization J Polym Sci, Part A: Polym Chem 50 2012 400 408
A. Debuigne, A.N. Morin, A. Kermagoret, Y. Piette, C. Detrembleur, and C. Jérôme Key role of intramolecular metal chelation and hydrogen bonding in the cobalt-mediated radical polymerization of N-vinyl amides Chem - Eur J 18 2012 12834 12844
A. Kermagoret, C.-A. Fustin, M. Bourguignon, C. Detrembleur, C. Jérôme, and A. Debuigne One-pot controlled synthesis of double thermoresponsive N-vinylcaprolactam-based copolymers with tunable LCSTs Polym Chem 4 8 2013 2575 2583
A. Kermagoret, A. Debuigne, C. Jérôme, and C. Detrembleur Precision design of ethylene- and polar-monomerbased copolymers by organometallic-mediated radical polymerization Nat Chem 6 2014 179 184
S. Maria, H. Kaneyoshi, K. Matyjaszewski, and R. Poli Effect of electron donors on the radical polymerization of vinyl acetate mediated by [Co(acac)2]: degenerative transfer versus reversible homolytic cleavage of an organocobalt(III) complex Chem - Eur J 13 9 2007 2480 2492
A. Debuigne, C. Michaux, C. Jérôme, R. Jérôme, R. Poli, and C. Detrembleur Cobalt-mediated radical polymerization of acrylonitrile: kinetics investigations and DFT calculations Chem - Eur J 14 2008 7623 7637
S. Li, B.d. Bruin, C.-H. Peng, M. Fryd, and B.B. Wayland Exchange of organic radicals with organo-cobalt complexes formed in the living radical polymerization of vinyl acetate J Am Chem Soc 130 40 2008 13373 13381
R.K. Sherwood, C.L. Kent, B.O. Patrick, and W.S. McNeil Controlled radical polymerisation of methyl acrylate initiated by a well-defined cobalt alkyl complex Chem Commun 46 14 2010 2456 2458
M. Hurtgen, A. Debuigne, C. Jérôme, and C. Detrembleur Solving the problem of bis(acetylacetonato)cobalt(II)-mediated radical polymerization (CMRP) of acrylic esters Macromolecules 43 2010 886 894
K.S.S. Kumar, Y. Li, Y. Gnanou, U. Baisch, Y. Champouret, and R. Poli Electronic and steric ligand effects in the radical polymerization of vinyl acetate mediated by β-ketoiminate complexes of cobalt(II) Chem - Asian J 4 8 2009 1257 1265
X.-J. Qi, Z. Li, Y. Fu, Q.-X. Guo, and L. Liu Anti-spin-delocalization effect in CoC bond dissociation enthalpies Organometallics 27 12 2008 2688 2698
G. Li, F.F. Zhang, H. Chen, H.F. Yin, H.L. Chen, and S.Y. Zhang Determination of CoC bond dissociation energies for organocobalt complexes related to coenzyme B12 using photoacoustic calorimetry J Chem Soc, Dalton Trans 1 2002 105 110
E.A. Svidchenko, A.L. Sigan, and A.A. Kuznetsov Photoinitiated controlled radical polymerization of vinyl acetate in the presence of the CoII(Salen) complex Dokl Chem 454 2 2014 32 35
C.-H. Peng, J. Scricco, S. Li, M. Fryd, and B.B. Wayland Organo-cobalt mediated living radical polymerization of vinyl acetate Macromolecules 41 7 2008 2368 2373
C.-M. Liao, C.-C. Hsu, F.-S. Wang, B.B. Wayland, and C.-H. Peng Living radical polymerization of vinyl acetate and methyl acrylate mediated by Co(Salen∗) complexes Polym Chem 4 10 2013 3098 3104
A. Debuigne, R. Poli, R. Jérôme, C. Jérôme, and C. Detrembleur Key role of metal-coordination in cobalt-mediated radical polymerization of vinyl acetate ACS Symp Ser 1024 2009 131 147
D.J. Darensbourg Making plastics from carbon dioxide: Salen metal complexes as catalysts for the production of polycarbonates from epoxides and CO2 Chem Rev 107 2007 2388 2410
L. Chiang, L.E.N. Allan, J. Alcantara, M.C.P. Wang, T. Storr, and M.P. Shaver Tuning ligand electronics and peripheral substitution on cobalt Salen complexes: structure and polymerisation activity Dalton Trans 43 2014 4295 4304
D.N. Kumar, and B.S. Garg Some new cobalt(II) complexes synthesis, characterization and thermal studies J Therm Anal Cal 69 2002 607 616
H. Yang, L. Zhang, W. Su, Q. Yang, and C. Li Asymmetric ring-opening of epoxides on chiral Co(Salen) catalyst synthesized in SBA-16 through the "ship in a bottle" strategy J Catal 248 2 2007 204 212