[en] The synthesis of ethylene-based block copolymers (BCPs) by using a single radical polymerization technique is attractive but remains to be a great challenge. The main difficulty relates to the difference in reactivity between ethylene and the comonomer, especially if polar vinyl monomers are considered. The present work explores the radical polymerization of ethylene via organometallic-mediated radical polymerization (OMRP) with the aim of overcoming this limitation. First, some organocobalt complexes demonstrated their ability to initiate the radical homopolymerization of ethylene. The molecular parameters of polyethylene (PE) were found to be dependent on the reaction conditions (solvent and temperature), but at this stage, data do not allow claiming the controlled character of this polymerization. Nonetheless, proper selection of the organocobalt complex initiator led to unique α-functional PE. Finally, BCPs composed of ethylene and polar vinyl monomers, for example, poly(vinyl acetate)-b-polyethylene (PVAc-b-PE) and poly(ethylene vinyl acetate)-b-polyethylene (EVA-b-PE), were prepared for the first time using cobalt-terminated polymers as macroinitiators. In this case, some triblock copolymers were also formed by radical coupling reactions during ethylene polymerization. Overall, this strategy is straightforward for preparing PE-based copolymers by using a single organocobalt complex.
Research center :
Center for Education and Research on Macromolecules (CERM) CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Demarteau, Jérémy; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Scholten, Philip ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium > Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (IOC), Germany
Kermagoret, Anthony ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
De Winter, Julien; University of Mons, Organic Synthesis and Mass Spectrometry Laboratory, Belgium
Meier, Michael A.; Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (IOC), Germany
Monteil, Vincent; Université de Lyon, Université Lyon 1, Laboratoire C2P2, Équipe LCPP, France
Debuigne, Antoine ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Detrembleur, Christophe ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Language :
English
Title :
Functional polyethylene (PE) and PE-basedl block copolymers by organometallic-mediated radical polymerization
Publication date :
26 November 2019
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society (ACS), United States - District of Columbia
Volume :
52
Issue :
22
Pages :
9053-9063
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE] FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture [BE] European Joint Doctorate (EJD) - Funmat
Franssen, N. M. G.; Reek, J. N. H.; de Bruin, B. Synthesis of Functional "polyolefins": State of the Art and Remaining Challenges. Chem. Soc. Rev. 2013, 42, 5809-5832, 10.1039/c3cs60032g
Sun, W.-H. Novel Polyethylenes via Late Transition Metal Complex Pre-Catalysts. Adv. Polym. Sci. 2013, 258, 163-178, 10.1007/12_2013_212
So, L. C.; Faucher, S.; Zhu, S. Synthesis of Low Molecular Weight Polyethylenes and Polyethylene Mimics with Controlled Chain Structures. Prog. Polym. Sci. 2014, 39, 1196-1234, 10.1016/j.progpolymsci.2013.08.002
Nakamura, A.; Ito, S.; Nozaki, K. Coordination-Insertion Copolymerization of Fundamental Polar Monomers. Chem. Rev. 2009, 109, 5215-5244, 10.1021/cr900079r
Briquel, R.; Mazzolini, J.; Le Bris, T.; Boyron, O.; Boisson, F.; Delolme, F.; D'Agosto, F.; Boisson, C.; Spitz, R. Polyethylene Building Blocks by Catalyzed Chain Growth and Efficient End Functionalization Strategies, Including Click Chemistry. Angew. Chemie., Int. Ed. 2008, 47, 9311-9313, 10.1002/anie.200804445
Nakamura, A.; Ito, S.; Nozaki, K. Coordination-Insertion Copolymerization of Fundamental Polar Monomers. Chem. Rev. 2009, 109, 5215-5244, 10.1021/cr900079r
Ito, S.; Munakata, K.; Nakamura, A.; Nozaki, K. Copolymerization of Vinyl Acetate with Ethylene by Palladium/Alkylphosphine-Sulfonate Catalysts. J. Am. Chem. Soc. 2009, 131, 14606-14607, 10.1021/ja9050839
Aggarwal, S. L.; Sweeting, O. J. Polyethylene: Preparation, Structure, and Properties. Chem. Rev. 1957, 57, 665-742, 10.1021/cr50016a004
Ghiass, M.; Hutchinson, R. A. Simulation of Free Radical High-Pressure Copolymerization in a Multizone Autoclave: Model Development and Application. Polym. React. Eng. 2003, 11, 989-1015, 10.1081/PRE-120026882
Dommanget, C.; D'Agosto, F.; Monteil, V. Polymerization of Ethylene through Reversible Addition-Fragmentation Chain Transfer (RAFT). Angew. Chemie., Int. Ed. 2014, 53, 6683-6686, 10.1002/anie.201403491
Kermagoret, A.; Debuigne, A.; Jérôme, C.; Detrembleur, C. Precision Design of Ethylene-and Polar-Monomer-Based Copolymers by Organometallic-Mediated Radical Polymerization. Nat. Chem. 2014, 6, 179-187, 10.1038/nchem.1850
Demarteau, J.; Kermagoret, A.; Jérôme, C.; Detrembleur, C.; Debuigne, A. Controlled Synthesis of Ethylene-Vinyl Acetate Based Copolymers by Organometallic Mediated Radical Polymerization. ACS Symp. Ser. 2015, 47-61, 10.1021/bk-2015-1188.ch004
Chen, Q.-B.; Zeng, T.-Y.; Xia, L.; Zhang, Z.; Hong, C.-Y.; Zou, G.; You, Y.-Z. A RAFT/MADIX Method Finely Regulating the Copolymerization of Ethylene and Polar Vinyl Monomers under Mild Conditions. Chem. Commun. 2017, 53, 10780-10783, 10.1039/c7cc06341e
Demarteau, J.; De Winter, J.; Detrembleur, C.; Debuigne, A. Ethylene/vinyl Acetate-Based Macrocycles via Organometallic-Mediated Radical Polymerization and CuAAC "Click" Reaction. Polym. Chem. 2018, 9, 273-278, 10.1039/c7py01891f
Nakamura, Y.; Ebeling, B.; Wolpers, A.; Monteil, V.; D'Agosto, F.; Yamago, S. Controlled Radical Polymerization of Ethylene Using Organotellurium Compounds. Angew. Chemie., Int. Ed. 2018, 57, 305-309, 10.1002/anie.201709946
Grau, E.; Broyer, J.-P.; Boisson, C.; Spitz, R.; Monteil, V. Unusual Activation by Solvent of the Ethylene Free Radical Polymerization. Polym. Chem. 2011, 2, 2328-2333, 10.1039/c1py00200g
Zarrouki, A.; Espinosa, E.; Boisson, C.; Monteil, V. Free Radical Copolymerization of Ethylene with Vinyl Acetate under Mild Conditions. Macromolecules 2017, 50, 3516-3523, 10.1021/acs.macromol.6b02756
Demarteau, J.; Debuigne, A.; Detrembleur, C. Organocobalt Complexes as Sources of Carbon-Centered Radicals for Organic and Polymer Chemistries. Chem. Rev. 2019, 119, 6906-6955, 10.1021/acs.chemrev.8b00715
Zhao, Y.; Wang, L.; Xiao, A.; Yu, H. The Synthesis of Modified Polyethylene via Coordination Polymerization Followed by ATRP, RAFT, NMRP or ROP. Prog. Polym. Sci. 2010, 35, 1195-1216, 10.1016/j.progpolymsci.2010.05.002
Keyes, A.; Basbug Alhan, H. E.; Ordonez, E.; Ha, U.; Beezer, D. B.; Dau, H.; Liu, Y.-S.; Tsogtgerel, E.; Jones, G. R.; Harth, E. Olefins and Vinyl Polar Monomers: Bridging the Gap for Next Generation Materials. Angew. Chemie., Int. Ed. 2019, 58, 12370-12391, 10.1002/anie.201900650
Chen, E. Y.-X. Coordination Polymerization of Polar Vinyl Monomers by Single-Site Metal Catalysts. Chem. Rev. 2009, 109, 5157-5214, 10.1021/cr9000258
Godoy Lopez, R.; D'Agosto, F.; Boisson, C. Synthesis of Well-Defined Polymer Architectures by Successive Catalytic Olefin Polymerization and Living/controlled Polymerization Reactions. Prog. Polym. Sci. 2007, 32, 419-454, 10.1016/j.progpolymsci.2007.01.004
Schellekens, M. A. J.; Klumperman, B. Synthesis of Polyolefin Block and Graft Copolymers. J. Macromol. Sci., Rev. Macromol. Chem. Phys. 2000, 40, 167-192, 10.1081/mc-100100583
Xu, Y.; Thurber, C. M.; Macosko, C. W.; Lodge, T. P.; Hillmyer, M. A. Poly(methyl Methacrylate)-Block-Polyethylene-Block-Poly(methyl Methacrylate) Triblock Copolymers as Compatibilizers for Polyethylene/Poly(methyl Methacrylate) Blends. Ind. Eng. Chem. Res. 2014, 53, 4718-4725, 10.1021/ie4043196
Yin, L.; Hillmyer, M. A. Disklike Micelles in Water from Polyethylene-Containing Diblock Copolymers. Macromolecules 2011, 44, 3021-3028, 10.1021/ma200242b
Yin, L.; Lodge, T. P.; Hillmyer, M. A. A Stepwise "Micellization-Crystallization" Route to Oblate Ellipsoidal, Cylindrical, and Bilayer Micelles with Polyethylene Cores in Water. Macromolecules 2012, 45, 9460-9467, 10.1021/ma302069s
Schmelz, J.; Schedl, A. E.; Steinlein, C.; Manners, I.; Schmalz, H. Length Control and Block-Type Architectures in Worm-like Micelles with Polyethylene Cores. J. Am. Chem. Soc. 2012, 134, 14217-14225, 10.1021/ja306264d
Demarteau, J.; Kermagoret, A.; German, I.; Cordella, D.; Robeyns, K.; De Winter, J.; Gerbaux, P.; Jérôme, C.; Debuigne, A.; Detrembleur, C. Halomethyl-Cobalt(bis-Acetylacetonate) for the Controlled Synthesis of Functional Polymers. Chem. Commun. 2015, 51, 14334-14337, 10.1039/C5CC04714E
Debuigne, A.; Champouret, Y.; Jérôme, R.; Poli, R.; Detrembleur, C.; Jerome, R.; Poli, R.; Detrembleur, C. Mechanistic Insights into the Cobalt-Mediated Radical Polymerization (CMRP) of Vinyl Acetate with cobalt(III) Adducts as Initiators. Chem.-Eur. J. 2008, 14, 4046-4059, 10.1002/chem.200701867
Meier, M. A. R.; Schubert, U. S. Evaluation of a New Multiple-Layer Spotting Technique for Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry of Synthetic Polymers. Rapid Commun. Mass Spectrom. 2003, 17, 713-716, 10.1002/rcm.961
Detrembleur, C.; Debuigne, A.; Hurtgen, M.; Jérôme, C.; Pinaud, J.; Fèvre, M.; Coupillaud, P.; Vignolle, J.; Taton, D. Synthesis of 1-Vinyl-3-Ethylimidazolium-Based Ionic Liquid (Co)polymers by Cobalt-Mediated Radical Polymerization. Macromolecules 2011, 44, 6397-6404, 10.1021/ma201041s
Kermagoret, A.; Chau, N. D. Q.; Grignard, B.; Cordella, D.; Debuigne, A.; Jérôme, C.; Detrembleur, C. Cobalt-Mediated Radical Polymerization of Vinyl Acetate and Acrylonitrile in Supercritical Carbon Dioxide. Macromol. Rapid Commun. 2016, 37, 539-544, 10.1002/marc.201500629
Randall, J. C.; Ruff, C. J.; Kelchtermans, M. 13C NMR Microstructure Determinations of Low-density Polyethylene Homopolymers and Copolymers. Recl. Trav. Chim. Pays-Bas 1991, 110, 543-552, 10.1002/recl.19911101207
Usami, T.; Takayama, S. Fine-Branching Structure in High-Pressure, Low-Density Polyethylenes by 50.10-MHz Carbon-13 NMR Analysis. Macromolecules 1984, 17, 1756-1761, 10.1021/ma00139a022
Reitz, W. Handbook of Polyethylene: Structure, Properties, and Applications; Peacock, A. J., Ed.; Materials and Manufacturing Processes; CRC Press, 2001; Vol. 16 (5), pp 737-738.
