[en] The use of CO2-based α-alkylidene cyclic carbonates in controlled radical polymerization has so far
not been exploited, despite the fact that the cyclic carbonate ring offers a multitude of possible modifications. Herein, the synthesis of well-defined copolymers of vinyl acetate (VAc) and 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one (DMMDO) using cobalt-mediated radical polymerization (CMRP) at 40 °C is reported. The controlled nature of the polymerization was confirmed while molecular weights of up to 25 000 g mol−1 and narrow dispersities (<1.4) were obtained. The copolymer structure was elucidated combining NMR, FT-IR, and MALDI-TOF analyses and consists of a polymer backbone with pendant carbonate rings. Further insights into the copolymer structure were gained through the monomers’ reactivity ratios, and a homogeneous distribution of the DMMDO monomer along the polymer chain was observed. A highly water-soluble poly(vinyl alcohol)-based copolymer was obtained by basic hydrolysis, whereas the chemoselective acidic hydrolysis of the acetate groups left the cyclic carbonate rings untouched, which were then exploited for further postmodification with amines. The precise copolymerization of VAc with CO2-sourced five-membered cyclic carbonates bearing an exomethylene moiety is therefore a powerful tool for the synthesis of new variants of poly(vinyl alcohol)-based copolymers.
Research Center/Unit :
CESAM Complex and Entangled Systems from Atoms to Materials (CESAM) Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Scholten, Philip ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM) > Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (IOC), Germany
Demarteau, Jérémy ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
Gennen, Sandro ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
De Winter, Julien; University of Mons, Organic Synthesis and Mass Spectrometry Laboratory, Belgium
Grignard, Bruno ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
Debuigne, Antoine ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
Meier, Michael A. R.; Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (IOC), Germany
Detrembleur, Christophe ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Merging CO2‑based building blocks with cobalt-mediated radical polymerization for the synthesis of functional poly(vinyl alcohol)s
Publication date :
08 May 2018
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society, United States - District of Columbia
The International Doctoral School in the frame of EJD-Funmat F.R.S.-FNRS - Fonds de la Recherche Scientifique FWO - Fonds Wetenschappelijk Onderzoek Vlaanderen The "Excellence of Science" (EOS) Program BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
Rokicki, G. Aliphatic Cyclic Carbonates and Spiroorthocarbonates as Monomers. Prog. Polym. Sci. 2000, 25 (2), 259-342, 10.1016/S0079-6700(00)00006-X
Clements, J. H. Reactive Applications of Cyclic Alkylene Carbonates. Ind. Eng. Chem. Res. 2003, 42 (4), 663-674, 10.1021/ie020678i
Alves, M.; Grignard, B.; Gennen, S.; Mereau, R.; Detrembleur, C.; Jerome, C.; Tassaing, T. Organocatalytic Promoted Coupling of Carbon Dioxide with Epoxides: A Rational Investigation of the Cocatalytic Activity of Various Hydrogen Bond Donors. Catal. Sci. Technol. 2015, 5 (9), 4636-4643, 10.1039/C5CY00891C
Martín, C.; Fiorani, G.; Kleij, A. W. Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates. ACS Catal. 2015, 5 (2), 1353-1370, 10.1021/cs5018997
Büttner, H.; Longwitz, L.; Steinbauer, J.; Wulf, C.; Werner, T. Recent Developments in the Synthesis of Cyclic Carbonates from Epoxides and CO2. Top. Curr. Chem. 2017, 375, 3, 10.1007/s41061-017-0136-5
Alves, M.; Grignard, B.; Mereau, R.; Jerome, C.; Tassaing, T.; Detrembleur, C. Organocatalyzed Coupling of Carbon Dioxide with Epoxides for the Synthesis of Cyclic Carbonates: Catalyst Design and Mechanistic Studies. Catal. Sci. Technol. 2017, 7 (13), 2651-2684, 10.1039/C7CY00438A
Fiorani, G.; Guo, W.; Kleij, A. W. Sustainable Conversion of Carbon Dioxide: The Advent of Organocatalysis. Green Chem. 2015, 17 (3), 1375-1389, 10.1039/C4GC01959H
Comerford, J. W.; Ingram, I. D. V.; North, M.; Wu, X. Sustainable Metal-Based Catalysts for the Synthesis of Cyclic Carbonates Containing Five-Membered Rings. Green Chem. 2015, 17 (4), 1966-1987, 10.1039/C4GC01719F
North, M.; Pasquale, R.; Young, C. Synthesis of Cyclic Carbonates from Epoxides and CO2. Green Chem. 2010, 12 (9), 1514, 10.1039/c0gc00065e
Cai, A.; Guo, W.; Martínez-Rodríguez, L.; Kleij, A. W. Palladium-Catalyzed Regio- and Enantioselective Synthesis of Allylic Amines Featuring Tetrasubstituted Tertiary Carbons. J. Am. Chem. Soc. 2016, 138 (43), 14194-14197, 10.1021/jacs.6b08841
Guo, W.; Martínez-Rodríguez, L.; Martin, E.; Escudero-Adán, E. C.; Kleij, A. W. Homogeneous Catalysis Highly Efficient Catalytic Formation of (Z)-1,4-But-2-Ene Diols Using Water as a Nucleophile. Angew. Chem., Int. Ed. 2016, 55 (37), 11037-11040, 10.1002/anie.201603638
Guo, W.; Martínez-Rodríguez, L.; Kuniyil, R.; Martin, E.; Escudero-Adán, E. C.; Maseras, F.; Kleij, A. W. Stereoselective and Versatile Preparation of Tri- and Tetrasubstituted Allylic Amine Scaffolds under Mild Conditions. J. Am. Chem. Soc. 2016, 138, 11970-11978, 10.1021/jacs.6b07382
Sopeña, S.; Laserna, V.; Guo, W.; Martin, E.; Escudero-Adán, E. C.; Kleij, A. W. Regioselective Organocatalytic Formation of Carbamates from Substituted Cyclic Carbonates. Adv. Synth. Catal. 2016, 358 (14), 2172-2178, 10.1002/adsc.201600290
Besse, V.; Camara, F.; Voirin, C.; Auvergne, R.; Caillol, S.; Boutevin, B. Synthesis and Applications of Unsaturated Cyclocarbonates. Polym. Chem. 2013, 4 (17), 4545-4561, 10.1039/c3py00343d
Blattmann, H.; Fleischer, M.; Bähr, M.; Mülhaupt, R. Isocyanate- and Phosgene-Free Routes to Polyfunctional Cyclic Carbonates and Green Polyurethanes by Fixation of Carbon Dioxide. Macromol. Rapid Commun. 2014, 35 (14), 1238-1254, 10.1002/marc.201400209
Maisonneuve, L.; Lamarzelle, O.; Rix, E.; Grau, E.; Cramail, H. Isocyanate-Free Routes to Polyurethanes and Poly(hydroxy Urethane)s. Chem. Rev. 2015, 115 (22), 12407-12439, 10.1021/acs.chemrev.5b00355
Gennen, S.; Grignard, B.; Tassaing, T.; Jerome, C.; Detrembleur, C. CO2-Sourced α-Alkylidene Cyclic Carbonates: A Step Forward in the Quest for Functional Regioregular Poly(urethane)s and Poly(carbonate)s. Angew. Chem., Int. Ed. 2017, 56 (35), 10394-10398, 10.1002/anie.201704467
Grignard, B.; Thomassin, J.-M.; Gennen, S.; Poussard, L.; Bonnaud, L.; Raquez, J.-M.; Dubois, P.; Tran, M.-P.; Park, C. B.; Jerome, C. et al. CO2 -Blown Microcellular Non-Isocyanate Polyurethane (NIPU) Foams: From Bio- and CO2 -Sourced Monomers to Potentially Thermal Insulating Materials. Green Chem. 2016, 18 (7), 2206-2215, 10.1039/C5GC02723C
Hu, J.; Ma, J.; Zhu, Q.; Qian, Q.; Han, H.; Mei, Q.; Han, B. Zinc(II)-Catalyzed Reactions of Carbon Dioxide and Propargylic Alcohols to Carbonates at Room Temperature. Green Chem. 2016, 18 (2), 382-385, 10.1039/C5GC01870F
Li, W.; Yang, N.; Lyu, Y. Theoretical Insights into the Catalytic Mechanism of N-Heterocyclic Olefins in Carboxylative Cyclization of Propargyl Alcohol with CO2. J. Org. Chem. 2016, 81 (13), 5303-5313, 10.1021/acs.joc.6b00559
Yuan, Y.; Xie, Y.; Zeng, C.; Song, D.; Chaemchuen, S.; Chen, C.; Verpoort, F. A Recyclable AgI/OAc - Catalytic System for the Efficient Synthesis of α-Alkylidene Cyclic Carbonates: Carbon Dioxide Conversion at Atmospheric Pressure. Green Chem. 2017, 19 (13), 2936-2940, 10.1039/C7GC00276A
Boyaval, A.; Méreau, R.; Grignard, B.; Detrembleur, C.; Jerome, C.; Tassaing, T. Organocatalytic Coupling of CO2 with a Propargylic Alcohol: A Comprehensive Mechanistic Study. ChemSusChem 2017, 10 (6), 1241-1248, 10.1002/cssc.201601524
Méreau, R.; Grignard, B.; Boyaval, A.; Detrembleur, C.; Jerome, C.; Tassaing, T. Tetrabutyl Ammonium Salts: Cheap Catalysts for the Facile and Selective Synthesis of α-Alkylidene Cyclic Carbonates from CO2 and Alkynol. ChemCatChem 2018, 10, 956-960, 10.1002/cctc.201701567
Cho, I.; Lee, T. Radical Polymerization of 4-Methylene-l,3-Dioxolan-2-One and Its Hydrolyzed Water-Soluble Polymer. Makromol. Chem., Rapid Commun. 1989, 10, 453-456, 10.1002/marc.1989.030100904
Ochiai, B.; Sano, Y.; Endo, T. Synthesis and Crosslinking of Oligo(carbonate-Ketone) Obtained by Radical Polymerization of 4-Methylene-5,5-Dimethyl-1,3-Dioxolan-2-One. J. Netw. Polym. Japan 2005, 26 (3), 132-137
Jana, S.; Yu, H.; Parthiban, A.; Chai, C. L. L. Controlled Synthesis and Functionalization of PEGylated Methacrylates Bearing Cyclic Carbonate Pendant Groups. J. Polym. Sci., Part A: Polym. Chem. 2010, 48 (7), 1622-1632, 10.1002/pola.23928
Palaskar, D. V.; Sane, P. S.; Wadgaonkar, P. P. A New ATRP Initiator for Synthesis of Cyclic Carbonate-Terminated Poly(methyl Methacrylate). React. Funct. Polym. 2010, 70 (12), 931-937, 10.1016/j.reactfunctpolym.2010.08.005
Hallensleben, M. L.; Fuss, R.; Mummy, F. Polyvinyl Compounds, Others. Ullmann's Encyclopedia of Industrial Chemistry 2015, 1-23, 10.1002/14356007.a21-743.pub2
Fink, J. K. Poly(vinyl Alcohol). In Handbook of Engineering and Specialty Thermoplastics: Water Soluble Polymers; 2011; Vol. 2, pp 39-68.
Ben Halima, N. Poly(vinyl Alcohol): Review of Its Promising Applications and Insights into Biodegradation. RSC Adv. 2016, 6 (46), 39823-39832, 10.1039/C6RA05742J
Moulay, S. Review: Poly(vinyl Alcohol) Functionalizations and Applications. Polym.-Plast. Technol. Eng. 2015, 54 (12), 1289-1319, 10.1080/03602559.2015.1021487
Debuigne, A.; Champouret, Y.; Jérôme, 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 (13), 4046-4059, 10.1002/chem.200701867
Kelen, T.; Tüdos, F. Analysis of the Linear Methods for Determining Copolymerization Reactivity Ratios. I. A New Improved Linear Graphic Method. J. Macromol. Sci., Chem. 1957, 9 (1), 1-27, 10.1080/00222337508068644
Ting, J. M.; Navale, T. S.; Bates, F. S.; Reineke, T. M. Precise Compositional Control and Systematic Preparation of Multimonomeric Statistical Copolymers. ACS Macro Lett. 2013, 2, 770-774, 10.1021/mz4003112
Wamsley, A.; Jasti, B.; Phiasivongsa, P.; Li, X. Synthesis of Random Terpolymers and Determination of Reactivity Ratios of N-Carboxyanhydrides of Leucine, β-Benzyl Aspartate, and Valine. J. Polym. Sci., Part A: Polym. Chem. 2004, 42 (2), 317-325, 10.1002/pola.11020
Skeist, I. Copolymerization: The Composition Distribution Curve. J. Am. Chem. Soc. 1946, 68 (9), 1781-1784, 10.1021/ja01213a031
Debuigne, A.; Caille, J. R.; Willet, N.; Jérôme, R. Synthesis of Poly(vinyl Acetate) and Poly(vinyl Alcohol) Containing Block Copolymers by Combination of Cobalt-Mediated Radical Polymerization and ATRP. Macromolecules 2005, 38 (23), 9488-9496, 10.1021/ma051246x
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 (7), 713-716, 10.1002/rcm.961
Harrisson, S.; Liu, X.; Ollagnier, J.-N.; Coutelier, O.; Marty, J.-D.; Destarac, M. RAFT Polymerization of Vinyl Esters: Synthesis and Applications. Polymers (Basel, Switz.) 2014, 6 (5), 1437-1488, 10.3390/polym6051437
Debuigne, A.; Michaux, C.; Jérôme, C.; Jérôme, R.; Poli, R.; Detrembleur, C. Cobalt-Mediated Radical Polymerization of Acrylonitrile: Kinetics Investigations and DFT Calculations. Chem.-Eur. J. 2008, 14 (25), 7623-7637, 10.1002/chem.200800371
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 (3), 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, 1188, 47-61, 10.1021/bk-2015-1188.ch004
Demarteau, J.; Améduri, B.; Ladmiral, V.; Mees, M. A.; Hoogenboom, R.; Debuigne, A.; Detrembleur, C. Controlled Synthesis of Fluorinated Copolymers via Cobalt-Mediated Radical Copolymerization of Perfluorohexylethylene and Vinyl Acetate. Macromolecules 2017, 50 (10), 3750-3760, 10.1021/acs.macromol.7b00578
Debuigne, A.; Jérôme, C.; Detrembleur, C. Organometallic-Mediated Radical Polymerization of "less Activated Monomers": Fundamentals, Challenges and Opportunities. Polymer 2017, 115, 285-307, 10.1016/j.polymer.2017.01.008
Bryaskova, R.; Willet, N.; Degée, P.; Dubois, P.; Jérôme, R.; Detrembleur, C. Copolymerization of Vinyl Acetate with 1-Octene and Ethylene by Cobalt-Mediated Radical Polymerization. J. Polym. Sci., Part A: Polym. Chem. 2007, 45 (1), 2532-2342, 10.1002/pola.21963
Banerjee, S.; Ladmiral, V.; Debuigne, A.; Detrembleur, C.; Poli, R.; Ameduri, B. M. Organometallic Mediated Radical Polymerization of Vinylidene Fluoride. Angew. Chem., Int. Ed. 2018, 57 (11), 2934-2937, 10.1002/anie.201712347
Dréan, M.; Guégan, P.; Detrembleur, C.; Jérôme, C.; Rieger, J.; Debuigne, A. Controlled Synthesis of Poly(vinylamine)-Based Copolymers by Organometallic-Mediated Radical Polymerization. Macromolecules 2016, 49 (13), 4817-4827, 10.1021/acs.macromol.6b00992
Debuigne, A.; Morin, A. N.; Kermagoret, A.; Piette, Y.; Detrembleur, C.; Jérôme, C.; Poli, R. Key Role of Intramolecular Metal Chelation and Hydrogen Bonding in the Cobalt-Mediated Radical Polymerization of N-Vinyl Amides. Chem.-Eur. J. 2012, 18 (40), 12834-12844, 10.1002/chem.201201456
Hurtgen, M.; Detrembleur, C.; Jerome, C.; Debuigne, A. Insight into Organometallic-Mediated Radical Polymerization. Polym. Rev. 2011, 51 (2), 188-213, 10.1080/15583724.2011.566401
Maria, S.; Kaneyoshi, H.; Matyjaszewski, K.; Poli, R. 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. 2007, 13 (9), 2480-2492, 10.1002/chem.200601457
Park, S.; Yoon, H. Acid-Catalyzed Hydrolysis Reaction of Poly(vinyl Acetate). Polymer 2005, 29 (3), 304-307
Detrembleur, C.; Stoilova, O.; Bryaskova, R.; Debuigne, A.; Mouithys-Mickalad, A.; Jérôme, R. Preparation of Well-Defined PVOH/C60 Nanohybrids by Cobalt-Mediated Radical Polymerization of Vinyl Acetate. Macromol. Rapid Commun. 2006, 27 (7), 498-504, 10.1002/marc.200500871
Bryaskova, R.; Willet, N.; Debuigne, A.; Jérôme, R.; Detrembleur, C. Synthesis of Poly(vinyl Acetate)-B-Polystyrene and Poly(vinyl Alcohol)-B-Polystyrene Copolymers by Cobalt-Mediated Radical Polymerization. J. Polym. Sci., Part A: Polym. Chem. 2007, 45 (1), 81-89, 10.1002/pola.21806
Hassan, C. M.; Peppas, N. A. Structure and Applications of Poly (Vinyl Alcohol) Hydrogels Produced by Conventional Crosslinking or by Freezing/Thawing Methods. Adv. Polym. Sci. 2000, 153, 37-65, 10.1007/3-540-46414-X-2
Arai, K.; Okuzono, M.; Shikata, T. Reason for the High Solubility of Chemically Modified Poly(vinyl Alcohol)s in Aqueous Solution. Macromolecules 2015, 48 (5), 1573-1578, 10.1021/ma502602r
Bernard, J.; Favier, A.; Zhang, L.; Nilasaroya, A.; Davis, T. P.; Barner-Kowollik, C.; Stenzel, M. H. Poly(vinyl Ester) Star Polymers via Xanthate-Mediated Living Radical Polymerization: From Poly(vinyl Alcohol) to Glycopolymer Stars. Macromolecules 2005, 38 (13), 5475-5484, 10.1021/ma050050u
