[en] There is an increasing interest in the specific physicochemical properties of gradient copolymers at interfaces. In this work, the phase behavior and interfacial properties of amphiphilic gradient copolymers at the water/CO2 interface are explored and compared to that of diblock copolymer counterparts. It is observed that spontaneous amphiphilic block-like gradient copolymers made of N,N-dimethylacrylamide, vinyl pivalate, and vinyl acetate exhibit slightly lower cloud point pressures in supercritical carbon dioxide (scCO2) than the corresponding diblock copolymers. Much more pronounced differences are established at the water/scCO2 interface, with larger critical aggregation concentration (CAC), much faster adsorption kinetics and equilibration, and lower surface tension for gradient copolymers. RAFT/MADIX polymerization allows the control of molar mass, composition, and microstructure of the copolymers of the study. These findings shed light on how microstructural control in amphiphilic copolymers can give access to a new range of macromolecular emulsifiers for CO2 media with improved properties.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM) CESAM Complex and Entangled Systems from Atoms to Materials (CESAM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Liu, Xuan; Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique (IMRCP), UMR 5623, University of Toulouse, France
Wang, Mingxi; Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique (IMRCP), UMR 5623, University of Toulouse, France
Harrisson, Simon; Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique (IMRCP), UMR 5623, University of Toulouse, France
Debuigne, Antoine ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
Marty, Jean-Daniel; Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique (IMRCP), UMR 5623, University of Toulouse, France
Destarac, Mathias; Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique (IMRCP), UMR 5623, University of Toulouse, France
Language :
English
Title :
Enhanced stabilization of water-scCO2 interface by block-like spontaneous gradient copolymers
Publication date :
06 November 2017
Journal title :
ACS Sustainable Chemistry and Engineering
eISSN :
2168-0485
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Volume :
5
Issue :
11
Pages :
9645-9650
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique ANR - Agence Nationale de la Recherche CSC - Chinese Scholarship Council CNRS - Centre National de la Recherche Scientifique
Da Rocha, S. R.; Harrison, K. L.; Johnston, K. P. Effect of Surfactants on the Interfacial Tension and Emulsion Formation between Water and Carbon Dioxide Langmuir 1999, 15 (2) 419-428 10.1021/la980844k
Girard, E.; Tassaing, T.; Marty, J. D.; Destarac, M. Structure-Property Relationships in CO2-Philic (Co)Polymers: Phase Behavior, Self-Assembly, and Stabilization of Water/CO2 Emulsions Chem. Rev. 2016, 116 (7) 4125-4169 10.1021/acs.chemrev.5b00420
Eastoe, J.; Bayazit, Z.; Martel, S.; Steytler, D. C.; Heenan, R. K. Droplet Structure in a Water-in-CO2 Microemulsion Langmuir 1996, 12 (6) 1423-1424 10.1021/la950546c
Eastoe, J.; Gold, S.; Rogers, S.; Wyatt, P.; Steytler, D. C.; Gurgel, A.; Heenan, R. K.; Fan, X.; Beckman, E. J.; Enick, R. M. Designed CO2-Philes Stabilize Water-in-Carbon Dioxide Microemulsions Angew. Chem., Int. Ed. 2006, 45 (22) 3675-3677 10.1002/anie.200600397
Sagisaka, M.; Oasa, J.; Hasegawa, S.; Toyokawa, R.; Yoshizawa, A. Novel Fluorinated Double-Tail Surfactant Having High Microemulsifying Ability in Water/Supercritical CO2 System J. Supercrit. Fluids 2010, 53 (1-3) 131-136 10.1016/j.supflu.2009.12.016
Heitz, M. P.; Carlier, C.; deGrazia, J.; Harrison, K. L.; Johnston, K. P.; Randolph, T. W.; Bright, F. V. Water Core within Perfluoropolyether-Based Microemulsions Formed in Supercritical Carbon Dioxide J. Phys. Chem. B 1997, 101 (34) 6707-6714 10.1021/jp9622243
Lim, K. T.; Hwang, H. S.; Ryoo, W.; Johnston, K. P. Synthesis of TiO2 Nanoparticles Utilizing Hydrated Reverse Micelles in CO2 Langmuir 2004, 20 (6) 2466-2471 10.1021/la035646u
Ribaut, T.; Oberdisse, J.; Annighofer, B.; Stoychev, I.; Fournel, B.; Sarrade, S.; Lacroix-Desmazes, P. SANS Study of the Self-Organization of Gradient Copolymers with Ligand Groups in Supercritical CO2 Soft Matter 2009, 5 (5) 4962-4970 10.1039/b912268k
Fulton, J. L.; Pfund, D. M.; McClain, J. B.; Romack, T. J.; Maury, E. E.; Combes, J. R.; Samulski, E. T.; DeSimone, J. M.; Capel, M. Aggregation of Amphiphilic Molecules in Supercritical Carbon Dioxide: A Small Angle X-ray Scattering Study Langmuir 1995, 11 (11) 4241-4249 10.1021/la00011a014
Alaimo, D.; Merino, H. D.; Grignard, B.; Bras, W.; Jerome, C.; Debuigne, A.; Gommes, J. C. Small-Angle X-ray Scattering Insights into the Architecture Dependent Emulsifying Properties of Amphiphilic Copolymers in Supercritical Carbon Dioxide J. Phys. Chem. B 2015, 119 (4) 1706-1716 10.1021/jp5086558
Drohmann, C.; Beckman, E. J. Phase Behavior of Polymers Containing Ether Groups in Carbon Dioxide J. Supercrit. Fluids 2002, 22 (2) 103-110 10.1016/S0896-8446(01)00111-5
Sarbu, T.; Styranec, T. J.; Beckman, E. J. Design and Synthesis of Low Cost, Sustainable CO2-philes Ind. Eng. Chem. Res. 2000, 39 (12) 4678-4683 10.1021/ie0003077
Tan, B.; Bray, C. L.; Cooper, A. I. Fractionation of Poly(vinyl acetate) and the Phase Behavior of End-Group Modified Oligo(vinyl acetate)s in CO2 Macromolecules 2009, 42 (20) 7945-7952 10.1021/ma901458a
Shen, Z.; McHugh, M. A.; Xu, J.; Belardi, J.; Kilic, S.; Mesiano, A.; Bane, S.; Karnikas, C.; Beckman, E.; Enick, R. CO2-Solubility of Oligomers and Polymers that Contain the Carbonyl Group Polymer 2003, 44 (5) 1491-1498 10.1016/S0032-3861(03)00020-X
Girard, E.; Tassaing, T.; Marty, J.-D.; Destarac, M. Influence of Macromolecular Characteristics of RAFT/MADIX Poly(vinyl acetate)-Based (Co)Polymers on their Solubility in Supercritical Carbon Dioxide Polym. Chem. 2011, 2 (10) 2222-2230 10.1039/c1py00209k
Yamago, S. Precision Polymer Synthesis by Degenerative Transfer Controlled/Living Radical Polymerization Using Organotellurium, Organostibine, and Organobismuthine Chain-Transfer Agents Chem. Rev. 2009, 109 (11) 5051-5068 10.1021/cr9001269
Debuigne, A.; Poli, R.; Jérôme, C.; Jérôme, R.; Detrembleur, C. Overview of Cobalt-Mediated Radical Polymerization: Roots, State of the Art and Future Prospects Prog. Polym. Sci. 2009, 34 (3) 211-239 10.1016/j.progpolymsci.2008.11.003
Moad, G.; Rizzardo, E.; Thang, S. H. Living Radical Polymerization by the RAFT Process-A Third Update Aust. J. Chem. 2012, 65 (8) 985-1076 10.1071/CH12295
Destarac, M.; Bzducha, W.; Taton, D.; Gauthier-Gillaizeau, I.; Zard, S. Z. Xanthates as Chain-Transfer Agents in Controlled Radical Polymerization (MADIX): Structural Effect of the O-Alkyl Group Macromol. Rapid Commun. 2002, 23 (17) 1049-1054 10.1002/marc.200290002
Harrisson, S.; Liu, X.; Ollagnier, J.-N.; Coutelier, O.; Marty, J.-D.; Destarac, M. RAFT Polymerization of Vinyl Esters: Synthesis and Applications Polymers 2014, 6 (5) 1437-1488 10.3390/polym6051437
Park, E. J.; Richez, A. P.; Birkin, N. A.; Lee, H.; Arrowsmith, N.; Thurecht, K. J.; Howdle, S. M. New Vinyl Ester Copolymers as Stabilisers for Dispersion Polymerisation in ScCO2 Polymer 2011, 52 (24) 5403-5409 10.1016/j.polymer.2011.09.038
Lee, H.; Terry, E.; Zong, M.; Arrowsmith, N.; Perrier, S.; Thurecht, K. J.; Howdle, S. M. Successful Dispersion Polymerization in Supercritical CO2 Using Polyvinylalkylate Hydrocarbon Surfactants Synthesized and Anchored via RAFT J. Am. Chem. Soc. 2008, 130 (37) 12242-12243 10.1021/ja8046156
Birkin, N. A.; Arrowsmith, N. J.; Park, E. J.; Richez, A. P.; Howdle, S. M. Synthesis and Application of New CO2-Soluble Vinyl Pivalate Hydrocarbon Stabilisers via RAFT Polymerisation Polym. Chem. 2011, 2 (6) 1293-1299 10.1039/c1py00062d
Girard, E.; Tassaing, T.; Camy, S.; Condoret, J. S.; Marty, J.-D.; Destarac, M. Enhancement of Poly(vinyl ester) Solubility in Supercritical CO2 by Partial Fluorination: The Key Role of Polymer-Polymer Interactions J. Am. Chem. Soc. 2012, 134 (29) 11920-11923 10.1021/ja304585d
Girard, E.; Liu, X.; Marty, J.-D.; Destarac, M. RAFT/MADIX (Co)Polymerization of Vinyl Trifluoroacetate: A Means to Many Ends Polym. Chem. 2014, 5 (3) 1013-1022 10.1039/C3PY01109G
Girard, E.; Tassaing, T.; Ladavière, C.; Marty, J.-D.; Destarac, M. Distinctive Features of Solubility of RAFT/MADIX-Derived Partially Trifluoromethylated Poly(vinyl acetate) in Supercritical CO2 Macromolecules 2012, 45 (24) 9674-9681 10.1021/ma302061v
Liu, X.; Coutelier, O.; Harrisson, S.; Tassaing, T.; Marty, J.-D.; Destarac, M. Enhanced Solubility of Polyvinyl Esters in ScCO2 by Means of Vinyl Trifluorobutyrate Monomer ACS Macro Lett. 2015, 4 (1) 89-93 10.1021/mz500731p
Hu, D.; Sun, S.; Yuan, P. Q.; Zhao, L.; Liu, T. Exploration of CO2-Philicity of Poly(vinyl acetate-co-alkyl vinyl ether) through Molecular Modeling and Dissolution Behavior Measurement J. Phys. Chem. B 2015, 119 (38) 12490-12501 10.1021/acs.jpcb.5b08393
Matyjaszewski, K.; Ziegler, M. J.; Arehart, S. V.; Greszta, D.; Pakula, T. Gradient Copolymers by Atom Transfer Radical Copolymerization J. Phys. Org. Chem. 2000, 13, 775-786 10.1002/1099-1395(200012)13:12<775::AID-POC314>3.0.CO;2-D
Kim, J.; Mok, M. M.; Sandoval, R. W.; Woo, D. J.; Torkelson, J. M. Uniquely Broad Glass Transition Temperatures of Gradient Copolymers Relative to Random and Block Copolymers Containing Repulsive Comonomers Macromolecules 2006, 39 (18) 6152-6160 10.1021/ma061241f
Mok, M. M.; Kim, J.; Wong, C. L. H.; Marrou, S. R.; Woo, D. J.; Dettmer, C. M.; Nguyen, S. T.; Ellison, C. J.; Shull, K. R.; Torkelson, J. M. Glass Transition Breadths and Composition Profiles of Weakly, Moderately, and Strongly Segregating Gradient Copolymers: Experimental Results and Calculations from Self-Consistent Mean-Field Theory Macromolecules 2009, 42 (20) 7863-7876 10.1021/ma9009802
Yañez-Macias, R.; Kulai, I.; Ulbrich, J.; Yildirim, T.; Sungur, P.; Hoeppener, S.; Guerrero-Santos, R.; Schubert, U. S.; Destarac, M.; Guerrero-Sanchez, C.; Harrisson, S. Thermosensitive Spontaneous Gradient Copolymers with Block- and Gradient-Like Features Polym. Chem. 2017, 8, 5023-5032 10.1039/C7PY00495H
Kim, J.; Sandoval, R. W.; Dettmer, C. M.; Nguyen, S. T.; Torkelson, J. M. Compatibilized Polymer Blends with Nanoscale or Sub-Micron Dispersed Phases Achieved by Hydrogen-Bonding Effects: Block Copolymer vs Blocky Gradient Copolymer Addition Polymer 2008, 49 (11) 2686-2697 10.1016/j.polymer.2008.04.008
Sandoval, R. W.; Williams, D. E.; Kim, J.; Roth, C. B.; Torkelson, J. M. Critical Micelle Concentrations of Block and Gradient Copolymers in Homopolymer: Effects of Sequence Distribution, Composition, and Molecular Weight J. Polym. Sci., Part B: Polym. Phys. 2008, 46 (24) 2672-2682 10.1002/polb.21592
Hoogenboom, R.; Lambermont-Thijs, H. M. L.; Jochems, M. J. H. C.; Hoeppener, S.; Guerlain, C.; Fustin, C.-A.; Gohy, J.-F.; Schubert, U. S. A Schizophrenic Gradient Copolymer: Switching and Reversing Poly(2-oxazoline) Micelles Based on UCST and Subtle Solvent Changes Soft Matter 2009, 5 (19) 3590-3592 10.1039/b912491h
Kravchenko, V. S.; Potemkin, I. I. Micelles of Gradient vs Diblock Copolymers: Difference in the Internal Structure and Properties J. Phys. Chem. B 2016, 120 (47) 12211-12217 10.1021/acs.jpcb.6b10120
Okabe, S.; Seno, K.-i.; Kanaoka, S.; Aoshima, S.; Shibayama, M. Micellization Study on Block and Gradient Copolymer Aqueous Solutions by DLS and SANS Macromolecules 2006, 39 (4) 1592-1597 10.1021/ma052334k
Harrisson, S.; Ercole, F.; Muir, B. W. Living Spontaneous Gradient Copolymers of Acrylic Acid and Styrene: One-pot Synthesis of pH-Responsive Amphiphiles Polym. Chem. 2010, 1 (3) 326-332 10.1039/B9PY00301K
Ribaut, T.; Lacroix-Desmazes, P.; Fournel, B.; Sarrade, S. Synthesis of Gradient Copolymers with Complexing Groups by RAFT Polymerization and their Solubility in Supercritical CO2 J. Polym. Sci., Part A: Polym. Chem. 2009, 47 (20) 5448-5460 10.1002/pola.23594
Ribaut, T.; Oberdisse, J.; Annighofer, B.; Fournel, B.; Sarrade, S.; Haller, H.; Lacroix-Desmazes, P. Solubility and Self-Assembly of Amphiphilic Gradient and Block Copolymers in Supercritical CO2 J. Phys. Chem. B 2011, 115 (5) 836-843 10.1021/jp108888x
Gasc, F.; Corso, B.; Causse, J.; Lacroix-Desmazes, P. Study of Self-Association of Gradient Copolymers in Supercritical CO2 Thanks to Synchrotron and in-house Small-Angle X-Rays Scattering Measurements J. Supercrit. Fluids 2016, 114, 26-31 10.1016/j.supflu.2016.04.002
Van Den Brink, M.; Smulders, W.; Van Herk, A. M.; German, A. L. Nonlinear Regression by Visualization of the Sum of Residual Space Applied to the Integrated Copolymerization Equation with Errors in All Variables. II. Application to the System Methyl Methacrylate-α-methylene-γ-butyrolactone Using On-Line Raman Spectroscopy J. Polym. Sci., Part A: Polym. Chem. 1999, 37 (20) 3804-3816 10.1002/(SICI)1099-0518(19991015)37:20<3804::AID-POLA9>3.0.CO;2-B
Van Der Meer, R.; German, A. L. Copolymerization of Vinyl Acetate with a Homologous Series of Vinyl Esters: A Comparative Study of Vinyl Acetate-Vinyl Ester and Ethylene-Vinyl Ester Copolymerization J. Polym. Sci., Polym. Chem. Ed. 1979, 17 (10) 3365-3373 10.1002/pol.1979.170171025
Kahn, D. J.; Horowitz, H. H. Evaluation of the Terpolymer Composition Equation J. Polym. Sci. 1961, 54 (160) 363-374 10.1002/pol.1961.1205416008
Silva, M. E. S. R.; Dutra, E. R.; Mano, V.; Machado, J. C. Preparation and Thermal Study of Polymers Derived from Acrylamide Polym. Degrad. Stab. 2000, 67 (3) 491-495 10.1016/S0141-3910(99)00149-4
Tewes, F.; Boury, F. Thermodynamic and Dynamic Interfacial Properties of Binary Carbon Dioxide-Water Syetems J. Phys. Chem. B 2004, 108 (7) 2405-2412 10.1021/jp030895c
Tewes, F.; Boury, F. Formation and Rheological Properties of the Supercritical CO2-Water Pure Interface J. Phys. Chem. B 2005, 109 (9) 3990-3997 10.1021/jp046019w
Favrelle, A.; Boyere, C.; Tran, K. M.; Alaimo, D.; Calvignac, B.; Paquot, M.; Boury, F.; Jerome, C.; Debuigne, A. Surface Activity of a Fluorinated Carbohydrate Ester in Water/Carbon Dioxide Emulsions J. Colloid Interface Sci. 2013, 398 (19) 273-275 10.1016/j.jcis.2013.02.023
Eastoe, J.; Gold, S.; Steytler, C. D. Surfactants for CO2 Langmuir 2006, 22 (24) 9832-9842 10.1021/la060764d
da Rocha, S. R. P.; Johnston, K. P.; Westacott, R. E.; Rossky, P. J. Molecular Structure of the Water-Supercritical CO2 Interface J. Phys. Chem. B 2001, 105 (48) 12092-12104 10.1021/jp012439z