[en] The supramolecular assembly of a series of copolymers combining a PEO-rich hydrophilic and fluorinated CO2-philic sequences is analysed by synchrotron small-angle xray scattering (SAXS) in supercritical CO2, as well as in water/CO2 emulsions. These copolymers were designed to have the same molecular weight and composition, and to differ only by their macromolecular architecture. The investigated copolymers have random, block, and palm-tree architectures. Besides, thermo-responsive copolymer is also analysed, having a hydrophilic sequence becoming water-insoluble around 41 °C, i.e. just above the critical point of CO2. At the length scale investigated by SAXS, only the random copolymer appears to self-assemble in pure CO2, in the form of a disordered microgel-like network. The random, block and thermo-responsive copolymers are all able to stabilize water/CO2 emulsions but not the copolymer with the palm-tree architecture, pointing at the importance of macromolecular architecture for the emulsifying properties. A modelling of the SAXS data shows that the block and the thermo-responsive copolymers form spherical micelle-like structures containing about 70 % water and 30 % polymer.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Physics Materials science & engineering
Author, co-author :
Alaimo, David ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Hermida Merino, Daniel; European Synchrotron Radiation Facility
Grignard, Bruno ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Bras, Wim; European Synchrotron Radiation Facility
Jérôme, Christine ; 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)
Gommes, Cédric ; Université de Liège - ULiège > Département de chimie appliquée > Département de chimie appliquée
Language :
English
Title :
Small Angle X-ray Scattering Insights into the Architecture-Dependent Emulsifying Properties of Amphiphilic Copolymers in Supercritical Carbon Dioxide
Publication date :
2015
Journal title :
Journal of Physical Chemistry B
ISSN :
1520-6106
eISSN :
1520-5207
Publisher :
American Chemical Society, Washington, United States - District of Columbia
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Bibliography
Gever, S.; Schulmeyr, J. Ecological and gentle technology - CO2 Extraction and Its Use in Food Technology. Innovations Food Technol. 2007, 34, 44-46.
Diaz-Reinoso, B.; Moure, A.; Dominguez, H.; Parajo, J. C. Supercritical CO2 Extraction and Purification of Compounds with Antioxidant Activity. J. Agric. Food Chem. 2006, 54 (7), 2441-69.
Mikami, K. Green Reaction Media in Organic Synthesis; Wiley-Blackwell, 2005; pp 125-182.
DeSimone, J. M.; Tumas, W. Green Chemistry Using Liquid and Supercritical Carbon Dioxide, Oxford University Press: Oxford, U.K., 2003; 48-63
Park, E. J.; Richez, A. P.; Birkin, N. A.; Lee, H.; Arrowsmith, N.; Thurecht, K. J.; Howdle, S. M. New Vinyl Ester Copolymers as Stabilizers for Dispersion Polymerization in scCO2. Polymer 2011, 52 (24), 5403-5409.
Galia, A.; Giaconia, A.; Iaia, V.; Filardo, G. Synthesis of Hydrophilic Polymers in Supercritical Carbon Dioxide in the Presence of a Siloxane-Based Macromonomer Surfactant: Heterogeneous Polymerization of 1-Vinyl-2 Pyrrolidone. J. Polym. Sci., Part A: Polym. Chem. 2003, 42 (1), 173-185.
Ma, Z.; Lacroix-Desmazes, P. Dispersion Polymerization of 2-Hydroxyethyl Methacrylate Stabilized by a Hydrophilic/CO2-Philic Poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) (PEO-b-PFDA) Diblock Copolymer in Supercritical Carbon Dioxide. Polymer 2004, 45 (20), 6789-6797.
Shiho, H.; Desimone, J. M. Dispersion Polymerization of Styrene in Supercritical Carbon Dioxide Utilizing Random Copolymers Containing a Fluorinated Acrylate for Preparing Micron-Size Polystyrene Particles. J. Polym. Sci., Part A: Polym. Chem. 2000, 38 (7), 1146-1153.
Hsiao, Y.-L.; Maury, E. E.; DeSimone, J. M.; Mawson, S.; Johnston, K. P. Dispersion Polymerization of Methyl Methacrylate Stabilized with Poly(1,1-dihydroperfluorooctyl acrylate) in Supercritical Carbon Dioxide. Macromolecules 1995, 28 (24), 8159-66.
Carson, T.; Lizotte, J.; Desimone, J. M. Dispersion Polymerization of 1-Vinyl-2-pyrrolidone in Supercritical Carbon Dioxide. Macromolecules 2000, 33 (6), 1917-1920.
Shiho, H.; DeSimone, J. M. Dispersion Polymerization of 2-Hydroxyethyl Methacrylate in Supercritical Carbon Dioxide. J. Polym. Sci., Part A: Polym. Chem. 2000, 38 (20), 3783-3790.
Psathas, P. A.; Janowiak, M. L.; Garcia-Rubio, L. H.; Johnston, K. P. Formation of Carbon Dioxide in Water Miniemulsions Using the Phase Inversion Temperature Method. Langmuir 2002, 18 (8), 3039-3046.
Lee, C. T., Jr.; Psathas, P. A.; Johnston, K. P.; DeGrazia, J.; Randolph, T. W. Water-in-Carbon Dioxide Emulsions: Formation and Stability. Langmuir 1999, 15 (20), 6781-6791.
Yazdi, A. V.; Beckman, E. J. Design of highly CO2-soluble chelating agents for carbon dioxide extraction of heavy metals. J. Mater Res. 1995, 10 (3), 530-537.
Yazdi, A. V.; Lepilleur, C.; Singley, E. J.; Liu, W.; Adamsky, F. A.; Enick, R. M.; Beckman, E. J. Highly Carbon Dioxide Soluble Surfactants, Dispersants and Chelating Agents. Fluid Phase Equilib. 1996, 117 (1-2), 297-303.
Shiho, H.; DeSimone, J. M. Dispersion Polymerization of Glycidyl Methacrylate in Supercritical Carbon Dioxide. Macromolecules 2001, 34 (5), 1198-1203.
Giles, M. R.; Griffiths, R. M. T.; Aguiar-Ricardo, A.; Silva, M. M. C. G.; Howdle, S. M. Fluorinated Graft Stabilizers for Polymerization in Supercritical Carbon Dioxide: The Effect of Stabilizer Architecture. Macromolecules 2000, 34 (1), 20-25.
Dickson, J. L.; Psathas, P. A.; Salinas, B.; Ortiz-Estrada, C.; Luna-Barcenas, G.; Hwang, H. S.; Lim, K. T.; Johnston, K. P. Formation and Growth of Water-in-CO2 miniemulsions. Langmuir 2003, 19 (12), 4895-4904.
Lepilleur, C.; Beckman, E. J. Dispersion Polymerization of Methyl Methacrylate in Supercritical CO2. Macromolecules 1997, 30 (4), 745-756.
Baran, N.; Deniz, S.; Akguen, M.; Uzun, I. N.; Dincer, S. Dispersion Polymerization of Styrene in Supercritical Carbon Dioxide using Monofunctional Perfluoropolyether and Silicone-Containing Fluoroacrylate Stabilizers. Eur. Polym. J. 2005, 41 (5), 1159-1167.
Shiho, H.; DeSimone, J. M. Dispersion Polymerization of Acrylonitrile in Supercritical Carbon Dioxide. Macromolecules 2000, 33 (5), 1565-1569.
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), 4241-9.
Londono, J. D.; Dharmapurikar, R.; Cocharn, H. D.; Wignall, G. D.; McClain, J. B.; Betts, D. E.; Canelas, D. A.; DeSimone, J. M.; Samulski, E. T.; Chillura-Martino, D.; et al. The Morphology of Block Copolymer Micelles in Supercritical Carbon Dioxide by Small-Angle Neutron and X-ray Scattering. J. Appl. Crystallogr. 1997, 30 (5), 690-695.
Liu, L.-Z.; Cheng, Z.; Inomata, K.; Zhou, S.; Chu, B. Synchrotron SAXS and Laser Light Scattering Studies of Aggregation Behavior of Poly(1,1-dihydroperfluorooctyl acrylate-b-vinyl acetate) Diblock Copolymer in Supercritical Carbon Dioxide. Macromolecules 1999, 32 (18), 5836-5845.
Lo Celso, F.; Triolo, A.; Triolo, F.; Donato, D. I.; Steinhart, M.; Kriechbaum, M.; Amenitsch, H.; Triolo, R. Synchrotron SAXS Investigation on Aggregation Phenomena in Supercritical CO2. Eur. Phys. J. E: Soft Matter Biol. Phys. 2002, 8 (3), 311-314.
Triolo, A.; Lo Celso, F.; Triolo, F.; Amenitsch, H.; Steinhart, M.; Thiyagarajan, P.; Wells, S.; DeSimone, J. M.; Triolo, R. Kinetics of Block Copolymer Aggregation in Supercritical CO2. J. Non-Cryst. Solids 2002, 307-310, 725-730.
Liu, J.; Han, B.; Li, G.; Zhang, X.; He, J.; Liu, Z. Investigation of Nonionic Surfactant Dynol-604 Based Reverse Microemulsions Formed in Supercritical Carbon Dioxide. Langmuir 2001, 17 (26), 8040-8043.
Liu, J.; Zhang, J.; Mu, T.; Han, B.; Li, G.; Wang, J.; Dong, B. An Investigation of Non-fluorous Surfactant Dynol-604 Based Water-in-CO2 Reverse Micelles by Small Angle X-ray Scattering. J. Supercrit. Fluids 2003, 26 (3), 275-280.
Zhang, J.; Han, B.; Liu, J.; Zhang, X.; Yang, G.; He, J.; Liu, Z.; Jiang, T.; Wang, J.; Dong, B. Effect of Compressed CO2 on the Size and Stability of Reverse Micelles. Small-Angle X-ray Scattering and Phase Behavior Study. J. Chem. Phys. 2003, 118 (7), 3329-3333.
Zhang, J.; Han, B.; Zhao, Y.; Li, J.; Yang, G. Switching Micellization of Pluronics in Water by CO2. Chem.-Eur. J. 2011, 17 (15), 4266-4272.
Ganapathy, H. S.; Hwang, H. S.; Lee, M. Y.; Jeong, Y. T.; Gal, Y.-S.; Lim, K. T. Stabilizer Architectures Based on Fluorinated Random and Block Copolymers for the Dispersion Polymerization of 2-Hydroxyethyl Methacrylate in Supercritical Carbon Dioxide. J. Mater. Sci. 2008, 43 (7), 2300-2306.
Oh, K. S.; Bae, W.; Kim, H. Dispersion Polymerization of 2-Hydroxyethyl Methacrylate (HEMA) Using Siloxane-Based Surfactant in Supercritical Carbon Dioxide and in Compressed Liquid Dimethyl Ether. Eur. Polym. J. 2008, 44 (2), 415-425.
Alaimo, D.; Beigbeder, A.; Dubois, P.; Broze, G.; Jerome, C.; Grignard, B. Block, Random and Palm-Tree Amphiphilic Fluorinated Copolymers: Controlled Synthesis, Surface Activity and Use as Dispersion Polymerization Stabilizers. Polym. Chem. 2014, 5 (18), 5273-5282.
Lutz, J.-F.; Akdemir, Ö.; Hoth, A. Point by Point Comparison of Two Thermosensitive Polymers Exhibiting a Similar LCST: Is the Age of Poly(NIPAM) Over? J. Am. Chem. Soc. 2006, 128 (40), 13046-13047.
Glinel, K.; Jonas, A. M.; Jouenne, T.; Leprince, J.; Galas, L.; Huck, W. T. S. Antibacterial and Antifouling Polymer Brushes Incorporating Antimicrobial Peptide. Bioconjugate Chem. 2009, 20 (1), 71-77.
Lutz, J.-F.; Hoth, A. Preparation of Ideal PEG Analogues with a Tunable Thermosensitivity by Controlled Radical Copolymerization of 2-(2-Methoxyethoxy)ethyl Methacrylate and Oligo(ethylene glycol) Methacrylate. Macromolecules 2005, 39 (2), 893-896.
Roy, D.; Brooks, W. L. A.; Sumerlin, B. S. New Directions in Thermoresponsive Polymers. Chem. Soc. Rev. 2013, 42 (17), 7214-7243.
de las Heras Alarcon, C.; Pennadam, S.; Alexander, C. Stimuli Responsive Polymers for Biomedical Applications. Chem. Soc. Rev. 2005, 34 (3), 276-285.
Glatter, O.; Kratky, O., Eds. Small Angle X-ray Scattering; Academic Press: New York, 1982; 515 pp.
Feigin, L. A.; Svergun, D. I. Structure Analysis by Small-Angle Xray and Neutron Scattering; Plenum Press: New York, 1987.
Pedersen, J. S. Analysis of Small-Angle Scattering Data from Colloids and Polymer Solutions: Modeling and Least-Squares Fitting. Adv. Colloid Interface Sci. 1997, 70 (0), 171-210.
Sivia, D. S. Elementary Scattering Theory: For X-ray and Neutron Users; Oxford University Press: Oxford, U.K., 2011.
Gommes, C. J.; Pirard, J.-P.; Goderis, B. Condensation-Induced Decrease of Small-Angle X-ray Scattering Intensity in Gelling Silica Solutions. J. Phys. Chem. C 2010, 114 (41), 17350-17357.
Stryjek, R.; Vera, J. H. PRSV: An Improved Peng-Robinson Equation of State for Pure Compounds and Mixtures. Can. J. Chem. Eng. 1986, 64 (2), 323-333.
Bras, W.; Dolbnya, I. P.; Detollenaere, D.; van Tol, R.; Malfois, M.; Greaves, G. N.; Ryan, A. J.; Heeley, E. Recent Experiments on a Small-Angle/Wide-Angle X-ray Scattering Beam Line at the ESRF. J. Appl. Crystallogr. 2003, 36 (3, Pt. 1), 791-794.
Hermida-Merino, D.; Portale, G.; Fields, P.; Wilson, R.; Bassett, S. P.; Jennings, J.; Dellar, M.; Gommes, C.; Howdle, S. M.; Vrolijk, B. C. M.; et al. A High Pressure Cell for Supercritical CO2 On-line Chemical Reactions Studied with X-ray Techniques. Rev. Sci. Instrum. 2014, 85 (9), No. 093905.
Huang, T. C.; Toraya, H.; Blanton, T. N.; Wu, Y. X-ray Powder Diffraction Analysis of Silver Behenate, a Possible Low-Angle Diffraction Standard. J. Appl. Crystallogr. 1993, 26 (2), 180-184.
Gommes, C. J.; Goderis, B. CONEX, a Program for Angular Calibration and Averaging of Two-Dimensional Powder Scattering Patterns. J. Appl. Crystallogr. 2010, 43 (2), 352-355.
Debye, P. Molecular-Weight Determination by Light Scattering. J. Phys. Colloid Chem. 1947, 51, 18-32.
Nakano, M.; Deguchi, M.; Matsumoto, K.; Matsuoka, H.; Yamaoka, H. Self-Assembly of Poly(1,1-diethylsilabutane)-block-poly-(2-hydroxyethyl methacrylate) Block Copolymer. 1. Micelle Formation and Micelle-Unimer-Reversed Micelle Transition by Solvent Composition. Macromolecules 1999, 32 (22), 7437-7443.
Hammouda, B. A New Guinier-Porod Model. J. Appl. Crystallogr. 2010, 43 (4), 716-719.
De Gennes, P.-G. Scaling Concepts in Polymer Physics; Cornell University Press: Ithaca, NY, USA, 1979.
Billmeyer, F. W., Jr. Textbook of Polymer Science, 3rd ed.; Tokyo Denki University Press: Tokyo, 1989.
Pedersen, J. S.; Gerstenberg, M. C. Scattering Form Factor of Block Copolymer Micelles. Macromolecules 1996, 29 (4), 1363-1365.
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