Subscriber access provided by FONDREN LIBRARY, RICE UNIVERSITY
Letter
2
Enhanced Stabilization of Water-scCO Interface by Block-like Spontaneous Gradient Copolymers Xuan Liu, Mingxi Wang, Simon Harrisson, Antoine Debuigne, Jean-Daniel Marty, and Mathias Destarac ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b02779 • Publication Date (Web): 03 Oct 2017 Downloaded from http://pubs.acs.org on October 4, 2017
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
ACS Sustainable Chemistry & Engineering is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 8
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
Enhanced Stabilization of Water-scCO2 Interface by Block-like Spontaneous Gradient Copolymers Xuan Liu,† Mingxi Wang,† Simon Harrisson,† Antoine Debuigne,‡ Jean-Daniel Marty,*, † Mathias Destarac*,† †IMRCP, UMR 5623, Université de Toulouse, 118, route de Narbonne, F-31062 Toulouse, Cedex 9, France ‡CERM, CESAM, University of Liège, 11, Allée du Six Août, B-4000 Liège, Belgium
KEYWORDS: Phase behavior, surface tension, gradient copolymer, supercritical carbon dioxide, RAFT/MADIX. E-mail:
[email protected];
[email protected] ABSTRACT: 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. CO2 and water are the two most abundant and inexpensive molecules on earth. They are environmentally benign, non-toxic and non-flammable fluids. Their combination in chemical processes would offer greener alternatives to traditional organic solvents. In comparison with other fluids, the supercritical state for CO2 (scCO2) is easily accessible since its critical point is located at 31.1 °C and 73.8bar. Using scCO2 as a reaction medium for chemical reactions offers many advantages such as complete elimination of the solvent via simple depressurization. Since water is a highly cohesive and polar solvent, its solubility in scCO2 is extremely low (
