Interfacial properties of branch-tailed fluorinated surfactants yielding a water/supercritical CO2 microemulsion

We have examined the interfacial properties of several fluorinated surfactants in a water/CO2 mixture with a pendant drop tensiometer and revealed the relationships between the interfacial properties, the surfactant structure, and the microemulsifying power. We employed the following Aerosol-OT analogue surfactants that have two fluorinated tails: bis(1H,1H,5H-octafluoropentyl)-2-sulfosuccinate (di-HCF4), sodium bis(1H,1H,9H-hexadecafluorononyl)-2-sulfosuccinate (di-HCF8), sodium bis(1H,1H,2H,2H-heptadecafluorodecyl)-2-sulfosuccinate (8FS(EO)2), and sodium bis((1H,1H,2H,2H-heptadecafluorodecyl)-oxyethylene)-2-sulfosuccinate (8FS(EO)4). To discuss the effect of the fluorocarbon/hydrocarbon ratio in single surfactant molecules, water/CO2 interfacial tension (IFT) of a hybrid surfactant with one fluorocarbon and one hydrocarbon tail, that of a surfactant with a single fluorinated tail, and that of a hydrocarbon surfactant, Aerosol-OT (AOT), were examined. The hybrid surfactant employed was sodium 1-oxo-1-[4-(tridecafluorohexyl)phenyl]-2-hexanesulfonate (FC6-HC4), and the single-tailed surfactant was perfluoropolyether ammonium carboxylate (PFPECOONH4, CF3CF2(CF2OCF(CF3))4COONH4). All of the fluorinated AOT analogue surfactants exhibited an excellent level of activity at the water/CO2 interface compared with other fluorinated surfactants and AOT. With a larger hydrocarbon chain number in the CO2-philic tails (i.e., from 0 to 2), the IFT of the AOT analogue surfactants was increased. The area occupied by one surfactant molecule at the water/CO2 interface, A, and the critical microemulsion concentration, cmicroc, were determined and used to examine the water-to-surfactant molar ratio within a reversed micelle, W0c, of the surfactants. The surfactants that form W/scCO2 microemulsions with a large W0c were found to lower the interfacial tension efficiently irrespective of increases in temperature. To achieve the most desirable W0C, the surfactant needs not only a high CO2-philicity of the tails but also a high Krafft point, properties which induce a low hydrophilic/CO2-philic balance.     

Optimum tail length of fluorinated double-tail anionic surfactant for water/supercritical CO2 microemulsion formation

The effect of surfactant tail structure on the stability of a water/supercritical CO2 microemulsion (W/scCO2 muE) was examined for various fluorinated double-tail anionic surfactants of different fluorocarbon chain lengths, F(CF2)n (n = 4, 6, 8, and 10), and oxyethylene spacer lengths, (CH2CH2O)(m/2) (m = 2 and 4). The phase behavior of the water/surfactant/CO2 systems was studied over a wide range of CO2 densities from 0.70 to 0.85 g/cm(3) (temperatures from 35 to 75 degrees C and pressures up to 500 bar) and corrected water-to-surfactant molar ratios (W0c). All of the surfactants yielded a W/scCO2 muE phase, that is, a transparent homogeneous phase with a water content larger than that permitted by the solubility of water in pure CO2. With increasing W0c, a phase transition occurred from the muE phase to a macroemulsion or a lamella-like liquid crystal phase. The maximum W0c value was obtained at a tail length of 12-14 A, indicating the presence of an optimum surfactant tail length for W/scCO2 muE formation.     

Self-assembly of phosphate fluorosurfactants in carbon dioxide

Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and H/F types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scatteringwas used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions.     

Phase behavior of CO2-expanded fluorinated microemulsions

The formation of CO2-expanded, fluorinated reverse microemulsions is demonstrated for the system of perfluoropolyether (PFPE) surfactant (ClPFPE-NH4, MW = 632) and PFPE oil (PFPE, MW = 580). The phase behavior of this system is examined as a function of temperature (25-45 degrees C), pressure, CO2 concentration, and water to surfactant molar ratios (W0 = 10 and 20). Visual observations of one-phase behavior consistent with reverse microemulsion formation are further supported by spectroscopic measurements that establish the existence of a bulk water environment within the aqueous core. Microemulsion formation is not observed in the absence of CO2 for this PFPE surfactant/PFPE oil system, and a CO2 content greater than 70 mol % is required to induce microemulsion formation. Over the range of water loadings and temperatures investigated, the lowest cloud point pressure is observed at 46 bar (5 wt % ClPFPE-NH4 in PFPE oil, W0 = 20, xCO2 = 0.7, T = 25 degrees C). In the regions where one-phase behavior is observed, the cloud point pressures increase with temperature, water loadings, and CO2 content. The driving forces of microemulsion formation in the CO2-expanded fluorinated solvent are discussed relative to traditional reverse microemulsions and CO2-continuous microemulsions.     

Effective and efficient surfactant for CO2 having only short fluorocarbon chains

A previous study (Langmuir2011, 27, 5772) found the fluorinated double-tail sulfogulutarate 8FG(EO)(2) to act as a superefficient solubilizer for water in supercritical CO(2) (W/CO(2)) microemulsions. To explore more economic CO(2)-philic surfactants with high solubilizing power as well as rapid solubilization rates, the effects of fluorocarbon chain length and linking group were examined with sodium 1,5-bis(1H,1H,2H,2H-perfluoroalkyloxy)-1,5-dioxopentane-2-sulfonates (nFG(EO)(2), fluorocarbon chain length n = 4, 6, 8) and sodium 1,4-bis(1H,1H,2H,2H-perfluoroalkyloxy)-1,4-dioxobutane-2-sulfonate (nFS(EO)(2), n = 4, 8). Visual observation and UV-vis spectral measurements with methyl orange as a reporter dye indicated a maximum water-to-surfactant molar ratio (W(0)) in the microemulsions, which was 60-80 for nFG(EO)(2) and 40-50 for nFG(EO)(2). Although it is normally expected that high solubilizing power requires long fluorocarbon surfactant chains, the shortest fluorocarbon 4FG(EO)(2) interestingly achieved the highest W(0) (80) transparent single-phase W/CO(2) microemulsion. In addition, a very rapid solubilization of loaded water into CO(2) was observed for 4FG(EO)(2) even at a high W(0) of ~80.     

Hybrid fluorocarbon-hydrocarbon CO2-philic surfactants. 1. synthesis and properties of aqueous solutions

Six different hybrid fluorocarbon-hydrocarbon (F-H) sulfate and sulfonate surfactants, with variations in the relative F/H carbon chain length, have been synthesized and characterized in aqueous solution. These compounds have been targeted for potential activity in densified CO2. Tensiometric data and chemical analyses were consistent with surfactants of high chemical purity. Fluorination in terms of the F/H ratio exerts a strong control over all the surfactant physicochemical properties, including critical micelle concentrations (cmc's) and adsorption isotherms. One of these partially fluorinated surfactants (the sulfonate phi-F6H4) achieves very low surface tensions in water (gamma(cmc) approximately 19 mN m(-1)) more reminiscent of fully fluorinated double-chain compounds. Detailed 19F NMR studies revealed that omega'-CF3 groups can exhibit separate signals for monomeric and micellized forms, hence facilitating cmc determinations. Small-angle neutron scattering investigations confirmed the presence of ellipsoidal or extended disklike micelles, depending on the F-H chain asymmetry. For example, a symmetric hybrid F8H8 generates disklike micelles, whereas chain asymmetry in F8H4 or phi-F6H4 tends to drive cylindrical aggregation structures. These changes are consistent with variations in the surfactant packing parameter caused by the different chain F/H ratios. Hence, adsorption and aggregation are shown to respond in a predictable way to the molecular structure of these unusual surfactants.     

Mild-temperature Mn2(CO)10-photomediated controlled radical polymerization of vinylidene fluoride and synthesis of well-defined poly(vinylidene fluoride) block copolymers

By contrast to typical high-temperature (100-250 °C) telo-/polymerizations of gaseous fluorinated monomers, carried out in high-pressure metal reactors, the visible light, Mn(2)(CO)(10)-photomediated initiation of vinylidene fluoride (bp = -83 °C) polymerization occurs readily from a variety of alkyl, semifluorinated, and perfluorinated halides at 40 °C, in low-pressure glass tubes and in a variety of solvents, including water and alkyl carbonates. Perfluorinated alkyl iodide initiators also induce a controlled radical polymerization via iodine degenerative transfer (IDT). While IDT proceeds with accumulation of the less reactive P(m)-CF(2)-CH(2)-I vs the P(n)-CH(2)-CF(2)-I chain ends, Mn(2)(CO)(10) enables their subsequent quantitative activation toward the synthesis of well-defined poly(vinylidene fluoride) block copolymers with a variety of other monomers.     

Dynamical and rheological properties of fluorinated surfactant films adsorbed at the pressurized CO2-H2O interface

The dynamics of adsorption, interfacial tension, and rheological properties of two phosphocholine-derived partially fluorinated surfactants FnHmPC, designed to compensate for the weak CO(2)-surfactant tail interactions, were determined at the pressurized CO(2)-H(2)O interface. The two surfactants differ only by the length of the hydrocarbon spacer (5 CH(2) in F8H5PC and 11 CH(2) in F8H11PC) located between the terminal perfluoroalkyl chain and the polar head. The length of this spacer was found to have a critical impact on the adsorption kinetics and elasticity of the interfacial surfactant film. F8H5PC is soluble in both water and CO(2) phases and presents several distinct successive interfacial behaviors when bulk water concentration (C(W)) increases and displays a nonclassical isotherm shape. The isotherms of F8H5PC are similar for the three CO(2) pressures investigated and comprise four regimes. In the first regime, at low C(W), the interfacial tension is controlled by the organization that occurs between H(2)O and CO(2). The second regime corresponds to the adsorption of the surfactant as a monolayer until the CO(2) phase is saturated with F8H5PC, resulting in a first inflection point. In this regime, F8H5PC molecules reach maximal compaction and display the highest apparent interfacial elasticity. In the third regime, a second inflection is observed that corresponds to the critical micelle concentration of the surfactant in water. At the highest concentrations (fourth regime), the interfacial films are purely viscous and highly flexible, suggesting the capacity for this surfactant to produce water-in-CO(2) microemulsion. In this regime, surfactant adsorption is very fast and equilibrium is reached in less than 100 s. The behavior of F8H11PC is drastically different: it forms micelles only in the water phase, resulting in a classical Gibbs interface. This surfactant decreases the interfacial tension down to 1 mN/m and forms a strongly elastic interface. As this surfactant forms a very cohesive interface, it should be suitable for formulating stable water-in-CO(2) emulsions. The finding that the length of the hydrocarbon spacer in partially fluorinated surfactants can drastically influence film properties at the CO(2)-H(2)O interface should help control the formation of microemulsions versus emulsions and help elaborate a rationale for the design of surfactants specifically adapted to pressurized CO(2).     

Extraction of lanthanides from aqueous solution by using room-temperature ionic liquid and supercritical carbon dioxide in conjunction

For the first time, the study of a three-step extraction system of water/ionic liquid/supercritical CO2 has been performed. Extraction of trivalent lanthanum and europium from an aqueous nitric acid solution to a supercritical CO2 phase via an imidazolium-based ionic liquid phase is demonstrated, and extraction efficiencies higher than 87 % were achieved. The quantitative extraction is obtained by using different fluorinated beta-diketones with and without the addition of tri(n-butyl)phosphate. The complexation phenomenon occurring in the room-temperature ionic-liquid (RTIL) phase was evidenced by using luminescence spectroscopy.     

Supercritical carbon dioxide processing of fluorinated surfactant templated mesoporous silica thin films

The effect of processing mesoporous silica thin films with supercritical CO2 immediately after casting is investigated, with a goal of using the penetration of CO2 molecules in the tails of fluorinated surfactant templates to tailor the final pore size. Well-ordered films with two-dimensional hexagonal close-packed pore structure are synthesized using a cationic fluorinated surfactant, 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)pyridinium chloride, as a templating agent. Hexagonal mesopore structures are obtained for both unprocessed films and after processing the cast films in CO2 at constant pressure (69-172 bar) and temperature (25-45 degrees C) for 72 h, followed by traditional heat treatment steps. X-ray diffraction and transmission electron microscopy analysis reveal significant increases in pore size for all CO2-treated thin films (final pore diameter up to 4.22 +/- 0.14 nm) relative to the unprocessed sample (final pore diameter of 2.21 +/- 0.20 nm) before surfactant extraction. Similar pore sizes are obtained with liquid and supercritical fluid treatments over the range of conditions tested. These results demonstrate that combining the tunable solvent strength of compressed and supercritical CO2 with the "CO2-philic" nature of fluorinated tails allows one to use CO2 processing to control the pore size in ordered mesoporous silica films.     

Adsorption of gemini surfactants with partially fluorinated chains at three different surfaces: neutron reflectometry results

The adsorption of six symmetrical cationic (dimethylammonium bromide) gemini surfactants with four different partially fluorinated chains at three different surfaces--the air/water, the hydrophilic silica/water, and the hydrophobic (octadecyltricholorosilane (OTS))/water--has been investigated by neutron reflectometry. The corresponding single chain trimethylammonium bromides have also been studied at the two solid surfaces. Four of the geminis with a C(6) spacer and chains with differing amounts of fluorocarbon have identical limiting areas per molecule at the air/water interface (106 ± 5 ?(2)). This is similar to the value for the corresponding hydrocarbon gemini with a C(6) spacer and C(12) side chains, but unlike the hydrocarbon gemini, it is significantly more than twice the area per molecule of the corresponding single chain cationic. In adsorbed aggregates on hydrophilic silica the area per molecule decreases from the air/water value by an average of about 25%, indicating a substantial improvement in the packing of these geminis in the aggregate, which can be attributed to the stronger interaction between the hydrophobic chains in the interior of the aggregates. On the hydrophobic OTS surface the area per molecule in the adsorbed monolayer for three partially fluorinated geminis decreased by about 15% from the air/water value, again indicating much more favorable packing next to the hydrophobic OTS, but for one of the geminis, fC(8)C(6)-C(6)-C(6)fC(8), the change in area was reversed. This reversal is accompanied by a marked thinning of the layer, which is attributed to a shift in the balance between the interactions of the hydrocarbon spacer and fluorocarbon chain fragments and the OTS surface.     

The synthesis of laterally fluorinated alkoxystilbazoles and some of their mesogenic complexes with Ir(I). The molecular structure of trans-4-undecyloxy-3-fluoro-4'-stilbazole

A series of 3-fluorinated 4-alkoxystilbazoles (n-3F-OPhVPy) and some of the related 2-fluorinated derivatives (n-2F-OPhVPy) have been synthesized; unlike their non-fluorinated counterparts, these new stilbazoles are non-mesomorphic. A single crystal structure determination of 3-fluoro-4-undecyloxy-4'-stilbazole shows the molecule to be planar, trans with respect to the double bond and to crystallize in only one of two possible extreme rotational conformers. Reaction of these fluorinated stilbazoles with [IrCl(COD)]₂ under CO affords the complexes cis-[IrCl(CO)₂(n-XF-OPhVPY)] which are non-mesomorphic for X = 3, but have monotropic phases for X = 2.     

Synthesis of polysiloxane xerogels with fluorine-containing groups in the surface layer and their sorption properties

Hydrolysis and polycondensation reactions of tetraethoxysilane (TEOS) with 3,3,3-trifluoropropyl-trimethoxysilane (TFMS) or 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFES) were used to synthesize xerogels functionalized with fluorine-containing groups. According to transmission electron microscopy, the skeletons of synthesized polysiloxane xerogels have globular structures and consist of agglomerates of particles with fluorinated groups on their surfaces. FTIR spectroscopy showed that primary xerogel particles possess spatial polysiloxane networks, with fluorinated groups along with silanol groups and water in the surface layer. According to thermal analyses, the water content was 3–8 wt.%, and it decreased with increasing length of the fluorinated chain. Thermal destruction of the surface layer starts above 300 °C. The sorbents that were obtained were predominantly mesoporous materials with well-developed porous structures (S_BET = 400–960 m² g⁻¹, V_s = 0.66–0.93 cm³ g⁻¹). The influence of the TEOS/functional silane ratio and the natures of the functional groups on the structural and adsorptive properties were shown. The samples synthesized are organophilic. The affinity for n-hexane increases with increasing length of the fluorine-containing chain (PFES) and the content of fluorinated groups in the surface layer. The hybrid organic–inorganic materials that were obtained can be used for adsorption of hydrocarbons, including oil, from water.     

活性聚合法合成结构精确的含氟嵌段共聚物

结构精确的含氟嵌段共聚物具有优异而独特的化学和物理性能,有广阔的应用前景,因此受到广泛的关注.含氟嵌段共聚物可分为两类,一类是侧基含氟嵌段共聚物,另一类是主链含氟嵌段共聚物.活性聚合为嵌段共聚物的合成提供了最为重要的方法,利用它可以合成结构精确、分子量可控、分子量分布窄的嵌段共聚物.根据单体的反应特性选择不同的聚合方法,可以得到不同的含氟嵌段共聚物.本文主要综述了近几年利用各种活性聚合方法合成结构精确的含氟嵌段共聚物方面的进展.     

Extraction of chromium(III) and chromium(VI) species from solid matrices using green solvent supercritical carbon dioxide.

Supercritical fluid extraction (SFE) provides an environmentally green technique to decontaminate chromium species from solid matrices using supercritical fluid carbon dioxide (ScCO2). Methanol and a small amount of water were found to significantly improve the extraction efficiency. The fluorinated chelating agent lithium bis(trifluoroethyl)-dithiocarbamate (LiFDDC) was effective in removing Cr ions in methanol-modified CO2 via in situ chelation/SFE technique. This paper indicates that the extraction efficiencies of Cr(III) and Cr(VI) from solid matrices can be greatly increased to more than 92% in the presence of a small amount of water, using 5% methanol-modified CO2 containing LiFDDC as an extractant. Chromium species in a wood waste sample in the form of chromated copper arsenate (CCA) can be extracted, but the extraction efficiency is not as good as expected, possibly due to the complications of the chemistry of Cr species in different oxidation states and to matrix effects.     

Optimisation of a gas chromatographic method for trace gaseous impurities in nitrogen trifluoride by column sequence reversal

Highly reactive fluorinated gaseous matrices require special equipment and techniques for the gas chromatographic analysis of trace impurities in these gases. The impurities that were analysed at the low mg/L levels included dioxygen (O2), dinitrogen (N2), carbon dioxide (CO2), carbon monoxide (CO), sulfur hexafluoride (SF6), methane (CH4) and nitrous oxide (N2O). Carbon tetrafluoride (CF4) is also present in the product at levels of 20-400mg/L and had to be analysed as well. This paper compares the use of a custom-built dual-channel gas chromatograph utilising single column back flush switching on one channel for the determination of O2, N2, CH4 and CO with column sequence reversal on a second channel for the determination of CO2, N2O, SF6 and CF4 to a similar system using a combination of dual-column back flush and heart-cut configurations. Pulsed discharge helium ionisation detectors were used on both channels in both configurations.     

Surfactant-mixing effects on the interfacial tension and the microemulsion formation in water/supercritical CO2 system

The effects of surfactant mixing on interfacial tension and on microemulsion formation were examined for systems of air/water and water/supercritical CO2 (scCO2) interfaces and for water/scCO2 microemulsions. A fluorinated surfactant, sodium bis(1H,1H,2H,2H-heptadecafluorodecyl)-2-sulfosuccinate (8FS(EO)2), was mixed with the three hydrocarbon surfactants, Pluronic L31, Tergitol TMN-6, and decyltrimethylammonium chloride (DeTAC), at equimolar ratio. For all the cases, the interfacial tension was significantly lowered by the mixing. The positive synergistic effect suggests that the mixed surfactants tend to pack more closely on the interface than the pure constituents. It was found, however, that the microemulsion formation in scCO2 was never facilitated by the mixing, except for the case of TMN-6. This is probably due to the segregation of the surfactants into hydrocarbon-rich and fluorocarbon-rich phases on the microemulsion surface.     

Preparation and applications of a variety of fluoroalkyl end-capped oligomer/hydroxyapatite composites

A variety of fluoroalkyl end-capped oligomers were applied to the preparation of fluorinated oligomer/hydroxyapatite (HAp) composites (particle size: 38-356 nm), which exhibit a good dispersibility in water and traditional organic solvents. These fluoroalkyl end-capped oligomer/HAp composites were easily prepared by the reactions of disodium hydrogen phosphate and calcium chloride in the presence of self-assembled molecular aggregates formed by fluoroalkyl end-capped oligomers in aqueous solutions. In these fluorinated HAp composites thus obtained, fluoroalkyl end-capped acrylic acid oligomers and 2-methacryloyloxyethanesulfonic acid oligomer/HAp nanocomposites afforded transparent colorless solutions toward water; however, fluoroalkyl end-capped N,N-dimethylacrylamide oligomer and acryloylmorpholine oligomer were found to afford transparent colorless solutions with trace amounts of white-colored HAp precipitants under similar conditions. HAp could be encapsulated more effectively into fluorinated 2-methacryloyloxyethanesulfonic acid oligomeric aggregate cores to afford colloidal stable fluorinated oligomer/HAp composites, compared to that of fluorinated acrylic acid oligomers. These fluorinated oligomer/HAp composites were applied to the surface modification of glass and PVA to exhibit a good oleophobicity imparted by fluorine. HAp formation was newly observed on the modified polyethylene terephthalate film surface treated with fluorinated 2-methacryloyloxyethanesulfonic acid oligomers and acrylic acid oligomer/HAp composites by soaking these films into the simulated body fluid.     

Alcohols solubilization in a nonionic fluorinated surfactant based system: effects on the characteristics of mesoporous silica

In this study, we have used hydrogenated alcohols with different chain lengths and one fluorinated alcohol as additives to determine their effect on the characteristics of mesoporous materials prepared from fluorinated micelles.     

Hybrid CO2-philic surfactants with low fluorine content

The relationships between molecular architecture, aggregation, and interfacial activity of a new class of CO(2)-philic hybrid surfactants are investigated. The new hybrid surfactant CF2/AOT4 [sodium (4H,4H,5H,5H,5H-pentafluoropentyl-3,5,5-trimethyl-1-hexyl)-2-sulfosuccinate] was synthesized, having one hydrocarbon chain and one separate fluorocarbon chain. This hybrid H-F chain structure strikes a fine balance of properties, on one hand minimizing the fluorine content, while on the other maintaining a sufficient level of CO(2)-philicity. The surfactant has been investigated by a range of techniques including high-pressure phase behavior, UV-visible spectroscopy, small-angle neutron scattering (SANS), and air-water (a/w) surface tension measurements. The results advance the understanding of structure-function relationships for generating CO(2)-philic surfactants and are therefore beneficial for expanding applications of CO(2) to realize its potential using the most economic and efficient surfactants.