Structural and transport properties of polydimethylsiloxane based polyurethane/silica particles mixed matrix membranes for gas separation

Mixed matrix membranes of synthesized polyurethane (PU) based on toluene diisocyanate (TDI), polydimethylsiloxane (PDMS) and polytetramethylene glycol (PTMG) with polyvinyl alcohol based polar silica particles were prepared by solution casting technique. The homogeneity and thermal properties of the prepared PDMS-PU/silica membranes were characterized using scanning electron microscope (SEM), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The SEM micrographs confirmed the distribution of silica particles in the polymer matrix without agglomerations. Gas permeation properties of membranes with different silica contents were studied for pure CO₂, CH₄, O₂, He and N₂ gases. The obtained results indicated the permeability of the condensable and polar CO₂ gas was enhanced whereas permeability of other gases decreased upon increasing the silica content of the mixed matrix membranes. The permeability of CO₂ and its selectivity over N₂ was increased from 68.4 Barrer and 22 in pure PDMS-PU to 96.7 Barrer and 64.4 in the mixed matrix membranes containing 10 wt% of the silica particles.     

Thermoplastic Polyurethane Elastomers with Aliphatic Hard Segments Based on Plant‐Oil‐Derived Long‐Chain Diisocyanates

Novel plant‐oil‐derived long‐chain (C₁₉ and C₂₃) α,ω‐diisocyanates, optionally in combination with the corresponding long‐chain diols, provide entirely aliphatic hard segments in segmented thermoplastic polyurethane elastomers (TPUs), with carbohydrate‐based poly(trimethylene glycol) soft segments. Compared to materials based on a mid‐chain monomer analog, phase separation is higher due to an increased flexibility of the aliphatic segments. Although melting points are slightly lower than for HDPE, the long‐chain TPU's solid‐state structure is still dominated by hydrogen‐bonding.     

In situ polymerization and characterization of polyester‐based polyurethane/nano‐silica composites

Polyester‐based polyurethane/nano‐silica composites were obtained via in situ polymerization and investigated by Fourier‐transform infrared spectroscopy (FTIR), or FTIR coupled with attenuated total reflectance (FTIR‐ATR), Transmission electron microscopy (TEM), atomic force microscopy (AFM), an Instron testing machine, dynamic mechanical analysis (DMA) and ultraviolet‐visible spectrophotometry (UV‐vis). FTIR analysis showed that in situ polymerization provoked some chemical reactions between polyester molecules and nano‐silica particles. FTIR‐ATR, TEM and AFM analyses showed that both surface and interface contained nano‐silica particles. Instron testing and DMA data showed that introducing nano‐silica particles into polyurethane enhanced the hardness, glass temperature and adhesion strength of polyurethane to the substrate, but also increased the resin viscosity. UV‐vis spectrophotometry showed that nano‐silica obtained by the fumed method did not shield UV radiation in polyurethane films. Copyright © 2003 Society of Chemical Industry     

Current Status and Future Prospect of Polymer‐Layered Silicate Mixed‐Matrix Membranes for CO2/CH4 Separation

The mixed‐matrix membrane (MMM), a state‐of‐the‐art polymer‐inorganic hybrid, is a relatively recent addition to the membrane family which adopts the synergistic advantages of the polymer and inorganic phase. Although marked improvement has been achieved by MMMs in CO₂/CH₄ separation, the development of a defect‐free structure to transcend the Robeson upper bound limit remains a challenge. In previous years, a number of inorganic materials with diverse nature have been studied for CO₂/CH₄ separation; however, layered silicates have not attracted much attention despite their superior thermal and mechanical properties. Analyses of the potential of using layered silicates as inorganic fillers in MMM fabrication for CO₂/CH₄ separation are reviewed. Additionally, the immediate challenges toward successful formation of layered silicate‐based MMM and future prospects are addressed.     

Synthesis and gas transport properties of novel hyperbranched polyimide–silica hybrid membranes

Physical and gas transport properties of hyperbranched polyimide (HBPI)—silica hybrid membranes prepared with a dianhydride monomer, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and triamine monomers, 1,3,5‐tris(4‐aminophenoxy)triazine (TAPOTZ), and 1,3,5‐tris(4‐aminophenyl)benzene (TAPB), were investigated and compared with those of 6FDA‐TAPOB HBPI system synthesized from 6FDA and 1,3,5‐tris(4‐aminophenoxy)benzene (TAPOB). Glass transition and 5% weight‐loss temperatures of the 6FDA‐based HBPI–silica hybrid membranes were increased with increasing silica content. 6FDA‐TAPOTZ HBPI system, however, showed relatively low 5% weight‐loss temperatures, suggesting thermal instability of triazine‐ring in the TAPOTZ moiety. CO₂/CH₄ permselectivity of the HBPI–silica hybrid membranes were increased with increasing silica content, tending to exceed the upper bound for CO₂/CH₄ separation. This result indicated that free volume elements effective for CO₂/CH₄ separation were created by the incorporation of silica for the HBPI–silica hybrid systems. Especially, 6FDA‐TAPB HBPI system had high gas permeabilities and CO₂/CH₄ separation ability, arising from high fractional free volume and characteristic size and distribution of free volume elements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication of Homogenous Polymer‐Zeolite Nanocomposites as Mixed‐Matrix Membranes for Gas Separation

Interfacial void‐free mixed‐matrix membranes (MMMs) of polyimide (PI)/zeolite were developed using 13X and Linde type A nano‐zeolites and tested for gas separation purposes. Fabrication of a void‐free polymer‐zeolite interface was verified by the decreasing permeability developed by the MMMs for the examined gases, in comparison to the pure PI membrane. The molecular sieving effect introduced by zeolite 13X improved the CO₂/N₂ and CO₂/CH₄ selectivity of the MMMs. Separation tests indicated that the manufactured nanocomposite membrane with 30 % loading of 13X had the highest permselectivity for the gas pairs CO₂/CH₄ and CO₂/N₂ at the three examined feed pressures of 4, 8 and 12 atm.     

Enhanced CO2 separation performance for tertiary amine‐silica membranes via thermally induced local liberation of CH3Cl

A facile method for the fabrication of amine‐silica membranes with enhanced CO₂ separation performance was proposed via the thermally induced liberation of small molecules from quaternary ammonium salt. Quaternary ammonium‐silica (QA‐SiO_1.5) xerogel powders/films were fabricated via sol‐gel processing and their thermal stability was systematically studied using thermogravimetric mass spectrometer, Fourier transform infrared, energy dispersive spectroscopy, and positron annihilation lifetime spectroscopy analysis. CO₂ sorption performances of QA‐SiO_1.5 derived xerogel powders were quantitatively compared after assigning their relevant parameters to a dual‐mode sorption model. The gas permeation performances of membranes derived from QA‐SiO_1.5 were evaluated in terms of kinetic diameter and temperature dependence of gas permeance, and activation energy (E_p) required for gas permeation. The results indicate that liberation of the CH₃Cl molecules from these membranes significantly improved both CO₂ permeation and CO₂/N₂ separation capabilities. Therefore, the present study provides insight that should be useful in the development of high‐performance CO₂ separation membranes via the effect of the thermally induced liberation of small molecules. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1528–1539, 2018     

Study on the preparation and thermal shrinkage properties of nano‐SiO2/UHMWPE/HDPE blend microporous membranes

Nano‐SiO₂/UHMWPE/HDPE blend microporous membranes (NBMs) with different content of nano‐SiO₂ particles were prepared via thermally induced phase separation process. Thermogravimetric analysis was used to investigation of the amount of nano‐SiO₂ particles reserved in NBMs. This approach showed that about 59% of total content of nano‐SiO₂ particles reserved in NBMs. The formation and development of the interface pores were studied by scanning electron microscopy. NBMs performance was characterized by a variety of metrics including thermal shrinkage, melting and crystallization behavior, porosity and pore diameter, and permeability. The results indicated that nano‐SiO₂ particles served as nucleating agent increasing the crystalline of NBMs. The comprehensive properties of NBMs were optimum when the content of nano‐SiO₂ particles was 1%. Compared with pure HDPE separators, NBMs exhibit higher porosity and lower thermal shrinkage due to its high crystalline and the enrichment of UHMWPE chains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41321.     

Waterborne poly(urethane‐urea) gas permeation membranes for CO2/CH4 separation

In this work, dense membranes from aqueous dispersions of poly(urethane‐urea) (PUU) based on poly(propylene glycol) (PPG) and a block copolymer composed of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG), EG‐b‐PG, with 7 wt % of the former were obtained. Nonpolluting formulations were synthesized with proportions of PPG and EG‐b‐PG as 1:0, 1:1, 1:3, and 3:1 in terms of equivalent number ratios. The effect of small and gradual increases in PEG segments was evaluated for the permeability of pure CO₂, CH₄, and N₂, at room temperature. Slight increases in PEG‐based segments in PUU promoted some remarkable properties, which led to a simultaneous increase in CO₂ permeability and ideal selectivity for CH₄ (300%) and N₂ (380%). Infrared spectroscopy showed that the PEG portions induced hydrogen bonds between ? NH of urethane and ether groups in the PEG portions, which promoted ordering of the flexible segments, confirmed by X‐ray diffractometry and small‐angle X‐ray scattering. Diffractometry techniques also confirmed the absence of crystalline domains, as did dynamic mechanical analysis. The produced membranes showed performance above Robeson's 2008 upper bound and seemed to be a superior polymeric material for CO₂/CH₄ and CO₂/N₂ separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46003.     

Experimental study of the effect of zeolite 4A treated with magnesium hydroxide on the characteristics and gas‐permeation properties of polysulfone‐based mixed‐matrix membranes

Nowadays, new methods for gas‐separation processes are being quickly developed. The separation of CH₄/CO₂ and CH₄/H₂ is usually the subject of most related research studies, especially in the membrane gas‐separation process, because of their important role in industry. In this study, we attempted to improve the separation properties of a polysulfone/zeolite 4A mixed‐matrix membrane by modifying the zeolite particle surface. The method included a simple ion‐exchange reaction of magnesium chloride with ammonium hydroxide that yielded the formation and precipitation of magnesium hydroxide whiskers on the surface of the zeolites. The whiskers could omit most of the nonselective voids by interlocking the polymer chains through them and, consequently, improve the permeability, selectivity, and elastic modulus of the membranes. X‐ray diffraction, energy‐dispersive X‐ray spectroscopy, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, and dynamic mechanical analysis proved all the changes recorded after the particle and membrane treatments. SEM images showed the petal‐like morphology of the whiskers that formed on the surface of the particles after the reaction against the smooth surface of the untreated zeolite. At a 30 wt % loading of particles in the polymeric matrix, the selectivities for H₂/CH₄ and CO₂/CH₄ increased by 69 and 56%, respectively; in contrast, the H₂ and CO₂ permeabilities decreased by 2.5 and 10%, respectively. The modulus of elasticity for the treated membrane also increased by 14 and 30% compared to those of the pure and untreated membranes, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44329.     

Gas permeation performance of cellulose hollow fiber membranes made from the cellulose/N‐methylmorpholine‐N‐oxide/H2O system

Cellulose hollow fiber membranes (CHFM) were prepared using a spinning solution containing N‐methylmorpholine‐N‐oxide as solvent and water as a nonsolvent additive. Water was also used as both the internal and external coagulant. It was demonstrated that the phase separation mechanism of this system was delayed demixing. The CHFM was revealed to be homogeneously dense structure after desiccation. The gas permeation properties of CO₂, N₂, CH₄, and H₂ through CHFM were investigated as a function of membrane water content and operation pressure. The water content of CHFM had crucial influence on gas permeation performance, and the permeation rates of all gases increased sharply with the increase of membrane water content. The permeation rate of CO₂ increased with the increase of operation pressure, which has no significant effect on N₂, H₂, and CH₄. At the end of this article a detailed comparison of gas permeation performance and mechanism between the CHFM and cellulose acetate flat membrane was given. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1873–1880, 2004     

Mixed matrix membranes of Pebax1657 loaded with iron benzene‐1,3,5‐tricarboxylate for gas separation

Mixed matrix membranes offer major advantages in gas separation processes due to desirable properties found in both organic and inorganic membranes. In this study, a novel mixed matrix membrane was prepared for such application by incorporating iron benzene‐1,3,5‐tricarboxylate (Fe‐BTC) into the poly(amide‐6‐b‐ethylene oxide) (Pebax1657) polymer. Membranes with various loadings of 5, 10, and 20 wt% Fe‐BTC in the polymer matrix were fabricated to investigate the effect of filler loading on the membrane performance. Membranes, prepared by solution‐casting were characterized by scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared, X‐ray diffraction, and tensile test. Pure gas separation of CO₂, CH₄, and N₂ and ideal gas selectivity of CO₂/CH₄ and CO₂/N₂ were performed and permeation tests were carried out under 4, 8, and 12 bar pressures. Results show that adding Fe‐BTC into the Pebax1657 matrix improved both permeability and selectivity of the filled membranes. For instance, 10 wt% loading of Fe‐BTC into the Pebax1657 matrix led to CO₂ permeability increase of 49% as well as CO₂/CH₄ and CO₂/N₂ selectivities enhancements of about 36% and 16%, respectively. POLYM. COMPOS., 38:1363–1370, 2017. © 2015 Society of Plastics Engineers     

Incorporation of carbon nanofibers into a Matrimid polymer matrix: Effects on the gas permeability and selectivity properties

Composite membranes containing carbon nanofibers (CNFs) and Matrimid were prepared by a solution‐casting method. Prepared Matrimid–CNF composite membranes were characterized with X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and mechanical testing techniques. The mechanical properties of the composite membranes increased over that of the pristine polymeric membranes. To develop a broad fundamental understanding of the connection between the composite architecture and gas‐transport properties, both the gas‐permeability and gas‐separation characteristics were evaluated. The gas‐transport properties of the Matrimid–CNF composite membrane was measured with a single gas‐permeation setup (He, H₂, N₂, CH₄ and CO₂) at ambient temperature with the variable‐volume method. The incorporation of CNFs (0.5–10 wt %) into the Matrimid matrix resulted in approximately a 22% reduction in the gas permeation of various gases, (H₂, He, CO₂, N₂, and CH₄). Moreover, an improvement of 1.5 times in the gas selectivity was observed for CO₂/CH₄, H₂/CH₄, He/CH₄, and H₂/N₂ compared to pristine polymeric membrane. Hence, such polymer–CNF composite membranes could be suitable for gas‐separation applications with high purity requirements. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46019.     

Development of ethanolamine‐based ionic liquid membranes for efficient CO2/CH4 separation

This study is focused on the development of ionic liquids (ILs) based polymeric membranes for the separation of carbon dioxide (CO₂) from methane (CH₄). The advantage of ILs in selective CO₂ absorption is that it enhances the CO₂ selective separation for the ionic liquid membranes (ILMs). ILMs are developed and characterized with two different ILs using the solution‐casting method. Three different blend compositions of ILs and polysulfone (PSF) are selected for each ILMs 10, 20, and 30 wt %. Effect of the different types of ILs such as triethanolamine formate (TEAF) and triethanolamine acetate (TEAA) are investigated on PSF‐based ILMs. Field emission scanning electron microscopy analysis of the membranes showed reasonable homogeneity between the ILs and PSF. Thermogravimetric analysis showed that by increasing the ILs loading thermal stability of the membranes improved. Mechanical analysis on developed membranes showed that ILs phase reduced the amount of plastic flow of the PSF phase and therefore, fracture takes place at gradually lower strains with increasing ILs content. Gas permeation evaluation was carried out on the developed membranes for CO₂/CH₄ separation between 2 bar to 10 bar feed pressure. Results showed that CO₂ permeance increases with the addition of ILs 10–30 wt % in ILMs. With 20–30 wt % TEAF‐ILMs and TEAA‐ILMs, the highest selectivity of a CO₂/CH₄ 53.96 ± 0.3, 37.64 ± 0.2 and CO₂ permeance 69.5 ± 0.6, 55.21 ± 0.3 is observed for treated membrane at 2–10 bar. The selectivity using mixed gas test at various CO₂/CH₄ compositions shows consistent results with the ideal gas selectivity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45395.     

Synthesis of polycarbonate‐silica nanocomposites from copolymerization of CO2 with allyl glycidyl ether,cyclohexene oxide,and sol‐gel

The copolymerization of carbon dioxide, allyl glycidyl ether, and cyclohexene oxide catalyzed by the system consisting of Y(CF₃CO₂)₃, Zn(Et)₂, and pyrogallol in the solvent of 1, 3‐dioxolane was performed in this study. The IR, ¹H NMR, and ¹³C‐NMR spectra, as well as the elemental analysis, indicated that the resulting copolymer was an alternating polycarbonate possessing more than 90% of carbonate units. The molecular weight could be as high as 1.5 × 10⁵, and the polydispersity index was 4.5. The resultant polycarbonate was found to effectively react with 3‐(trimethoxysilyl)propyl methacrylate via a free radical reaction to result in a precursor used in the sol‐gel process to synthesize a polycarbonate‐silica nanocomposite. The nanocomposites were characterized by SEM, ²⁹Si NMR, TGA, DSC, and UV–Vis. Silica particles with size less than 100 nm were found to disperse uniformly in the nanocomposites. It was also found that the thermal properties were dependent on the content of cyclohexene carbonate units. Both the thermal and mechanical properties of the resultant nanocomposites could be adjusted with silica content, while the transparency was comparable to the base copolymer even at high silica contents. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 750–757, 2005     

Hydrogen and carbon dioxide adsorption with tetra‐n‐butyl ammonium semi‐clathrate hydrates for gas separations

Gas adsorption rates of H₂, CO₂, and H₂‐CO₂ gas mixture (H₂/CO₂ = 3.4) with tetra‐n‐butyl ammonium salt (bromide, chloride, and fluoride) semi‐clathrate hydrate particles were measured at 269 K to assess their properties for gas separation. Equilibrium gas occupancies in the S‐cages of the particles were in order of (high to low) for hexagonal structure‐I, tetragonal structure‐I, and superlattice of cubic structure‐I structures with the maximum fractional occupancy by CO₂ being about 40%. The CO₂ diffusion rate depended on the anion size of the salt, which is attributed to distortion of the S‐cage that is close to the molecular size of CO₂. Simulations of semi‐clathrate hydrate particles with theory showed that H₂/CO₂ selectivities could be as high as 36 (3.0 mol% TBAF) and that selectivities for an ideal membrane (3.3 mol% TBAF) could be >100 (269 K, 0.3–4.5 MPa). Semi‐clathrate hydrates have wide application as separation media for gas mixtures. © 2014 American Institute of Chemical Engineers AIChE J, 61: 992–1003, 2015     

Removal of hydrogen sulfide from methane using PEO-segmented copolymer-based multilayer composite membrane

The thermoplastic poly(urethane-urea) (PUU) was synthesized using polyethylene-glycol, 4,4?-methylenediphenyl diisocyanate (MDI), and 1,2-ethandiamine (EDA) as a chain extender. A novel multilayer composite membrane consisting of the synthesized PUU, as a selective layer, a silicon rubber, as an interlayer, and the polyacrylonitrile (PAN) microporous support was prepared for the removal of acid gas. Moreover, the physical properties of the synthesized PEG-based polyurethane were investigated. Based on Differential Scanning Calorimeter (DSC) and ANDFourier Transform Infra-red Spectroscopy (FTIR) analyses, a higher microphase separation of hard and soft segments was observed for PUU. The permeabilities of pure CO₂, pure CH₄, and a ternary mixture of CH₄, CO₂, and H₂S through the multilayer composite membrane were measured at different temperatures and pressures. The maximum values of selectivity, i.e., 52 and 15 for H₂S/CH₄ and CO₂/CH₄, respectively, were found at 25°C and 5 bar. The permeances of H₂S and CO₂ in the ternary mixture decreased on increasing the feed pressure because of membrane compression. The higher the temperature, the higher was the permeability of the gases due to the more molecular movement of the polymer chains. Therefore, the gas selectivity in the synthesized composite membrane decreased by increasing the temperature. The experiments showed that replacing the pure-gas measurements with the gas mixture measurements can substantially produce more relevant results.     

Synthesis,characterization, and performance evaluation of PES/EDA‐functionalized TiO2 mixed matrix membranes for CO2/CH4 separation

Poor adhesion between hydrophobic polymers and hydrophilic inorganic fillers is a challenge that encumbers a high separation performance of mixed matrix membrane (MMM). In this study, Titanium(IV) oxide (TiO₂) nanoparticles were functionalized using ethylenediamine (EDA) before embedment in poly(ether sulfone) (PES) polymer matrix. MMMs were synthesized through dry phase inversion technique. Membranes morphology and nanoparticles dispersion was drastically enhanced posterior amine modification indicating an improved adhesion between the polymer and filler particles. Membranes thermal stability was likewise improved as higher degradation temperatures were perceived for PES/EDA–TiO₂ MMMs. Gas separation evaluation for pure carbon dioxide (CO₂) and methane (CH₄) gases revealed a remarkably enhanced separation performance upon amine‐grafting of TiO₂ as EDA‐TiO₂ MMMs exhibited a higher separation performance as compared to MMMs with pristine TiO₂. The highest ideal separation factor achieved was 41.52 with CO₂ permeability of 10.11 Barrer at an optimum loading of 5% wt of EDA‐TiO₂ which is threefold higher as compared to neat PES membrane and approximately twofold higher than MMMs with pristine TiO₂, respectively, at the same filler loading. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45346.     

Thermal and thermo‐oxidative degradation study of a model LDPE/EVA based TPE system: Effect of nano silica and electron beam irradiation

The effect of nano‐silica on the thermal degradation behavior of Low density polyethylene‐poly(ethylene‐ co‐vinyl acetate) (LDPE‐EVA) based thermoplastic elastomeric (TPE) system was monitored using thermo gravimetric analysis (TGA) in nitrogen and oxygen atmospheres (air), respectively. The pristine nano silica was melt‐blended with the LDPE‐EVA system at different loadings by varying the sequence of addition. In one of the compositions, coupling agent (Si69) was used. In nitrogen, thermal stability of such systems remained unchanged. However, in oxygen atmosphere, the TGA thermograms reflected a dramatic change. A two staged degradation was observed for all the samples. The enhancement in thermal stability particularly upto the low conversion levels was interpreted in terms of the barrier effect of silica particles on the O₂ flow into the sample. The activation energies of degradation up to lower range of conversions were determined by nonisothermal and isothermal kinetic analyses. These were found to register a similar trend for various systems studied. Upon electron beam irradiation of such filled LDPE/EVA systems at controlled doses (20 and 40 kGy), the thermal stabilities were enhanced marginally. Overall, the thermal stabilities of the TPE nanocomposites are the function of sequence and extent of nano silica addition, presence of coupling agent and extent of irradiation. POLYM. COMPOS., 31:1387–1397, 2010. © 2009 Society of Plastics Engineers     

Rhodium‐Catalyzed Hydrogenation of Alkenes by Rhodium/Tris(fluoroalkoxy)phosphane Complexes in Fluorous Biphasic System

The reaction of [Ir(μ‐Cl)(COD)]₂ with various fluorous derivatives of triphenylphosphane containing a para‐, meta‐, or ortho‐(1H,1H‐perfluoroalkoxy)‐substituted fluorous phosphane P(C₆H₄‐ORf)₃ (Rf=CH₂C₇F₁₅, CH₂CH₂CH₂C₈F₁₇) and CO (1 atm) gives the corresponding trans‐[Ir(μ‐Cl)(CO){P(C₆H₄ORf)₃}₂]. The IR ν_CO values of these complexes give some information on the donor/acceptor properties of the phosphanes. These fluorous derivatives of triphenylphosphane, as well as a phosphane bearing two (1H,1H‐perfluoroalkyloxy) chains at the 3,5‐positions, were used in association with [Rh(μ‐Cl)(COD)]₂ or [Rh(COD)₂]PF₆ in the reduction of methyl cinnamate, 2‐cyclohexen‐1‐one, cinnamaldehyde, and methyl α‐acetamidocinnamate in a two‐phase system D‐100/ethanol under 1 bar hydrogen at room temperature. Some differences in catalytic activity were observed in the reduction of methyl cinnamate, the most active catalyst being the rhodium complex containing the phosphane with the p‐fluorous ponytail. Recycling of the fluorous catalyst was possible, particularly using the p‐substituted phosphane, where no significant loss of catalyst or activity was observed, and generally with very low leaching of rhodium or phosphane in the organic phase.