Membranes of poly(phenylene oxide) and its copolymers: Synthesis,characterization, and application in recovery of propylene from a refinery off‐gas mixture

Copolymers of 2,6‐dimethyl‐phenol (DMP) and 2,6‐diphenyl‐phenol (DPP) were synthesized in the initial molar ratio of 100 : 0 (S(PPO)), 90 : 10 (Co‐A), 75 : 25 (Co‐B), 65 : 35 (Co‐C), and 0 : 100 (PDPPO). Dense membranes of 30 μm thickness were tested for single gas permeation and binary mixture separation of 55:45 (in mol %) propylene‐propane at 30°C ± 2°C. Their performance was ultimately examined in the enrichment of propylene from a refinery off‐gas mixture (ROG or also called as absorber tail gas, ATG) having the same composition as the ATG of a fluid catalytic cracking (FCC) unit of HPCL refinery, Visakhapatnam. The mixture contains C₁–C₅ hydrocarbons and nonhydrocarbons such as CO, CO₂, H₂, and N₂. A detailed permeation study of the hydrocarbon part of ATG revealed that using S(PPO) and Co‐A, propylene could be upgraded from ～ 29 mol % (on nonhydrocarbon free basis) to 62.2 and 74.4 mol % with propylene/propane selectivity ratio of 5.99 and 8.45, respectively. The structure of polymers was characterized by Fourier transform infrared (FTIR), proton nuclear magnetic resonance (Proton NMR), viscosity measurements. Scanning electron microscope (SEM), wide angle X‐ray diffraction (WAXD), density and fractional free volume measurements were used for studying membrane morphology. Dynamic mechanical thermal analyzer (DMTA) and tensile testing were carried to find glass transition temperature (T_g) and mechanical properties. The relative differences observed in gas permeation of these polymers were correlated with the physical properties measured. S(PPO) and Co‐A were identified as potential materials for the upgradation of propylene from refinery off‐gas streams. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Propylen/Propan‐Trennung im Festbettadsorber und durch Membranpermeation

The metal‐organic framework Mg₂(dhtp) with the linker dihydroxyterephthalate is known as MOF‐74 or CPO‐27. Mg₂(dhtp) has been synthesized as powder to measure breakthrough curves in a fixed‐bed adsorber and adsorption isotherms, and as a supported thin membrane layer for permeation studies. The measurement of the breakthrough curves of the binary propylene/propane mixture shows that separation with the fixed bed adsorber is possible. Propylene shows a higher affinity to Mg₂(dhtp). Although the single gas propane flux is slightly higher than the one of propylene, the binary propane/propylene mixture is not separated.     

Surface adsorption of propane, propylene and propane/propylene mixed gas on polyimide observed with X-ray and neutron reflectivity

We observed the surface adsorption layer of propylene, propane and propane/propylene mixed gas on a polyimide film as a function of pressure using X-ray (XR) and neutron (NR) reflectivity. It was initially confirmed by NR that the surface layer is an adsorption layer of propylene using deuterated gas. We have determined by XR the adsorption isotherms of these gases and found that the thickness of the surface adsorption layer of propane and propane/propylene mixed gas is much larger than that of propylene and the isotherm of propane/propylene mixed gas is similar to that of propane. The former and the latter findings predict that the affinity of propane to the polyimide is greater than propylene and the content of propane is much higher than that of propylene in the adsorption layer. We also evaluated the permeability coefficients of these gases as a function of the applied pressure, and found that the permeability coefficients begin to increase at a pressure corresponding to the onset of the adsorption layer. This suggests that the surface adsorption layer of the gas plays an important role in the hydrocarbon gas permeation mechanism in a polymer membrane, while a swelling of the polyimide film is the basis for the increase in the permeability with pressure.     

Synthesis,aggregation and adsorption behaviour of a thermoresponsive pentablock copolymer

Poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) triblock copolymer (Pluronic F127) was modified by introducing poly(N‐isopropylacrylamide) (PNIPAM) at both the PEO ends, and the pentablock copolymer (PNIPAM₄₁–F127–PNIPAM₄₁, PN41) so prepared was characterized using gel permeation chromatography and ¹H NMR spectroscopy. The degree of polymerization of NIPAM blocks at the two ends was 41. The solution behaviour and microstructure of PN41 aggregates in water were examined using UV–visible spectroscopy, micro‐differential scanning calorimetry and small‐angle neutron scattering (SANS) and compared with F127. Two lower critical solution temperatures (LCSTs) were observed for the pentablock copolymer, corresponding to PPO and PNIPAM blocks, respectively. The adsorption of PN41 on thiol‐grafted hydrophobic gold surfaces at various temperatures was investigated using a quartz crystal microbalance. It was found that the adsorption behaviour and mechanism of PN41 were mainly determined by the interactions of the pentablock copolymers with different chain conformations in dilute aqueous solutions at various temperatures. SANS measurements were used to determine the temperature‐dependent structural evolution of polymer micelles in aqueous solution. A NOESY study revealed that above the LSCT of PNIPAM, the interaction of PPO and PNIPAM protons increases and the distance between PPO and PNIPAM decreases. © 2019 Society of Chemical Industry     

Enhanced solubility of hydrogen and carbon monoxide in propane‐ and propylene‐expanded liquids

Conventional propylene hydroformylation occurs in a gas‐expanded liquid phase. Reliable knowledge of the phase equilibria of such systems, including the solubilities of CO and H₂ in propylene‐expanded solvents, is essential for rational process design and development. Herein, we report the vapor–liquid equilibrium (VLE) data of the following ternary systems involving CO, H₂, propane, propylene, toluene and NX‐795 at temperatures from 70 to 90°C and pressures up to 1.5 MPa: propane/H₂/toluene, propane/CO/toluene, propylene/H₂/toluene, propylene/CO/toluene, propane/H₂/NX‐795, propane/CO/NX‐795, propylene/H₂/NX‐795 and propylene/CO/NX‐795. The solubilities of H₂ and CO in either propane‐expanded or propylene‐expanded phases are observed to be greater than those in the neat organic solvents, by as high as 78% at 70°C and 1.5 MPa. By modeling the vapor and the liquid phases as pseudo‐binary systems, the Peng‐Robinson equation of state (PR‐EoS) with van der Waals’ mixing rules and binary interaction parameters is shown to satisfactorily predict the experimental VLE data. © 2017 American Institute of Chemical Engineers AIChE J, 64: 970–980, 2018     

Micropore size estimation on gas separation membranes: A study in experimental and molecular dynamics

The effect of the gas molecular size and its affinity to the pore surface on gas permeation properties through the ceramic membranes was studied by both the gas permeation experiments and gas permeation simulations using a nonequilibrium molecular dynamics (MD) technique. A modified gas permeation model equation based on the gas translation (GT) mechanism was presented. MD simulation revealed that the effective diffusion length in a micropore depended on the gas molecular size, and the pre‐exponential coefficient of a modified GT model equation showed good correlation with the kinetic diameter of the gas molecules. Also presented is a simple method to estimate the mean pore size of microporous membranes. The estimated pore sizes were consistent with observed kinetic diameter dependencies of gas permeance for real silica membranes. The pore size of a Deca‐Dodecasil 3R (DDR) zeolite membrane was also reasonably estimated at ～0.4 nm from the reported gas permeation data. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2179–2194, 2013     

Permeation of gases through modified polymer films. V. Permeation and diffusion of helium,nitrogen, methane,ethane, and propane through γ-ray crosslinked polyethylene

The permeation and diffusion of helium, nitrogen, methane, ethane, and propane through γ-irradiated polyethylene films were investigated. These studies were carried out with two objectives in mind: (1) to determine the effect of crosslinking by γ irradiation on permeability and diffusivity using the gas molecules as molecular probes; and (2) to study the plasticizing effects of the low hydrocarbons on the polyethylene film. The γ-ray-induced crosslinking efficiency of polyethylene was investigated in the following irradiation atmospheres: vacuum, acetylene, and nitrogen–acetylene mixtures. Results showed that irradiation in acetylene decreased the crosslinking efficiency while an acetylene–nitrogen atmosphere increased the efficiency compared to irradiation in vacuum. Both the permeation constants and the diffusion coefficients were found to decrease with increasing irradiation dose while the activation energies increased. The permeation constants of the organic gases through polyethylene increased with molecular diameter while the diffusion coefficients decreased. This increase in permeability was attributed to an increase in the solubility due to solubilization of the membrane by the penetrant. For example, the molecular diameter of propane is 4.397 Å compared with 2.807 Å for methane; however, propane permeated the polyethylene film at a rate twice that of methane. Nitrogen and methane have approximately the same molecular diameters—2.7085 and 2.807 Å, respectively—but owing to the plasticizing effect of methane, it permeated the film at a rate three times greater than that of nitrogen. It is interesting to note that the stronger the plasticizing ability of the penetrant, the greater the effect of the irradiation dose. The permeability of propane decreased by 40.7%, while the permeability of helium decreased by 6.4% after an irradiation dose of 50 Mrad.     

Polyester resins with carbazole ring

3‐(9‐Carbazolyl)propane‐1,2‐diol was obtained in the reaction of 9‐(2,3‐epoxypropyl)carbazole with water. The obtained diol was further used for modification of unsaturated polyester resin to produce enhanced thermal and heat resistance in comparison with classic resins. The properties of polyesters and polyester resins modified with 3‐(9‐carbazolyl)propane‐1,2‐diol were studied in detail. When 3‐(9‐carbazolyl)propane‐1,2‐diol is used instead of propylene glycol the unsaturated polyester resins possess enhanced thermal stability.© 2013 Society of Chemical Industry     

Facilitated transport separation of propylene–propane: Experimental and modeling study

Supported liquid membrane, as one type of facilitated transport membranes, was used for the separation of propylene–propane mixtures. The effect of trans-membrane pressure and carrier concentration on membrane separation performance were evaluated in terms of mixed-gas selectivity, propylene and propane permeances and propylene and propane permeation fluxes. A general dimensionless model for the transport of components across the membrane was proposed and solved numerically by orthogonal collocation method. Experimental results showed that for a 70:30 (vol.%) propylene–propane mixture, at pressure 120 kPa and carrier concentration 20 wt.%, a propylene permeation flux of 1.46 × 10⁻⁴ mol/m² s was obtained. Mathematical results are in well agreement with experimental results. The average deviation between experimental and modeling results was found to be 5.3% for propylene permeation flux and 0.03% for propane permeation flux.     

Formation and analysis of a polyimide layer in composite membranes

Composite membranes containing a thin‐film layer of aromatic polyimides (PI) ensure an advantageous combination of selectivity and permeability in gas separation. A series of rigid‐chain PI with different chemical structures were studied as a thin active layer. Composite membranes were prepared by coating a solution of poly(amic acid) (PAA) and an imidization catalyst on a poly(phenylene oxide) (PPO) support with pores filled by decane. The subsequent stage of solid‐state catalytic transformation of the PAA/PPO membrane into the PI/PPO membrane determines the specific structure of the PI layer and the transport properties of the PI/PPO composite membranes. The structure of composite membranes was determined by scanning electron microscopy and analyzed in the terms of the resistance model of gas transport in composite membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1026–1032, 2000     

Surface immobilization of star‐shaped poly(ethylene oxide) on poly(dimethylsiloxane)

A thin layer of star‐shaped poly(ethylene oxide) (PEO) (starPEO), on the polydimethylsiloxane (PDMS) membrane was prepared by a simple immobilization procedure. Photoreactive molecules were introduced on the surface of the polymeric support to achieve the formation of thin starPEO film from the materials having no functional groups. This novel technique enabled us to immobilize any kind of chemical, especially one that had no functional groups, and readily to control the amount of immobilization. The gas permeation properties of the starPEO‐immobilized PDMS membranes were investigated for pure propane and propylene. The permeance of gases were found to decrease in the starPEO‐immobilized PDMS membranes, although the ideal separation factors for propylene/propane were increased with the loading amount of silver ions, because of the facilitation action of silver ions in the immobilized PEO unit on the PDMS membranes, as propylene carriers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2369–2373, 2002     

Preparation of Carbon Membranes Derived from Polymer Blends in the Presence of a Thermally Labile Polymer

Abstract

Carbon membranes for gas separation were prepared from the polymer blend consisting of poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) and polyvinylpyrrolidone (PVP) as the thermally stable and labile polymer, respectively. The PPO/PVP derived carbon membranes with lower PVP concentrations than 0.6 wt% showed decreased gas permeances and increased permselectivity due to decrease in the pore properties (pore volume and surface area). Meanwhile, gas permeance increased for the carbon membranes prepared with higher PVP concentrations than 0.6 wt% due to the enhanced diffusional pathways for the gas transport through carbon membranes especially in the domain of the thermally labile polymer. It is considered that the introduction of the thermally labile polymer leads to control the pore structure through the permeation results for the carbon membrane derived from the polymer blend.     

Effect of polystyrene stars with fullerene C60 cores on pervaporation properties of poly(phenylene oxide) membrane

Star‐shaped macromolecules with six arms of polystyrene grafted onto a fullerene C₆₀ core, or fullerene‐containing polystyrene (FPS), were used for the modification of poly(phenylene oxide) (PPO) and the preparation of a dense thin‐film membrane. The membrane structure was studied using scanning electron microscopy. The effect of FPS modifier on membrane density and mass transfer of methanol and ethylene glycol through the membrane was studied. Sorption and pervaporation tests were used to determine degree of sorption, diffusion coefficients, flux through the membrane and separation factor. In the pervaporation of a methanol–ethylene glycol mixture over the concentration range of 10–30 wt% methanol in the feed, all membranes showed high affinity to methanol. The separation factor reached a maximum at 5 wt% FPS in the membrane. The PPO/FPS membranes exhibit the best separation properties when the feed is enriched with ethylene glycol. © 2016 Society of Chemical Industry     

Synthesis of biodegradable amphiphilic thermo‐responsive multiblock polycarbonate and its self‐aggregation behavior in aqueous solution

Amphiphilic thermo‐responsive multiblock polycarbonates consisting of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) were facilely synthesized using triphosgene as coupling agent. The structures and molecular characteristics of the polycarbonates were confirmed by ¹H‐NMR, FT‐IR and Gel permeation chromatography (GPC). The crystallization behavior and thermal properties of the polycarbonates were studied using X‐ray diffraction (XRD), Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Surface tension measurements confirmed that the critical micelles concentration of polymeric micelles were concentration ranges, which varied from about 2–70 mg/L to 5–40 mg/L with increasing PEO/PPO composition ratio from 0.8 to 1. Dynamic light scattering (DLS) experiments showed bimodal size distributions, the aggregates size increased with increasing the concentration of the polycarbonates aqueous solutions. The size of the aggregates acquired from TEM was smaller than that from DLS owing to the fact that TEM gave size of the aggregates in dry state rather than the hydrodynamic diameter. The degradation process revealed that the degradation rate of the aggregates could be accelerated with an increase in temperature. Moreover, the more the polycarbonate was hydrophilic, the faster was its degradation. Rheological measurements suggested that these multiblock polycarbonates were thermo‐responsive and by regulating the PEO/PPO composition ratio they could form a gel at 37°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Simultaneously enhanced cryogenic mechanical behaviors of cyanate ester/epoxy resins by poly(ethylene oxide)‐co‐poly(propylene oxide)‐co‐poly(ethylene oxide) (PEO‐PPO‐PEO) block copolymer and clay

Cryogenic mechanical properties are important parameters for thermosetting resins used in cryogenic engineering areas. The hybrid nanocomposites were prepared by modification of a cyanate ester/epoxy/poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) (PEO‐PPO‐PEO) system with clay. It is demonstrated that the cryogenic tensile strength, Young's modulus, ductility (failure strain), and fracture resistance (impact strength) are simultaneously enhanced by the addition of PEO‐PPO‐PEO and clay. The results show that the tensile strength and Young's modulus at 77 K of the hybrid nanocomposite containing 5 wt% PEO‐PPO‐PEO and 3 wt% clay were enhanced by 31.0% and 14.6%, respectively. The ductility and impact resistance at both room temperature and 77K are all improved for the hybrid composites. The fracture surfaces of the neat BCE/EP and its nanocomposites were examined using scanning electron microscopy (SEM). Finally, the dependence of the coefficients of thermal expansion (CTE) on the clay and PEO‐PPO‐PEO contents was examined by thermal dilatometer. POLYM. COMPOS., 38:2237–2247, 2017. © 2015 Society of Plastics Engineers     

Preparation and properties of novel poly(propylene oxide)‐block‐polylactide‐based polyurethane foams

A novel degradable flexible polyurethane (PU) foam was prepared by varying the ratio of poly(propylene oxide) (PPO) and triarm poly(propylene oxide)‐block‐polylactide copolymer (PPO‐b‐PLA), and was compared with conventional PU foams based on toluene diisocyanate (TDI) and PPO. Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) showed that introducing PLA segments were able to result in a transition from a microphase separated state to a microphase mixed state and improve the microphase mixing. The changes in structure and domain size distribution associated with this transition were found to have led to enhanced mechanical properties such as the tensile strength, the elongation at break, and the rebound resilience for the PU foams containing PLA segments. Furthermore, it was observed that the network structure was destroyed by hydrolytic degradation in alkali solution (10 wt%/vol%) at 80°C for 50 h, and that as the PLA content increased, the degradation rate of PU foams enhanced. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Tailoring of phase‐segregation structures in two‐soft‐segment urethane/urea polymer membranes

The synthesis of two‐soft‐segment urethane/urea polymeric membranes with various proportions of the two soft segments, poly(propylene oxide) and polybutadiene, yielded very distinct morphologies depending on the degree of phase segregation. The morphologies were identified with transmission electron microscopy. With a low concentration of polybutadiene, this soft segment segregated into ellipsoidal microdomains dispersed in a poly(propylene oxide) matrix. With an intermediate concentration of polybutadiene, the morphology was characterized by nanoscale phase separation and could be described as a disordered, wormlike domain structure. With a high concentration of polybutadiene, a single phase was observed. This was attributed to molecular mixing of the two soft segments and was associated with membranes that under the application of a shear stress developed bands that efficiently scattered light. These bands were identified by field emission scanning electron microscopy with a periodicity of approximately 4–5 μm. The change in the membrane morphology from microscale phase segregation to nanoscale phase segregation led to very different membrane gas‐permeation properties, that is, a reduction of the CO₂ permeability from 191 to 90 Barrer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 315–320, 2007     

Modified zeolitic–midazolate framework 8/poly(ether‐block‐amide) mixed‐matrix membrane for propylene and propane separation

In this study, we fabricated a dual‐layer PES–poly(ether‐block‐amide) (PEBA) composite membrane that included zeolitic–midazolate framework 8 (ZIF‐8) particles and evaluated it for propylene and propane separation under pure and mixed feed conditions. To improve the performance, compatibility, and distribution of particles in the polymer matrix, the ZIF‐8 particles were modified by 3‐(triethoxysilyl) propyl amine (APTES) and 3‐(trimethoxysilyl) propyl amine (APTMS) amino silane coupling agents. Particle modification did not have much effect on the structure and particle size and slightly reduced the membrane specific surface area. The modified particles tended to be in the soft section. At the high loading rate of modified particles, their appropriate compatibility increased the membrane gas permeability () and selectivity. APTES with the proper chain length compared with APTMS had a higher and the same selectivity. The best performance (by 32.1 gpu) was found in PES–PEBA–ZIF‐8–APTES 20%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46273.     

Blending PPO‐based molecules with Pebax MH 1657 in membranes for gas separation

This work explores the possibilities to blend block copolymers, i.e., Pebax MH 1657, with a variety of cheap poly(propylene oxide)‐rich molecules which could potentially play a double role in the resulting membranes as dispersing/stabilizing agents in multi‐component casting solutions and as a gas transport medium in the final membrane. These membranes were prepared by solution casting and were characterized by differential scanning calorimetry, scanning electron microscopy, atomic force microscopy, X‐ray diffraction, density measurements, and Fourier transform infrared‐attenuated total reflection, while additive incorporation was also studied with theoretical calculations. Gas permeation measurements showed that this approach resulted in increased permeabilities at the expense of mixed‐gas selectivity. An interpretation of the blend structure was finally made using gas transport models. The compatibility of these additives with the synthesis of selective gas separation membranes may enable a potential double role in membrane synthesis, i.e., as stabilizing agents in membrane synthesis and as a gas transport medium in the final membrane. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46433.     

Synthesis and characterization of degradable triarm low unsaturated poly(propylene oxide)‐block‐polylactide copolymers

A series of novel degradable triarm poly(propylene oxide)‐block‐polylactide (PPO‐b‐PLA) copolymers was synthesized by ring‐opening polymerization of L ‐lactide (LLA) or D ,L ‐lactide (DLLA) using low unsaturated PPO triols as macromolecular initiator. The chemical structures of the resulting copolymers were characterized by Fourier transform infrared (FTIR), gel permeation chromatography (GPC), and proton nuclear magnetic resonance (¹H‐NMR) spectroscopy. Combination of FTIR, GPC, and NMR results confirmed the formation of PPO‐b‐PLA copolymers. One glass transition was observed by differential scanning calorimetry (DSC), suggesting good miscibility between PPO and PLA segments in the copolymers. DSC and wide‐angle X‐ray diffraction demonstrated that PPO‐b‐PLLA copolymers were semicrystalline materials, and the crystallinity increased with increasing the PLLA content. In contrast, PPO‐b‐PDLLA copolymers were totally amorphous. The PPO‐b‐PLA copolymers exhibited improved thermal stability when compared with PPO polyols according to thermogravimetric analysis. The thermal degradation behavior of the copolymers depended on the composition. Polyurethane foams were prepared by crosslinking PPO and PPO‐b‐PLA copolymers using isocyanate. Alkaline degradation of the foams was investigated in 10 wt/vol % NaOH at 80°C. The results show that the novel PPO‐b‐PLA copolymers could be promising as degradable polymeric materials. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010