Synthesis and gas permeation properties of poly(4-methyl-2-pentyne)

Poly(4-methyl-2-pentyne) [PMP] is an amorphous, glassy, di-substituted acetylene-based polymer. PMP has a low density of 0.78 g/cm³ and a high fractional free volume of 0.28. The permeabilities for helium, hydrogen, nitrogen, oxygen, carbon dioxide, methane, ethane, propane, and n-butane were determined at temperatures from 20 to 65°C and pressures from 10 to 150 psig. PMP is the most permeable purely hydrocarbon-based polymer known; its permeabilities are only exceeded by poly(1-trimethylsilyl-1-propyne) [PTMSP] and poly(1-trimethylgermyl-1-propyne) [PTMGeP]. The oxygen permeability of PMP at 25°C is 2700 × 10⁻¹⁰ cm³(STP) cm/cm² s cmHg and the nitrogen permeability is 1330 × 10⁻¹⁰ cm³(STP) cm/cm² s cmHg. The high gas permeabilities in PMP result from its very high free volume, and probably, interconnectivity of the free-volume-elements. For a glassy polymer, PMP exhibits unusual organic vapor permeation properties. Permeabilities in PMP are higher for large, condensable gases, such as n-butane, than for small, permanent gases such as helium. The permeabilities of condensable gases and permanent gases decrease as the temperature is increased. This behavior is completely unexpected for a glassy polymer and has been observed previously in only high-free-volume glassy PTMSP.     

Gas-permeation continuous flow coulometric analysis: determination of sulphur dioxide

 A gas permeation system using two gaseous streams flowing on both sides of a membrane is developed. This gas permeation device and a coulometric detector are adapted for the continuous measurement of relatively high concentrations of sulphur dioxide. The interferences of other gases (NO₂, NO and CO₂) can be eliminated by using a scrubber behind the gas permeation device in the acceptor stream. The effects of the donor flow rates and gas pressure as well as the membrane thickness on the signal are discussed. The relative standard deviation is 1.3% (n=7) for 2.002×10^-3 mol/mol certified sulphur dioxide. Received: 19 July 1996/Revised: 22 October 1996/Accepted: 29 October 1996     

Gas and vapor transport properties of amorphous perfluorinated copolymer membranes based on 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole/tetrafluoroethylene

Teflon AF 2400 (Du Pont) is an amorphous, glassy perfluorinated copolymer containing 87 mol% 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole and 13 mol% tetrafluoroethylene. The polymer has an extremely high fractional free volume of 0.327. Permeability coefficients for helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, ethane, propane, and chlorodifluoromethane (Freon 22) were determined at temperatures from 25 to 60°C and pressures from 20 to 120 psig. Permeation properties were also determined at a feed pressure of 200 psig at 25°C with a 2 mol% n-butane/98 mol% methane mixture. Permeabilities of permanent gases in Teflon AF 2400 are among the highest of all known polymers; the oxygen permeability coefficient at 25°C is 1600 × 10⁻¹⁰ cm³ (STP) cm/cm² s cmHg and the nitrogen permeability coefficient is 780 × 10⁻¹⁰ cm³ (STP) cm/cm² s cmHg. The permeabilities of organic vapors increase up to 20-fold as the vapor activity increases from 0.1 to unity, indicating that Teflon AF 2400 is easily plasticized. Although Teflon AF 2400 is an ultrahigh-free-volume polymer like poly(1-trimethylsilyl-1-propyne) [PTMSP], their gas permeation properties differ significantly. Teflon AF 2400 shows gas transport behavior similar to that of conventional, low-free-volume glassy polymers. PTMSP, on the other hand, acts more like a nanoporous carbon than a conventional glassy polymer.     

Theoretical study on concentration polarization in gas separation membrane processes

A mathematical model was established successfully to analyze the gas separation concentration polarization which becomes an important problem due to the rapid development of membranes, especially the increase of permeation rate. The influences of membrane performance and operation parameters on concentration polarization were studied in terms of permeation fluxes of the more and the less permeable gases and separation factor. Sample calculations were presented for the two typical gas separation applications, hydrogen recovery and air separation, with shell side feed in hollow fiber module. The permeation rate was found to be a dominating factor in affecting concentration polarization, while the influences of separation factor to be significant initially and to level off gradually. Increasing feed gas velocity leads to a decrease in the concentration polarization. Operation pressures' effect is limited and the composition of feed gas shows no effect. The range in which concentration polarization is significant has been identified by studying the combined effects of the permeation rate, separation factor and feed gas velocity. Concentration polarization is important for process analysis and design when the permeation rate of the more permeable gas is larger than 1×10⁻⁴ cm³ (STP) cm⁻² s⁻¹ cmHg⁻¹ (100 GPU).     

辐照三嵌段聚苯乙烯-丁二烯-4-乙烯基吡啶共聚物离子交换膜性能的研究——Ⅱ.共聚物膜的基本性能及分离实验

 本文研究了以辐照聚苯乙烯-丁二烯-4-乙烯基吡啶嵌段共聚物为膜基体所制成的嵌镶离子交换膜的基本性能.研究表明所制备的嵌镶膜在两端浓度分别为0.1及0.001 mol/L KCl 中的水渗析系数及电解质渗析系数分别是2.40×10^-5mol/cm²·min及2.10×10^-8mol/cm²·s.用所制备的嵌镶离子交换膜测试了牛血清白蛋白(M=67,000)与KCl混合溶液,蔗糖(M=343)与KCl混合溶液的膜分离效果.实验表明对上述两种非电解质均不能通过膜、而电解质KCl则可以.上述两种混合溶液中KCl渗透系数分别为J_KCl(牛血清白蛋白)=1.08×10^-8mol/cm²·s及J_(KCl)(蔗糖)=1.10×10^-8mol/cm²·s.     

CO2-induced plasticization phenomena in glassy polymers

A typical effect of plasticization of glassy polymers in gas permeation is a minimum in the relationship between the permeability and the feed pressure. The pressure corresponding to the minimum is called the plasticization pressure. Plasticization phenomena significantly effect the membrane performance in, for example, CO₂/CH₄ separation processes. The polymer swells upon sorption of CO₂ accelerating the permeation of CH₄. As a consequence, the polymer membrane loses its selectivity. Fundamental understanding of the phenomenon is necessary to develop new concepts to prevent it.In this paper, CO₂-induced plasticization phenomena in 11 different glassy polymers are investigated by single gas permeation and sorption experiments. The main objective was to search for relationships between the plasticization pressure and the chemical structure or the physical properties of the polymer. No relationships were found with respect to the glass-transition temperature or fractional free volume. Furthermore, it was thought that polar groups of the polymer increase the tendency of a polymer to be plasticized because they may have dipolar interactions with the polarizable carbon dioxide molecules. But, no dependence of the plasticization pressure on the carbonyl or sulfone density of the polymers considered was observed. Instead, it was found that the polymers studied plasticized at the same critical CO₂ concentration of 36±7 cm³ (STP)/cm³ polymer. Depending on the polymer, different pressures (the plasticization pressures) are required to reach the critical concentration.     

Gas permeation properties of poly(lactic acid)

The need for the development of polymeric materials based on renewable resources has led to the development of poly(lactic acid) (PLA) which is being produced from a feedstock of corn rather than petroleum. The present study examines the permeation of nitrogen, oxygen, carbon dioxide, and methane in amorphous films of PLA cast from solution. The properties of PLA are compared to other commodity plastics and it is shown that PLA permeation closely resembles that of polystyrene. At 30°C, N₂ permeation in PLA is 1.3 (10⁻¹⁰ cm³ (STP) cm/cm² s cmHg) and the activation energy is 11.2 kJ/mol. For oxygen the corresponding values are 3.3 (10⁻¹⁰ cm³(STP) cm/cm² s cm Hg) and 11.1 kJ/mol. The values for carbon dioxide permeation are 1.2 (10⁻¹⁰ cm³ (STP) cm/cm² s cmHg) and 6.1 kJ/mol. For methane values of 1.0 (10⁻¹⁰ cm³ (STP) cm/cm² s cmHg) and an activation energy of 13.0 kJ/mol are found. Studies with pure gases show that polymer chain branching and small changes in l:d stereochemical content have no effect on permeation properties. Crystallinity is found to dominate permeation properties in a biaxially oriented film. The separation factor for a CO₂/CH₄ mixed gas system is measured between 0 and 50°C and does not deviate significantly from the calculated ideal separation factor; at 0°C the separation factor is 16, a value that suggests continued studies of PLA as a separation medium are warranted.     

Pure and mixed gas acetone/nitrogen permeation properties of polydimethylsiloxane [PDMS]

The permeability of polydimethylsiloxane [PDMS] to acetone, nitrogen, and acetone/nitrogen mixtures has been determined at 28°C. In pure gas experiments, the permeability of PDMS to nitrogen was 245 × 10⁻¹⁰ cm³(STP) · cm/cm² · s · cmHg and was independent of pressure. The permeability of PDMS to acetone vapor increased exponentially with increasing acetone pressure. PDMS is much more permeable to acetone than to nitrogen; acetone/nitrogen selectivity increases from 85 to 185 as acetone partial pressure in the feed increases from 0 to 67% of saturation. In mixed gas permeation experiments, the nitrogen permeability coefficient is independent of acetone relative pressure and is equal to the pure gas permeability coefficient. The acetone permeability coefficient has the same value in both mixed gas and pure acetone permeation experiments. Average acetone diffusivity in PDMS, determined as the ratio of permeability to solubility, decreases with increasing acetone concentration due to mild clustering of acetone in the polymer (because acetone is a poor solvent for PDMS) and changes in the polymer–penetrant thermodynamic interactions which influence diffusion coefficients. A Zimm–Lundberg analysis of the acetone sorption isotherm is also consistent with acetone clustering in PDMS. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 289–301, 1998     

Polymer membranes with selective gas and vapor permeation properties

Since many years synthetic membranes have been used in reverse osmosis or ultrafiltration for the separation of aqueous mixtures. More recently the separation of gases and vapors by selective membrane permeation has gained significant technical and commercial interest. The recovery of hydrogen from petrochemical purge gases and ammonia production processes or the removal of CO₂ from natural gas by selective membrane permeation are today state of the art procedures. The recovery of organic solvents from waste air streams is another very promising application of synthetic membranes. In this paper the main parameters determining the performance of a membrane in gas and vapor separation are described. The requested intrinsic properties of the polymer to be useful as a barrier for a selective gas and vapor transport are discussed. The preparation of appropriate membranes is described. Their performance in practicle applications is illustrated in selected examples.     

纤维素中空纤维膜气体加湿性能的研究

采用纤维素N甲基吗啉N氧化物(NMMO)水三元纺丝体系,以去离子水为芯液,自来水为凝胶浴,湿法纺制了纤维素中空膜.经自然干燥后该膜的轴向、径向都明显收缩,断面呈现均质致密结构.干膜在水中会明显溶胀,重新润湿后具有气密性.考察了加湿水温、水气压力差等因素对膜的水渗透通量的影响,并初步测试了膜对质子交换膜燃料电池(PEMFC)反应气体H2和O2的加湿性能.实验结果表明该膜透水性能较优,气体加湿效果明显,具有应用于PEMFC反应气体加湿系统的潜力.     

High‐Flux Carbon Molecular Sieve Membranes for Gas Separation

Carbon membranes have great potential for highly selective and cost‐efficient gas separation. Carbon is chemically stable and it is relative cheap. The controlled carbonization of a polymer coating on a porous ceramic support provides a 3D carbon material with molecular sieving permeation performance. The carbonization of the polymer blend gives turbostratic carbon domains of randomly stacked together sp² hybridized carbon sheets as well as sp³ hybridized amorphous carbon. In the evaluation of the carbon molecular sieve membrane, hydrogen could be separated from propane with a selectivity of 10 000 with a hydrogen permeance of 5 m³(STP)/(m²hbar). Furthermore, by a post‐synthesis oxidative treatment, the permeation fluxes are increased by widening the pores, and the molecular sieve carbon membrane is transformed from a molecular sieve carbon into a selective surface flow carbon membrane with adsorption controlled performance and becomes selective for carbon dioxide.     

High-Flux Carbon Molecular Sieve Membranes for Gas Separation

Carbon membranes have great potential for highly selective and cost-efficient gas separation. Carbon is chemically stable and it is relative cheap. The controlled carbonization of a polymer coating on a porous ceramic support provides a 3D carbon material with molecular sieving permeation performance. The carbonization of the polymer blend gives turbostratic carbon domains of randomly stacked together sp² hybridized carbon sheets as well as sp³ hybridized amorphous carbon. In the evaluation of the carbon molecular sieve membrane, hydrogen could be separated from propane with a selectivity of 10 000 with a hydrogen permeance of 5 m³(STP)/(m²hbar). Furthermore, by a post-synthesis oxidative treatment, the permeation fluxes are increased by widening the pores, and the molecular sieve carbon membrane is transformed from a molecular sieve carbon into a selective surface flow carbon membrane with adsorption controlled performance and becomes selective for carbon dioxide.     

Selective olefin permeation through Ag(I) contained silicone rubber-graft-poly(acrylic acid) membranes

The silicone rubber (SR) based graft copolymer, SR-graft-poly(acrylic acid) (SR-g-AA), was modified by incorporating silver ion (SR-g-AA-Ag⁺) for C₄ olefin/paraffin gases separation. Olefin could be transported across the complex membrane by the silver ion facilitated transport. The permeation properties, as measured by gas chromatography equipped with a gas permeability analyzer, implied a facilitating effect for olefin. Typical trans-2-butene/n-butane selectivity in the 95.6% grafted complex membrane at 25°C is 4.0. Also, the influences of AA% grafting, measuring temperature and pressure to the permeation properties of C₄ gases were studied. In addition, the sorption behaviors of C₄ gases in SR based membranes are presented and discussed by the Flory-Huggins equation. Finally, the selectivity of solubility and diffusivity in these SR based membranes are also discussed.     

Gas permeation through water-swollen hydrogel membranes

This work deals with water-swollen hydrogel membranes for potential CO₂ separation applications, with an emphasis on elucidating the role of water in the membrane for gas permeation. A series of hydrogel membranes with a wide range of water contents (0.9–10 g water/g polymer) were prepared from poly(vinyl alcohol), chitosan, carboxyl methyl cellulose, alginic acid and poly(vinylamine), and the permeation of CO₂, H₂, He and N₂ through the membranes at different pressures (200–800 kPa) was studied. The gas permeabilities through the dry dense membranes were measured as well to evaluate the resistance of the polymer matrix in the hydrogel membranes. It was shown that the gas permeability in water-swollen membrane is lower than the gas permeability in water, and the selectivity of the water-swollen membranes to a pair of gases is close to the ratios of their permeabilities in water. The permeability of the water-swollen membranes increases with an increase in the swelling degree of the membrane, and the membrane permeability tends to level off when the water content is sufficiently high. A resistance model was proposed to describe gas permeation through the hydrogel membranes, where the immobilized water retained in the polymer matrix was considered to form transport passageways for gas permeation through the membrane. It was shown that the permeability of hydrogel membranes was primarily determined by the water content in the membrane. The model predictions were consistent with the experimental data for various hydrogel membranes with a wide range of water contents (0.4–10 g water/g polymer).     

Performance of solvent-resistant membranes for non-aqueous systems: solvent permeation results and modeling

Membrane processes like reverse osmosis (RO) and nanofiltration (NF) can be low energy consuming operations as compared to the traditional chemical engineering unit operations and have been widely used for aqueous systems. Since such membrane processes are low energy consuming operations, their use in non-aqueous systems would offer considerable energy savings. Thus, the study is directed towards development and experimental verification of membrane materials and transport models to explain permeation properties of non-aqueous solvent systems. The understanding of polymer–solvent interactions is critical towards the development of suitable materials and also the prediction of the transport mechanisms.Pure solvent permeation studies were conducted to understand the mechanism of solvent transport through polymeric membranes. Different membrane materials (hydrophilic and hydrophobic) as well as different solvents (polar and non-polar) were used for the study. Pure solvent fluxes for hydrophilic membranes used showed that polar solvents (methanol, ethanol, iso-propanol) had a significantly higher flux (8–10 times) than that of the non-polar solvents (pentane, hexane, octane). On the contrary, the non-polar solvent flux was two to four times that of the polar solvents for hydrophobic membranes. For example, hexane flux at ∼13 bar through a hydrophobic silicone based NF membrane was ∼0.6×10⁻⁴ cm³/cm² s. And that through a hydrophilic aromatic polyamide based NF membrane was ∼6×10⁻⁴ cm³/cm² s. A simple model based on a solution-diffusion approach is proposed for predicting the pure solvent permeation through hydrophobic polymeric membranes. The model uses molar volume and viscosity of the solvent as parameters for predicting the pure solvent permeability. The model reasonably predicts the pure solvent permeation (R²=0.89, S.E.∼4%) for hydrophobic membranes. The model has also been experimentally verified using high solution temperatures and also literature experimental data. To extend the predictions to different membranes (hydrophilic and hydrophobic), surface energy and sorption values have been used as a parameter along with the solvent physical properties.     

Transport of organic vapors through poly(1-trimethylsilyl-1-propyne)

Poly(1-trimethylsilyl-1-propyne) [PTMSP], a high-free-volume glassy polymer, has the highest gas permeability of any known synthetic polymer. In contrast to conventional, low-free-volume, glassy polymers, PTMSP is more permeable to large, condensable organic vapors than to permanent gases. The organic-vapor/permanent-gas selectivity of PTMSP based on pure gas measurements is low. In organic-vapor/permanent-gas mixtures, however, the selectivity of PTMSP is much higher because the permeability of the permanent gas is reduced dramatically by the presence of the organic vapor. For example, in n-butane/methane mixtures, as little as 2 mol% n-butane (relative n-butane pressure 0.16) lowers the methane permeability 10-fold from the pure methane permeability. The result is that PTMSP shows a mixed-gas n-butane/methane selectivity of 30. This selectivity is the highest ever observed for this mixture and is completely unexpected for a glassy polymer. In addition, the gas mixture n-butane permeability of PTMSP is considerably higher than that of any known polymer, including polydimethylsiloxane, the most vapor-permeable rubber known. PTMSP also shows high mixed-gas selectivities and vapor permeabilities for the separation of chlorofluorocarbons from nitrogen. The unusual vapor permeation properties of PTMSP result from its very high free volume - more than 20% of the total volume of the material. The free volume elements appear to be connected, forming the equivalent of a finely microporous material. The large amount of condensable organic vapor sorbed into this finely porous structure causes partial blocking of the small free-volume elements, reducing the permeabilities of the noncondensable permanent gases from their pure gas values.     

Characterization of the PPO dense membrane prepared at different temperatures by ESR,atomic force microscope and gas permeation

Dense (homogeneous) membranes were prepared from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) by using 1,1,2-trichloroethylene as a solvent at different solvent evaporation temperatures (22,4 and −10°C). The effect of temperature used during evaporation of solvent on the characteristics of the membrane was studied by using electron spin resonance, atomic force microscopy and gas permeation rate. The morphology of the surfaces of the membrane, the shape of spin probe in the membrane, and the selectivity of gases depend on the temperature of evaporation of solvent. The permeation rate of CO₂ increased with the decrease in the temperature used for the preparation of the membrane. However methane permeation rate increased in the membrane prepared at −10°C. It is suggested that Langmuir sites could be favorable for the CH₄ permeation.     

Gas transport properties of asymmetric polyimide membranes prepared by ion‐beam irradiation

Ion beam irradiation has been widely used to modify the structure and properties of membrane surface layers. In this study, the gas permeability and selectivity of an asymmetric polyimide membrane modified by He ion irradiation were investigated using a high vacuum apparatus equipped with a Baratron absolute pressure gauge at 76 cmHg and 35 °C. Specifically, we estimated the effects of the gas diffusion and solubility on the gas permeation properties of the asymmetric membranes with the carbonized skin layer prepared by ion irradiation. The asymmetric polyimide membranes were prepared by a dry–wet phase inversion process, and the surface skin layer on the membrane was irradiated by He ions at fluences of 1 × 10¹⁵ to 5 × 10¹⁵ ions/cm² at 50 keV. The increase in the gas permeability of the He⁺‐irradiated asymmetric polyimide membrane is entirely due to an increase in the gas diffusion, and the gas selectivity increases of the membranes were responsible for the high gas diffusion selectivities. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 262–269, 2007.     

Characterization and gas permeation of polycarbonateliquid crystal composite membrane

Polymer/liquid crystal composite membranes were cast from a 1,2-dichloroethane solution of polycarbonate (PC) and N-(4-ethoxybenzylidene-4'-n- butylaniline) (EBBA). The mixing state of the polymer/liquid crystal composite membrane was investigated on the basis of differential scanning calorimetry, x-ray, density, sorption isotherm and sorption—desorption studies and also by electron microscopic observations. EBBA molecules in the composite membrane exist in an almost molecularly dispersed state up to an EBBA fraction of 30 wt%, and in the case of EBBA fractions above 30 wt% form a crystal domain as the mutual continuous phase among the network of polycarbonate fibrils. The composite membrane containing EBBA of 60 wt% can be handled as a homogeneous medium when considering gas permeation.The diffusive permeability coefficient to water reveals a distinct jump in the vicinity of the crystal—liquid crystal phase transition temperature of EBBA. The permeability coefficients, P, to hydrocarbon gases increases 100-200 times over several degrees in the phase transition temperature range. P for hydrocarbon gases decreases with increasing number of carbon atoms below the phase transition temperature, but increases with increasing number of carbon atoms above it. These results suggest that the permeation process is predominantly controlled by diffusion mechanism below the transition temperature of EBBA, while the solubility factor significantly affects gas permeation above it.     

Solution and Diffusion Behavior of Pure Gases and Gas Mixtures in Glassy Polymer Membranes

A general model for the solution and diffusion behavior in pure gas-polymer membrane systems and gas mixture-polymer membrane systems has been developed. Proved by experiments on different glassy and rubbery polymer membranes at various temperatures and pressures, this model can achieve the prediction of permeation behavior of pure gases and gas mixtures in polymer membranes only using the model parameters obtained from experiments on pure gases. The calculated results are in good agreement with experimental.