Phase behavior on the binary and ternary mixtures of poly(isooctyl acrylate) + supercritical fluid solvents + isooctyl acrylate and CO2 + isooctyl acrylate system

Experimental cloud‐point data to the temperature of 180 °C and the pressure up to 2000 bar are presented for ternary mixtures of poly(isooctyl acrylate) + supercritical fluid solvents + isooctyl acrylate systems. Cloud‐point pressures of poly(isooctyl acrylate) + CO₂ + isooctyl acrylate system is measured in the temperature range of 60–180°C and to pressures as high as 2000 bar with isooctyl acrylate concentration of 0–44.5 wt. This system changes the pressure–temperature slope of the phase behavior curves from upper critical solution temperature (UCST) region to lower critical solution temperature (LCST) region as the isooctyl acrylate concentration increases. Poly(isooctyl acrylate) does dissolve in pure CO₂ to the temperature of 180°C and the pressure of 2000 bar. The phase behavior for poly(isooctyl acrylate) + CO₂ + 9.5, 14.8, 30.6, and 41.9 wt % dimethyl ether (DME) mixture show the curve changes from UCST to LCST as the DME concentration increases. Also, the cloud‐point curves are measured for the binary mixtures of poly(isooctyl acrylate) in supercritical propane, propylene, butane, and 1‐butene. High pressure phase behaviors are measured for the CO₂ + isooctyl acrylate system at 40, 60, 80, 100, and 120°C and pressure up to 200 bar. This system exhibits type‐I phase behavior with a continuous mixture‐critical curve. The experimental results for the CO₂ + isooctyl acrylate system are modeled using the Peng‐Robinson equation of state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

PMMA‐modified divinylester/styrene resins: Phase diagrams and morphologies

Binary and ternary experimental cloud‐point curves (CPCs) for systems formulated with a low molar mass synthesized divinylester (DVE) resin, styrene (St), and poly(methyl methacrylate) (PMMA) were determined. The CPCs results were analyzed with the Flory–Huggins (F‐H) thermodynamic model taking into account the polydispersity of the DVE and PMMA components, to calculate the different binary interaction parameters and their temperature dependences. The St‐DVE system is miscible in all the composition range and down to the crystallization temperature of the St; therefore, the interaction parameter expression reported for a higher molar mass DVE was adapted. The interaction parameters obtained were used to calculate the phase diagrams of the St‐PMMA and the DVE‐PMMA binary systems and that of the St‐DVE‐PMMA ternary system at three different temperatures. Quasiternary phase diagrams show liquid–liquid partial miscibility of the St‐PMMA and DVE‐PMMA pairs. At room temperature, the St‐DVE‐PMMA system is miscible at all compositions. Final morphologies of PMMA‐modified cured St‐DVE materials were generated by polymerization‐induced phase separation (PIPS) mechanism from initial homogeneous mixtures. SEM and TEM micrographs were obtained to analyze the generated final morphologies, which showed a direct correlation with the initial miscibility of the system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4539–4549, 2006     

用拟二元方法研究iPP-DBP-DOP三元体系的热致相分离热力学

采用拟二元方法研究等规聚丙烯（iPP）‐邻苯二甲酸二丁酯（DBP）‐邻苯二甲酸二辛酯（DOP）三元聚合物溶液的热致相分离热力学,得出了拟二元相图的数学关联方法.采用光学显微镜法测定浊点温度, 采用差式扫描量热法（DSC）测定熔点、动态结晶温度.利用浊点测定数据回归聚合物-共溶剂的交互作用参数 χ的表达式,χ是共溶剂配比和温度的函数,以此为基础计算的拟二元相图与实验数据吻合较好.发现共溶剂中DBP份数增加,相分离类型由单纯固液分相形式转变为液液分相、固液分相依次发生形式,共溶剂配比能调控拟二元相图结构.研究表明,只需测定一个较低冷却速率下几种共溶剂配比的拟二元溶液的浊点温度、分别测定几个冷却速率下iPP–DOP二元溶液的动态结晶温度即可掌握该三元溶液热致相分离热力学的全部信息.其可用来指导制膜过程,并能准确预测形成的膜结构形貌.     

Thermally induced phase separation in poly(lactic acid)/dialkyl phthalate systems

Thermally induced phase separation in poly(lactic acid)/dialkyl phthalate systems was investigated. Poly(DL ‐lactic acid) (PDLLA) and poly(L ‐lactic acid) (PLLA) with different molecular weights were used. A series of dialkyl phthalates, with different numbers of carbon atoms in the alkyl chain, were employed as solvents to control the interaction between polymer and solvent. The liquid–liquid phase‐separation temperature of the poly(lactic acid) solutions decreased systematically with a shorter alkyl chain in the phthalate. Based on the interaction between polymer and solvent and the molecular weight of polymer influencing liquid–liquid phase‐separation temperature significantly but crystallization temperature only slightly, proper thermal conditions were employed to investigate competitive phase separation and crystallization in PLLA solutions. Factors that can influence the final morphology of PLLA solutions were examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2224–2232, 2003     

Estimation of phase diagrams for copolymer‐diluent systems in thermally induced phase separation

The binary interaction model was introduced to estimate phase diagrams of copolymer‐diluent systems in thermally induced phase separation. The crystallization curves and cloud points of poly(ethylene‐co‐vinyl alcohol) (EVOH) with 1,4‐butanediol, EVOH/1,3‐propanediol, and EVOH/glycerol were calculated and compared with experimental value or literature data. Fair agreement was obtained. To confirm the importance of incorporating intramolecular interactions, calculations with and without the consideration of intramolecular interactions were performed and compared. It was found that better results can be obtained if intramolecular interaction was introduced. The reason for the small differences between the calculated value and the experimental data of the liquid–liquid phase separation is discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Liquid–liquid phase separation in polysulfone/polyethersulfone/N‐methyl‐2‐ pyrrolidone/water quaternary system

To construct a phase diagram of the polysulfone (PSF)/polyethersulfone (PES)/N‐methyl‐2‐pyrrolidone (NMP)/water quaternary system, cloud point measurements were carried out by a titration method. The miscible region in the PSF/PES/NMP/water quaternary system was narrow compared to the PSF/NMP/water and PES/NMP/water ternary systems. The binary interaction parameters between PSF and PES were estimated by water sorption experiments. The calculated phase diagram based on the Flory–Huggins theory fit the experimental cloud points well. In addition to the usual polymer–liquid phase separation, polymer–polymer phase separation, which resulted in a PSF‐rich phase and a PES‐rich phase, was observed with the addition of a small amount of nonsolvent. The boundary separating these two modes of phase separation could be well described and predicted from the calculated phase diagrams with the estimated binary interaction parameters of the components. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2113–2123, 1999     

Porous cellulose acetate membrane prepared by thermally induced phase separation

Microporous cellulose acetate membranes were prepared by a thermally induced phase separation (TIPS) process. Two kinds of cellulose acetate with acetyl content of 51 and 55 mol % and two kinds of diluents, such as 2‐methyl‐2,4‐pentandiol and 2‐ethyl‐1,3‐hexanediol, were used. In all polymer‐diluent systems, cloud points were observed, which indicated that liquid–liquid phase separation occurred during the TIPS process. The growth of droplets formed after the phase separation was followed using three cooling conditions. The obtained pore structure was isotropic, that is, the pore size did not vary across the membrane. In addition, no macrovoids were formed. These pore structures were in contrast with those usually obtained by the immersion precipitation method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3951–3955, 2003     

Phase behavior and mechanism of formation of protofiber morphology of solution spun poly(acrylonitrile) copolymers in DMF‐water system

Phase diagrams of a series of copolymers of acrylonitrile (AN) and acrylic acid (AAc) were constructed using linearized cloud point correlation. The miscibility region in the phase diagram was found to increase with the increase in AAc content of the copolymers. For various compositions, χ₁₃ (polymer–water interaction parameter) values were estimated by sorption experiment. As the hydrophilic nature of the polymer increased with the increase in the content of acrylic acid, the χ₁₃ interaction parameter was found to decrease from poly(acrylonitrile) homopolymer to its copolymer with 50 mol % acrylic acid (AA50B). The polymer–solvent interaction parameters (χ₂₃) and composition at the critical points for all the polymers were determined by fitting the theoretical bimodal curves to the experimental cloud point curves using Kenji Kamide equations. The polymer composition at the critical point was found to increase by 400% with increasing AAc content. The polymers were solution spun in DMF‐water coagulation bath at 30°C and their protofiber structures were investigated under scanning electron microscopy. The observed morphological differences in protofibers were explained on the changes brought about in the phase separation behavior of the polymer–solvent–nonsolvent systems. The copolymers with higher acrylic acid content could be solution spun into void free homogeneous fibers even at conditions that produced void‐filled inhomogeneous fibers in poly(acrylonitrile) and its copolymers with lower AAc content. The experiments demonstrate the important role of thermodynamics in deciding the protofiber morphology during coagulation process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Liquid-liquid phase separation in polysulfone/solvent/water systems

The cloud point curves for polysulfone (PSf)/solvent/water systems were determined by a titration method. A small amount of water was needed to induce liquid-liquid demixing and the temperature effect was small. From numerical calculations, it was found that the binary interaction parameters for the PSf/solvent/water system enlarges the homogeneous region in the phase diagram with a smaller nonsolvent-polymer interaction parameter χ₁₃, a greater nonsolvent-solvent interaction parameter χ₁₂, and a smaller solvent-polymer interaction parameter χ₂₃ and the effect of polymer molecular weight was negligible except in the range of low molecular weight. The phase diagrams, calculated with constant χ₁₂ that was chosen from the concentration-dependent interaction parameter g₁₂ value of the concentration range, were similar to the results obtained with g₁₂. The slope of the tie lines indicated that demixing of the ternary system occurred at relatively similar nonsolvent concentration in both phases. A value of 2.7 for the water-PSf interaction parameter was obtained by fitting the experimental cloud point curve with the calculated binodal lines. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2643–2653, 1997     

Liquid membrane transport and separation of Zn2+ and Cd2+ from sulfate media using organophosphorus acids as mobile carriers

The transport and separation of Zn²⁺ and Cd²⁺ from binary sulfate solutions in a supported liquid membrane using di(2‐ethylhexyl)phosphoric acid (D2EHPA) and 2‐ethylhexylphosphonic acid mono‐2‐ethylhexyl ester (PC88A) as mobile carriers was studied. Batch solvent extraction experiments were conducted to obtain the reaction stoichiometries. Experiments were performed at different metal concentrations (1.4–14.5 mol m^?3), metal concentration ratios (0.4–9.2), pH (2–5), and carrier concentrations (0.1–0.6 mol dm^?3). A mass transfer model was proposed that considers diffusion in the aqueous feed and strip stagnant layers, and within the membrane. The interfacial reactions were assumed to approach equilibrium instantaneously. It was shown that the proposed model was applicable for binary Zn²⁺/Cd²⁺ systems (standard deviation, 5%). The larger separation factors of Zn²⁺ over Cd²⁺ with PC88A than D2EHPA under equilibrium (batch solvent extraction) and non‐equilibrium (liquid membrane) conditions were also evaluated and discussed. Copyright © 2003 Society of Chemical Industry     

Preparation of porous hollow fiber membranes with a triple‐orifice spinneret

A triple‐orifice spinneret has been applied for the preparation of hollow fiber microfiltration membranes with a high surface porosity. Considering the general rules of diffusion induced phase separation, a low polymer concentration is required at the outer layer to obtain a highly interconnected open‐porous structure. Therefore, by using N‐methylpyrrolidone (NMP) as the external liquid at the outside orifice of the spinneret, a highly porous surface can be obtained. For a polymer solution containing a low molecular weight additive and with an initial concentration close to the cloud point, this technique shows slightly improvement on the pure water and gas fluxes since the major resistance of the membrane is located at the substructure and the inner skin. However, for a solution containing a high molecular weight additive and with an initial concentration far from the cloud point, a porous shell surface is obtained, resulting in a significant improvement in water flux. The effect of various external liquids on the morphology has been investigated as well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2151–2157, 2003     

Phase separation behavior of poly(ether imide)/N,N‐dimethyl acetamide/nonsolvent systems

The phase separation behavior of a poly(ether imide) (PEI)/N,N‐dimethyl acetamide (DMAc)/nonsolvent system was investigated. Three kinds of nonsolvents were used in the study: H₂O, ethanol, and acetic acid (AA). It was found that the three systems (PEI/DMAc/H₂O, PEI/DMAc/ethanol, and PEI/DMAc/AA) agree with the linearized cloud point (LCP) relation. The binodal lines of the three systems were calculated according to the LCP relation. The binodal line of the PEI/DMAc/(H₂O + DMAc) system was also calculated according to the LCP relation of the PEI/DMAc/H₂O system. The phase separation of the PEI/DMAc/(H₂O + AA) system was studied, and the results agree with the LCP relation. These results can offer useful information for the establishment of dope and coagulation media using for the fabrication of a PEI membrane. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 875–881, 2003     

Cloud Point Extraction of Glycyrrhizic Acid from Licorice Root

Abstract

An attempt has been made to extract glycyrrhizic acid (GA) from licorice root by surfactant mediated cloud point extraction (CPE) using non‐ionic surfactant (Triton X‐100). Almost all of the GA molecules were concentrated in the surfactant‐rich phase (also called coacervate phase) after phase separation. The pH is the most critical factor regulating the distribution of GA in the micelle which related to the ionization form. The other effects of the concentration of GA and the surfactant, the temperature, and the salt concentration on the extraction efficiency of GA in the coacervate phase and aqueous phase have been studied. The mechanism of CPE of GA was explored with transmitting electron microscopy. It was deduced that aggregate GA molecules were adsorbed on micelles' outer poler mantle and inner cross‐linked micelles at high GA concentrations in coacervate phase.     

Thermodynamic analysis of phase separation in an epoxy/polystyrene mixture

The phase separation process of an epoxy prepolymer based on diglycidyl ether of bisphenol A (DGEBA) with a thermoplastic polystyrene (PS) was thermodynamically studied in the frame of the Flory-Huggins theory. The thermodynamic treatment was carried out in two steps: first analysing the phase separation in cloud point conditions, and second analysing the advance of the phase separation for two compositions of 2 and 10% in volume of PS. The effect of the polydispersity of thermoplastic on phase separation was also studied. The polydispersity of PS produces a displacement of the threshold temperature to lower thermoplastic volume fraction (between 2 and 3%) and higher temperature value and the fact that the shadow curve and coexistence curves do not superimpose with the cloud point curve. Theoretical calculations of molecular weight distributions of PS at different degrees of phase separation were realized and different average molecular properties were obtained in each separated phase.     

Cloud Point Extraction and Separation of Scandium and Yttrium (III) with Triton X‐114 in the Presence or Absence 8‐Hydroquiloline as an Added Chelate

Abstract

In this paper, the cloud point extraction and separation of scandium and yttrium (III) via use of Triton X‐114 with and without 8‐hydroquiloline (HQ) as an added chelate agent are investigated. The effects of various parameters, such as the aqueous phase pH, HQ concentration, Triton X‐114 concentration, heating temperature, and incubation time, on the cloud point extraction of scandium and yttrium (III) are studied. The results demonstrate that, there are different extraction and separation behaviors for scandium and yttrium (III) with and without HQ as an added chelate. And in contrast to solvent extraction, cloud point extraction is an excellent method to extract and separate scandium and yttrium (III).     

Liquid–liquid phase separation and crystallization of polydisperse isotactic polypropylene solutions

Phase diagrams were calculated based on Flory-Huggins solution thermodynamics to investigate the effects of polydispersity of polymer molecules and interaction parameter on the phase equilibria of crystallizable polymer solutions. The polydispersity was modeled with blends of two monodisperse polymers differing in chain lengths as a simplification. It was found that a longer chain length component could be separated easily to a polymer-rich phase by liquid demixing, but a shorter chain length component might exist at relatively constant concentration in each phase on fractionation. The influence of polydispersity on the liquid–solid phase equilibrium was small, and the phase boundary could be moved significantly in the region of low concentration of polymer by a small change of temperature. Liquid–liquid phase separation was more sensitive to the interaction between polymer and solvent than liquid–solid phase transition. Numerical calculations showed that the temperature at which liquid–liquid phase separation was coupled with liquid–solid phase equilibrium increased with a lower concentration of the polymer due to polydispersity of polymer chain lengths, and this phenomenon was observed at a lower temperature with more favorable interaction. The results were consistent with the experimental observations of isotactic polypropylene solutions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 849–857, 1998     

Preparation of microporous PVDF membrane via tips method using binary diluent of DPK and PG

Microporous polyvinylidene fluoride (PVDF) membrane was prepared via thermally induced phase separation (TIPS) method using a binary diluent of diphenyl ketone (DPK) and 1,2‐propylene glycol (PG). The phase diagram for the PVDF/binary diluent of DPK and PG system was measured in the range of the PG/DPK mass ratio changing from 0 to 2/3. Then the effects of the PG/DPK mass ratio and the PVDF concentration on membrane cross‐section structures and tensile strength were also investigated. The results showed that the addition of PG brought about a shift of the cloud point curve to a higher temperature and the extension of the liquid–liquid phase separation region to a higher polymer concentration. Therefore a bicontinuous cross‐section structure was obtained when the PG/DPK mass ratio was 3/7 and the polymer concentration was 30 wt %. As an increase of the PG/DPK mass ratio, the tensile strength increased gradually at a fixed PVDF concentration. Moreover, for the same PG/DPK mass ratio, the cross‐section microstructure changed from a bicontinuous or a cellular structure to a spherulitic structure, and the tensile strength increased drastically as the polymer concentration increased from 20 to 50 wt %. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of poly(ethylene‐co‐vinyl alcohol) membranes via thermally induced liquid–liquid phase separation

Porous membranes were prepared through the thermally induced phase separation of poly(ethylene‐co‐vinyl alcohol) (EVOH)/glycerol mixtures. The binodal temperature and dynamic crystallization temperature were determined by optical microscopy and differential scanning calorimetry measurements, respectively. It was determined experimentally that the liquid–liquid phase boundaries were shifted to higher temperatures when the ethylene content in EVOH increased. For EVOHs with ethylene contents of 32–44 mol %, liquid–liquid phase separation occurred before crystallization. Cellular pores were formed in these membranes. However, only polymer crystallization (solid–liquid phase separation) occurred for EVOH with a 27 mol % ethylene content, and the membrane morphology was the particulate structure. Scanning electron microscopy showed that the sizes of the cellular pores and crystalline particles in the membranes depended on the ethylene content in EVOH, the polymer concentration, and the cooling rate. Furthermore, the tendency of the pore and particle sizes was examined in terms of the solution thermodynamics of the binary mixture and the crystallization kinetics. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 853–860, 2003     

Extraction of Parabens from Water Samples Using Cloud Point Extraction with a Non-Ionic Surfactant with β-Cyclodextrin as Modifier

A cloud point extraction process using a silicone non-ionic surfactant to extract selected parabens compounds from water samples was investigated using reversed phase high performance liquid chromatography. The cloud point extraction process, in the presence of β-cyclodextrin (β-CD) as a modifier, is a new extraction process which was optimized with five parameters, i.e. salt concentration, pH of the solution, temperature, surfactant concentration and β-CD concentration. The developed method with the β-CD modifier results in an excellent performance on detection of parabens from water samples with limits of detection in the range of 0.017–0.043 μg/L and percentage recoveries from 90.5 to 98.9 %.     

Poly(sulfobetaine)s and corresponding cationic polymers. IX. Synthesis and aqueous solution properties of zwitterionic poly(sulfobetaine) derived from a styrene–N,N‐dimethylaminopropyl maleamidic acid copolymer

A styrene–N,N‐dimethyl(maleamidic acid)propyl ammonium propane sulfonate (SDMMAAPS) copolymer was synthesized through an amidoacidation reaction of a styrene–maleic anhydride alternating copolymer with N,N‐dimethylaminopropylamine (ring‐opening reaction) and then reacted with propane sultone. The cloud point and minimum salt concentration (msc) of this ampholytic SDMMAAPS copolymer were determined in aqueous salt solutions. The effects of counterions on the cloud point and msc of SDMMAAPS were not entirely the same as those of other zwitterionic poly(sulfobetaine)s. The greatest difference from other poly(sulfobetaine)s, such as styrene–N,N‐dimethyl(maleimido propyl)ammonium propane sulfonate copolymers, was the carboxylic group on the polymer chain unit of SDMMAAPS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1884–1889, 2003