Surface structures of solvent‐cast films prepared from poly(ethylene oxide)‐segmented nylons

The surface structures of three kinds of poly(ethylene oxide)‐segmented nylon (PEO‐Ny) films prepared by the solvent‐cast method were investigated with electron spectroscopy for chemical analysis (ESCA). The PEO‐Ny's used were high‐crystalline PEO‐segmented poly(iminosebacoyliminohexamethylene), low‐crystalline PEO‐segmented poly(iminosebacoylimino‐m‐xylene), and amorphous PEO‐segmented poly(iminoisophthaloyliminomethylene‐1,3‐cyclohexylenemethylene), and the PEO contents in the bulk polymers were approximately 10 wt %. The ESCA results showed that the PEO segment was enriched on the top surfaces of all the films, and the degrees of enrichment were different. The mechanism of the PEO enrichment was examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 10–16, 2002     

Polyether-segmented nylon hemodialysis membranes. IV. Membrane morphologies and permeability characteristics of dialysis membrane composed of poly(ethylene oxide)-segmented Ny69/M10

Dialysis membrane was prepared by a phase inversion method using a new polyether-segmented nylon which dissolves in common organic solvents such as dimethylsulfoxide. The polyether-segmented nylon contained poly(ethylene oxide) block and nylon block (random copolyamide: Ny69/M10) prepared by sebacic acid, azelaic acid, m-xylenediamine, and hexamethylenediamine. The morphologies and permeability characteristics of the membranes were investigated. It was shown by scanning electron microscope observation that the membrane had a fingerlike structure when dimethylsulfoxide was used as a polymer solvent, and a spongelike structure when an additive such as calcium chloride was added to the polymer solution. The high permeability for the solutes such as urea and vitamin B₁₂ were observed in comparison with the polyether-segmented Ny610 membranes prepared by a phase inversion method. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1731–1737, 1997     

Polyether-segmented nylon hemodialysis membrane. VI. Effect of polyether segment on morphology and surface structure of membrane

Amorphous nylon, poly(iminoisophthaloyliminomethylene-1,3-cyclohexylenemethylene) (NyBI) and poly(ethylene oxide) (PEO)-segmented NyBI (PEO–NyBI) membranes were prepared by a phase-inversion method using water/dimethyl sulfoxide (DMSO) mixtures as coagulants. The influence of the PEO segment and coagulant compositions on the morphology of the membranes was investigated. The cloud-point curves in the polymer/DMSO/water ternary system showed that PEO–NyBI and NyBI had the same coagulation processes, that is, instantaneous liquid–liquid phase separation occurred, resulting in a fingerlike structure in the cross section of the membranes. The membrane morphologies observed under a scanning electron microscope (SEM) agreed with the prediction. The PEO segment had little or no effect on the membrane morphologies which were prepared in the coagulants with a low DMSO concentration, and it promoted the change of the phase-separation style from the instantaneous to the delayed one in the case of the DMSO-rich coagulant. The PEO segment, however, significantly influenced the ultrafiltration rate. Additionally, the relationship between the surface composition of the PEO–NyBI membrane and the coagulation condition was also investigated by use of electron spectroscopy for chemical analysis (ESCA) and static secondary ion mass spectrometry (SSIMS). A small enrichment of the PEO segment at the top surface of the membranes was observed with the increase of the DMSO concentration in the coagulant. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1645–1659, 1998     

Water vapor transmission of poly(ethylene oxide)‐based segmented block copolymers

This article discusses the rate of water vapor transmission (WVT) through monolithic films of segmented block copolymers based on poly(ethylene oxide) (PEO) and monodisperse crystallisable tetra‐amide segments. The polyether phase consisted of hydrophilic PEO or mixtures of PEO and hydrophobic poly(tetramethylene oxide) (PTMO) segments. The monodisperse tetra‐amide segments (T6T6T) were based on terephthalate units (T) and hexamethylenediamine (6). By using monodisperse T6T6T segments the crystallinity in the copolymers was high (～ 85%) and, therefore, the amount of noncrystallised T6T6T dissolved in the polyether phase was minimal. The WVT was determined by using the ASTM E96BW method, also known as the inverted cup method. By using this method, there is direct contact between the polymer film and the water in the cup. The WVT experiments were performed in a climate‐controlled chamber at a temperature of 30°C and a relative humidity of 50%. A linear relation was found between the WVT and the reciprocal film thickness of polyether‐T6T6T segmented block copolymers. The WVT of a 25‐μm thick film of PTMO₂₀₀₀‐based copolymers was 3.1 kg m^?2 d^?1 and for PEO₂₀₀₀‐based copolymers 153 kg m^?2 d^?1. Of all the studied copolymers, the WVT was linear related to the volume fraction of water absorbed in the copolymer to the second power. The results were explained by the absorption‐diffusion model. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of hydrophilic segmented block copolymers based on poly(ethylene oxide)‐ran‐poly(propylene oxide)

The present article discusses the synthesis and various properties of segmented block copolymers with random copolymer segments of poly(ethylene oxide) and poly(propylene oxide) (PEO‐r‐PPO) together with monodisperse amide segments. The PEO‐r‐PPO contained 25 wt % PPO units and the segment presented a molecular weight of 2500 g/mol. The synthesized copolymers were analyzed by differential scanning calorimetry, Fourier transform infra‐red spectroscopy, atomic force microscopy and dynamic mechanical thermal analysis. In addition, the hydrophilicity and the contact angles (CAs) were studied. The PEO‐r‐PPO segments displayed a single low glass transition temperature, as well as a low PEO crystallinity and melting temperature, which gave enhanced low‐temperature properties of the copolymer. The water absorption values remained high. In comparison to mixtures of PEO/PPO segments, the random dispersion of PPO units in the PEO segments was more effective in reducing the PEO crystallinity and melting temperature, without affecting the hydrophilicity. Increasing the polyether segment length with terephthalic groups from 2500 to 10,000 g/mol increased the hydrophilicity and the room temperature elasticity. Furthermore, the CAs were found to be low 22–39° and changed with the crosslink density. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117:1394–1404, 2010     

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     

Role of poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) in the modification of polysulfone membranes for ultrafiltration

In this study polysulfone membranes with antifouling and hydrophilic properties were synthesized using poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) (AMPS) as an additive for the first time. Different wt % of AMPS was used to prepare polysulfone membranes by phase inversion method. The role of AMPS on the porosity, pore size distribution, hydrophilicity, and antifouling nature was investigated and analyzed in detail. Characterization techniques like field emission scanning electron microscope, atomic force microscopy, and imageJ software were used to characterize the morphology of prepared membranes. There is positive effect of the additive addition on all the membrane parameters like Pure water flux [101.76 L/(m² h)] (MR0) to 464.06 L/(m² h) (MR4)], hydraulic permeability [0.65 (MR0) to 2.01 (MR4)], equilibrium water content [21.74 (MR0) to 71.45 (MR4)], and porosity [0.024 (MR0) to 0.58 (MR4)]. Response surface methodology was used for the optimization of bovine serum albumin (BSA) flux and rejection. The results of the morphological as well as permeation studies depicted that permeate flux and antifouling nature were increased with the amount of AMPS present in the membrane matrix. The antifouling study of the prepared membranes was undertaken by using BSA solution of 1000 mg/L. Positive results were seen with the increase in amount of AMPS, since, the total membrane resistance has been decreased from 0.95 (MR0) to 0.74 (MR4). Separation of humic acid from aqueous medium was also performed with the best performing membrane (MR4, having the highest amount of AMPS). Separation efficiency of 100% and 94% were obtained using 10 mg/L and 50 mg/L of HA, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45290.     

Study on the synthesis of poly(ether‐block‐amide) copolymer based on nylon6 and poly(ethylene oxide) with various block lengths

Various segmented block copolyetheramides based on nylon6 (N6) and poly(ethylene oxide) (PEO) with different compositions and block length of the hard and soft segments were synthesized. The effect of composition of the hard and soft segments was studied via FTIR spectroscopy based on the characteristic peak of ester group at wave number of 1730 cm^?1. The average block length of the hard and soft segments in block copolymers was determined from H‐NMR analysis. Differential thermal analysis thermograms confirmed a microphase separated morphology over a broad range of temperature, leading to two separated crystalline domains. An increase in the interconnectivity of the polyamide segments controlled by chain extension, greatly improved the formation of polyamide lamellae crystals determined by X‐ray diffractometry. Atomic force microscopy images indicated different morphologies of dispersed phase in the dominant phase, which plays an important role in their performance for membrane processes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

MesoDyn modeling study of the phase morphologies of miktoarm poly(ethylene oxide)‐b‐poly(methyl methacrylate) copolymers doped with nanoparticles

Earlier studies have shown that poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blocks are compatible at 270 and 298 K, and that their Flory–Huggins interaction parameters have the same blending ratio dependence at both temperatures. At a much higher temperature (400 K), the behavior of PEO/PMMA blends is strikingly different as both components become incompatible, while the Flory–Huggins parameters are low. Here we investigate the effect of doping with nanoparticles on the degree of incompatibility of twelve miktoarm PEO‐b‐PMMA copolymers at 400 K. Since PEO tends to be semicrystalline and long chains aggregate easily, PEO‐rich and long‐chain copolymer blends feature the highest degree of incompatibility for all nanoparticle arrangements and present cubic phase morphologies. In addition, the largest nanoparticles can reinforce the microscopic phase separation of all PEO‐b‐PMMA copolymers. This shows that the main factor affecting the phase morphology is the size of the nanoparticles. Also, only the asymmetric Da3‐type PEO‐rich copolymers show a hexagonal cylindrical phase morphology, which illustrates the effect induced by the nanoparticles on the microscopic phase separation changes of the PEO‐b‐PMMA copolymers. These induced effects are also related to the composition and molecular architecture of the copolymers. © 2013 Society of Chemical Industry     

Microporous membranes prepared from blends of polysulfone and sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide)

Membranes were prepared from solutions containing Udel‐type polysulfone (PSf) and sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO). Polymer solutions in 1‐methyl‐2‐pyrrolidone were cast on a nonwoven textile and precipitated in a water bath. The permeabilities and selectivities of the prepared membranes depended on the concentrations of both polymers in the casting solution. The higher the concentration of PSf, the lower were the permeabilities to water and average pore sizes of the membranes. On the other hand, a very small amount of SPPO in the casting solution (about 1–4 wt % relative to the casting solution weight) brought about a considerable increase in water permeabilities and had a small influence on the average pore sizes. The effects were most pronounced if SPPO with a degree of sulfonation of 20–40% was used. The considerable increase in water permeabilities was explained by separation of the PSf and SPPO phases during precipitation in water and by the concentration of hydrophilic SPPO on the surface of the membrane and its pores. The determinations of the oriented concentration potentials proved the presence of a negative surface charge in the membranes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 134–142, 2001     

Synthesis and characterization of copolymers based on poly(butylene terephthalate) and ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide

A series of thermoplastic elastomers based on ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide (EO‐PDMS‐EO), as the soft segment, and poly(butylene terephthalate) (PBT), as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reaction of dimethyl terephthalate (DMT) with 1,4‐butanediol (BD) and α,ω‐dihydroxy‐(EO‐PDMS‐EO). Copolymers with a content of hard PBT segments between 40 and 90 mass % and a constant length of the soft EO‐PDMS‐EO segments were prepared. The siloxane prepolymer with hydrophilic terminal EO units was used to improve the miscibility between the polar comonomers, DMT and BD, and the nonpolar PDMS. The molecular structure and composition of the copolymers were determined by ¹H‐NMR spectroscopy, whereas the effectiveness of the incorporation of α,ω‐dihydroxy‐(EO‐PDMS‐EO) into the copolymer chains was verified by chloroform extraction. The effects of the structure and composition of the copolymers on the melting temperatures and the degree of crystallinity, as well as on the thermal degradation stability and some rheological properties, were studied. It was demonstrated that the degree of crystallinity, the melting and crystallization temperatures of the copolymers increased with increasing mass fraction of the PBT segments. The thermal stability of the copolymers was lower than that of PBT homopolymer, because of the presence of thermoliable ether bonds in the soft segments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface modification of polysulfone membranes by low‐temperature plasma–graft poly(ethylene glycol) onto polysulfone membranes

A novel and general method of modifying hydrophobic polysulfone (PSF) to produce highly hydrophilic surfaces was developed. This method is the low‐temperature plasma technique. Graft polymer‐modified surfaces were characterized with the help of Fourier transform infrared attenuated total reflection (FTIR–ATR) and X‐ray photoelectron spectroscopy (XPS). Study results demonstrated that poly(ethylene glycol) (PEG) could be grafted onto the PSF membrane surface by low‐temperature plasma. The hydrophilic character of the modified surfaces was increased in comparison with that of the parent membrane. The contact angle for a modified PSF membrane was reduced apparently. We analyzed the effectiveness of this approach as a function of plasma operating variables including plasma treatment power and treatment time. Hence, plasma‐induced graft polymer modification of membranes can be used to adjust membrane performance by simultaneously controlling the surface hydrophilicity and hemocompatibility. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 979–985, 2000     

Reaction‐induced phase separation in hexamethylene diisocyanate‐based poly(propylene oxide)/poly(ethylene oxide) bi‐soft segment oligomers

Oligomeric bi‐soft segment isocyanate‐terminated polyurethanes (ITPUs) are semi‐finished materials crucial for the synthesis of various PU products like foams, thermoplastic parts, dispersions or elastomers. Incompatibilities and thus phase separation phenomena play an essential role in tailoring the properties of the final products. Therefore, a detailed knowledge of these phenomena is mandatory in order to design products with properties meeting the requirements of a given application. In this study the reaction‐induced phase separation during the formation of ITPUs by application of two partially miscible soft segments is presented. The physicochemical basics of this process as well as the extent of the resulting phase separation are discussed on the basis of the initial phase diagram of the reactants. Reaction monitoring by NCO content titration and UV–visible spectroscopy reveals a dependency between the onset of phase separation and conversion. It is found that an increase of the initial content of hexamethylene diisocyanate delays the onset of phase separation. Differential scanning calorimetry reveals further that the phase separation is a direct consequence of the incompatibility of the soft segments. Overall, the findings support the hypothesis that the mechanism and the extent of phase separation are closely related to the ternary phase diagram of the reactants. © 2018 Society of Chemical Industry     

Effect of nylon 6 on fracture behavior and morphology of tough blends of poly(2, 6‐dimethyl‐1,4‐phenylene oxide) and maleated styrene‐ethylene‐butadiene‐styrene block copolymer

Ternary blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO), nylon 6, and styrene‐ethylene‐butadiene‐styrene block copolymer grafted with maleic anhydride (SEBS‐g‐MA) were prepared via a melt extrusion, and the fracture behavior, morphology, mechanical properties, and rheology were studied. The compatibilization of the blended components was confirmed by differential scanning calorimetry (DSC) analysis. Mechanical properties evaluation demonstrated that incorporation of nylon 6 resulted in an improvement of the tensile strength, but reduction of both the notched Izod impact strength and elongation at break. Transmission electron microscopy (TEM) observation revealed that the network structure of SEBS‐g‐MA domain was gradually destroyed by incorporating the nylon 6. A conversion of SEBS‐g‐MA domain from the network to the irregular dispersed phase took place when the nylon 6 content reached 20 wt %, which resulted in a reduction of the impact strength. Fracture morphology implied that increase of the tensile strength was caused by the plastic deformation of matrix. Rheology investigation indicated that the melt viscosities could be reduced significantly with increasing the content of nylon 6; thus, the processability was improved. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3336–3343, 2006     

Effect of diisocyanates and chain extenders on the physicochemical properties and morphology of multicomponent segmented polyurethanes based on poly(l‐lactide), poly(ethylene glycol) and poly(trimethylene carbonate)

Multicomponent segmented polyurethanes (SPUs) based on poly(ethylene glycol), poly(l ‐lactide) and poly(trimethylene carbonate) as macrodiols, 2,4‐toluene diisocyanate (2,4‐TDI) or 1,6‐hexane diisocyanate (HDI) as diisocyanate, and 1,4‐butanediol (BDO) or 2,2‐bis(hydroxymethyl)propionic acid (DMPA) as chain extenders were synthesized. The molecular, thermal, dynamic mechanical and morphological features of this set of uncrosslinked polyurethanes are characterized using ¹H NMR, gel permeation chromatography, differential scanning calorimetry, dynamic mechanical thermal analysis (DMTA) and atomic force microscopy techniques. The lower reaction rate of HDI in comparison with 2,4‐TDI allows for better control of the SPU compositions, so that the intrinsic properties of each block can be better combined and modulated. HDI‐based SPUs are semi‐crystalline, while those based on 2,4‐TDI are amorphous, affecting the mechanical properties of these polyurethanes. All SPUs are heterogeneous, presenting morphologies of a disperse phase in a matrix which varies with the macrodiol ratios as well as with the nature of the diisocyanate and chain extender (a finer dispersion of the disperse phase is observed for SPUs of HDI and BDO). DMTA results indicate that the phases are complex mixtures of the different blocks with at least one rich in PLLA. The PEG content is shown to be the most important factor influencing the water sorption capability, while the incorporation of hindering carboxylic acid groups by the use of DMPA allows the water uptake of SPUs to be controlled by the solution pH. All SPUs show a significant loss of molar mass in hydrolytic degradation experiments and, in general, the PLLA‐rich SPUs are more susceptible to degradation. © 2015 Society of Chemical Industry     

Synthesis and surface properties of polystyrene‐graft‐poly(ethylene glycol) copolymers

Polystyrene‐graft‐poly(ethylene glycol) copolymers (PS‐g‐PEG) were successfully synthesized using the “grafting‐through” method. The graft copolymers and the surface properties of their coats were characterized by 1 H‐NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), static contact angle measurement, and atomic force microscopy (AFM). Both DSC and TEM indicated that the graft copolymers had a microphase separated structure. AFM showed the microphase separated structure also occurred at the coat surface, especially at high PEG content, which could also be indirectly confirmed by the XPS and contact angle results. The formation mechanism of the microphase separated structure was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1458–1465, 2007     

Anti‐biofouling anion exchange membrane using surface modified quaternized poly(ether imide) for microbial fuel cells

This article deals with a novel way of improving the anti‐biofouling potential of an anion exchange membrane (AEM) by surface modification with ethanol amine (AEOH), a low cost material without affecting the chemical structure and morphology of Quaternized Poly(ether imide) ( QPEI), the host membrane. The anti‐biofouling potential of the AEM was evaluated using bacteria anti‐adhesion test, hydrophilicity, surface roughness, water uptake, and the AEOH modification time. The data reveal that power density in all MFCs attain the highest in the sixth batch and thereafter declined albeit in a varying rate as expected measuring the least for QPEI‐30. Periodical measurement of internal resistance and protein content on the membrane surfaces were found to be the least for QPEI‐30 when compared with others. A reduced biofouling with improved anti‐biofouling property is attributed to the enhanced hydrophilicity due to surface modification. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44432.     

Modification of bismaleimide resin by poly(ethylene phthalate‐co‐ethylene terephthalate), poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate), and poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)

Aromatic polyesters were prepared and used to improve the brittleness of bismaleimide resin, composed of 4,4′‐bismaleimidodiphenyl methane and o,o′‐diallyl bisphenol A (Matrimid 5292 A/B resin). The aromatic polyesters included PEPT [poly(ethylene phthalate‐co‐ethylene terephthalate)], with 50 mol % of terephthalate, PEPB [poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate)], with 50 mol % of 4,4′‐biphenyl dicarboxylate, and PEPN [poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)], with 50 mol % 2,6‐naphthalene dicarboxylate unit. The polyesters were effective modifiers for improving the brittleness of the bismaleimide resin. For example, inclusion of 15 wt % PEPT (MW = 9300) led to a 75% increase in fracture toughness, with retention in flexural properties and a slight loss of the glass‐transition temperature, compared with the mechanical and thermal properties of the unmodified cured bismaleimide resin. Microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The toughening mechanism was assessed as it related to the morphological and dynamic viscoelastic behaviors of the modified bismaleimide resin system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2352–2367, 2001     

Physicochemical investigation of radiation‐grafted poly(acrylic acid)‐graft‐poly(tetrafluoroethylene–ethylene) copolymer membranes and their use in metal recovery from aqueous solution

ET‐g‐PAAc membranes were obtained by radiation grafting of acrylic acid onto poly(tetrafluoroethylene–ethylene) copolymer films using a mutual technique. The ion selectivity of the grafted membranes was determined toward K⁺, Ag⁺, Hg²⁺, Co²⁺, and Cu²⁺ in a mixed aqueous solution. The ion‐exchange capacity of the grafted membranes was measured by back titration and atomic absorption spectroscopy. The Hg²⁺ ion content of the membrane was more than that of either the K⁺ or Ag⁺ ions. The presence of metal ions in the membranes was studied by infrared and energy‐dispersive spectroscopy measurements. Scanning electron microscopy of the grafted and metal‐treated grafted membranes showed modification of the morphology of the surface due to the adsorption of K⁺ and Ag⁺ ions. No change was observed for the surface of the membrane that was treated with Hg²⁺ ions. The thermal stability of different membranes was improved more with Ag⁺ and Hg²⁺ ions than with K⁺ ions. It was found that the modified grafted membranes possessed good hydrophilicity, which may make them promising candidates for practical applications, such as for cation‐exchange membranes in the recovery of metals from an aqueous solution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2692–2698, 2002     

Polyphosphazene membranes. III. Solid‐state characterization and properties of sulfonated poly[bis(3‐methylphenoxy)phosphazene]

Poly[bis(3‐methylphenoxy)phosphazene] was sulfonated in a solution with SO₃ and solution‐cast into 100–200‐μm‐thick membranes from N,N‐dimethylacetamide. The degree of polymer sulfonation was easily controlled and water‐insoluble membranes were fabricated with an ion‐exchange capacity (IEC) as high as 2.1 mmol/g. For water‐insoluble polymers, there was no evidence of polyphosphazene degradation during sulfonation. The glass transition temperature varied from −28°C for the base polymer to −10°C for a sulfonated polymer with an IEC of 2.1 mmol/g. The equilibrium water swelling of membranes at 25°C increased from near zero for a 0.04‐mmol/g IEC membrane to 900 % when the IEC was 2.1 mmol/g. When the IEC was < 1.0 mmol/g, SO₃ attacked the methylphenoxy side chains at the para position, whereas sulfonation occurred at all available aromatic carbons for higher ion‐exchange capacities. Differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized microscopy showed that the base polymer, poly[bis(3‐methylphenoxy)phosphazene], was semicrystalline. For sulfonated polymers with a measurable IEC, the 3‐dimensional crystal structure vanished but a 2‐dimensional ordered phase was retained. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 387–399, 1999