Novel ultrafiltration membranes with adjustable charge density based on sulfonated poly(arylene ether sulfone) block copolymers and their tunable protein separation performance

A novel poly(arylene ether sulfone) (PAES) block copolymer was prepared from previously synthesized fluoride terminated oligomer (A₁₆) and hydroxyl terminated oligomer (B₁₂) by aromatic nucleophilic substitution polycondensation reaction. PAES was subsequently sulfonated under controlled conditions to yield a copolymer (S-PAES) with sulfonic acid groups selectively in the B₁₂ segments and without chain degradation. Non-solvent induced phase separation method was used to prepare a series of ultrafiltration membranes from blends of S-PAES and PAES with varied ratios and, hence, sulfonic acid group densities. Porous membrane morphologies, structure and surface properties were characterized comprehensively using scanning electron microscopy, Fourier transform infrared spectroscopy in the attenuated total reflection mode, as well as contact angle and zeta potential measurements. Studies of membrane performance revealed systematically increasing water permeabilities and reduced protein fouling tendencies with increasing fraction of S-PAES in the membrane. The protein transmission as function of pH value (and hence protein charge) was studied for two model proteins (bovine serum albumin and lysozyme) and found to be controlled by combined size exclusion and charge effects. The selectivity for the separation of the binary protein mixture could be systematically increased with increasing membrane charge density (by increasing S-PAES fraction). Consequently, the trade-off relationship between permeability and selectivity for conventional ultrafiltration membranes where separation is based on size exclusion solely could be overcome. Due to their high stability and tunable functionality, the PAES block copolymers have also large potential as membrane material for other applications.     

Comb-shaped block poly(arylene ether sulfone ketone)s for anion exchange membranes

A well-designed architecture is presented here to construct high-performance anion exchange membranes (AEMs). A series of quaternized fluorene-containing block poly(arylene ether sulfone ketone)s (QFPESK-m-n) is synthesized as the main chains, and grafted with comb-shaped C8 long alkyl chains for the AEMs. By varying the hydrophilic segment’ length, there has been a significant change in the microstructure as well as phase separation morphology of the membranes, as confirmed by atomic force microscopy. Hence the as-prepared AEMs with moderate ion exchange capacities (IECs) show enhanced hydroxide conductivities in the range of 28.8―94.7 mS⋅cm⁻¹ from 30 to 80°C. Furthermore, based on the block backbones and hydrophobic comb-shaped alkyl chains, the AEMs show low-level swelling ratios of 4.3% to 9.2% at 30°C and from 6.2% to 13.2% at 80°C, and superior ratios of conductivity to swelling. In addition, the QFPESK-m-n AEMs also depict acceptable mechanical properties, good thermal stability and an optimizable alkaline stability.     

Spray coating of polysulfone/poly(ethylene glycol) block polymer on macroporous substrates followed by selective swelling for composite ultrafiltration membranes

Polysulfone(PSF) is extensively used for the production of ultrafiltration(UF) membranes thanks to its high strength,chemical stability,and good processibility.However,PSF is intrinsically hydrophobic,and hydrophilic modification is always required to PSF-based membranes if they are intended to be used in aqueous systems.Facile strategies to prepare hydrophilic PSF membranes are thus highly demanded.Herein we spray coat a PSF-based amphiphilic block polymer onto macroporous substrates followed by selective swelling to prepare flat-sheet PSF UF membranes.The polymer is a triblock polymer containing PSF as the majority middle block tethered with shorter block of polyethylene glycol(PEG) on both ends,that is,PEG-b-PSF-b-PEG.We use the technique of spray coa ting to homogeneously dispense diluted triblock polymer solutions on the top of macroporous supports,instantly resulting in uniform,defect-free polymer coating layers with the thickness down to ～1.2 μm.The bi-layered composite structures are then immerged in ethanol/acetone mixture to generate mesoscale pores in the coating layers following the mechanism of selective swelling-induced pore generation,thus producing composite membranes with the mesoporous triblock polymer coating as the selective layers.This facile strategy is free from additional hydrophilic modification and much smaller dosages of polymers are used compared to conventional casting methods.The pore sizes,porositie s,hydrophilicity,and consequently the separation properties of the membranes can be flexibly tuned by changing the swelling duration and the composition of the swelling bath.This strategy combining spray coating and selective swelling is upscalable for the production of highperformance PSF UF membranes.     

Preparation and characterization of hydrophilic and antifouling poly(ether sulfone) ultrafiltration membranes modified with Zn–Al layered double hydroxides

Zn–Al layered double hydroxide (LDH)‐entrapped poly(ether sulfone) (PES) ultrafiltration membranes with four different weight percentages, 0.5, 1.0, 2.0, and 3.0%, were prepared by a phase‐inversion method. Characterization by scanning electron microscopy, atomic force microscopy and contact angle (CA), equilibrium water content, porosity, average pore size, mechanical strength, and ζ potential measurement were used to evaluate the morphological structure and physical and chemical properties of membranes. Static protein adsorption, filtration, and rejection experiments were conducted to study the antifouling properties, water permeability, and removal ability of the modified membranes. The results show that significant change occurred in the membrane morphology and that better hydrophilicity, water permeability, and antifouling ability were also achieved for the PES/LDH membranes when a proper amount of LDH was used. For example, the CA value decreased from 66.60 to 50.21°, and the pure water flux increased from 80.21 to 119.10 L m^?2 h^?1 bar^?1 when the LDH loading was increased from 0 to 2.0 wt %. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43988.     

Antifouling and blood‐compatible poly(ether sulfone) membranes modified by zwitterionic copolymers via In situ crosslinked copolymerization

A novel and simple but practical method for the preparation of modified poly(ether sulfone) (PES) membranes was provided by the in situ crosslinked copolymerization of sulfobetaine methacrylate (SBMA) and sodium p‐styrene sulfonate (NaSS) in PES solution followed by a phase‐separation technique. Then, semi‐interpenetrating network membranes modified by the crosslinked copolymers of poly(sulfobetaine methacrylate‐co‐sodium p‐styrene sulfonate) [P(SBMA‐co‐NaSS)] were prepared. The SBMA‐containing copolymer‐modified membranes showed improved protein antifouling properties with flux recovery ratios above 90%. Furthermore, the anticoagulant properties of the NaSS‐containing copolymer‐modified membranes were obviously enhanced; their activated partial thromboplastin time could be prolonged to about 115 s. Thus, the P(SBMA‐co‐NaSS) zwitterionic copolymer‐modified membranes showed improved antifouling properties and blood compatibility and will provide wide choices for their specific applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41585.     

Multiblock poly(arylene ether nitrile) disulfonated poly(arylene ether sulfone) copolymers for proton exchange membranes: Part 1 synthesis and characterization

A series of multiblock copolymers based upon alternating segments of a hydrophilic disulfonated poly(arylene ether sulfone) and a hydrophobic fluorine-terminated poly(arylene ether benzonitrile) (6FPAEB) were synthesized and characterized for use as proton exchange membranes (PEM). The ion-exchange capacity of the block copolymers were varied by utilizing 4,4′-biphenol or hydroquinone in combination with 3,3′-disulfonated-4,4′-dichlorodiphenyl sulfone (SDCDPS) to form the hydrophilic segments. The alternating block copolymer morphology was achieved by using mild temperatures to link the oligomers together and minimize ether–ether interchange reactions. Both the 4,4′-biphenol and hydroquinone based membranes showed high proton conductivity with moderate water uptake and good mechanical properties. The block copolymers displayed nanophase separated morphologies, confirmed by transmission electron microscopy (TEM) and small angle x-ray scattering (SAXS). The strong membrane performance was attributed to the multi-phase morphology.     

Random sulfonated poly(arylene ether sulfone) and sulfonated poly(arylene ether ketone) membranes for fuel cell applications

In this study, sulfonated poly(arylene ether sulfone) (SPAES) and sulfonated poly(arylene ether ketone) (SPAEK) were randomly synthesized, employing a presulfonation process. This presulfonation process resulted in a more controlled and reproducible sulfonation level. The respective polymers were prepared using 2,2-Bis(4-hydroxyphenyl) propane at 50% molar ratio, which also provided some membrane elasticity. The resulting polymers, each had 25% of the block containing the sulfonic domains (SPAES A 25 and SPAEK A 25). Better conductive membranes were achieved for the random sulfone polymers than for the random ketone polymers, with values, respectively, of 0.24 and 0.07 S cm⁻¹ at 80°C. The lower proton conductivity from the ketone-based polymer was compensated with very low methanol permeability (0.25 × 10⁻⁶ cm² s⁻¹) and outstanding oxidative stability. The selectivity of both polymer membranes exceeded the reported values for the state-of-the-art Nafion® 117 and other commercially available options. Both polymer membranes, with their unique combination of ionic domains, elastomeric blocks, and resulting morphology, could be viable candidates for fuel cell applications.     

磺化聚苯并咪唑/磺化聚醚砜酸碱复合质子交换膜的制备与表征

为提高膜的尺寸稳定性和阻醇性能,以磺化聚苯并咪唑(S-PBI)与高磺化度聚醚砜(ABPS)两种聚合物为原料,采用溶液共混的方法,制备了系列酸碱复合质子交换膜。研究了复合膜的甲醇溶胀性、吸水率、甲醇渗透系数、质子传导率随S-PBI含量的变化规律。研究表明,随着S-PBI含量的增加,膜的阻醇性能和尺寸稳定性明显提高;同时,复合膜具有较好的质子传导率,有望应用于直接甲醇燃料电池。     

Adhesion property of sulfonated poly(arylene ether sulfone)s

Sulfonated poly(arylene ether sulfone)s (S‐PESs) were synthesized from sulfonated 4,4′‐dichlorodiphenylsulfone (S‐DCDPS), 4,4′‐dichlorodiphenylsulfone (DCDPS), and 4,4′‐biphenol through variations in the molar ratio of S‐DCDPS to DCDPS from 10/90 to 40/60. The S‐PES sodium form was characterized with Fourier transform infrared, ¹H‐NMR, thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis, and the intrinsic viscosity and solubility were also evaluated. The sodium form was then subjected to acidification by immersion in 1.5M HCl for 24 h at room temperature, which was followed by washing with deionized water. The S‐PES adhesive properties were measured with single laboratory shear samples with aluminum alloys, and the failure mode was investigated. The synthesized S‐PESs exhibited increased glass‐transition temperatures with increased S‐DCDPS/DCDPS ratios; their acid forms provided much lower glass‐transition temperatures than their sodium forms. In addition, the S‐PES sodium form exhibited a high intrinsic viscosity, which indicated a high molecular weight. The S‐PES acid form exhibited an adhesion strength similar to that of the sodium form, and the single‐lap‐shear strength increased with 10% S‐PES and then decreased with 20, 30, and 40% S‐PES. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1211–1218, 2004     

Viscometric behavior of disulfonated poly(arylene ether sulfone) random copolymers used as proton exchange membranes

tert-Butylphenyl-terminated disulfonated poly(arylene ether sulfone) random copolymers with a sulfonation degree of 35 mol% (BPS35) and controlled molecular weights (M_n), 20-50 kg mol⁻¹, were successfully prepared by direct copolymerization of the two activated halides, 4,4′-dichlorodiphenyl sulfone (DCDPS) and 3,3′-disulfonate-4,4′-dichlorodiphenyl sulfone (SDCDPS) with 4,4′-biphenol and the endcapper, 4-tert-butylphenol. Dilute viscosity measurements of the BPS35 random copolymers were successfully conducted in NMP containing various concentrations of LiBr from 0.01 to 0.2 M and mostly at 0.05 M according to the measured theory. The effects of salt concentration and molecular weights of the copolymers on the viscometric behavior were studied and compared with published data for sulfonated polystyrene. The charge density parameter (ξ) for the BPS35 copolymers was determined to be smaller than 1, suggesting that no counterion condensation occurs. Studies of the effect of ionic strength (I) on the intrinsic viscosities ([η]) under theta condition were obtained by plotting [η] vs. I^−1/2 and extrapolating to infinite ionic strength. For salt-free BPS35 solutions, the viscometric behavior was shown to fit well with the Liberti-Stivala equation, providing a way to determining intrinsic viscosity when the copolymer charge is fully screened. Intrinsic viscosity and molecular weight characterization of BPS35 copolymers by SEC and static light scattering are also presented. The results are very useful for characterizing polymeric electrolyte membrane (PEM) for fuel cells, reverse osmosis and ionic transducer membranes.     

Hydrophilic-hydrophobic multiblock copolymers based on poly(arylene ether sulfone)s as novel proton exchange membranes - Part B

There has been growing evidence, both experimental and theoretical, that block copolymer systems with well-defined sulfonated regions may provide enhanced proton transport, especially at low relative humidity. We have recently demonstrated a novel way to make hydrocarbon hydrophobic-hydrophilic block copolymers. While the chemical structure and chemical compositions are very similar to random copolymers, the microstructure and the morphology are very different. The self-diffusion coefficients of water, as measured by Pulse Gradient Stimulated Echo (PGSE) NMR techniques, have indicated a significant improvement in water transport after reaching a particular block length. At that block length (10 kg/mol:10 kg/mol), the multiblocks display better proton conductivity under partially hydrated conditions than the random copolymers. The presence of increased free water content in the multiblocks with increasing block lengths was confirmed by states of water analysis. A significant change in the distribution of three types of water was also observed compared to the random copolymers. This paper will discuss the structure-property relationships of these multiblock copolymers for potential application as proton exchange membranes.     

Preparation of anion exchange membrane based on homogeneous quaternization of bromomethylated poly(arylene ether sulfone)

This article presented the synthetic and preparation route of quaternary ammonium functionalized anion exchange membranes (AEMs), which were derived from an engineering plastics polymer, poly(arylene ether sulfone) with 3,3′,5,5′‐tetramethyl‐4,4′‐dihydroxybipheny moiety (PAES‐TM). The benzylmethyl groups on the main‐chain of PAES‐TM were converted to the bromomethyl groups via a radical reaction, thereby avoiding complicated chloromethylation, which required carcinogenic reagents. The chemical structure of the bromomethylated PAES was characterized by ¹H NMR spectrum. Following a homogeneous quaternization with trimethylamine in the solution, a series of flexible and tough membranes were obtained by a solution casting and anion exchange process. The ion exchange capacity values were ranging from 1.03 to 1.37 meq g^?1. The properties of the membranes, including water uptake, hydroxide conductivity, and methanol permeability were evaluated in detail. The AEM showed a high conductivity above 10^?2 S cm^?1 at room temperature and extremely low methanol permeability of 4.16–4.94 × 10^?8 cm² s^?1. The high hydroxide conductivity of TMPAES‐140‐NOH could be attributed to the nano‐scale phase‐separated morphology in the membrane, which was confirmed by their transmission electron microscopy images. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40256.     

Antifouling ultrafiltration membrane fabricated from poly (arylene ether ketone) bearing hydrophilic hydroxyl groups

A new kind of membrane formation polymer, cardo poly(arylene ether ketone) bearing hydrophilic hydroxyl groups (PEK‐OH) was synthesized from the biphenol monomer 2‐(2‐hydroxyethyl)‐3, 3‐bis (4‐hydroxyphenyl)‐isoindolin‐1‐one (PPH‐OH), and 4, 4′‐difluorodiphenylketone. PEK‐OH asymmetric ultrafiltration membranes were prepared using the immersion coagulation phase inversion method. The PEK‐OH membrane prepared using the optimized conditions exhibited a pure water flux of 516 ± 18 L·m^?2·h^?1 and a 99.1 ± 1.4% rejection of bovine serum albumin (BSA) at an operating pressure of 0.1 MPa. The contact angle of PEK‐OH membrane was 66.0 ± 2.4 lower than these of the PEK‐C membrane (87.0 ± 2.8°, prepared from polymer PEK‐C under the same membrane formation condition as PEK‐OH membrane) and the UE50 membrane (84.0 ± 1.6°, a commercial PES ultrafiltration membrane). The amount of BSA protein adsorbed to the PEK‐OH membrane under static condition was measured to be 3.12 μg·cm^?2, which was greatly lower than that of 88.71 μg·cm^?2 and 74.40 μg·cm^?2 for the PEK‐C and the UE50 ultrafiltration membranes, respectively. Under dynamic filtration of BSA experiments, the PEK‐OH ultrafiltration membrane showed a 78.3% water flux recovery ratio, while only a 39.7% for the PEK‐C membrane and 46.5% for UE50 membrane were detected in the first cycle. After three cycles of BSA and LYZ filtration, the flux recovery ratio of PEK‐OH ultrafiltration membrane changed to be stable at 75% and 73%, while that of PEK‐C and UE50 ultrafiltration membranes remained declining gradually. Thus, hydrophilic PEK‐OH improves antifouling membrane property. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42809.     

Cellulose acetate–poly(ether sulfone) blend ultrafiltration membranes. II. Application studies

Ultrafiltration membranes are largely applied as macromolecular solutes and heavy‐metal‐ion separation from aqueous streams. Cellulose acetate and poly(ether sulfone) blend ultrafiltration membranes were prepared by the precipitation phase‐inversion technique in 100/0, 95/5, 85/15, and 75/25% polymer blend compositions in the absence and presence of a polymeric additive, poly(ethylene glycol) 600, at different additive concentrations and were used for the rejection of proteins trypsin, pepsin, egg albumin, and bovine serum albumin; a maximum of 94% rejection was achieved. The toxic heavy metal ions copper, nickel, and cadmium from dilute aqueous solutions were subjected to rejection by the blend membranes by complexation of the ions with the water‐soluble polymeric ligand, polyethyleneimine (PEI). Permeate flux studies of proteins and metal ions were performed simultaneously with the rejection experiments. The atomic absorption spectra results reveal maximum rejection for copper complex and a minimum rejection of about 60% for the cadmium complex. The rejection and permeate flux of the blend membranes were compared with those of pure cellulose acetate membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3659–3665, 2004     

Protein‐grafted carboxylic poly(ether sulfone) membranes: Preparation and characterization

Carboxylic poly(ether sulfone) membranes were prepared by a controlled acetylating and surface‐oxidating reaction followed by the grafting of bovine serum albumin (BSA) and bovine serum fibrinogen (BFG) onto the surfaces. Attenuated total reflection–Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and Micro BCA Protein Assay Kits confirmed that the proteins were successfully grafted onto the surfaces of the membranes. The protein grafting degrees were measured at different time intervals and under different conditions. The modified membranes showed higher hydrophilicity, lower protein (BSA and BFG) adsorption, and suppressed platelet adhesion values. Because of the binding of calcium ions in blood, the modified membranes showed longer plasma recalcification times, activated partial thromboplastin times, prothrombin times, and whole blood clotting times. The results indicate that the blood compatibility of the poly (ether sulfone) membranes could be improved after surface carboxylic modification and protein immobilization and that the modified membranes could be used in the blood purification field. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of novel heterogeneous cation‐permeable membranes from blends of sulfonated poly(phenylene sulfide) and poly(ether sulfone)

Novel heterogeneous cation‐exchange membranes using poly (ether sulfone)(PES) as binder and sulfonated poly(phenylene sulfide) (SPPS) powder as polyelectrolyte were prepared by the solution casting‐immersion method. Compared with a conventional route for heterogeneous membrane, the steps of milling resin into fine powders and the pressing at high temperature are avoided, and thus permits a simple technique for the preparation of such membrane. The effect of the particle size and loading of SPPS resin on the properties of the membranes such as ion‐exchange capacity, water content, electrical resistance, transport number, diffusion coefficient of electrolytes, etc., have been studied. It is shown that the membrane fundamental properties are largely dependent on both the resin loading and the particle size of SPPS resin. By adjusting these two important parameters, one can obtain heterogeneous membrane with both good conductivity, selectivity, and proper water content for different industrial purposes such as electrodialysis, diffusional dialysis, etc. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 167–174, 2004     

Primary study of novel poly(acrylic sodium)/poly(ether sulfone) composite ultrafiltration membranes (I) the preparation of composite membrane

The poly(acrylic sodium) (PAS)/poly(ether sulfone) (PES) composite ultrafiltration membranes were prepared by coating PAS membrane solution on PES support membrane. The effects of substrate membrane, the composition of PAS solution such as PAS concentration, the choice of the solvent and the additive, and the thickness of PAS active layer on the performance of the composite membranes were extensively investigated. The experimental results have indicated the optimal PAS/PES composite membranes, containing a PES substrate with MWCO of 70,000, together with a PAS top layer having a thickness of about 20 μm, were tested at room temperature and under the pressure of 0.6 MPa with the mass concentration of 0.005 g/L poly(ethylene glycol) (PEG) (Mw = 1000 g/mol) solution, a flux of 32.6 L/(m² h) and a rejection of 92.2% were obtained, which are superior to those of the common commercial membranes reported.     

Electrospun fiber membranes from blends of poly(vinylidene fluoride) with fouling‐resistant zwitterionic copolymers

Nonwoven super‐hydrophobic fiber membranes have potential applications in oil–water separation and membrane distillation, but fouling negatively impacts both applications. Membranes were prepared from blends comprising poly(vinylidene fluoride) (PVDF) and random zwitterionic copolymers of poly(methyl methacrylate) (PMMA) with sulfobetaine methacrylate (SBMA) or with sulfobetaine‐2‐vinylpyridine (SB2VP). PVDF imparts mechanical strength to the membrane, while the copolymers enhance fouling resistance. Blend composition was varied by controlling the PVDF‐to‐copolymer ratio. Nonwoven fiber membranes were obtained by electrospinning solutions of PVDF and the copolymers in a mixed solvent of N,N‐dimethylacetamide and acetone. The PVDF crystal phases and crystallinities of the blends were studied using wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). PVDF crystallized preferentially into its polar β‐phase, though its degree of crystallinity was reduced with increased addition of the random copolymers. Thermogravimetry (TG) showed that the degradation temperatures varied systematically with blend composition. PVDF blends with either copolymer showed significant increase of fouling resistance. Membranes prepared from blends containing 10% P(MMA‐ran‐SB2VP) had the highest fouling resistance, with a fivefold decrease in protein adsorption on the surface, compared to homopolymer PVDF. They also exhibited higher pure water flux, and better oil removal in oil–water separation experiments. © 2018 Society of Chemical Industry     

Preparation and characterization of antifouling and antibacterial polysulfone ultrafiltration membranes incorporated with a silver–polydopamine nanohybrid

A silver–polydopamine (Ag–PDA) nanohybird was used to produce polysulfone (PSf) ultrafiltration membranes with excellent antifouling and antibacterial properties. First, the catechol functional groups of polydopamine (PDA) helped with the in situ immobilization of silver (Ag) nanoparticles (<10 nm) on the PDA sphere surface; this led to the formation of the Ag–PDA nanohybrid. Then, Ag–PDA/PSf hybrid membranes were prepared via the phase‐inversion method, and the influence of Ag–PDA loading on the hybrid membrane properties was systematically investigated. When the content of Ag–PDA was 0.5 wt %, the hybrid membrane achieved optimal separation performance, including a dramatically increased pure water flux and a well‐maintained bovine serum albumin rejection. Furthermore, the Ag–PDA/PSf hybrid membranes presented a significantly enhanced protein‐fouling resistance and a good antibacterial activity. These improvements were attributed to the unique structure and properties of the Ag–PDA nanohybrid because of the synergistic effect of the hydrophilic PDA substrate and well‐distributed Ag nanoparticles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46430.     

Synthesis and characterization of poly(ether sulfone) and poly(ether sulfone ketone) copolymers

Poly(ether sulfone) and poly(ether sulfone ketone) copolymers (I–V) were synthesized by the nucleophilic substitution reaction of 4,4′-dihydroxy diphenyl sulfone (DHDPS, A) with various mole proportions 4,4′-difluoro benzophenone (DFBP, B) and 4,4′-difluoro diphenyl sulfone (DFDPS, C) using sulfolane as solvent in the presence of anhydrous K₂CO₃. The polymers were characterized by physicochemical and spectroscopic techniques. All polymers were found to be amorphous, and the glass transition temperature (T_g) was found to increase with the sulfonyl content of the polymers. ¹³C-nuclear magnetic resonance (NMR) spectral data was interpreted in terms of the compositional triads, BAB, BAC, CAC, ABA, and ABB, and indicate that transetherification occurs at high concentration of DFBP units in the polymer (IV). The good agreement between the observed and calculated feed ratios validates the triad analysis. Thermal decomposition studies reveal that the thermal stability of the polymers increases with increase in the carbonyl content in the polymer. Activation energies for thermal decomposition were found to be in the range of 160–203 kJ mol⁻¹ with the cleavage of ϕ SO₂ bond being the preponderant mode of decomposition and depended on the block length of the sulfonyl unit. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2113–2121, 1999