Synthesis and properties of new poly(ether sulfone)amides

High molecular-weight aromatic polyamides were obtained from 1,5- and 2,6-bis-(4′-carboxy-4-phenylenoxy-sulfonyl)naphthalene by direct polycondensation reaction in N-methyl-2-pyrrolidone with various aromatic diamines, using triphenyl phosphite and pyridine as condensing agents. The polymers were characterized by elemental analysis, thermogravimetric analysis, differential scanning calorimetry, and infrared analysis. The polyamides, obtained in quantitative yield, possessed inherent viscosities in the range 0.42–1.70 dL/g, glass transition temperatures between 245–310°C, and 10% weight loss temperatures in nitrogen and air above 435 and 424°C, respectively. Most of the polymers were soluble in aprotic solvents. The effect of the structure on properties, such as solubility, T_g, and thermal behavior, were also studied. © 1996 John Wiley & Sons, Inc.     

Synthesis and properties of segmented aromatic poly(ether sulfone)-amide and poly(ether sulfone)-imide copolymers

New segmented aromatic poly(ether sulfone)-amide and poly(ether sulfone)-imide copolymers were synthesized by the chain extension of α,w-diamine-terminated poly(ether sulfone) oligomer with both aromatic dicarboxylic acid chlorides and tetracarboxylic dianhydrides, respectively. Crystallization of the poly(ether sulfone)unit was suppressed by the introduction of amide or imide linkage along the polymer backbone, giving amorphous copolymers that were +eadily soluble in various organic solvents. The copolymers had somewhat higher glass transition temperatures than the parent poly(ether sulfone). They afforded transparent and tough films by solution casting. © 1992 John Wiley & Sons, Inc.     

Physical aging of poly(ether sulfone)-modified epoxy resin

The physical aging process of 4,4′-diaminodiphenylsulfone (DDS) cured diglycidyl ether bisphenol-A (DGEBA) blended with poly(ether sulfone) (PES) was studied by differential scanning calorimetry (DSC) at four aging temperatures between T_g-50°C and T_g-10°C. At aging temperatures between T_g-50 and T_g-30°C, the experimental results of epoxy resin blended with 20 wt% of PES showed two enthalpy relaxation processes. One relaxation process was due to the physical aging of PES, the other relaxation process was due to the physical aging of epoxy resin. The distribution of enthalpy relaxation process due to physical aging of epoxy resin in the blend was broader and the characteristic relaxation time shorter than those of pure epoxy resin at the above aging temperatures (between T_g-50 and T_g-30°C). At an aging temperature between T_g-30 and T_g-10°C, only one enthalpy relaxation process was found for the epoxy resin blended with PES, the relaxation process was similar to that of pure epoxy resin. The enthalpy relaxation process due to the physical aging of PES in the epoxy matrix was similar to that of pure PES at aging temperatures between T_g-50 and T_g-10°C. © 1997 John Wiley & Sons, Inc.     

Synthesis and characterization of aromatic poly(ether sulfone imide)s derived from sulfonyl bis(ether anhydride)s and aromatic diamines

Two sulfonyl group-containing bis(ether anhydride)s, 4,4′-[sulfonylbis(1,4-phenylene)dioxy]diphthalic anhydride ( IV ) and 4,4′-[sulfonylbis(2,6-dimethyl-1,4-phenylene)dioxy]diphthalic anhydride (Me- IV ), were prepared in three steps starting from the nucleophilic nitrodisplacement reaction of the bisphenolate ions of 4,4′-sulfonyldiphenol and 4,4′-sulfonylbis(2,6-dimethylphenol) with 4-nitrophthalonitrile in N,N-dimethylformamide (DMF). High-molar-mass aromatic poly(ether sulfone imide)s were synthesized via a conventional two-stage procedure from the bis(ether anhydride)s and various aromatic diamines. The inherent viscosities of the intermediate poly(ether sulfone amic acid)s were in the ranges of 0.30–0.47 dL/g for those from IV and 0.64–1.34 dL/g for those from Me- IV. After thermal imidization, the resulting two series of poly(ether sulfone imide)s had inherent viscosities of 0.25–0.49 and 0.39–1.19 dL/g, respectively. Most of the polyimides showed distinct glass transitions on their differential scanning calorimetry (DSC) curves, and their glass transition temperatures (T_g) were recorded between 223–253 and 252–288°C, respectively. The results of thermogravimetry (TG) revealed that all the poly(ether sulfone imide)s showed no significant weight loss before 400°C. The methyl-substituted polymers showed higher T_g's but lower initial decomposition temperatures and less solubility compared to the corresponding unsubstituted polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1649–1656, 1998     

Controlled sulfonation of poly(arylene ether sulfone)s and poly(arylene ether ketone)s with different molecular structures for polymer electrolyte membranes

Poly(arylene ether sulfone) copolymers derived from 9,9-bis(4-hydroxyphenyl)fluorene, bisphenol S and 4,4′-difluorodiphenylsulfone and poly(arylene ether ketone) copolymers derived from 4-phenoxybiphenyl, diphenyl ether and isophthaloyl chloride were prepared as precursor polymers for sulfonation reaction in which sulfonic groups are introduced quantitatively into specified positions. Sulfonation reaction for these two series of copolymers by concentrated sulfuric acid was successfully carried out to give sulfonated polymers with controlled positions and degree of sulfonation. Thermal stability, moisture absorption and proton conductivity for these two series of copolymers were measured and the results were compared to those of perfluorosulfonic acid polymers.     

Synthesis,curing and properties of poly(phthalazione ether sulfone ketone) copolymers crosslinked by click chemistry

Functionalized poly(phthalazinone ether sulfone ketone) was synthesized by successive chloromethylation and azidation, followed by curing reaction with the propargyl end-groups of various molecular weight crosslinking agents in the presence of Cu(Ⅰ) catalyst via the azide-alkyne click reaction. The influences of the chain length of crosslinking agents on the poly(phthalazinone ether sulfone ketone) system were studied. FTIR and DSC tests demonstrated certain crosslinking by azide-alkyne reaction with the formation of triazole ring. DSC results showed that curing temperature shifted to lower temperatures considerably in the presence of Cu(Ⅰ) catalyst. TGA showed cured polymers were of much higher thermal stability, including higher thermal decomposition temperatures and higher char-yielding properties. After being cured, the polymers became insoluble in organic solvents and the gel fraction of the cured polymers exceeded 71%. Wide-angle X-ray diffraction results indicated there was a short distance order in the poly(ether sulfone)(PES) main chain except for the azido methyl poly(phthalazinone ether sulfone ketone) and 4,4'-bis(2-propynyloxy) biphenyl( AMPPESK-BP) system.     

聚酰胺6／聚醚砜共混体系的结晶与熔融行为

聚醚砜（ＰＥＳ）是一种非晶特种工程塑料，具有强度好，使用温度高等特点，但熔体粘度高，加工上有一定困难．聚酰胺６（ＰＡ６）是部分结晶的工程塑料，有很好的强度和耐磨性能．加入适量的ＰＡ６，可显著地降低ＰＥＳ的熔体粘度，且可基本保持ＰＥＳ的原有性能［１］．...     

Microstructure of poly(methyl methacrylate-co-isopropyl acrylate) studied by 13C NMR

The distribution of configurational–compositional sequences of poly(methyl methacrylate-co-isopropyl acrylate) (PMMA/iPrA) has been determined from the carbonyl and β-CH₂ signals in the 100?MHz ¹³C NMR spectra of the copolymer. The carbonyl signal provided information on configurational–compositional sequences up to heptads, whereas β-CH₂ signals offered complementary information on even sequences up to hexads. The assignment of the sequences to the respective signals was based on a comparison with the spectra of respective homopolymers, that is, PMMA and PiPrA followed by a computer simulation applying an incremental calculation of chemical shifts of the individual sequences.     

Poly(aryl ether)s containing o‐terphenyl subunits. II. Random poly(ether sulfone)s

The synthesis of a new A₂X‐type difluoride monomer, N‐2‐pyridyl‐4′,4″‐bis‐(4‐fluorobenzenesulfonyl)‐o‐terphenyl‐3,6‐dimethyl‐4,5‐dicarboxylic imide ( 3 ), is described. The monomer 3 was incorporated into a series of copoly(aryl ether sulfone)s by polymerization of 4,4′‐isopropylidenediphenol and 4,4′‐difluorophenylsulfone. The incorporation of monomer 3 had an observable effect on both the glass‐transition temperature of poly(aryl ether sulfone)s and the tendency for macrocyclic oligomers to form during polymerization. Replacement of the pyridyl imide group via a transimidization reaction with propargyl amine proceeded quantitatively and without polymer degradation. The acetylene containing copoly(aryl ether sulfone) could be crosslinked by simple thermal treatment, resulting in an increase in the glass‐transition temperature and solvent resistance. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 9–17, 2000     

Novel electroactive poly(arylene ether sulfone) copolymers containing pendant oligoaniline groups: Synthesis and properties

We present a series of novel poly(arylene ether sulfone) copolymers containing pendant oligoaniline groups. A novel monomer containing oligoaniline, 2,6‐difluorobenzoyl aniline tetramer (DFAT), was synthesized by reaction of 2,6‐difluorobenzoyl chloride and parent aniline tetramer and incorporated into the aforementioned copolymers via direct copolymerization with 4,4′‐dichlorodiphenyl sulfone (DCDPS), and 4,4′‐isopropylidene diphenol (BPA) using N,N′‐dimethylacetamide as solvent. The structures of these copolymers were confirmed by FTIR, ¹H NMR, and GPC. Spectral analysis of the copolymers in different oxidation states was investigated via UV‐visible spectra. The copolymers exhibited outstanding thermal stability and good solubility in various organic solvents. Their electroactivity, explored with cyclic voltammetry, was found to increase as the content of oligoaniline in the polymer increased. The electric and dielectric properties of the copolymers were also studied in detail. The electrochromic performance of the copolymers was investigated by electrochromic photographs and transmittance spectra; the color of the copolymer thin films changes from grey (at 0.0 V), to green (at 0.4 V), to blue (at 0.6 V) and to pearl blue (at 1.0 V) and the maximum transmittance change (ΔT) at 700 nm is 42.6% (90.7% ? 48.1%). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of hydrophilicity-controlled poly(arylene ether sulfone) copolymers with phenolphthalein-based carboxylic acid groups for separation membrane applications

Abstract

Hydrophilicity-controlled poly(arylene ether sulfone) copolymers with phenolphthalein-based carboxylic acid groups (PES-COOH-X) were synthesized via direct copolymerization by adjusting the feed molar ratio. The chemical structures of the obtained copolymers were confirmed by ¹H nuclear magnetic resonance (NMR) spectroscopy. The copolymers showed good solubility in common aprotic solvents and exhibited excellent mechanical properties. The water contact angles of the obtained copolymers could be reduced by approximately 52% from 92.1° to 44.2° with increasing content of phenolphthalein-derived monomer, 2-[bis(4-hydroxyphenyl)methyl] benzoic acid (PPH-COOH), in the feed molar ratio. A series of PES-COOH-X membranes was prepared via a conventional immersion precipitation phase inversion method. The effects of the monomer feed molar ratio on the morphology, hydrophilicity, pure water flux, and water uptake of the prepared membranes were investigated. The results showed that the pure water flux of the PES-COOH-X membranes was significantly enhanced by almost a factor of two as compared to the pristine PES membrane. From the water contact angle data, it was identified that the hydrophilicity of the membranes was increased rapidly with increasing PPH-COOH content in the membranes. These hydrophilicity-controlled poly(arylene ether sulfone) copolymers may be considered as good candidates for separation membrane materials.     

A DSC study of miscibility and phase separation in crystalline polymer blends of phenolphthalein poly(ether ether sulfone) and poly(ethylene oxide)

The miscibility of blends of phenolphthalein poly(ether ether sulfone) (PES-C) and poly(ethylene oxide) (PEO) was established on the basis of the thermal analysis results. Differential scanning calorimetry (DSC) studies showed that the PES-C/PEO blends prepared by casting from N,N-dimethylformamide (DMF) possessed a single, composition-dependent glass transition temperature (T_g), and thus that PES-C and PEO are miscible in the amorphous state at all compositions at lower temperature. At higher temperature, the blends underwent phase separation, and the PES-C/PEO blend system was found to display a lower critical solution temperature (LCST) behavior. The phase separation process in the blends has also been investigated by using DSC. Annealed at high temperatures, the PES-C/PEO blends exhibited significant changes of thermal properties, such as the enthalpy of crystallization and fusion, temperatures of crystallization and melting, depending on blend composition when phase separation occurred. These changes reflect different characteristics of phase structure in the blends, and were taken as probes to determine phase boundary. From both the thermal analysis and optical microscopy, the phase diagram of the blend system was established. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1383–1392, 1997     

Microstructural study of poly(methyl methacrylate-co-n-propyl acrylate) by 13C NMR

Analysis of carbonyl and β-CH₂ signals in the 100?MHz ¹³C NMR spectra of poly(methyl methacrylate-co-n-propyl acrylate) (PMMA/nPrA), provided distribution of configurational-compositional sequences for a series of the copolymer samples of different composition at pentad level for carbonyl signal and hexad level for the backbone methylene carbons. Computer simulation of the spectra based on incremental calculation of the chemical shifts for individual sequences provided very good agreement with the experimental spectra.     

Synthesis and characterization of poly(arylene ether sulfone) copolymers with sulfonimide side groups for a proton‐exchange membrane

A sulfonimide‐containing comonomer derived from 4,4′‐dichlorodiphenylsulfone was synthesized and copolymerized with 4,4′‐dichlorodiphenylsulfone and 4,4′‐biphenol to prepare sulfonimide‐containing poly(arylene ether sulfone) random copolymers (BPSIs). These copolymers showed slightly higher water uptake than disulfonated poly(arylene ether sulfone) copolymer (BPSH) controls, but their proton‐conductivity values were very comparable to those of the BPSH series with similar ion contents. The proton conductivity increased with the temperature for both systems. For samples with 30 mol % ionic groups, BPSI showed less temperature dependence in proton conductivity and slightly higher methanol permeability in comparison with BPSH. The thermal characterization of the sulfonimide copolymers showed that both the acid and salt forms were stable up to 250 °C under a nitrogen atmosphere. The results suggested that the presumed enhanced stability of the sulfonimide systems did not translate into higher protonic conductivity in liquid water. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6007–6014, 2006     

Effect of sepiolite nanoparticles on the properties of novel poly(sulfone ether imide)

A new poly(sulfone ether imide) was prepared, and related nanocomposites were produced through introduction of sepiolite nanoparticles into the matrix of polymer. Inherent viscosity, thermal and mechanical features of pristine poly(sulfone ether imide), and nanocomposite samples were evaluated and compared. The crystallinity was also investigated. Dispersion and distribution behaviors of nanocomposite samples and cross‐sectional morphology of nanocomposite films were also studied. Also, the optimized amounts of sepiolite nanoparticles in the matrix of polymer were determined by microscopic techniques (scanning electron microscope and transmission electron microscope). By introduction of 3 wt% of sepiolite, superior thermal and mechanical properties were observed. Copyright © 2016 John Wiley & Sons, Ltd.     

聚醚砜醚酮的合成与性能

以4,4′-二羟基二苯砜和4,4′-二氟二苯酮为单体, 通过溶液缩聚合成了聚醚砜醚酮(PESEK), 其分子结构相当于聚醚砜(PES)与聚醚醚酮(PEEK)的交替共聚物. 在共聚物分子中, 存在砜基、醚基和酮基, 整个结构单元形成了大共轭体系, 聚合物属无定形聚合物, 玻璃化转变温度(Tg)为198 ℃, 介于PEEK和PES的Tg之间, 其热稳定性和加工性能优于PES, 而力学性能与PES接近.     

Synthesis and properties of new block copolymers based on poly(ether sulfone) and polyimides

New poly(ether sulfone)-polyimide block copolymers were synthesized from α,ω-diamineterminated poly(ether sulfone) oligomer, aromatic diamines, and aromatic tetracarboxylic dianhydrides by low-temperature solution polymerization and subsequent thermal imidization. The block copolymers were insoluble in organic solvents. The multiblock copolymers obtained by the two-pot method showed microphase separation, while the random block copolymers by the one-pot method had single phase morphology. The mechanical properties of the block copolymers were greatly improved by the introduction of polyimide into the poly(ether sulfone). © 1993 John Wiley & Sons, Inc.     

Poly(ether ether ketone)/poly(aryl ether sulfone) blends: Melt rheological behavior

Dynamic rheological measurements were carried out on blends of poly(ether ether ketone) (PEEK)/poly(aryl ether sulfone) (PES) in the melt state in the oscillatory shear mode. The data were analyzed for the fundamental rheological behavior to yield insight into the microstructure of PEEK/PES blends. A variation of complex viscosity with composition exhibited positive–negative deviations from the log‐additivity rule and was typical for a continuous‐discrete type of morphology with weak interaction among droplets. The point of transition showed that phase inversion takes place at composition with a 0.6 weight fraction of PEEK, which agreed with the actual morphology of these blends observed by scanning electron microscopy. Activation energy for flow, for blend compositions followed additive behavior, which indicated that PEEK/PES blends may have had some compatibility in the melt. Variation of the elastic modulus (G′) with composition showed a trend similar to that observed for complex viscosity. A three‐zone model used for understanding the dynamic moduli behavior of polymers demonstrated that PEEK follows plateau‐zone behavior, whereas PES exhibits only terminal‐zone behavior in the frequency range studied. The blends of these two polymers showed an intermediate behavior, and the crossover frequency shifted to the low‐frequency region as the PEEK content in PES increased. This revealed the shift of terminal‐zone behavior to low frequency with an increased PEEK percentage in the blend. Variation of relaxation time with composition suggested that slow relaxation of PEEK retards the relaxation process of PES as the PEEK concentration in the blend is increased because of the partial miscibility of the blend, which affects the constraint release process of pure components in the blend. A temperature‐independent correlation observed in the log–log plots of G′ versus loss modulus (G″) for different blend systems fulfilled the necessary condition for their rheological simplicity. Further, the composition‐dependent correlations of PEEK/PES blends observed in a log–log plot of G′ versus G″ showed that the blends are either partially miscible or immiscible and form a discrete‐continuous phase morphology. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1548–1563, 2004     

Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions

Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H⁺/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by ¹H and ¹⁹F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117^® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117^® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956