Radiation degradation of poly(arylene ether ketone)s

The resistance of five poly(arylene ether ketone)s with related chemical structures to degradation by ionizing radiation has been studied by ESR spectroscopy and yields of volatile products. All of the polymers showed high resistance to radiation with low yields of radicals after irradiation in vacuum at 77 K (when up to 84% of the radicals were identified as radical anions) and much lower yields at 300 K. The yields of volatile products were much less than reported for poly(arylene sulfone)s [1, 2]. Methyl substitution on a main-chain aromatic ring decreased the radiation resistance, but methane only comprised 10% of the volatile products from the methyl-substituted polymers. A polymer containing an isopropylidene group in the main chain and a substituent aromatic carbonyl showed significantly decreased radiation resistance. Extremely low radical yields were obtained after irradiation in air at 300 K, contrary to many polymers. XPS analysis showed an increase in C–O bonds on the surface after irradiation in air.     

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.     

Poly(arylene ether)s,poly(arylene thioether)s,and poly(arylene sulfone)s derived from a dihydroxy(imidoarylene) monomer

Novel poly(arylene ether)s, poly(arylene thioether)s, and poly(arylene sulfone)s were synthesized from the dihydroxy(imidoarylene) monomer 1 . The syntheses of poly(arylene ether)s were carried out in DMAc in the presence of anhydrous K₂CO₃ by a nucleophilic substitution reaction between the bisphenol and activated difluoro compounds. Poly(arylene thioether)s were synthesized according to the recently discovered one-pot polymerization reaction between a bis(N,N′-dimethyl-S-carbamate) and activated difluoro compounds in the presence of a mixture of Cs₂CO₃ and CaCO₃. The bis(N,N′-dimethyl-S-carbamate) 3 was synthesized by the thermal rearrangement reaction of bis(N,N′-dimethylthiocarbamate) 2 , which was synthesized from 1 by a phase-transfer catalyzed reaction. The poly(arylene thioether)s were further oxidized to form poly(arylene sulfone)s, which would be very difficult, if not impossible, to synthesize by other methods. All of the polymers described have extremely high T_gs and thermal stability as determined from DSC and TGA analysis. Poly(arylene sulfone)s have the highest T_gs and they are in the range of 298–361°C. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1201–1208, 1998     

Synthesis and properties of poly(arylene ether sulfone)s and poly(arylene ether ketones) derived from 4,4″-dihydroxy-o-terphenyl

Novel poly(arylene ether)s with a rigid and zigzag 4,4″-o-terphenyldiyl structure, introduced into the polymer backbone were synthesized by nucleophilic displacement reaction of 4,4″-dihydroxy-o-terphenyl with several activated aromatic dihalides in virtually quantitative yields. The poly(arylene ether)s having high molecular weight show both good solubility in common organic solvents and high thermal stability up to 545°C. They are amorphous with glass transition temperatures of 160–200°C.     

Development of an efficient route to hyperbranched poly(arylene ether sulfone)s

A two‐step route to an AB₂ monomer that underwent polymerization via nucleophilic aromatic substitution to afford hyperbranched poly(arylene ether sulfone)s (HB PAES) was developed. The synthesis of 3,5‐difluoro‐4′‐hydroxydiphenyl sulfone ( 4 ) was accomplished by the reaction of 3,5‐difluorophenylmagnesium bromide with 4‐methoxyphenylsulfonyl chloride, followed by deprotection of the phenol group with HBr in acetic acid. The polymerization of 4 in the presence of 3,4,5‐trifluorophenylsulfonyl benzene or tris(3,4,5‐trifluorophenyl)phosphine oxide as a core molecule afforded HB PAES with number‐average molecular weights ranging from 3400 to 8400 Da and polydispersity index values ranging from 1.5 to 4.8. The presence of cyclic oligomeric species, formed by an intramolecular cyclization process, was a contributing factor to the relatively low molecular weights. The degree of branching (DB) of the HB PAES samples was estimated by a comparison of the ¹⁹F NMR spectra of the polymer samples with those of a series of model compounds, and DB values ranging from 0.51 to 0.70 were determined. The glass‐transition temperatures for the HB PAES samples were in the range of 205–222 °C, as determined by differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:3178–3187, 2005     

Synthesis and characterization of soluble,fluorescent poly(arylene ether)s,poly(arylene thioether)s,and poly(arylene sulfone)s containing 1,3,5‐triphenylbenzene segments

The bisphenol 4,4″‐dihydroxy‐5′‐phenyl‐m‐terphenyl ( 4 ), containing a 1,3,5‐triphenylbenzene moiety, was synthesized from a pyrylium salt obtained by the reaction of benzaldehyde with p‐methoxyacetophenone with boron trifluoride etherate as a condensing agent. Polymers were obtained from 4 by a nucleophilic displacement reaction with various activated difluoro monomers and with K₂CO₃ as a base. A series of new poly(arylene ether)s ( 8a – 8f ) were obtained that contained phenyl‐substituted m‐terphenyl segments in the polymer chain. Polymers with inherent viscosities of 0.41–0.99 dL/g were obtained in yields greater than 96%. The polymers were soluble in a variety of organic solvents, including nonpolar solvents such as toluene. Clear, transparent, and flexible films cast from CHCl₃ showed high glass‐transition temperatures (T_g = 198–270 °C) and had excellent thermal stability, as shown by temperatures of 5% weight loss greater than 500 °C. 4 was converted via N,N‐dimethyl‐O‐thiocarbamate into the masked dithiol 4,4″‐bis(N,N′‐dimethyl‐S‐thiocarbamate)‐5′‐phenyl‐m‐terphenyl and was polymerized with activated difluoro compounds in the presence of a mixture of Cs₂CO₃ and CaCO₃ as a base in diphenyl sulfone as a solvent. A series of new poly(arylene thioether)s ( 9a – 9e ) were obtained with T_g values similar to those of 8a – 8e . 9a – 9e were further oxidized into poly(arylene sulfone)s with T_g values 40–80 °C higher than those for 8a – 8e and 9a – 9e . These polymers also had good solubility in organic solvents. A sulfonic acid group was selectively introduced onto the pendent phenyl group of polymers 8a and 8f by reaction with chlorosulfonic acid. The polymers were soluble in dipolar aprotic solvents and formed films via casting from dimethylformamide. Polymers 8a – 8f , 11a , and 11f showed blue and red fluorescence under ultraviolet–visible light with emission maxima at 380–440 nm. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 496–510, 2002; DOI 10.1002/pola.10136     

Effects of the structure on the properties of new poly(arylene ether sulfone)s containing naphthalene units

A series of new poly(arylene ether sulfone)s has been obtained by solution condensation polymerisation starting from 1,5- and 2,6-bis-(4-fluorosulfonyl)naphthalene with various aromatic dihydroxy compounds. The polymers, obtained in quantitative yields, possessed inherent viscosities in the range 0.28-0.68 dl g⁻¹, had good thermal stability (10% weight loss temperatures were above 405 and 420 °C respectively in nitrogen and air) and high glass transition temperatures (in the range 217-258 °C). They have been characterised by elemental and infrared analyses, GPC and wide-angle X-ray diffraction. The properties of these poly(arylene ether sulfone)s have been compared with those of the corresponding poly(arylene ether ketone)s.     

The degradation mechanism of sulfonated poly(arylene ether sulfone)s in an oxidative environment

The degradation of sulfonated aromatic hydrocarbons based polymer electrolyte membranes is an important issue for fuel cell stability. However, its mechanism is relatively unclear. We have conducted accelerated radical tests and degradation product analysis for various sulfonated poly(arylene ether sulfone) (SPES) compounds. We evaluated the chemical durability of SPES, and observed its degradation mechanism under oxidative attack by hydrogen peroxide. Various SPES compounds were synthesized from 4,4′-biphenol, 4,4′-dihydroxy diphenyl sulfone, and 4,4′-dihydroxy benzophenone comonomers, and their physical properties were evaluated. SPES copolymerized with 4,4′-dihydroxy diphenyl sulfone had a higher durability towards oxidative attack compared with the other compounds studied, and SPES copolymerized with 4,4′-dihydroxy benzophenone exhibited the lowest durability.     

Synthesis and characterization of multiblock partially fluorinated hydrophobic poly(arylene ether sulfone)‐hydrophilic disulfonated poly(arylene ether sulfone) copolymers for proton exchange membranes

Hydrophobic‐hydrophilic sequence multiblock copolymers, based on alternating segments of phenoxide terminated fully disulfonated poly(arylene ether sulfone) (BPS100) and fluorine‐terminated poly(arylene ether sulfone) (6FBPS0) were synthesized and evaluated for application as proton exchange membranes. By utilizing mild reaction conditions the ether–ether interchange reactions were minimized, preventing the randomization of the multiblock copolymers. Tough, ductile, transparent membranes were solution cast from the block copolymers and were characterized with regard to intrinsic viscosity, morphology, water uptake, and proton conductivity. The conductivity values of the 6FBPS0‐BPSH100 membranes were compared to Nafion 212 and a partially fluorinated sulfonated poly(arylene ether sulfone) random copolymer (6F40BP60). The nanophase separated morphology was confirmed by transmission electron microscopy and small angle X‐ray scattering, and enhanced proton conductivity at reduced relative humidity was observed with longer block lengths. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Thermal decomposition products of copoly(arylene ether sulfone)s characterized by direct pyrolysis mass spectrometry

Pyrolysis products with mass of up to 850 Da were detected by direct pyrolysis mass spectrometric (DPMS) analysis of a series of copoly(arylene ether sulfone)s (PES-PPO) synthesized by nucleophilic condensation of either 4,4′-dichlorodiphenylsulfone (CDPS) or 4,4′-bis-(4-chlorophenyl sulfonyl) biphenyl (long chain dichloride, LCDC) with different molar ratios of hydroquinone (HQ) or dihydroxydiphenylsulfone (HDPS). Pyrolysis products retaining the repeating units of the initial copolymers were formed at temperatures ranging from 420 °C to 470 °C (near the initial decomposition temperature). At temperatures higher than 450 °C were observed products containing biphenyl units, formed by the elimination process of SO₂ from diphenyl sulfone bridges. Products having biphenyl and dibenzofuran moieties were detected in the mass spectra recorded at temperatures above 550 °C. These units were formed by loss of hydrogen atom from diphenyl ether bridges. Although the EI (18 eV) mass spectra of the pyrolysis products of the samples investigated were very similar, it was found that the relative intensity of some ions reflects the molar composition of the copolymers analysed. Cyclic and linear oligomers with very low molecular mass, present in the crude copolymers, were also detected by DPMS. Thermogravimetric analysis also showed their excellent thermal stability below 400 °C. It indicates that the copolymers yield a char residue of 40-45% at 800 °C, which increases with the PPO mole fraction in the samples.     

Synthesis and characterizations of novel phosphorous-nitrogen containing poly(ether sulfone)s

The synthesis of novel phosphorus-nitrogen synergism aromatic poly(ether sulfone)s was carried out successfully by using phosphorus-containing and nitrogen-containing biphenol-like monomers, 1,1′-bis(4-hydroxyphenyl)-metheylene-bispheny-1-oxophosphine oxide (DOPO-PhOH) and 1,2-dihydro-4-(4-hydroxyphenyl)phthalazin-1(2H)-one (DHPZ), in the usual synthesis procedure. Polymers with sufficient molecular weights could be obtained. The structure of the phosphorus-nitrogen containing poly(ether sulfone)s was characterized by means of Fourier transform infrared spectra (FTIR) and nuclear magnetic resonance spectroscopy (¹H NMR, ³¹P NMR). The influence of monomer ratio on their thermal stability was also investigated by adjusting the proportion of DOPO-PhOH/DHPZ (mol/mol) from 80/20 to 20/80. The molecular weight and glass-transition temperatures (T_g′s) of the polymers increased with increasing content of the DHPZ monomer. The high thermal stabilities were depended on the different proportion of diol type incorporated.     

交联型聚芳醚砜两亲嵌段聚合物的合成与表征

首先分别合成了主链上含有查尔酮结构的疏水段和侧链上含有叔胺的亲水段,然后通过疏水段与亲水段的末端缩合反应合成了一系列光敏性聚芳醚砜两亲嵌段聚合物,其结构和热性能分别通过1 H NMR,FT-IR,UV-Vis光谱,TGA和万能力学试验机等进行表征测试.该两亲性嵌段聚合物具有良好的溶解性、热稳性、力学性能和光敏性,在紫外光谱322nm处有最大吸收峰,在常温下经紫外光照射,分子链之间发生[2+2]环加成反应,聚合物分子之间形成交联结构,最大交联度可达到64%.     

Synthesis and properties of poly(arylene ether phenyl-s-triazine)s

A series of new poly(arylene ether phenyl-s-triazine)s was prepared by the nucleophilic aromatic substitution polymerization of the potassium salt of bisphenols with 2,4-bis (halophenyl)-6-phenyl-s-triazine in N-methyl-2-pyrrolidone at elevated temperature. The polymers with inherent viscosities exceeding 0.5 were obtained after polymerization for 1 h using 2,4-bis(fluorophenyl)-6-phenyl-s-triazine as a monomer. The glass transition temperatures of the resulting polymers ranged from 200 to 260°C depending on the bisphenol used in the polymer synthesis. The poly(arylene ether phenyl-s-triazine)s demonstrated excellent thermal stabilities in excess of 490°C (5% weight loss in air). The isothermal TGA measurements (400°C under air or nitrogen atmosphere) revealed that the 4,4'-biphenol- and hydroquinone-based poly(arylene ether phenyl-s-triazine)s belong to the most superior class of heat resistant polymers, such as polyimide Kapton?. The mechanical properties of these polymers are also described. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(arylene ether imidazole)s

Poly(arylene ether imidazole)s were prepared by the aromatic nucleophilic displacement reaction of a bisphenol imidazole with activated aromatic dihalides. The polymers had glass transition temperatures ranging from 230 to 318°C and number-average molecular weights as high as 82,000 g/mol. Thermogravimetric analysis showed a 5% weight loss occurring ～ 400°C in air and ～ 500°C in nitrogen. Typical neat resin mechanical properties obtained at room temperature included tensile strength and tensile modulus of 14.2 and 407 ksi and fracture energy (G_lc) of 23 in. lb/in.² Titanium-to-titanium tensile shear strengths measured at 23 and 200°C were 4800 and 3000 psi, respectively. In addition, preliminary data were obtained on carbon fiber laminates. The chemistry, physical, and mechanical properties of these polymers are discussed.     

Partially fluorinated sulfonated poly(arylene sulfone)s blended with polybenzimidazole

A partially fluorinated and sulfonated poly(arylene sulfone) (SPSO) was successfully synthesized via nucleophilic polycondensation of 2,2‐bis(4‐fluorophenyl)hexafluoro‐propane with 4,4′‐thiobisbenzenethiol (TBBT). In a second step, the prepared poly(arylene sulfide) was oxidized to SPSO. The polymer was blended with the polybenzimidazole PBIOO^® to obtain a mechanically stable membrane. This film was compared with other polymer blends, which were synthesized in our group in the last years. We were especially interested in the influence of different bridging groups such as ether, ketone, and sulfone groups. The affect on properties such as water uptake (WU), thermal stability, proton conductivity, and oxidative stability were analyzed in this work. Additionally, the blend membranes were characterized by gel permeation chromatography. The novel SPSO blend shows a high molecular weight, and its blend membrane with PBIOO has an excellent onset of ? SO₃H group splitting‐off temperature (T_onset) of 334 °C. The proton conductivity amounts to 0.11 S cm^?1, and the water uptake reaches 30%. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Mechanical and morphological studies of sulfonated poly(arylene ether sulfone)s for potential application in fuel cell membrane

Two groups of synthesized sulfonated poly(ether sulfone)s with similar structures but different size of repeat units were selected. Investigation of the properties of these copolymers with different sulfonation contents for application as fuel cell membrane was the main aim of this study. These groups of copolymers showed different thermal behavior, mechanical properties, dimensional and oxidative stability, ion exchange capacity, water uptake, and proton conductivity. Structure–property relation was surveyed, and the copolymers showed acceptable results for use as fuel cell membrane. The swelling ratio of the copolymers was in the range of 3.3–6.6%, and the proton conductivity of them was about 0.020–0.077 S/cm at 25°C. These data were comparable with Nafion 115 with 8.15% of swelling ratio and 0.085 S/cm of proton conductivity. Copyright © 2017 John Wiley & Sons, Ltd.     

Synthesis and properties of poly(arylene ether imide ketone)s

Poly(arylene ether ketone)s containing imide units were prepared by the aromatic nucleophilic displacement reaction of the potassium salts of bisphenols with bis(4-fluorobenzoyl)phthalimides in N-methyl-2-pyrrolidone at elevated temperature. The polymers having inherent viscosities of 0.34–0.77 dL/g were obtained in 2 h. The polymers exhibited glass transition temperatures ranging from 216 to 268°C and decomposition temperatures (5% weight loss under air atmosphere) ranging from 450–570°C mainly depending on the bisphenols used in the polymer synthesis. The isothermal TGA measurements (400°C under air or nitrogen atmosphere) revealed that the 4,4'-biphenol- and hydroquinone-based poly(arylene ether ketone imide)s belong to a superior class of heat resistant polymers. The mechanical properties of these polymers are also described. © 1994 John Wiley & Sons, Inc.     

Structure and thermal characterisation of poly(arylene ether sulphone)s

Structurally different poly(arylene ether sulphone) (PES) copolymers were synthesized by reacting stoichiometric amount of dichlorodiphenyl sulphone (DCDPS) with bisphenols. The molar ratio of bisphenol-A and phenolphthalein (ESP)/hydroquinone (ESH)/resorcinol (ESR) was varied to prepare nine copolymer samples. Structural characterization was done by FT-IR and ¹H-NMR studies. The initial decomposition temperature as well as temperature of maximum rate of mass loss in ESR and ESH copolymers were similar and a marginal decrease in these decomposition temperatures were observed by increasing the isopropylidine units in the backbone. High char residue at 800°C was observed in polymers having high content of phthalein units.The paper was presented at Thermans 2004 held at Baroda, January 20–22, 2004.Reliance Industries Limited is gratefully acknowledged for creating a Chair at IIT Delhi (I. K. Varma) and Council of Scientific and Industrial Research for providing scholarship to one of the authors (R. T. S. Muthu Lakshmi).     

Synthesis and characterization of new fluorescent poly(arylene ether)s

The poly(arylene ether)s were prepared by the nucleophillic aromatic substitution polymerization of phenolphthalin and its derivatives with activated aromatic difluorides. The polymers had glass transition temperatures ranging from 210 to 240°C. Though the monomers have no fluorescence, the resulting polymers fluoresced a light green color in solid and solution states. The maximum excitation and emission wavelengths are 420 nm and 470 nm, respectively. In the polymer solutions, the fluorescence intensity decreased gradually, but the intensity was recovered by heating the polymer at 220°C for a few minutes. The fluorescent polymer had a stable radical. A model compound having the same repeating unit of the polymer was also prepared. The fluorescence properties of this model were almost the same as those of the polymers. © 1994 John Wiley & Sons, Inc.     

Free volume in glassy poly(arylene ether ketone)s

Amorphous polyarylene ether ketones were examined in the glassy state by positron annihilation lifetime spectroscopy (PALS) and in the melt by standard rheological techniques. Specimens were well-characterized fractions of two isomeric structures. PALS clearly shows that the polymer with meta linkages in its backbone contains larger voids (> 0.25 nm radius). Thus despite their similar bulk densities, the two materials must pack very differently on a local scale. On the other hand, the free volumes inferred from the WLF treatment of melt viscosity data are practically identical in both materials ca. 4% at T_g. The comparison between techniques sheds some light on the distribution of free volume. © 1992 John Wiley & Sons, Inc.