The properties of some poly(arylene ether sulfones)

Some 2,4′-substituted poly(arylene ether sulfones) have been prepared and their properties compared with those of the conventional 4,4′ homopolymer. The introduction of the comonomer leads to a small increase in yield stress and to a greater tendency to brittle fracture, which can be demonstrated from fracture surface micrographs.     

Poly(arylene ether ketone)s with low dielectric constants derived from polyhedral oligomeric silsesquioxane and difluorinated aromatic ketones

Preparation of low‐dielectric‐constant poly(arylene ether ketone)s (PAEKs) containing polyhedral oligomeric silsesquioxane (POSS) in the main chains with high molecular weights (up to η_inh = 0.65 dL/g) is reported. The polymers (DDSQ‐PAEKs) were synthesized from a diphenol POSS [2OH‐DDSQ, or 3,13‐di(2‐methoxy‐4‐propylphenol)octaphenyl DDSQ] and three difluorinated aromatic ketones via nucleophilic aromatic substitution polycondensation. All of the DDSQ‐PAEKs exhibited lower dielectric constants in the range of 1.95–2.21 at 1 MHz at room temperature compared with the corresponding traditional PAEKs. In particular, DDSQ‐PEEK demonstrated good combined characteristics, including low dielectric constant of 1.95 at 1 MHz, high static water contact angle (CA) of 100°, low water sorption of 0.09%, and organosolubility. The relationship between chemical structure and the properties of the DDSQ‐PAEKs were investigated in detail. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46084.     

Chemical transformations of poly(arylene ether ketones) containing side functional groups

Conditions for chemical transformations of poly(arylene ether ketones) containing side carboxyl and phthalimidine functional groups have been investigated. The reason why the chemical modification of poly(arylene ether ketones) with side acid chloride groups leads in some cases to the formation of insoluble products is established. Ionogenic and comb-shaped poly(arylene ether ketones) with hydrophobic fragments in side branches are obtained through chemical transformations of previously synthesized polymers containing side carboxyl, hydroxyl (alcohol), and phthalimidine groups. The properties of poly(arylene ether ketones) can be varied in a wide range via chemical reactions of side reactive groups.     

Hydrophobic properties of poly(arylene ether)s derived from linear polydimethysiloxanes and decafluorobiphenyl

A series of novel poly(arylene ether)s were synthesized with diphenol liner polydimethysiloxanes with different silicon numbers (2OH‐PDMS‐P; P = 2, 6, 10, 12, 16) and decafluorobiphenyl via a two‐step nucleophilic substitution polymerization. The chemical structures of the polymers were confirmed by Fourier transform infrared spectrometer, ¹⁹F‐NMR and ¹H‐NMR spectra. All the polymers provided outstanding hydrophobic properties, high thermal stability and good solubility. The water contact angle (WCA) first increased and then suddenly decreased with the increasing of silicon numbers in PDMS. The highest WCA about 112° was obtained when silicon numbers was ten. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46187.     

Crosslinking of poly(arylene disulfide)s and poly(arylene sulfane)s derived from cyclic(arylene disulfide) oligomers

Cyclic(arylene disulfide) and polycyclic(arylene sulfide) oligomers were synthesized by catalytic oxidation of arylenedithiols or arylenetrithiols with oxygen in the presence of a copper‐amine catalyst. These cyclic(arylene sulfide) oligomers can undergo free radical ring‐opening polymerization at an elevated temperature in the melt or solution. Polycyclic(arylene sulfide) oligomers can be used to crosslink poly(arylene disulfide)s and poly(arylene sulfane)s derived from cyclic(arylene disulfide) oligomers and elemental sulfur. The crosslinking reactions were investigated by differential scanning calorimetry and by solubility of the cured products. The minimum concentrations of polycyclic(arylene sulfide) oligomers for producing a well crosslinked poly(arylene disulfide) and poly(arylene sulfane) are 7 wt % and 10 wt %, respectively. The crosslinking reactions between poly(arylene disulfide)s, poly(arylene sulfane)s, and triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione (TTT) were also investigated. TTT is more efficient for crosslinking than the synthesized polycyclic(arylene disulfide) oligomers. The crosslinkable poly(arylene disulfide)s and poly(arylene sulfane)s could be potentially used as high temperature coatings, sealants, adhesives, and as matrices for high performance thermoset composites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3069–3077, 1999     

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.     

Synthesis and characterization of novel sulfonated poly(arylene ether ketone)s derived from 4,4'-sulfonyldiphenol

Summary Novel sulfonated poly(arylene ether ketone)s were prepared directly by aromatic nucleophilic polycondensation of 4,4'-sulfonyldiphenol with various ratios of 4,4'-difluorobenzophenone to 5,5'-carbonylbis(2-fluorobenzenesulfonate) in dimethyl sulfoxide. The resulting polyelectrolytes were characterized by IR, NMR, TGA and DSC. The 10% weight loss temperature of the products is higher than 510°C, and their glass transition temperature is above 260°C. The introduction of 4,4'-sulfonyldiphenol with powerful electron-withdrawing group, -SO₂₋, into the main chain of sulfonated poly(arylene ether ketone)s improves the thermal stability against desulfonation. The ion-exchange capacity and swelling of the polyelectrolyte membranes were measured, which are higher than 1.23meq/g and not higher than 20.9%, respectively. The membranes show very good perspectives in polymer electrolyte fuel cell (PEMFC) application. Received: 27 March 2002 / Revised version: 7 May 2002 / Accepted: 13 May 2002     

New possibilities for efficient effect of charge transport in phthalide-containing poly(arylene ether ketones)

Random phthalide-containing poly(arylene ether ketones) have been synthesized. The properties of the polymers have been studied by the thermostimulated-current and thermostimulated-depolarization methods. An extremal dependence of the electrophysical properties on the content of phthalide groups in macromolecules is observed with a maximum at their concentration of 10–15%. These dependences are explained in terms of the Sworakowski model in which the role of polarization energy of phthalide-containing molecular fragments is distinguished. The feasibility of targeted variations in the electrophysical properties of nonconjugated polymers through incorporation of functional blocks into them is discussed.     

Polymer electrolyte membranes derived from novel fluorine-containing poly(arylene ether ketone)s by controlled post-sulfonation

Precise assignment with ¹H, ¹³C and some two dimensional NMR measurements showed that sulfonation reaction by concentrated sulfuric acid at 30 °C of fluorine-containing poly(arylene ether ketone) copolymers derived from 4,4′-bis(2,4,5,6-pentafluorobenzoyl)diphenyl ether (BPDE) and 9,9-bis(4-hydroxypehnyl)fluorene (HF) and 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (6FBA) yielded quantitative introduction of sulfonic groups onto 2- and 7-positions of fluorene ring in HF unit. A series of sulfonated poly(arylene ether ketone)s with different ion exchange capacity was prepared by using this method with different compositions of HF and 6FBA, and membranes obtained from these polymers were characterized by TGA, moisture and water uptake, proton conductivity, methanol permeability, and Fenton testing. These membranes showed sufficient thermal stability, high proton conductivity at high humidified condition for PEFC and good balance in proton conductivity in water and methanol permeability for DMFC. On the other hand, they showed relatively high swelling by water probably due to weak intermolecular interaction caused by the existence of fluorine atoms in the polymer structure.     

Poly(ether ether sulfone)s and sulfonated poly(ether ether sulfone)s derived from functionalized 1,1‐diphenylethylene derivatives

Symmetrically disubstituted 1,1‐diphenylethylene derivatives, 1,1‐bis[4‐(t‐butyldimethylsiloxy)phenyl]ethylene and 1,1‐bis(4‐hydroxyphenyl)ethylene, were prepared by new synthesis methods and employed as functionalized monomers in the preparation of new poly(ether ether sulfone) derivatives, with the introduction of the 1,1‐diphenylethylene unit along the polymer backbone. A series of parent 1,1‐diphenylethylene based poly(ether ether sulfone)s were prepared via (a) the cesium fluoride catalysed polycondensation reactions of dihalogenated diaryl sulfones with silylated bisphenols and (b) the base catalysed aromatic nucleophilic substitution polycondensation reaction between aromatic dihalogenated diaryl sulfones with bisphenols. The post‐polymerization sulfonation reaction via the thiol‐ene addition reaction of the poly(ether ether sulfone) precursor containing the 1,1‐diphenylethylene unit along the backbone, with sodium 3‐mercapto‐1‐propane sulfonate, afforded well‐defined sulfonated poly(ether ether sulfone), with the alkyl sulfonate group introduced pendant to the polymer backbone. The organic compounds and different polymer derivatives were characterized by standard chromatography, spectroscopy, spectrometry, thermal analyses, microscopy and X‐ray diffraction measurements. © 2016 Society of Chemical Industry     

Hyperbranched poly(arylene ether phosphine oxide)s

Summary New AB₂ and A₂B monomers, bis(4-fluorophenyl)-4'-hydroxyphenylphosphine oxide and bis(4-hydroxyphenyl)-4'-fluorophenyl-phosphine oxide were prepared and converted to corresponding hyperbranched poly(arylene ether phosphineoxide)s with hydroxyphenyl and fluorophenyl end functional groups. While the dihydroxy monomer gave a low molecular weight polymer, the difluoro monomer produced a high molecular weight hyperbranched polymer. The glass transition temperature of the obtained polymers was 266°C and 230°C, and 5% weight loss temperature was 491 °C and 391 °C, respectively. The fluorophenyl-terminated hyperbranched polymer was soluble in CHCl₃, but the hydroxyphenyl-terminated polymer was not soluble in CHCl3 even though it has lower molecular weight than the fluorophenyl-terminated polymer, indicating that properties of the hyperbranched polymers markedly depend on end functional groups as well as their molecular weight. Received: 23 August 2000/Revised version: 19 October 2000/Accepted: 31 October 2000     

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.     

Perfectly alternating poly(arylene ether ketone sulfone)'s

Summary In this study, the synthesis of perfectly alternating poly(arylene ether ketone sulfone)'s (PAEKS) via their soluble poly(arylene ether ketimine sulfone) (PAEKetS) intermediates was described. In the first stage of this procedure a new bishalide monomer, 1,1'-bis(4-fluoro(n-benzohydroxylidene aniline)) sulfone (FBHAS) was synthesized. In the second stage, the polymerization of this monomer with various aromatic bisphenols to form the amorphous PAEKetS's and then the hydrolysis of the ketimine groups on the PAEKetS's backbones to ketones in mild acidic conditions in order to obtain perfectly alternating PAEKS's was conducted. Received: 19 July 1999/Revised version: 14 January 2000/Accepted: 14 January 2000     

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。     

含芴可交联聚芳醚酮的合成

以4,4′-二氟二苯甲酮、双酚芴和二烯丙基双酚A为单体,调整双酚芴和二烯丙基双酚A的摩尔比,通过亲核取代逐步加成反应合成了一系列含芴可交联的聚芳醚酮（PAEK）;用红外光谱仪、核磁共振波谱仪、差示扫描量热仪、热重分析仪对所制备的含芴可交联PAEK的结构、热交联行为、热稳定性等进行了表征。结果表明,所制备的聚合物可通过热引发交联,交联后的聚合物具有优良的耐热性能,交联后聚合物的耐溶剂性能得到提高,最高凝胶含量达到97.5 %。     

聚芳醚腈砜的合成与介电性能

以2,6-二氯苯甲腈(DCBN)和4,4-二羟基二苯砜(DHDPS)为原料,通过常压溶液缩聚合成了一种耐高温的无定形聚芳醚腈砜(PENS)。用FT-IR,DSC,TG等手段对PENS聚合物的结构和热性能进行了研究,同时表征了PENS薄膜的介电性能。结果表明:PENS具有很高的玻璃化转变温度(215.4℃),5%热失重温度为453℃。PENS具有很好的介电性能,其介电常数为3.6~4.1 F/m,在玻璃化转变温度前具有很好的介电稳定性。     

Novel poly(arylene ether)s containing multi-substituted pentaphenylene moiety

Three novel 2-trifluoromethyl-activated bisfluoro monomers have been synthesized successfully using a Suzuki-coupling reaction of 4-fluoro-3-trifluoromethyl phenyl boronic acid with 4,4′-dibromo-p-terphenyls with varied phenyl substitution on the middle phenylene ring. Three monomers were converted to a series of phenyl substituted poly(arylene ether)s by nucleophilic displacement of the fluorine atoms on the terminal benzene ring with several bisphenols. The polymers obtained by displacement of the fluorine atoms exhibit weight-average molecular weight up to 2.25 × 10⁵ g/mol in GPC. Thermal analysis studies indicated that these polymers did not show melting endotherms but did show ultrahigh T_g values up to 334 °C in DSC and outstanding thermal stability up to 671 °C for 5% weight loss in TGA under nitrogen atmosphere. The polymers are soluble in a wide range of organic solvents: THF, CHCl₃, NMP, DMAc, DMF, toluene, etc., and are insoluble in DMSO and acetone at room temperature. Transparent and flexible films were easily prepared by solution casting from chloroform solution of each of the polymers. The UV absorption spectra of thin films showed no absorption in the visible light region of the spectrum, suggesting a good application to optical transparent materials in the visible light region of the spectrum.     

Poly(arylene ether sulphones) by polyetherification: 2. Polycondensations

Several alkali metal halogenophenylsulphonyl phenoxides have been polymerized in the melt and in solution. Poly(arylene ether sulphones) have also been prepared by polycondensation of 4-halogenophenylsulphonyl compounds with phenols in the presence of potassium fluoride. The effects of structural factors on the ease with which polymers of high molecular weight could be obtained were examined and found to correlate with previous data concerning functional group reactivities. A procedure for the synthesis of polymer samples containing branched macromolecules has been devised and evaluated.