Synthesis and characterization of quaternized poly(phthalazinone ether sulfone ketone)for anion-exchange membrane

Chloromethylated poly（phthalazinone ether sulfone ketone） （CMPPESK） was prepared from poly（phthalazinone ether sulfone ketone） （PPESK） using chloromethyl octyl ethers （CMOE） with lower toxicity as chloromethylated regent. CMPPESK was soluble in N-methyl-2-pyrrolidone （NMP）, N,N-dimethylacetamide （DMAc） and chloroform. Quaternized poly（phthalazinone ether sulfone ketone） （QAPPESK） was prepared from CMPPESK by quaternization. QAPPESK had excellent solvent resistance, which was only partly soluble in sulfuric acid （98%） and swollen in N,N-dimethylformamide （DMF）. The vanadium redox flow battery （V-RFB） using QAPPESK anion-exchange membrane had better performance with 88.3% of overall energy efficiency.

Synthesis and characterization of novel poly(aryl ether sulfone ketone)s containing phthalazinone and biphenyl moieties

A novel series of poly（aryl ether sulfone ketone）s （PPESKs） containing phthalazinone and biphenyl moieties were prepared by two-step nucleophilic polycondensation reaction. The ^-Mw values of these copolymers were between 38,330 and 67,900. The glass transition temperatures （Tg） and 5% decomposition temperatures were ranged in 253-269 ℃ and 488-500 ℃, respectively, The structures of these copolymers were confirmed by FT-IR and ^1H NMR. Moreover, all the resultant copolymers were amorphous determined by wide angle X-ray diffraction （WAXD）.

Allyl-containing Poly(aryl ether sulfone): Synthesis and Crosslinking

A novel type of crosslinkable poly（aryl ether sulfone）（PAES） bearing an allyl pendant（PES-OAllyl） was synthesized by a grafting reaction of hydrophenyl-containing PAES（PES-OH） and allyl bromide. PES-OH was prepared by a demethylation reaction of a methoxyphenylated PAES（PES-OCH3） in the presence of pyridine/hydrochlo- ride. The PES-OCH3 was synthesized by an aromatic nucleophilic substitution of bis（4-chlorophenyl）sulfone and （p-methoxy）phenylhydroquinone. Both DSC and solubility investigation were used to study the crosslinking behavior of PES-OAllyl. After heat treatment, the glass transition temperature（Tg） value of PES-OAllyl sharply increased from 165 ℃ to 227 ℃. Meanwhile, PES-OAllyl changed from a soluble polymer to an insoluble thermoset. In addition, TGA（thermogravimetric analysis） result suggests that the thermal stability of the crosslinked product was improved. All the data prove that the crosslinked PES-OAllyl could be a potential solvent-resistance high-performance material.

Proton-exchange Sulfonated Poly（ether ether ketone）/Sulfonated Phenolphthalein Poly（ether sulfone） Blend Membranes in DMFCs

A sulfonated poly（ether ether ketone） （SPEEK） membrane with fairly high degree of sulfonation （DS） swells excessively and even dissolves at high temperature. To solve these problems, sulfonated phenolphthalein poly（ether sulfone） （SPES-C, DS= 53.7%） is blended with the SPEEK matrix （DS= 55.1%, 61.7%） to prepare SPEEKJSPES-C blend membrane. The decrease in swelling degree and methanol permeability of the membrane is dose-dependent. Pure SPEEK （DS = 61.7%） membrane dissolves completely in water at 70℃, whereas the swelling degree of the SPEEK （DS = 61.7%）/SPES-C （40%, by mass） membrane is 29.7% at 80℃. From room temperature to 80℃, the methanol permeability of all SPEEK （DS = 55.1%）/SPES-C blend membranes is about one order of magnitude lower than that of Nafion 115. At higher temperature, the addition of SPES-C polymer increases the dimensional stability and greater proton conductivity can be achieved. The SPEEK （DS = 55.1%）/SPES-C （40%, by mass） membrane can withstand temperatures up to 150℃. The proton conductivity of SPEEK （DS = 55.1%）/SPES-C （30%, by mass） membrane approaches 0.16 S·cm^-1, matching that of Nafion 115 at 140℃ and 100% RH, while pure SPEEK （DS = 55.1%） membrane dissolves at 90℃. The SPEEK/SPES-C blend membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.

Synthesis and Characterization of Ion-exchange Sulfonated Poly (ether sulfone)

N,N＇-Bis（3-hydroxyphenyl）-1,8,4,5-naphthalenetetracarboxylic bisimide was prepared from the reaction of 1,8,4,5-naphthalenetetrcarboxylic acid dianhydride and 2-aminophenol in N, N-dimethylformamide. Polymerization of this bisimide with 4,4＇-difluorodiphenylsulfone and disodium 3,3＇-disulfonate4,4＇-difluorodiphenylsulfone gave ion-exchange sulfonated poly（ether sulfone）. The structure of the title compound was characterized with H-NMR and its polymer was characterized with FT-IR.

Synthesis and properties of soluble poly（aryl ether sulfone ether ketone）s copolymers containing pendant methyl groups

A series of Poly（arly ether sulfone ether ketone）s containing pendant methyl groups were synthesized by the reaction of 4,4＇-[sulfonylbis （1,4-phenylene）dioxy] dibenzoyl chloride （SODBC） with 4,4＇- diphenoxy diphenylsulfone （DPODPS）, 4,4＇- di（2-methylphenoxy） diphenylsulfone （o-Me-DPODPS）, 4,4＇- di（3-methylphenoxy） diphenylsulfone （m-Me-DPODPS）, 4,4＇- di （2,6-bimethylphenoxy） biphenylsulfone（o-Me2-DPODPS） respectively, in a mixture of 1,2-dichloroethane （DCE） and N-methylpyrrolidone （NMP）. These reactions were catalyzed by anhydrous aluminum chloride （AlCl）. The characteristic of copolymers were studied by means of advanced analytical techniques such as FT-IR,1H-NMR, DSC, TGA and WAXD. The results show glass transition temperature （Tg） in the range of 193-206℃, thermally stable in excess of 434℃ and excellent solubility in polar solvents. Methyl-substituted Poly（aryl ether sulfone ketone）s had higher glass transition temperatures, lower initial decomposition temperatures than the unsubstituted ones.

The Rheological and Extrusion Behaviour of Blends Based on Phenolphthalein Poly(ether-ether-sulfone)and Thermotropic Liquid Crystalline Polymer

A novel engineering thermoplastic, phenolphthalein poly(ether ether sulfone)(PES C) was blended with a commercial thermotropic liquid crystalline polymer(TLCP), Vectra A950, up to 30 weight percent of TLCP. A rheometrics dynamic spectrometer (RDS Ⅱ) and a CEAST capillary rheometer, a rheoscope 1000 were employed to investigate the melt rheology and extrusion behaviour at both the low and high shearing rates. The morphologies of the blends under different shearing were observed with a scanning electron microscope(SEM) and correlated to the observed rheology. The principal normal stress differences measured with cone and plate geometry give a temperature independent correlation for both blend and PES C when they are plotted against shear stress. But the extrudate swell of the blends showed a strong temperature dependence at each shear stress. The concentration dependence of extrudate swell shows a contrary behaviour to that of the inorganic filled system. A reasonable hypothesis based on the relaxation and disorientation of TLCP during flowing in the capillary and exiting was given to explain it. The melt fracture was checked after extrusion from capillary and was discussed.

SYNTHESIS AND CHARACTERIZATION OF PHTHALAZINONE POLY(ARYL ETHER SULFONE KETONE)WITH CARBONYL GROUP

A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)- 1 (2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin in sulfolane in the presence of K2CO3 to produce high molecular weight polymers which can be dissolved in some polar solvents such as chloroform and nitrobenzene at room temperature and can be easily cast into flexible, yellowish and transparent films. PPESK is an amorphous polymer having a decomposition temperature above 400degreesC, which indicates that it has high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agent indicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (A-E) of the cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively. Therefore, the cross-linking reaction is approximately a first order reaction.

Synthesis and Characterization of Poly (Ether Sulfone Ketone) Containing the Phthalazinone Moiety

A novel poly (ether sulfone ketone) containing the phthalazinone moiety was prepared by the reaction of 4-)4-hydroxyphenyl) (2H) phthalazin-1-one with activated dichloro-monomers. The polymer was characterized by FT-IR, H-1-NMR, DSC, TGA and X-ray diffraction.

Proton-Exchange Sulfonated Poly （ether ether ketone） （SPEEK）/SiOx-S Composite Membranes in Direct Methanol Fuel Cells

A sulfonated poly（ether ether ketone） （SPEEK） membrane with a fairly high degree of sulfonation （DS） can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups （SiOx-S） was added into the SPEEK matrix （DS = 55.1%） to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80℃, whereas the SPEEK/SiOx-S （15%, by mass） membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that ofNafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiO4-S （20%, by mass） membrane could withstand temperature up to 145℃, at which in 100% relative humidity （RH） its proton conductivity exceeded slightly that of Nafion 1 15 membrane and reached 0.17 S·cm^-1, while pure SPEEK membrane dissolved at 90℃. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.

Synthesis of Poly(phthalazinone ether ketone) Containing Sodium Sulfonate Groups via Direct Polymerization

1, 2-Diliydro-4-(4-hydroxyphenyl)(2H)phthalazin-1-one(DHPZ) was sulfonated in concentrated Sulfuric acid. Poly(phthalazinone ether ketone) containing pendant sodium sulfonate group was synthesized from sulfonated and pure 1,2-dihydro-4-(4-hydroxyphenyl)(2H)phthalazin-1-one, and 4,4'-difluorodiphenylketone. The sulfonated monomer and sulfonated polymer were characterized with FT-IR and H-1-NMR.

SYNTHESIS AND PROPERTIES OF SULFONATED POLY(ARYLENE ETHER) CONTAINING TRIPHENYL METHANE MOIETIES FROM ISOCYNATE MASKED BISPHENOL

A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N＇-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton＇s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly （MEA） prepared with the asmade film （706 EW, 100 μm dry thickness） shows better cell performance than Nation 115-MEA in the whole current density range.

Sulfonated fluorinated multi-block copolymer hybrid containing sulfonated(poly ether ether ketone) and graphene oxide: A ternary hybrid membrane architecture for electrolyte applications in proton exchange membrane fuel cells

A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine （UTM） curves and alternating current （AC） impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope （FE-SEM） and atomic force microscope （AFM）. Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity （RH）. In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.

Ex situ aging effect on sulfonated poly(ether ether ketone) membrane:Hydration-dehydration cycling and hydrothermal treatment

Prolonged hydrothermal treatment for sulfonated poly(ether ether ketone) membranes induces mechanical degradation and developing hydrophilic-hydrophobic phase separation, simultaneously. The enhanced phase separation provides incremental proton conductivity to the membranes, whereas mechanical degradation drastically reduces device stability. On this basis, we describe here the effects of two different ex situ aging processes on sulfonated poly(ether ether ketone) membranes: hydrationdehydration cycling and prolonged hydrothermal treatment. Both aged membranes exhibited enhanced phase separation under the hydrated conditions, as characterized by small angle X-ray scattering.However, when the aged membranes were dried again, the nanostructure of the membranes aged via the hydration-dehydration cycling was recoverable, whereas that of the membranes aged via prolonged hydrothermal treatment was irreversible. Furthermore, the two differently aged membranes showed clear differences in thermal, mechanical, and electrochemical properties. Finally, we implemented both aged membranes in fuel cell application. The sample aged via hydration-dehydration cycling maintained its improved cell performance, whereas the sample aged via hydrothermal treatment showed drastically reduced cell performance after durability test for 50 h.

Sulfonated poly(aryl ether ketone sulfone)modified by polyoxometalates LaW_(10) clusters for proton exchange membranes with high proton conduction performance

Polyoxometalates(POMs)are classified as solid superacids which can exhibit notable proton conductivity,making them a promising functional inorganic filler for enhancing the proton conductivity of proton exchange membranes(PEMs).In this study,a series of hybrid membranes were obtained by molecular-level hybridization of Weakley-type POM Na_(7)H_(2)LaW_(10)O_(36)(LaW_(10))clusters into sulfonated poly(aryl ether ketone sulfone)(SPAEKS).All hybrid membranes exhibited greater proton conductivity than the pristine membrane in the 30–80℃temperature range.When the doping amount of LaW 10 reached 7 wt.%,the proton conductivity of M-LaW 10^(-7)achieved 64 mS·cm^(−1)at 80℃.Lanthanide ions'high coordination number property and variable coordination environment can aid to attract more water molecules from the environment.LaW 10 and these bound water can construct denser hydrogen bonds with–SO_(3)H of SPAEKS.These intensive hydrogen bonds will facilitate the constitution of more continuous proton transport channels,and improve the proton conductivity of the hybrid membrane.This work off ers a fresh approach to using POMs containing rare-earth components in PEMs.

亚临界萃取和膜技术精制元宝枫籽油的工艺优化

为了提高元宝枫籽油(ASO)的质量特性和储藏稳定性,对亚临界萃取得到的元宝枫籽油进行精制,以去除磷脂、过氧化物和游离脂肪酸。本文对亚临界萃取ASO的提取工艺进行优化,并对得到的原油利用膜分离技术进行脱胶精制,以膜通量,脱胶率、碘值、过氧化值、酸价为指标,对不同孔径的陶瓷膜和不同截留分子量的聚醚砜膜进行筛选。考察膜截留分子量、温度和压力对膜通量的影响;通过响应面法,确定ASO精制的最佳工艺参数。同时采用气相色谱-质谱法比较精制前后脂肪酸的含量。结果表明,当粒径为30目、萃取温度50℃,固液比为1:4 g/mL,聚醚砜膜分子量为100 kD,温度44℃,压力1.9 MPa,ASO得油率均值为35.92%,脱胶率为86.73%,通量为12.51 L/m2·h,碘值为116.93 g/100 g,过氧化值为0.06 g/100 g,酸价为3.66 g/100 g,与原油相比脂肪酸含量无明显损失。研究结果显示,用膜分离法脱胶是一种提高油脂品质的有效手段,本研究可为优质元宝枫籽油的生产提供技术支持。

Preparation and Properties of Poly(aryl ether sulfone ketone)Ultrafiltration Membrane Containing Fluorene Group for High Temperature Condensed Water Treatment

Novel poly（aryl ether sulfone ketone）s （PAESK） were synthesized from bisphenol A （BPA）, 9,9＇-bis（4-hydroxyphenyl） fluorene （BHPF）, 4,4＇-dichlorodiphenylsulfone （DCS） and 4,4＇-difluorobenzophenone （DFB） via nucleophilic substitution polymerization, which were subsequently used to fabricate ultrafiltration membrane by phase-inversion method for high temperature condensed water treatment. The obtained high molecular weight co-polymers with fluorene group with good solubility and good thermal stability, can be easily cast into flexible, white and non-transparent fiat films. The influence of molar ratio of BPA and BHPF on the properties of the prepared co-polymers and membranes was investigated in detail. SEM study of the morphology of the membranes indicated that the prepared membranes possessed homogeneous pores on the top surface and were sponge-like or finger-like in cross-section. Pure water flux of the membranes increased from 71.87 L·m-2.h-1 to 247.65 L·m-2.h-1, while the retention of BSA decreased slightly, and the water contact angle decreased from 82.1 ° to 55.6° with the PVP concentration from 0 wt% to 10 wt%. With increasing concentration of PVP, the mechanical properties of membranes decreased, while the thermal stability increased. The permeate flux measurement showed that the PAESK membrane had the potential for high temperature condensed water treatment.

A Facile Method for Preparation of Cardo Poly(aryl ether sulfone) Bearing Pendent Sulfoalkyl Groups as Proton Exchange Membranes

A series of cardo poly（aryl ether sulfone） copolymers bearing pendent sulfonic acid groups （SPES-X） have been prepared by a facile chemical graft method. The structure was confirmed by 1H-NMR spectra. The side-chain-type SPES-X membranes show significantly reduced swelling behavior and excellent mechanical properties as well as appropriate proton conductivity compared to the main-chain-type sulfonated polymers with similar ion exchange capacity （IEC） value. Moreover, they show methanol permeability in the range of 0.6 × 10^-7-5.7 × 10^-7 cmE/s which is lower than that of Nafion 117. All the results indicate that the SPES-Xmembranes are promising candidates for the direct methanol fuel cells.

HYDROPHILIC MODIFICATION OF PPESK POROUS MEMBRANES VIA AQUEOUS SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

Hydrophilic surface modification of poly(phthalazinone ether sulfone ketone)(PPESK) porous membranes was achieved via surface-initiated atom transfer radical polymerization(ATRP) in aqueous medium.Prior to ATRP.chloromethyl groups were introduced onto PPESK main chains by chloromethylation.Chloromethvlated PPESK(CMPPESK) was fabricated into porous membrane through phase inversion technique.Hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate)(P(PEGMA)) brushes were grafted from CMPPESK membrane ...