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.

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.

Synthesis and characterization of new soluble poly(aryl ether nitrile)s containing phthalazinone moiety

A series of novel poly（aryl ether nitrile）s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers （I） with 2,6-difluorobenzonitrile. The inherent viscosities ranged from 0.46 to 1.07 dL g^-1. The glass transition temperatures were in the range of 277-295℃, and the temperatures for 10% weight loss in nitrogen atmosphere were found between 495 and 527 ℃. The structures of these resultant polymers were confirmed by FT-IR and 1^H NMR. Moreover, the properties of poly（aryl ether nitrile）s including solubility and crystallinity were also studied.

UV-induced Self-initiated Graft Polymerization of Acrylamide onto Poly(ether ether ketone)

Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly（ether ether ketone） （PEEK） with the aim of extending its applications to biological fields. PEEK sheets were surface modified by grafting of acrylamide（AAm） with ultraviolet（UV） irradiation in the presence or absence of benzophenone（BP）. The effects of BP, irradiation time and monomer concentration on the surface wettability of PEEK were investigated. Characteriza tion of modified PEEK using scanning electron microscopy（SEM）, energy-disperse spectrometer（EDS） and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP. With the increase in irradiation time and monomer concentration, contact angles decrease to as low as 30°, demonstrating a significant improvement of surface hydrophilicity. In agreement with the decrease in contact angle, under identical conditions, the nitrogen concentration increases, suggesting the increase in grafting degree of the grafting polymerization. This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer. Though the graft polymerization proceeds more readily in the presence of BP, the self-initiated graft polymerization is clearly observed.

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 and Adsorption Property of Two Polymeric Adsorbents with Pendent Ether Bonds

Two polymeric adsorbents, poly(methyl p-vinylbenzyl ether) and poly(phenyl p-vinylbenzyl ether), were synthesized from chloromethylated polystyrene. Their adsorption property for phenol in hexane solution was investigated. The results showed that the two adsorbents adsorb phenol from hexane solution through hydrogen-bonding and π-π stacking interaction.

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 of Novel Poly(aryl ether amide)s Containing the Phthalazinone Moiety

Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl] (2H)phthalazin-1-one and 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)-3,5-dimethylphenyl](2H)phthalazin-1-one were successfully synthesized from readily available heterocyclic bisphenol-like monomers in two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety were successfully prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents.

Tetra-alkylsulfonate functionalized poly(aryl ether) membranes with nanosized hydrophilic channels for efficient proton conduction

The microstructure of polymer electrolyte membranes plays a key role in ion conductivity and water transport.Herein,fluorinated poly(aryl ether)s with tetra-alkylsulfonate side chains(SFPAEs)have been successfully synthesized from the copolymerization of a newly developed tetra-allyl-containing bisphenol(TABP)monomer,followed by the thiol-ene addition with sodium 3-mercapto-1-propanesulfonate to attach the ionic groups at the end of the flexible chains.Being the first of its kind,the densely distributed and lengthy alkylsulfonate group possesses the benefit of ease to self-assemble into hydrophilic domains during membrane preparation via solution casting.Indeed,the TEM characterizations revealed that distinct hydrophilic channels of 1-2 nm width had been formed,much larger than those of a home-made control sample where only di-alkylsulfonate side chains were attached.The SFPAE-4-45 with an IECw of 2.0 mmol g^-1 exhibited an enhanced proton conductivity of 143.7 m S cm^-1 at room temperature,which was superior to that of Nafion 212(91.0 m S cm^-1).Furthermore,the oxidative stabilities of SFPAEs were significantly higher than those of non-fluorinated analogs in literature.This study offered a new route to engineering the pendent structure of ionomers for well-defined microscopic morphologies.

Immobilization of Bovine Serum Albumin on Poly(ether ether ketone) for Surface Biocompatibility Improvement

UV-induced graft polymerization of acrylic acid（AA） on poly（ether ether ketone）（PEEK） films was carried out to introduce ―COOH for the subsequent immobilization of bovine serum albumin（BSA）.BSA was introduced on PEEK surface based on the condensation reaction between ―NH 2 and ―COOH.The modified surface（PEEK-BSA） was characterized by energy-disperse spectrometry（EDS）,X-ray photoelectron spectroscopy（XPS）,water contact angle measurement and UV spectrum analysis.The contact angle was found to decrease from 104° for the virgin PEEK films to 63° for the BSA-immobilized PEEK films,demonstrating a significant improvement of surface hydrophilicity.Moreover,the appearance of nitrogen on PEEK film confirmed by XPS and EDS indicates the immobilization of BSA on PEEK surface.

THERMAL DEGRADATION OF POLY(ARYLENE SULFIDE SULFONE)/NMETHYLPYRROLIDONE CRYSTAL SOLVATE

The thermal degradation of poly（arylene sulfide sulfone）/N-methylpyrrolidone （PASS/NMP） crystal solvate was studied by thermogravimetric analysis （TGA） and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger＇s method, which does not require knowledge of the reaction mechanism （RM）, to be 174.18 kJ/mol which was lower than that for pure PASS （E = 214 kJ/mol）. The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.