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.

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）.

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.

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 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.

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 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.

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.

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 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.

Synthesis of Novel Cyclic Aryl Ether Thioether Ketone (Sulfone) Oligomers

Two kinds of macrocyclic oligomers containing aromatic sulfide linkages have been synthesized by the solution polycondensation in high yield. The cyclic compounds were characterized by H-1 and C-13 NMR, by and MALDI - TOF MS.

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.

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.

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 Thermal Crosslinking Behavior of Poly(aryl ether ketone)s Containing 1,4-Naphthalene Moieties

A new monomer, 1,4-bis(4-fluorobenzoyl) naphthalene(compound 2) was synthesized via a two-step reaction. 1,4-Naphthalenedicarboxylic acid chloride(compound 1) was prepared by using the acyl chlorization reaction of 1,4-naphthalenedicarboxylic acid with thionyl chloride. The Friedel-Crafts acylation of compound 1 with fluorobenzene afforded compound 2 in a 80% yield. The polycondensation of compound 2 with various bisphenols in tetramethylene sulfone(TMS) in the presence of excess potassium carbonate as a condensation reagent was carried out at 210 ℃ to quantitatively afford the corresponding poly(aryl ether ketone)s(compounds 3_8) containing 1,4-naphthalene moieties. Thermal analyses showed that the polymers have T g values ranging from 496 to 500 K and are thermally stable in air with initial mass loss above 500 ℃. These novel polymers exhibited an excellent solubility in organic solvents including NMP, DMAc, and chloroform, etc. In addition, the glass transition temperatures of these polymers increased and the polymers became insoluble in chloroform after treated at 260 ℃, indicating the occurrence of a thermal crosslinking reaction.

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 CHARACTERIZATION OF POLY(ARYL ETHER KETONE)CONTAINING BIPHENYLPHTHALAZINONE MOIETY

A new poly(aryl ether ketone) containing biphenylphthalazinone moiety was prepared by the reaction of 4-(4-hydroxybiphenyl) phthalazine-1-one with 4, 4'-difluorobenzophenone. The monomer and the polymer were characterized by FT-IR and H-1-NMR. Some properties of this polymer were described.

SYNTHESIS AND CHARACTERIZATION OF POLY(ARYL ETHER KETONE)FROM 4-(3-PHENYL-4-HYDROXYPHENYL)PHTHALAZINONE

A novel soluble poly(aryl ether ketone) was prepared by the reaction of 4-(3-phenyl-4-hydroxyphenyl)phthalazinone with 4,4'-difluorobenzophenone. The polymer was characterized by DSC, TGA and X-ray diffraction.

Synthesis and Characterization of Reactive Poly(Aryl Ether Ketone Ketone) Containing Cyclohexene Ring

A novel heterocyclic poly (aryl ether ketone ketone) (PPEKK) containing cyclohexenering was prepared from 1-methyl-cyclohex-1-ene-4, 5 -diyl-bis(4-chlorophenyl methanone) and 4 (4-hydroxyphenyl)(2H) phthalazin-1-one. The polymer was characterized by FTIR, 1HNMR, DSC,TG and X-ray analysis.