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）.

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.

Characterization and tribological investigation of self-assembled trimethoxysilyl-functionalized poly(phthalazinone ether ketone)thin films on glass substrates

Trimethoxysilyl-functionalized PPEK（PKGS） films had been designed to serve as wear resistant coatings for silicon surfaces. These surface films were formed by a dip-coating technique applied to self-assembled monolayers（SAMs）.The formation and wetting behavior of PKGS films were characterized by means of contact angle measurement.The friction coefficient of the film prepared is very low（about 0.1）,and the anti-wear behavior is good,with a lack of failure after sliding over 1800 s.

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 trimethoxysilyl-functionalized poly(phthalazinone ether ketone)

A novel alkoxysilyl-functionalized poly(phthalazinone ether ketone) (PPEK) was prepared for the boundary lubricant application in micro-electro-mechanical system (MEMS). The synthesis of functionalized PPEK was started from the hydroxylation of PPEK, then following with the corresponding ring-opening reaction of 3-glycidoxypropyltrimethoxysilane (GPTMS). The structures of the functional PPEK were confirmed by FTIR, 1H NMR, 29Si NMR, and UV–vis spectrum.

Synthesis and Characterization of Poly (Aryl Ether Ketone) Containing Phthalazinone and Naphthalene Moieties

A novel poly (aryl ether ketone) (PPEK) containing phthalazinone and naphthalene moieties was prepared by the nucleophilic displacement reaction of 4-(4-hydroxyphenyl) (2H) phthalazin-1-one with 1-chloro-4-(4-chlorobenzoyl) naphthalene. The polymer was characterized by FTIR, H-1-NMR, DSC, TGA and WAXD.

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.

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 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.

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.

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.

Poly(ether ether ketone ketone) based imidazolium as anion exchange membranes for alkaline fuel cells

An imidazolium functionalized poly(ether ether ketone ketone)(PEEKK-DIm OH)anion exchange membrane(AEM)readily soluble in certain low-boiling-point solvents(isopropanol)is prepared.The solubility results are consistent with the results of molecular dynamics simulations.By varying the chloromethylation reaction temperature or concentrated sulfuric acid concentration of PEEKK,the degrees of chloromethylation of PEEKK are changed from 54% to 92%,the corresponding PEEKK-DIm OH AEMs with the ion exchange capacities(IECs)of 1.14–1.65 mmol·g^(-1).The PEEKK-DIm OH 92% AEM shows high hydroxide conductivity(31 m S·cm^(-1)),suitable water uptake(94%)and acceptable swelling ratio(39%)at 60°C.In addition,the PEEKK-DIm OH AEMs possess good thermal and alkaline stability.The maximum power density(46.16 mW·cm^(-2))of fuel cell prepared with PEEKK-DIm OH 92%AEM as exchange membrane and ionomer is much higher than that with commercial AHA membranes.All the above results indicate that the PEEKK used in this study is a promising AEM matrix material for alkaline fuel cells.

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.

Synthesis and Properties of Poly(aryl ether ketone) Copolymers Containing 2,7-Naphthalene Moieties

Poly（ aryl ether ketone） copolymers containing 2,7-naphthylene and hydroquinone（HQ） moieties with various compositions were prepared by the reaction of 4,4＇-difluorobenzophenone（DFB） 2,7-naphthylene and hydroquinone in the presence of sodium carbonate and potassium carbonate （ 19： 1, mass ratio） in diphenyl sulfone （DPS）. The thermal analysis results of the copolymers show that the glass transition temperatures（Tgs） increase, while the melting temperatures（Tra） and tile 5.0% weight loss temperatures （ Td ） decrease with the increase of the 2,7-naphthalene moieties. For the copolymers synthesized at a molar fraction of 2,7-naphthalene in the difluoro monomers being over 0.30, no peaks corresponding to the cold crystallization temperature and the melting temperature could be detected, indicating that these copolymers are almost amorphous. The crystal structures of the copolymers with a molar fraction of 2,7-naphthalene being less than 0. 30 are rhombic.

STRUCTURE AND PROPERTIES OF PHOSPHROUS-CONTAINING POLY(ARYLETHER KETONE)WITH BISPHENOL-A MOIETY

A phosphrous-containing poly（aryl ether ketone） was synthesized derived from bisphenol-A and bis[4-（4- fluorobenzoyl）phenyl] phenyl phosphine oxide （FPPPO） by nucleophilic substitution reaction. The structure of the polymer was characterized by FT-IR, ^1H-NMR and ^31p-NMR. The thermal property of the PAEK was measured by DSC and TGA. The glass transition temperature （Tg） of the polymer was 205℃, and the 5% weight loss temperature under nitrogen was 475℃. Good solubility of the polymer in organic solvents, such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide and chloroalkanes was observed, flexible film was obtained from the polymer＇s CH2Cl2 solution. The limiting oxygen index （LOI） of the PAEK was 40, which indicated that organic phosphorus moiety can offer good flame retardant property to the polymer.