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 antibacterial activity of brominated 2′(4′)-nitro-3-hydroxy diphenyl ethers

Eight new brominated 2＇（4＇）-nitro-3-hydroxy diphenyl ethers have been designed and synthesized. The structures of new compounds were confirmed by ^1H NMR, IR and HRMS. The bioactivity tests showed that these compounds possessed antibacterial activities against the tested bacteria. These new compounds cannot be transformed into dioxins when they were manufactured and used.

Effect of nano Al_(2)O_(3) addition on cycling performance of poly(ether block amide)based solid-state lithium metal batteries

A novel poly(ether block amide)(PEBA)based solid-state polymer electrolyte(SPE)was prepared using a casting method,in which 20wt%lithium(Li)bis-(trifluoromethanesulfonyl)imide(LiTFSI)and aluminum oxide(Al_(2)O_(3))nanoparticles were used as the Li salt and solid plasticizer,respectively.In the case of addition of 3wt%Al_(2)O_(3) nanoparticles,ion conductivity of the obtained PEBA 2533-20wt%LiTFSI-3wt%Al_(2)O_(3) SPE was 3.57×10^(−5) S cm^(−1) at 25°C.Furthermore,the Li symmetrical battery assembled with it showed excellent cycling stability(1000 h)at 0.1 mA cm^(−2).While,the assembled all-solid-state Li/PEBA 2533-20%LiTFSI-3wt%Al_(2)O_(3)/LiFePO 4(areal capacity:0.15 mAh cm^(−2))battery maintained 94.9%of the maximal capacity(133.9 mAh g^(−1@0.1) mA cm^(−2))at 60°C even after 650 cycles with a superior average coulombic efficiency(CE)of 99.84%.By using X-ray photoelectron spectroscope(XPS),self-aggregation layer(SAL)of polyamide 12(PA12)of PEBA 2533 was discovered,which should contribute to promoting the robustness of lithium fluoride(LiF)enriched solid-electrolyte interphase(SEI)layer.In addition,it is considered that the state of interface between SPE and cathode should be the cause of voltage polarization of the full cell.

Flotation of carbonaceous copper shale-quartz mixture with poly(ethylene glycol) alkyl ethers

The influence of different poly（ethylene glycol） alkyl ethers（CnH2n＋1O（C2H4O）mH, CnEm） on flotation of carbonaceous copper shale mixed with quartz as a gangue mineral was investigated. The results show that all of the ethers C4E1, C4E2, C4E3, C2E2, C6E2 investigated can be used for the flotation of carbonaceous copper shale. The best selectivity of separation in the flotation of the carbonaceous copper shale and quartz mixture is obtained with the C4E2 and C2E2 ethers. The obtained data can be used for developing separation of organic carbon present in carbonaceous shale at a rougher flotation stage on an industrial scale.

ABSORPTION SPECTRA OF 4f ELECTRON TRANSITIONS OF NEODYMIUM COMPLEX WITH 8-HYDROXYQUINOLINE AND OCTYLPHENOL POLY(ETHYLENEGLYCOL)ETHER

In this paper the absorption spectra of 4f electron transitions of the neodymlum complex with 8-hydroxyquinoline and octylphenol poly(ethyleneglycol)ether have been studied. The marked intensification of the band at low octylphenol poly(ethyleneglycol)ether concentration is found normally at 575 nm, and its resolution into three sharp bands centering at 572, 580 and 584 nm. The absorbances of the absorption maxima are 3.5 (at 572 nm), 7.2 (at 580 nm) and 10.2 (at 584 nm) times greater than that of the chloride.

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 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.

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.

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 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.

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）.

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.

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.

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.

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 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.

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 Poly(ether imide)s Containing m-Methyl and Phthalazinone Moieties

Three novel poly(ether imide)s were synthesized by one-step solution polymerization from 2-(3, 4-dicarboxyl-N-phenyl)-4-(3, 4-dicarboxyl-phenoxyl-4-(2-methyl)-phenyl)-2, 3- phthal-azin-1-one dianhydride and three amines, and characterized. The polymers show good solubility and thermal properties.

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.