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 viscositie...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.展开更多
Ion segregation is critically important for achieving high ion conductivity for anion exchange membranes(AEMs).Herein,a new bisphenol monomer bearing ten electron-rich phenyl groups was designed and polymerized with v...Ion segregation is critically important for achieving high ion conductivity for anion exchange membranes(AEMs).Herein,a new bisphenol monomer bearing ten electron-rich phenyl groups was designed and polymerized with various amounts of electron-deficient 4,4′-dihydroxydiphenylsulfone and 4,4′-difluorobenzophenone to yield dense and selective reaction sites for chloromethylation and quaternization.As the most challenging step,chloromethylation was optimized by tuning the reaction temperature,reaction time,and reactant ratios.Ion exchange capacity,water uptake,anion conductivity,mechanical stability,and alkaline stability of the resulting AEMs were characterized in detail.It is found that chloromethylation reaction needed to be carried out at low equivalent of chloromethylation agents to avoid undesirable crosslinking.The QA-PAEKS-20 sample with an IEC of 1.19 mmol·g^-1 exhibited a Cl^–conductivity of 11.2 mS·cm^-1 and a water uptake of 30.2%at80°C,which are promising for AEM applications.展开更多
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 ...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.展开更多
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,...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.展开更多
Novel blue light-emitting poly（aryl ether）s comprising of bipolar oligofluorene pendants as chromophores have been designed and synthesized, in which pyrimidine and arylamine moieties are utilized as the electron ac...Novel blue light-emitting poly（aryl ether）s comprising of bipolar oligofluorene pendants as chromophores have been designed and synthesized, in which pyrimidine and arylamine moieties are utilized as the electron acceptor and electron donor, respectively. Through varying n bridge length from monofluorene to bifluorene and end-cappers from hydrogen to carbazole and diphenylamine, the emission color of the resulting polymers covers from deep blue to greenish blue, and their HOMO and LUMO levels can be modulated to facilitate charge injection to improve the device performance. Polymer light- emitting diodes （PLEDs） are fabricated with the device structure of ITO/poly（3,4-ethylenedioxythiophene）：poly（styrene sulfonic acid） （PEDOT：PSS） （50 nm）/polymer （80 nm）/Ca （10 nm）/Al （200 nm）. Among these polymers, P2Cz5F-Py with bifluorene bridge and carbazole end-capper shows excellent trade-off between the efficiency and emission wavelength, having a peak luminous efficiency as high as 1.26 cd/A and Commission Internationale de L＇Eclairage （CIE） coordinates of （0.17,0.17）.展开更多
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...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）.展开更多
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 pre...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.展开更多
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...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.展开更多
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 chara...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.展开更多
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 syn...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.展开更多
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-cha...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.展开更多
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.
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. ...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.展开更多
A new poly (aryl ether ketone) was successfully synthesized by nucleophilic substitution of bis-1,4-(4-chlorobenzoyl) benzene (BCBB) by 1,2-dihydro-4-(4-hydroxy phenyl) (2H)phthatazin-1-one (DHPZ) in appropriate condi...A new poly (aryl ether ketone) was successfully synthesized by nucleophilic substitution of bis-1,4-(4-chlorobenzoyl) benzene (BCBB) by 1,2-dihydro-4-(4-hydroxy phenyl) (2H)phthatazin-1-one (DHPZ) in appropriate condition. The polymer was characterized by FT-IR, H-1-NMR, DSC and TGA etc.展开更多
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 ...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.展开更多
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 hydroqu...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.展开更多
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...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.展开更多
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 d...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.展开更多
A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone ...A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone and 4,4’-biphenol by one-pot and two-pot polymerization.;H-NMR and FTIR spectra confirmed the structure that sulfonic acid groups were introduced precisely on the poly(arylene ether sulfone)s by post-sulfonation which resulted in controllable sulfonation degree.The proton exchange membranes(PEMs)-based SPAES displayed excellent dimensional,thermal,antioxidant stability,proton conductivity and mechanical properties(maximum tensile stress>35 MPa).Thermogravimetric analysis indicated the prepared SPAES began to degrade above 310℃.The effects of polymerization processes,those were,one-pot hydrophobic segment process,one-pot hydrophilic segment process and two-pot process,on the properties of polymers were investigated.The proton conductivity and microphase separation of SPAES PEMs increased in order of those prepared by one-pot hydrophobic segment process,two-pot process and one-pot hydrophilic segment process.The highest conductivities of SPAES synthesized by the above processes under 80℃ and 100%relative humidity were 213(MS4),297(MB3)and 360 mS·cm^(-1)(MQ2),respectively.展开更多
Vanadium flow batteries(VFBs)have drawn considerable attention as an emerging technology for largescale energy storage systems(ESSs).One of the pivotal challenges is the availability of eligible ion exchange membranes...Vanadium flow batteries(VFBs)have drawn considerable attention as an emerging technology for largescale energy storage systems(ESSs).One of the pivotal challenges is the availability of eligible ion exchange membranes(ICMs)that provide high ion selectivity,proton conductivity,and stability under rigorous condition.Herein,a‘side-chain-type’strategy has been employed to fabricate highly stable phenolphthalein-based cardo poly(arylene ether ketone)s(PAEKs)membrane with low area resistance(0.058Ωcm^(2)),in which flexible alkyl spacers effectively alleviated inductive withdrawing effect from terminal ion exchange groups thus enabling a stable backbone.The assembled VFBs based on PAEKs bearing pendent alkyl chain terminated with quaternary ammonium(Q-PPhEK)demonstrated an energy efficiency above 80%over 700 cycles at 160 mA/cm^(2).Such a remarkable results revealed that the side-chain-type strategy contributed to enhancing the ICMs stability in strong oxidizing environment,meanwhile,more interesting backbones would be woken with this design engaging in stable ICMs for VFBs.展开更多
基金by the National Science Council of the People’s Republic of China(No.2003AA33G030)
文摘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.
基金financially supported by the National Natural Science Foundation of China (Nos. 51873037 and 51503038)
文摘Ion segregation is critically important for achieving high ion conductivity for anion exchange membranes(AEMs).Herein,a new bisphenol monomer bearing ten electron-rich phenyl groups was designed and polymerized with various amounts of electron-deficient 4,4′-dihydroxydiphenylsulfone and 4,4′-difluorobenzophenone to yield dense and selective reaction sites for chloromethylation and quaternization.As the most challenging step,chloromethylation was optimized by tuning the reaction temperature,reaction time,and reactant ratios.Ion exchange capacity,water uptake,anion conductivity,mechanical stability,and alkaline stability of the resulting AEMs were characterized in detail.It is found that chloromethylation reaction needed to be carried out at low equivalent of chloromethylation agents to avoid undesirable crosslinking.The QA-PAEKS-20 sample with an IEC of 1.19 mmol·g^-1 exhibited a Cl^–conductivity of 11.2 mS·cm^-1 and a water uptake of 30.2%at80°C,which are promising for AEM applications.
文摘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.
基金Supported by the National Natural Science Foundation of China(No.5 0 2 0 30 0 4 )
文摘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.
基金financially supported by the 973 Project(Nos.2009CB623601 and 2009CB930603)National Natural Science Foundation of China(No.21074130)Science Fund for Creative Research Groups(No.20921061)
文摘Novel blue light-emitting poly（aryl ether）s comprising of bipolar oligofluorene pendants as chromophores have been designed and synthesized, in which pyrimidine and arylamine moieties are utilized as the electron acceptor and electron donor, respectively. Through varying n bridge length from monofluorene to bifluorene and end-cappers from hydrogen to carbazole and diphenylamine, the emission color of the resulting polymers covers from deep blue to greenish blue, and their HOMO and LUMO levels can be modulated to facilitate charge injection to improve the device performance. Polymer light- emitting diodes （PLEDs） are fabricated with the device structure of ITO/poly（3,4-ethylenedioxythiophene）：poly（styrene sulfonic acid） （PEDOT：PSS） （50 nm）/polymer （80 nm）/Ca （10 nm）/Al （200 nm）. Among these polymers, P2Cz5F-Py with bifluorene bridge and carbazole end-capper shows excellent trade-off between the efficiency and emission wavelength, having a peak luminous efficiency as high as 1.26 cd/A and Commission Internationale de L＇Eclairage （CIE） coordinates of （0.17,0.17）.
文摘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）.
基金Supported by the National Natural Science Foundation of China(No.50973040)the Science and Technology Development Plan of Jilin Province, China(No.20090322)
文摘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.
基金financial support under Heilongjiang Postdoctoral Fund (No.LBH-Z09175)
文摘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.
基金This work was supported by the National Natural Science Foundation of China.
文摘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.
基金supported by the National Natural Science Foundation of China (Grant Nos. 51503038 and 51873037)
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.51203151)the Program of Jilin Education Department(No.93201201)
文摘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.
基金This work was supported by the National Natural Science Foundation.
文摘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.
文摘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.
文摘A new poly (aryl ether ketone) was successfully synthesized by nucleophilic substitution of bis-1,4-(4-chlorobenzoyl) benzene (BCBB) by 1,2-dihydro-4-(4-hydroxy phenyl) (2H)phthatazin-1-one (DHPZ) in appropriate condition. The polymer was characterized by FT-IR, H-1-NMR, DSC and TGA etc.
基金This work was financially supported by the National Science Foundation of China (NSFC) (Key project, No. 29734120)the China High-Tech Development 863 Program (No. 2003AA302410)+1 种基金Natural Science Foundation of Guangdong Province (Excellent Team Project, No. 015007)Canton Province Sci & Tech Bureau (Key Strategic Project, No. A1100402) and Guangzhou Sci & Tech Bureau
文摘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.
文摘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.
基金This work was supported by the National Natural Science Foundation of China(No.50203008).
文摘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.
基金This work was supported by National Science Foundation of China （No. 20264001 ）, National Science Foundation of Jiangxi Province, Innovation Fund for Technology Based Firms of China （No. 06C26213601342）.
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.21306010)。
文摘A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone and 4,4’-biphenol by one-pot and two-pot polymerization.;H-NMR and FTIR spectra confirmed the structure that sulfonic acid groups were introduced precisely on the poly(arylene ether sulfone)s by post-sulfonation which resulted in controllable sulfonation degree.The proton exchange membranes(PEMs)-based SPAES displayed excellent dimensional,thermal,antioxidant stability,proton conductivity and mechanical properties(maximum tensile stress>35 MPa).Thermogravimetric analysis indicated the prepared SPAES began to degrade above 310℃.The effects of polymerization processes,those were,one-pot hydrophobic segment process,one-pot hydrophilic segment process and two-pot process,on the properties of polymers were investigated.The proton conductivity and microphase separation of SPAES PEMs increased in order of those prepared by one-pot hydrophobic segment process,two-pot process and one-pot hydrophilic segment process.The highest conductivities of SPAES synthesized by the above processes under 80℃ and 100%relative humidity were 213(MS4),297(MB3)and 360 mS·cm^(-1)(MQ2),respectively.
基金the financial support of the National Natural Science Foundation of China(Nos.22075276,U19A2016,U22B6012)CAS Strategic Leading Science&Technology Program(A)(No.XDA21070000)+2 种基金Dalian High Level Talent Innovation Support Program(No.2020RD05)the Development of Scientic and Technological Project of the Jilin Province(No.20210101126JC)International Partnership Program of Chinese Academy of Sciences(No.121421KYSB20210028)。
文摘Vanadium flow batteries(VFBs)have drawn considerable attention as an emerging technology for largescale energy storage systems(ESSs).One of the pivotal challenges is the availability of eligible ion exchange membranes(ICMs)that provide high ion selectivity,proton conductivity,and stability under rigorous condition.Herein,a‘side-chain-type’strategy has been employed to fabricate highly stable phenolphthalein-based cardo poly(arylene ether ketone)s(PAEKs)membrane with low area resistance(0.058Ωcm^(2)),in which flexible alkyl spacers effectively alleviated inductive withdrawing effect from terminal ion exchange groups thus enabling a stable backbone.The assembled VFBs based on PAEKs bearing pendent alkyl chain terminated with quaternary ammonium(Q-PPhEK)demonstrated an energy efficiency above 80%over 700 cycles at 160 mA/cm^(2).Such a remarkable results revealed that the side-chain-type strategy contributed to enhancing the ICMs stability in strong oxidizing environment,meanwhile,more interesting backbones would be woken with this design engaging in stable ICMs for VFBs.
