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
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
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 amin...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.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
The development of efficient method to prepare poly(silyl ether)s(PSEs)is highly desirable.Herein,an environmentally sustainable copper-catalyzed dehydrocoupling polymerization was developed with good yields and high ...The development of efficient method to prepare poly(silyl ether)s(PSEs)is highly desirable.Herein,an environmentally sustainable copper-catalyzed dehydrocoupling polymerization was developed with good yields and high molecular weight(up to 48,400 of Mn and up to 97%yield).Monomers of different types(AB type or AA and BB type)are suitable to afford PSEs.The PSEs show good thermal stability and low glass-transition temperature.展开更多
Two novel heteroatom-bridged his (benzo-12-crown-4 ether)s, i.e. his [2-nitro-4,5 (1,4,7,10-tetraoxadecamethylene) disulfide 1 and diselenide 2, have been synthesized. X ray crystallographic structure was obtained for...Two novel heteroatom-bridged his (benzo-12-crown-4 ether)s, i.e. his [2-nitro-4,5 (1,4,7,10-tetraoxadecamethylene) disulfide 1 and diselenide 2, have been synthesized. X ray crystallographic structure was obtained for 1. Ion selective electrodes (ISE) for Ag+, containing 1 and 2 in PVC membrane as neutral carriers, were prepared, and their selectivity coefficients for Ag^+ (K_(Ag.M)^(pot)) were determined against other heavy metal ions, alkali and alkaline-earth metal ions. and ammonium ion. These ISEs showed excellent Ag^+ selectivities, log K_(Ag.M)^(pot) ≤ -3.8, against most of the interfering canons examined, except for Hg^+.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
A novel poly(ether imide)s containing phthalazinone and isopropyl moieties derived from 2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl]-phthalazin-1-one and bisphenol-A diphthalic anhydride was synthesized by one-step ...A novel poly(ether imide)s containing phthalazinone and isopropyl moieties derived from 2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl]-phthalazin-1-one and bisphenol-A diphthalic anhydride was synthesized by one-step solution condensation polymerization in nr-cresol. The polymer was characterized by FTIR, NMR, molecular weights, glass transition temperature, thermal degradation temperature and WAXD.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
A non-isocyanate route for synthesizing thermoplastic polyurethanes with excellent thermal and mechanical properties was described. Melt transurethane polycondensation of 1,6-bis（hydroxyethyloxy carbonyl amino）hexan...A non-isocyanate route for synthesizing thermoplastic polyurethanes with excellent thermal and mechanical properties was described. Melt transurethane polycondensation of 1,6-bis（hydroxyethyloxy carbonyl amino）hexane with four poly（ethylene glycol）s （PEGs）, i.e. PEG400, PEG600, PEG1000, or PEG1500, was conducted at different molar ratios. A series of thermoplastic poly（ether urethane）s （TPEUs） with long PEG sequences were prepared. The TPEUs were characterized via gel permeation chromatography, FTIR, 1H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray scattering, and tensile tests. The TPEUs exhibit Tg between 12.4 ℃ and -40.4 ℃, Tm of up to 149.8 ℃, and initial decomposition temperature over 239.4 ℃. The tensile strength of the TPEUs reaches 38.39 MPa with a strain at break of 852.92%.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
A new homologous series of thermotropic liquid crystalline copoly(arylidene-ether)s based on 4-teriary butyl cyclohexanone moiety were synthesized by solution polycondensation of 4,4’-diformyl-α,ω-diphenoxyalkanes,...A new homologous series of thermotropic liquid crystalline copoly(arylidene-ether)s based on 4-teriary butyl cyclohexanone moiety were synthesized by solution polycondensation of 4,4’-diformyl-α,ω-diphenoxyalkanes, Ia-d or 4,4’- diformyl-2,2’-dimethoxy-α,ω-diphenoxyalkanes IIa-d with the 4-teriary butyl-cyclohexanone III and cyclopentanone. A model compound IV was synthesized from the monomer III with benzaldehyde and characterized by elemental and spectral analyses. The inherent viscosities of the resulting polymers were in the range 0.22 - 0.92 dI/g. All the copoly(arylidene-ether)s were insoluble in common organic solvents but dissolved completely in concentrated H2SO4 and formic acid. The mesomorphic properties of these polymers were studied as a function of the diphenoxyalkane space length. Their thermotropic liquid crystalline properties were examined by DSC and optical polarizing microscopy and demonstrated that the resulting polymers form nematic mesophases over wide temperature ranges. The thermogravimetric analyses of those polymers were evaluated by TGA and DSC measurements and correlated to their structural units. X-Ray analysis showed that copolymers having some degree of crystallinity in the region 2q = 5° -60°. In addition, the morphological properties of selected examples were tested by Scanning electron microscopy.展开更多
Two series of poly（imide-ester）s （PIEs） and poly（ether-imide-ester）s （PEIEs）, having benzoxazole or benzothiazole pendent groups, were conveniently prepared by the diphenylchlorophosphate-activated direct poly...Two series of poly（imide-ester）s （PIEs） and poly（ether-imide-ester）s （PEIEs）, having benzoxazole or benzothiazole pendent groups, were conveniently prepared by the diphenylchlorophosphate-activated direct polyesterification of two bis（imide-carboxylic acid）s （1）, such as 2-[3,5-bis（N-trimellitimidoyl）phenyl]benzoxazole （lo） and 2-[3,5-bis（N- trimellitimidoyl）phenyl]benzothiazole （Is） and two bis（imide-ether-carboxylic acid）s （2）, such as 2-[3,5-bis（4- trimellitimidophenoxy）-phenyl]benzoxazole （2o）, and 2-[3,5-bis（4-trimellitimidophenoxy）-phenyl]benzothiazole （2s） with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. The structures, solubilities and thermal properties of obtained polymers were investigated in detail. All of the resulting polymers were characterized by FTIR and IH-NMR spectroscopy and elemental analysis. All of the resulting polymers exhibited excellent solubility in common organic solvents, such as pyridine, tetrahydrofuran and m-cresol, as well as in polar organic solvents, such as N-methyl-2- pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and dimethyl sulfoxide. The modified polymers were obtained in quantitative yields with inherent viscosities between 0.47 and 0.67 dl·g^-1 Experimental results indicated that all the polymers had glass transition temperature between 198 ℃ and 262 ℃, the decomposition temperature at 10% weight loss between 398 ℃ and 531 ℃ under nitrogen.展开更多
A novel aromatic diacid, 4, 4'-bis[2-(4-carboxyphenyl)phthalazin-1-one-4-yl]-bisphenyl ether III, containing bisphthalazinone and ether linkages was prepared from nucleophilic substitution of p-chlorobenzonitril...A novel aromatic diacid, 4, 4'-bis[2-(4-carboxyphenyl)phthalazin-1-one-4-yl]-bisphenyl ether III, containing bisphthalazinone and ether linkages was prepared from nucleophilic substitution of p-chlorobenzonitrile with the bisphenol-like monomer I, followed by alkaline hydrolysis of the intermediate dinitrile II. A series of poly(ether amide)s containing bisphthala- zinone and ether linkages derived from diacid III and aromatic diamines were synthesized by one-step solution condensation polymerization using triphenyl phosphite and pyridine as condensing agents. Moreover, the properties of poly(ether amide)s including thermal stability, solubility and crystallinity were also studied.展开更多
In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) are reported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydro...In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) are reported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydroquinone along the nucleophilic substitution route. The thermal properties were investigated by using DSC and TGA. The crystallization behavior of PEEKEK under several conditions, i.e., crystallization from the molten state (melt crystallization), crystallization from a quenched sample (cold crystallization) and crystallization induced by exposing glassy sample to methylene chloride (solvent-induced crystallization) has also been investigated. The results show that crystallization of PEEKEK could be induced by the above methods, and no polymorphism was found. The differences in the crystallization of PEEKEK induced by the above methods are seen in their degree of crystallinity.展开更多
Two poly（aryl ether）s containing naphthyl moieties were prepared from bis（3,5-dimethyl-4-hydroxyphenyl）naphthyl methane （monomer 1） via nucleophilic aromatic substitution polycondensation with bis（4-fluoropheny...Two poly（aryl ether）s containing naphthyl moieties were prepared from bis（3,5-dimethyl-4-hydroxyphenyl）naphthyl methane （monomer 1） via nucleophilic aromatic substitution polycondensation with bis（4-fluorophenyl） ketone and bis（4-fluorophenyl） sulfone. The structures of these polymers were confirmed by 1H NMR. The Mn values of the two polymers were 96,200 and 88,600, respectively. The polymers exhibited good thermal stabilities with 5% mass loss at T 〉 400 and high glass-transition temperature （Ts） of T 〉 250 ℃. Moreover, the resultant polymers were amorphous determined by wide angle X-ray diffraction （WAXD）. ？2009 Lei Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All fights reserved.展开更多
Compared with conventional π-conjugated polymers,poly（arylene ether）s（PAEs） may take advantages of excellent thermal properties,well-defined effective conjugated length and no catalyst contamination.Recently,thei...Compared with conventional π-conjugated polymers,poly（arylene ether）s（PAEs） may take advantages of excellent thermal properties,well-defined effective conjugated length and no catalyst contamination.Recently,their applications have been extended from engineering plastics to optoelectronic materials.In this review,various kinds of functional PAEs used as fluorescent polymers,host polymers and phosphorescent polymers in organic light-emitting diodes（OLEDs） are outlined,and their molecular design,synthesis and device performance are overviewed.展开更多
A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were deter...A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were determined by ^1H-NMR and IR, respectively. Their molecular weights were measured by gel permeation chromatography （ GPC ）, which showed that all the polymers had high molecule weights （ 〉 42 000）. Due to the long side chains of polymers, all the polymers had good solubility （soluble in NMP, DMAc, THF, etc. ）. The differential scanning calorimeter （DSC） detected their excellent glass transition temperatures （ Tg ） up to 195 ℃. The Tg increased with the content of carboxylic units in the polymer chains, because the interactions of H bonds increased with increasing content of carboxylic. The polymers could form transparent and flexible films, which make them a candidate for membrane materials.展开更多
Based on several unsymmetrical, twist, noncoplanar phthalazinone-containing monomers 2a-2e and an active bis（4-fluorophenyl）phenyl phosphine oxide （BFPPO） monomer, a series of novel poly（phthalazinone ether phosp...Based on several unsymmetrical, twist, noncoplanar phthalazinone-containing monomers 2a-2e and an active bis（4-fluorophenyl）phenyl phosphine oxide （BFPPO） monomer, a series of novel poly（phthalazinone ether phosphine oxide）s （PPEPO） was synthesized by anhydrous K2CO3 mediated N-C coupling reaction in DMAc. The polymers exhibited good thermal properties with Tgs ranging from 267℃ to 306℃ and 5% weight loss temperatures in nitrogen higher than 430℃, together with high char yield upon prolonged heating at 800℃ （35%-56%）. Moreover, the polymers were readily soluble in common organic solvents, such as N-methyl-2-pyrrolidone, chloroform and m-cresol. These polymers had inherent viscosities in the range of 0.45-0.72 dL/g and could be cast into flexible and colorless films by spin coating or casting approach.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.
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This work was sponsored by the National Natural Science Foundation of China (No. 59473901).
文摘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.
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）.
基金support from National Natural Science Foundation of China(No.21690074)Chinese Academy of Sciences(Nos.XDB17020300,DICP I202015)is acknowledged.
文摘The development of efficient method to prepare poly(silyl ether)s(PSEs)is highly desirable.Herein,an environmentally sustainable copper-catalyzed dehydrocoupling polymerization was developed with good yields and high molecular weight(up to 48,400 of Mn and up to 97%yield).Monomers of different types(AB type or AA and BB type)are suitable to afford PSEs.The PSEs show good thermal stability and low glass-transition temperature.
文摘Two novel heteroatom-bridged his (benzo-12-crown-4 ether)s, i.e. his [2-nitro-4,5 (1,4,7,10-tetraoxadecamethylene) disulfide 1 and diselenide 2, have been synthesized. X ray crystallographic structure was obtained for 1. Ion selective electrodes (ISE) for Ag+, containing 1 and 2 in PVC membrane as neutral carriers, were prepared, and their selectivity coefficients for Ag^+ (K_(Ag.M)^(pot)) were determined against other heavy metal ions, alkali and alkaline-earth metal ions. and ammonium ion. These ISEs showed excellent Ag^+ selectivities, log K_(Ag.M)^(pot) ≤ -3.8, against most of the interfering canons examined, except for Hg^+.
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.
文摘A novel poly(ether imide)s containing phthalazinone and isopropyl moieties derived from 2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl]-phthalazin-1-one and bisphenol-A diphthalic anhydride was synthesized by one-step solution condensation polymerization in nr-cresol. The polymer was characterized by FTIR, NMR, molecular weights, glass transition temperature, thermal degradation temperature and WAXD.
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.
基金financially supported by the National Natural Science Foundation of China(Nos.21244006 and 50873013)
文摘A non-isocyanate route for synthesizing thermoplastic polyurethanes with excellent thermal and mechanical properties was described. Melt transurethane polycondensation of 1,6-bis（hydroxyethyloxy carbonyl amino）hexane with four poly（ethylene glycol）s （PEGs）, i.e. PEG400, PEG600, PEG1000, or PEG1500, was conducted at different molar ratios. A series of thermoplastic poly（ether urethane）s （TPEUs） with long PEG sequences were prepared. The TPEUs were characterized via gel permeation chromatography, FTIR, 1H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray scattering, and tensile tests. The TPEUs exhibit Tg between 12.4 ℃ and -40.4 ℃, Tm of up to 149.8 ℃, and initial decomposition temperature over 239.4 ℃. The tensile strength of the TPEUs reaches 38.39 MPa with a strain at break of 852.92%.
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.
文摘A new homologous series of thermotropic liquid crystalline copoly(arylidene-ether)s based on 4-teriary butyl cyclohexanone moiety were synthesized by solution polycondensation of 4,4’-diformyl-α,ω-diphenoxyalkanes, Ia-d or 4,4’- diformyl-2,2’-dimethoxy-α,ω-diphenoxyalkanes IIa-d with the 4-teriary butyl-cyclohexanone III and cyclopentanone. A model compound IV was synthesized from the monomer III with benzaldehyde and characterized by elemental and spectral analyses. The inherent viscosities of the resulting polymers were in the range 0.22 - 0.92 dI/g. All the copoly(arylidene-ether)s were insoluble in common organic solvents but dissolved completely in concentrated H2SO4 and formic acid. The mesomorphic properties of these polymers were studied as a function of the diphenoxyalkane space length. Their thermotropic liquid crystalline properties were examined by DSC and optical polarizing microscopy and demonstrated that the resulting polymers form nematic mesophases over wide temperature ranges. The thermogravimetric analyses of those polymers were evaluated by TGA and DSC measurements and correlated to their structural units. X-Ray analysis showed that copolymers having some degree of crystallinity in the region 2q = 5° -60°. In addition, the morphological properties of selected examples were tested by Scanning electron microscopy.
文摘Two series of poly（imide-ester）s （PIEs） and poly（ether-imide-ester）s （PEIEs）, having benzoxazole or benzothiazole pendent groups, were conveniently prepared by the diphenylchlorophosphate-activated direct polyesterification of two bis（imide-carboxylic acid）s （1）, such as 2-[3,5-bis（N-trimellitimidoyl）phenyl]benzoxazole （lo） and 2-[3,5-bis（N- trimellitimidoyl）phenyl]benzothiazole （Is） and two bis（imide-ether-carboxylic acid）s （2）, such as 2-[3,5-bis（4- trimellitimidophenoxy）-phenyl]benzoxazole （2o）, and 2-[3,5-bis（4-trimellitimidophenoxy）-phenyl]benzothiazole （2s） with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. The structures, solubilities and thermal properties of obtained polymers were investigated in detail. All of the resulting polymers were characterized by FTIR and IH-NMR spectroscopy and elemental analysis. All of the resulting polymers exhibited excellent solubility in common organic solvents, such as pyridine, tetrahydrofuran and m-cresol, as well as in polar organic solvents, such as N-methyl-2- pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and dimethyl sulfoxide. The modified polymers were obtained in quantitative yields with inherent viscosities between 0.47 and 0.67 dl·g^-1 Experimental results indicated that all the polymers had glass transition temperature between 198 ℃ and 262 ℃, the decomposition temperature at 10% weight loss between 398 ℃ and 531 ℃ under nitrogen.
文摘A novel aromatic diacid, 4, 4'-bis[2-(4-carboxyphenyl)phthalazin-1-one-4-yl]-bisphenyl ether III, containing bisphthalazinone and ether linkages was prepared from nucleophilic substitution of p-chlorobenzonitrile with the bisphenol-like monomer I, followed by alkaline hydrolysis of the intermediate dinitrile II. A series of poly(ether amide)s containing bisphthala- zinone and ether linkages derived from diacid III and aromatic diamines were synthesized by one-step solution condensation polymerization using triphenyl phosphite and pyridine as condensing agents. Moreover, the properties of poly(ether amide)s including thermal stability, solubility and crystallinity were also studied.
基金This project was financial supported by National Natural Science Foundation of China and the Chinese "863" High Technology Funds.
文摘In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) are reported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydroquinone along the nucleophilic substitution route. The thermal properties were investigated by using DSC and TGA. The crystallization behavior of PEEKEK under several conditions, i.e., crystallization from the molten state (melt crystallization), crystallization from a quenched sample (cold crystallization) and crystallization induced by exposing glassy sample to methylene chloride (solvent-induced crystallization) has also been investigated. The results show that crystallization of PEEKEK could be induced by the above methods, and no polymorphism was found. The differences in the crystallization of PEEKEK induced by the above methods are seen in their degree of crystallinity.
基金supported by Natural Science Foundation of Guangdong Province(No.7301357)Science and Technology Projects of Shenzhen City(No.200724).
文摘Two poly（aryl ether）s containing naphthyl moieties were prepared from bis（3,5-dimethyl-4-hydroxyphenyl）naphthyl methane （monomer 1） via nucleophilic aromatic substitution polycondensation with bis（4-fluorophenyl） ketone and bis（4-fluorophenyl） sulfone. The structures of these polymers were confirmed by 1H NMR. The Mn values of the two polymers were 96,200 and 88,600, respectively. The polymers exhibited good thermal stabilities with 5% mass loss at T 〉 400 and high glass-transition temperature （Ts） of T 〉 250 ℃. Moreover, the resultant polymers were amorphous determined by wide angle X-ray diffraction （WAXD）. ？2009 Lei Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All fights reserved.
基金the National Natural Science Foundation of China(Nos.51573182,51203149,21204084,91333205)the 973 Project(No.2015CB655000)for financial support of this research
文摘Compared with conventional π-conjugated polymers,poly（arylene ether）s（PAEs） may take advantages of excellent thermal properties,well-defined effective conjugated length and no catalyst contamination.Recently,their applications have been extended from engineering plastics to optoelectronic materials.In this review,various kinds of functional PAEs used as fluorescent polymers,host polymers and phosphorescent polymers in organic light-emitting diodes（OLEDs） are outlined,and their molecular design,synthesis and device performance are overviewed.
基金Supported by Open Project of State Key Laboratory of Supramolecular Structure and Materials(SKLSSM201114)the National Natural Science Foundation of China(51103010)
文摘A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were determined by ^1H-NMR and IR, respectively. Their molecular weights were measured by gel permeation chromatography （ GPC ）, which showed that all the polymers had high molecule weights （ 〉 42 000）. Due to the long side chains of polymers, all the polymers had good solubility （soluble in NMP, DMAc, THF, etc. ）. The differential scanning calorimeter （DSC） detected their excellent glass transition temperatures （ Tg ） up to 195 ℃. The Tg increased with the content of carboxylic units in the polymer chains, because the interactions of H bonds increased with increasing content of carboxylic. The polymers could form transparent and flexible films, which make them a candidate for membrane materials.
基金supported by the National Natural Science Foundation of China(Nos.50673031 and 50973036)
文摘Based on several unsymmetrical, twist, noncoplanar phthalazinone-containing monomers 2a-2e and an active bis（4-fluorophenyl）phenyl phosphine oxide （BFPPO） monomer, a series of novel poly（phthalazinone ether phosphine oxide）s （PPEPO） was synthesized by anhydrous K2CO3 mediated N-C coupling reaction in DMAc. The polymers exhibited good thermal properties with Tgs ranging from 267℃ to 306℃ and 5% weight loss temperatures in nitrogen higher than 430℃, together with high char yield upon prolonged heating at 800℃ （35%-56%）. Moreover, the polymers were readily soluble in common organic solvents, such as N-methyl-2-pyrrolidone, chloroform and m-cresol. These polymers had inherent viscosities in the range of 0.45-0.72 dL/g and could be cast into flexible and colorless films by spin coating or casting approach.
