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 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
Block copolymers with different backbone compositions have been prepared by the condensation of dimethylamino terminated poly（dimethylsiloxane） （PDMS） and hydroquinone terminated poly（phthalazinone ether nitrile...Block copolymers with different backbone compositions have been prepared by the condensation of dimethylamino terminated poly（dimethylsiloxane） （PDMS） and hydroquinone terminated poly（phthalazinone ether nitrile） （PPEN） in the presence of chlorobenzcne/N-methyl pyrrolidone （NMP） as solvents. The products were characterized by FTIR, ^1H NMR and gel permeation chromatography. Differential scanning calorimetry analysis indicated that the block copolymers showed separated microphase.展开更多
A novel aromatic diamine, 1, 2-dihydro-2-（4-aminophenyl）-4-[3-methoxy-4-（4-aminophenoxy）]-2, 3-phthalazin-l-one （OO-DA） containing aza heterocyclic structure was synthesized from the bisphenol-like monomer in tw...A novel aromatic diamine, 1, 2-dihydro-2-（4-aminophenyl）-4-[3-methoxy-4-（4-aminophenoxy）]-2, 3-phthalazin-l-one （OO-DA） containing aza heterocyclic structure was synthesized from the bisphenol-like monomer in two steps and used for preparing new aromatic polyamides with high inherent viscosity of 0.89-1.03 dL.g^-1. The structures of diamine and polymers obtained were confirmed by MS, PT-IR, WAXD and ^1H-NMR. The synthesized polymers exhibited high glass transition temperature in the range of 281-307℃ and good solubility in polar solvents.展开更多
A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through ...A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine （UTM） curves and alternating current （AC） impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope （FE-SEM） and atomic force microscope （AFM）. Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity （RH）. In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.展开更多
A series of hyperbranched poly(ester-amide-ether)s (H-PEAEs) were synthesized via the A2+CB3 approach by the self-transesterification of ethyl ester-amide-ethers end-capped with three hydroxyl groups and ethyl ester g...A series of hyperbranched poly(ester-amide-ether)s (H-PEAEs) were synthesized via the A2+CB3 approach by the self-transesterification of ethyl ester-amide-ethers end-capped with three hydroxyl groups and ethyl ester group at two terminals.The molecular structures were characterized with 1H NMR and FT-IR spectroscopy.The number average molecular weights were estimated by GPC analysis to possess bimodal wide distribution from 1.57 to 2.09.The strong inherent blue fluorescence was observed at 330 nm for excitation and 390 nm for emission.Moreover,the emission intensity and fluorescence quantum yield increased along with the incorporated ether chain length,as well as almost linearly with the H-PEAE concentration in an aqueous solution.For comparing the fluorescence performance,the linear poly(ester-amide-ether) (L-PEAE) and hyperbranched poly(ester-amide) (H-PEA) were synthesized.The results showed that the coexistence of ether bond and carboxyl group in the molecular chain was essential for generating the strong fluorescence.However,the compact backbone of H-PEAE would be propitious to the enhancement of fluorescence properties.展开更多
A series organosoluble and heterocyclic poly（ether-amide）s （PEA）s were synthesized from a new diamine containing pyridine moiety and four aliphatic-aromatic dicarboxylic acids by direct polycondensation reactions....A series organosoluble and heterocyclic poly（ether-amide）s （PEA）s were synthesized from a new diamine containing pyridine moiety and four aliphatic-aromatic dicarboxylic acids by direct polycondensation reactions. Dicarboxilic acids 4a-4d containing ether groups were synthesized in two step reactions. At first, dialdehydes 3a-3d were synthesized from four dibromo alkanes la-ld and 4-hydroxybenzaldehyde 2, then dicarboxilic acids 4a-4d were synthesized from dialdehydes 3a-3d and malonic acid in a solvent free reaction. On the other hand, the new diamine 8 containing pyridine ring was synthesized in two step reactions. The structures of synthesized monomers and polymers were proven by FTIR, NMR spectroscopy and elemental analysis. Also all of the above polymers were fully characterized by inherent viscosity, solubility tests, gel permeation chromatography （GPC）, differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）. The resulted PEAs have shown good inherent viscosities, solubility and thermal properties.展开更多
Two novel heterocylic diamine monomers: l,2-dihydro-2-(4-aminophenyl)-4-4-(4-aminophenoxy) phenyl]-(2H)-phthalazin-l-one and 1,2-Dihydro-2-( 4-aminophenyl )-4-[4-(4-aminophenoxy-3, 5-dimethylphenyl]-(2H)-phthalazin-1-...Two novel heterocylic diamine monomers: l,2-dihydro-2-(4-aminophenyl)-4-4-(4-aminophenoxy) phenyl]-(2H)-phthalazin-l-one and 1,2-Dihydro-2-( 4-aminophenyl )-4-[4-(4-aminophenoxy-3, 5-dimethylphenyl]-(2H)-phthalazin-1-one were successfully synthesized using readily available heterocyclic bisphenol-like monomers through two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety with inherent viscosities of 1.16–1.67 dL/g were prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in a variety of solvents such as N,N -dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide ( DMSO ), N-methyl-2-pyrrolidinone (NMP), and pyridine. The polymers had high glass transition temperatures ( Tg) in the 291–329°C range.展开更多
Nonisothermal melt crystallization kinetics of thio-ether-contained poly(ether ether ketone ketone) copolymers was studied by DSC. The result shows that the crystallization activation energy was increased accompanied ...Nonisothermal melt crystallization kinetics of thio-ether-contained poly(ether ether ketone ketone) copolymers was studied by DSC. The result shows that the crystallization activation energy was increased accompanied by the introduction of thio-ether structure. The random copolymer possesses a higher crystallization activation energy than the block one at the same thio-ether ratio.展开更多
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.
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.
文摘Block copolymers with different backbone compositions have been prepared by the condensation of dimethylamino terminated poly（dimethylsiloxane） （PDMS） and hydroquinone terminated poly（phthalazinone ether nitrile） （PPEN） in the presence of chlorobenzcne/N-methyl pyrrolidone （NMP） as solvents. The products were characterized by FTIR, ^1H NMR and gel permeation chromatography. Differential scanning calorimetry analysis indicated that the block copolymers showed separated microphase.
基金This project is financially supported by Hi-tech Research and Development Program(2003AA33g-030)the National Natural Science Foundation of China(Contract grant number:50143013).
文摘A novel aromatic diamine, 1, 2-dihydro-2-（4-aminophenyl）-4-[3-methoxy-4-（4-aminophenoxy）]-2, 3-phthalazin-l-one （OO-DA） containing aza heterocyclic structure was synthesized from the bisphenol-like monomer in two steps and used for preparing new aromatic polyamides with high inherent viscosity of 0.89-1.03 dL.g^-1. The structures of diamine and polymers obtained were confirmed by MS, PT-IR, WAXD and ^1H-NMR. The synthesized polymers exhibited high glass transition temperature in the range of 281-307℃ and good solubility in polar solvents.
基金supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(No.20164030201070)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT and future Planning(NRF-2017R1A2B4005230)
文摘A ternary hybrid membrane architecture consisting of sulfonated fluorinated multi-block copolymer （SFMC）, sulfonated （poly ether ether ketone） （SPEEK） and I or 5 wt% graphene oxide （GO） was fabricated through a facile solution casting approach. The simple, but effective monomer sulfonation was performed for SFMC to create compact and rigid hydrophobic backbone structures, while conventional random sulfonation was carried-out for SPEEK. Hydrophilic-hydrophobic-hydrophilic structure of SFMC enhances the compatibility with SPEEK and GO and allows for an unprecedented approach to alter me- chanical strength and proton conductivity of ternary hybrid membrane, as verified from universal test machine （UTM） curves and alternating current （AC） impedance plots. The impact of GO integration on the morphology and roughness of hybrid membrane was scrutinized using field emission scanning electron microscope （FE-SEM） and atomic force microscope （AFM）. Ternary hybrid showed uniform intercalation of GO nanosheets throughout the entire surface of membrane with an increased surface roughness of 8.91 nm. The constructed ternary hybrid membrane revealed excellent water absorption, ion exchange capacity and gas barrier properties, while retaining reasonable dimensional stability. The well-optimized ternary hybrid membrane containing 5 wt% GO revealed a maximum proton conductivity of 111.9 mS/cm, which is higher by a factor of two-fold with respect to that of bare SFMC membrane. The maximum PEMFC power density of 528.07mW/cm2 was yielded by ternary hybrid membrane at a load current density of 1321.1 mA/cm2 when operating the cell at 70 ℃ under 100% relative humidity （RH）. In comparison, a maximum power density of only 182.06 mW/cm2 was exhibited by the bare SFMC membrane at a load current density of 455.56 mA/cm2 under same operating conditions.
基金support of the National Natural Science Foundation of China(50633010) is gratefully acknowledged
文摘A series of hyperbranched poly(ester-amide-ether)s (H-PEAEs) were synthesized via the A2+CB3 approach by the self-transesterification of ethyl ester-amide-ethers end-capped with three hydroxyl groups and ethyl ester group at two terminals.The molecular structures were characterized with 1H NMR and FT-IR spectroscopy.The number average molecular weights were estimated by GPC analysis to possess bimodal wide distribution from 1.57 to 2.09.The strong inherent blue fluorescence was observed at 330 nm for excitation and 390 nm for emission.Moreover,the emission intensity and fluorescence quantum yield increased along with the incorporated ether chain length,as well as almost linearly with the H-PEAE concentration in an aqueous solution.For comparing the fluorescence performance,the linear poly(ester-amide-ether) (L-PEAE) and hyperbranched poly(ester-amide) (H-PEA) were synthesized.The results showed that the coexistence of ether bond and carboxyl group in the molecular chain was essential for generating the strong fluorescence.However,the compact backbone of H-PEAE would be propitious to the enhancement of fluorescence properties.
文摘A series organosoluble and heterocyclic poly（ether-amide）s （PEA）s were synthesized from a new diamine containing pyridine moiety and four aliphatic-aromatic dicarboxylic acids by direct polycondensation reactions. Dicarboxilic acids 4a-4d containing ether groups were synthesized in two step reactions. At first, dialdehydes 3a-3d were synthesized from four dibromo alkanes la-ld and 4-hydroxybenzaldehyde 2, then dicarboxilic acids 4a-4d were synthesized from dialdehydes 3a-3d and malonic acid in a solvent free reaction. On the other hand, the new diamine 8 containing pyridine ring was synthesized in two step reactions. The structures of synthesized monomers and polymers were proven by FTIR, NMR spectroscopy and elemental analysis. Also all of the above polymers were fully characterized by inherent viscosity, solubility tests, gel permeation chromatography （GPC）, differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）. The resulted PEAs have shown good inherent viscosities, solubility and thermal properties.
基金Project (No. 59473019) supported by the National Natural Science Foundation of China.
文摘Two novel heterocylic diamine monomers: l,2-dihydro-2-(4-aminophenyl)-4-4-(4-aminophenoxy) phenyl]-(2H)-phthalazin-l-one and 1,2-Dihydro-2-( 4-aminophenyl )-4-[4-(4-aminophenoxy-3, 5-dimethylphenyl]-(2H)-phthalazin-1-one were successfully synthesized using readily available heterocyclic bisphenol-like monomers through two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety with inherent viscosities of 1.16–1.67 dL/g were prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in a variety of solvents such as N,N -dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide ( DMSO ), N-methyl-2-pyrrolidinone (NMP), and pyridine. The polymers had high glass transition temperatures ( Tg) in the 291–329°C range.
文摘Nonisothermal melt crystallization kinetics of thio-ether-contained poly(ether ether ketone ketone) copolymers was studied by DSC. The result shows that the crystallization activation energy was increased accompanied by the introduction of thio-ether structure. The random copolymer possesses a higher crystallization activation energy than the block one at the same thio-ether ratio.
