(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically af...(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically afford the corresponding (Z)-2-sulfonyl-substituted 1,3-enynes 3 in high yields.展开更多
Chloromethylated poly(phthalazinone ether sulfone ketone) (CMPPESK) was prepared from poly(phthalazinone ether sulfone ketone) (PPESK) using chloromethyl octyl ethers (CMOE) with lower toxicity as chlorometh...Chloromethylated poly(phthalazinone ether sulfone ketone) (CMPPESK) was prepared from poly(phthalazinone ether sulfone ketone) (PPESK) using chloromethyl octyl ethers (CMOE) with lower toxicity as chloromethylated regent. CMPPESK was soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc) and chloroform. Quaternized poly(phthalazinone ether sulfone ketone) (QAPPESK) was prepared from CMPPESK by quaternization. QAPPESK had excellent solvent resistance, which was only partly soluble in sulfuric acid (98%) and swollen in N,N-dimethylformamide (DMF). The vanadium redox flow battery (V-RFB) using QAPPESK anion-exchange membrane had better performance with 88.3% of overall energy efficiency.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
The thermal degradation of poly(arylene sulfide sulfone)/N-methylpyrrolidone (PASS/NMP) crystal solvate was studied by thermogravimetric analysis (TGA) and was compared with pure PASS in order to determine the w...The thermal degradation of poly(arylene sulfide sulfone)/N-methylpyrrolidone (PASS/NMP) crystal solvate was studied by thermogravimetric analysis (TGA) and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger's method, which does not require knowledge of the reaction mechanism (RM), to be 174.18 kJ/mol which was lower than that for pure PASS (E = 214 kJ/mol). The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.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
The oxidative desulfurization(ODS) process is one of the new desulfurization processes for the production of clean fuels. Despite the benefits of the ODS process, this process faces several important challenges. One o...The oxidative desulfurization(ODS) process is one of the new desulfurization processes for the production of clean fuels. Despite the benefits of the ODS process, this process faces several important challenges. One of the most important challenges of this process is the management of a waste which is rich of sulfone compounds.In the present study, a new strategy which is the addition of waste to the bitumen with other solid waste such as high density polyethylene(HDPE) waste has been investigated. The experimental design method was applied to investigate the effect of addition of the sulfone and HDPE wastes to the properties of the bitumen blends including degree of penetration, softening point, and mass loss. It was found that the sulfone waste can be added to the bitumen as a softener. The results showed that several grades of bitumen including 50/60, 60/70, 85/100 can be produced through the addition of sulfone waste along with the HDPE waste to the base 60/70 bitumen.In general, the application of simple processes such as mixing the wastes with the bitumen can reduce the cost of waste management, considerably.展开更多
Cyclic oligomers of phenolphthalein polyarylene ether sulfone(ketone) were prepared through cyclo-depolymerisation of corresponding polymers using CsF as the catalyst in dipolar aprotic solvent DMAc and DMF, and a fam...Cyclic oligomers of phenolphthalein polyarylene ether sulfone(ketone) were prepared through cyclo-depolymerisation of corresponding polymers using CsF as the catalyst in dipolar aprotic solvent DMAc and DMF, and a family of macrocycles containing from dimer up to at least heptamer were confirmed by GPC, HPLC and MALDI-TOF-MS. The yields of cyclics get as high as 86.3% and 87.9% respectively.展开更多
N,N'-Bis(3-hydroxyphenyl)-1,8,4,5-naphthalenetetracarboxylic bisimide was prepared from the reaction of 1,8,4,5-naphthalenetetrcarboxylic acid dianhydride and 2-aminophenol in N, N-dimethylformamide. Polymerization...N,N'-Bis(3-hydroxyphenyl)-1,8,4,5-naphthalenetetracarboxylic bisimide was prepared from the reaction of 1,8,4,5-naphthalenetetrcarboxylic acid dianhydride and 2-aminophenol in N, N-dimethylformamide. Polymerization of this bisimide with 4,4'-difluorodiphenylsulfone and disodium 3,3'-disulfonate4,4'-difluorodiphenylsulfone gave ion-exchange sulfonated poly(ether sulfone). The structure of the title compound was characterized with H-NMR and its polymer was characterized with FT-IR.展开更多
Abstract: We described the synthesis of two 5-substituted γ-lactams Ⅰand Ⅱ by sulfone-baaed α-amidoalkylation method. This constitiutes the formal synthesis of ant venom alkaloids 2 and 3 in racemic form. The key ...Abstract: We described the synthesis of two 5-substituted γ-lactams Ⅰand Ⅱ by sulfone-baaed α-amidoalkylation method. This constitiutes the formal synthesis of ant venom alkaloids 2 and 3 in racemic form. The key intermediate 18 for the chiral synthesis of 2 and 3 was prepared from new chiral sulfone 7 by the same method.展开更多
Phenylseleno and sulfonyl substituted allyl alcohols were synthesized stereoselectively by the three-component reaction of acetylenic sulfone, phenylselenomagnesium bromide and ketones in one-pot.
The cyano-bridged bimetallic complex K3(TMS)2(H2O)2Cr(CN)6 with three- dimensional microporous structure was synthesized and characterized. The title complex (C14H20CrK3N, Mr = 601.78) crystallizes in monoclinic, sp...The cyano-bridged bimetallic complex K3(TMS)2(H2O)2Cr(CN)6 with three- dimensional microporous structure was synthesized and characterized. The title complex (C14H20CrK3N, Mr = 601.78) crystallizes in monoclinic, space group C2/c with a = 14.357(4), b = 9.331(3), c = 19.180(6) ?, β = 96.754(5)o, V = 2551.6(13) ?3, Z = 4, Dc = 1.567 g/m3, μ(MoKα) = 1.141 mm-1, F(000) = 1228, the final R = 0.0440 and wR = 0.0990 for 1760 observed reflections (I > 2σ(I)). In the crystal, two [Cr(CN) ]3- units, four K+ ions and two oxygen atoms of two 6 TMS molecules are linked to form a sixteen-membered ring and an extended three-dimensional structure.展开更多
The microwave-assisted coupling reaction of electrondeficient aryl halides with sulfinic acid salts through SNAr-based addition reactions within 5-30 min. No catalysts were required under our conditions.
Polychlorinated dibenzothiophenes(PCDTs)and their corresponding sulfone(PCDTO2)compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations...Polychlorinated dibenzothiophenes(PCDTs)and their corresponding sulfone(PCDTO2)compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations of electrostatic potentials(ESPs)on molecular surface have been performed for all 135 PCDTs and 135 PCDTO2 congeners at the HF/6-31G*level of theory.A number of statistically-based parameters have been extracted.Linear relationship between gas-chromatographic retention index(RI)and the structural descriptors have been established by multiple linear regression.The result shows that two descriptors derived from positive electrostatic potential on molecular surface,σ+^2 andπ,together with the molecular volume(Vmc)and the energy of the lowest unoccupied molecular orbital(ELUMO)can be well used to express the quantitative structure-retention relationship(QSRR)of PCDTs and PCDTO2.Predictive capability of the two models has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient(RCV)of 0.996 and 0.997,respectively.Furthermore,the predictive power of the models is further examined for the external test set.Correlation coefficients(R)between the observed and predicted RI values for the external test set are 0.997 and0.998,respectively,validating the robustness and good prediction of our model.The QSRR model established may provide again a powerful method for predicting chromatographic properties of aromatic organosulfur compounds.展开更多
A new aromatic thermotropic liquid crystalline polyester-ether sulfone(PEES)was prepared from 4,4-bis(4-hydroxyphenoxy)diphenyl sulfone(BHPDS),terephthalic acid(TPA)and p-hydroxybenzoic acid(P-HBA).Some factors that a...A new aromatic thermotropic liquid crystalline polyester-ether sulfone(PEES)was prepared from 4,4-bis(4-hydroxyphenoxy)diphenyl sulfone(BHPDS),terephthalic acid(TPA)and p-hydroxybenzoic acid(P-HBA).Some factors that affected melting viscosity of polymer such as prepolymerization reaction medium and post-polymerization etc,were discussed.The liquid crystalline properties were characterized by DSC,polarizing microscope with a hot stage and WAXD measurements.展开更多
A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacem...A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)- 1 (2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin in sulfolane in the presence of K2CO3 to produce high molecular weight polymers which can be dissolved in some polar solvents such as chloroform and nitrobenzene at room temperature and can be easily cast into flexible, yellowish and transparent films. PPESK is an amorphous polymer having a decomposition temperature above 400degreesC, which indicates that it has high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agent indicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (A-E) of the cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively. Therefore, the cross-linking reaction is approximately a first order reaction.展开更多
One novel carbon-carbon bond insertion reaction of arynes has been developed. By this reaction β-keto sulfones can insert the triple bond of arynes to prepare polysubstituted ortho-keto benzyl sulfones.
基金the National Natural Science Foundation of China(No.20462002)Natural Science Foundation of Jiangxi Province(No.0420015)for financial support.
文摘(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically afford the corresponding (Z)-2-sulfonyl-substituted 1,3-enynes 3 in high yields.
基金partly financed by the Major State Basic Research Development Program of China(No.2003 CB615700)the National Natural Science Foundation of China(No.20604005).
文摘Chloromethylated poly(phthalazinone ether sulfone ketone) (CMPPESK) was prepared from poly(phthalazinone ether sulfone ketone) (PPESK) using chloromethyl octyl ethers (CMOE) with lower toxicity as chloromethylated regent. CMPPESK was soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc) and chloroform. Quaternized poly(phthalazinone ether sulfone ketone) (QAPPESK) was prepared from CMPPESK by quaternization. QAPPESK had excellent solvent resistance, which was only partly soluble in sulfuric acid (98%) and swollen in N,N-dimethylformamide (DMF). The vanadium redox flow battery (V-RFB) using QAPPESK anion-exchange membrane had better performance with 88.3% of overall energy efficiency.
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 863 program of China(No.2007AA 03Z561)
文摘The thermal degradation of poly(arylene sulfide sulfone)/N-methylpyrrolidone (PASS/NMP) crystal solvate was studied by thermogravimetric analysis (TGA) and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger's method, which does not require knowledge of the reaction mechanism (RM), to be 174.18 kJ/mol which was lower than that for pure PASS (E = 214 kJ/mol). The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.
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the supports provided by National Iranian Oil Engineering and Construction Company(NIOEC)。
文摘The oxidative desulfurization(ODS) process is one of the new desulfurization processes for the production of clean fuels. Despite the benefits of the ODS process, this process faces several important challenges. One of the most important challenges of this process is the management of a waste which is rich of sulfone compounds.In the present study, a new strategy which is the addition of waste to the bitumen with other solid waste such as high density polyethylene(HDPE) waste has been investigated. The experimental design method was applied to investigate the effect of addition of the sulfone and HDPE wastes to the properties of the bitumen blends including degree of penetration, softening point, and mass loss. It was found that the sulfone waste can be added to the bitumen as a softener. The results showed that several grades of bitumen including 50/60, 60/70, 85/100 can be produced through the addition of sulfone waste along with the HDPE waste to the base 60/70 bitumen.In general, the application of simple processes such as mixing the wastes with the bitumen can reduce the cost of waste management, considerably.
文摘Cyclic oligomers of phenolphthalein polyarylene ether sulfone(ketone) were prepared through cyclo-depolymerisation of corresponding polymers using CsF as the catalyst in dipolar aprotic solvent DMAc and DMF, and a family of macrocycles containing from dimer up to at least heptamer were confirmed by GPC, HPLC and MALDI-TOF-MS. The yields of cyclics get as high as 86.3% and 87.9% respectively.
基金This project is supported by the National Natural Science Foundation of China(No.20104001).
文摘N,N'-Bis(3-hydroxyphenyl)-1,8,4,5-naphthalenetetracarboxylic bisimide was prepared from the reaction of 1,8,4,5-naphthalenetetrcarboxylic acid dianhydride and 2-aminophenol in N, N-dimethylformamide. Polymerization of this bisimide with 4,4'-difluorodiphenylsulfone and disodium 3,3'-disulfonate4,4'-difluorodiphenylsulfone gave ion-exchange sulfonated poly(ether sulfone). The structure of the title compound was characterized with H-NMR and its polymer was characterized with FT-IR.
文摘Abstract: We described the synthesis of two 5-substituted γ-lactams Ⅰand Ⅱ by sulfone-baaed α-amidoalkylation method. This constitiutes the formal synthesis of ant venom alkaloids 2 and 3 in racemic form. The key intermediate 18 for the chiral synthesis of 2 and 3 was prepared from new chiral sulfone 7 by the same method.
基金supported by the National Natural Science Foundation of China(No.29772007)
文摘Phenylseleno and sulfonyl substituted allyl alcohols were synthesized stereoselectively by the three-component reaction of acetylenic sulfone, phenylselenomagnesium bromide and ketones in one-pot.
基金Supported by the Innovation Foundation for College Students of Nankai University and the National Natural Science Foundation of China (No. 50242001)
文摘The cyano-bridged bimetallic complex K3(TMS)2(H2O)2Cr(CN)6 with three- dimensional microporous structure was synthesized and characterized. The title complex (C14H20CrK3N, Mr = 601.78) crystallizes in monoclinic, space group C2/c with a = 14.357(4), b = 9.331(3), c = 19.180(6) ?, β = 96.754(5)o, V = 2551.6(13) ?3, Z = 4, Dc = 1.567 g/m3, μ(MoKα) = 1.141 mm-1, F(000) = 1228, the final R = 0.0440 and wR = 0.0990 for 1760 observed reflections (I > 2σ(I)). In the crystal, two [Cr(CN) ]3- units, four K+ ions and two oxygen atoms of two 6 TMS molecules are linked to form a sixteen-membered ring and an extended three-dimensional structure.
基金the Municipal Government of Shanghai(No.03DZ19209)Shanghai Hua-Yi Group for financial support.
文摘The microwave-assisted coupling reaction of electrondeficient aryl halides with sulfinic acid salts through SNAr-based addition reactions within 5-30 min. No catalysts were required under our conditions.
基金supported by the Science and Technology Project of Zhejiang Province(2016C33039)the Public Technology Research Project(Analysis and Measurement)of Zhejiang Province(LGC19B070004)+1 种基金State Key Laboratory of Environmental Chemistry and Ecotoxicology,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences(KF2018-15)Natural Science Foundation of Zhejiang Province(LY18C030003)
文摘Polychlorinated dibenzothiophenes(PCDTs)and their corresponding sulfone(PCDTO2)compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations of electrostatic potentials(ESPs)on molecular surface have been performed for all 135 PCDTs and 135 PCDTO2 congeners at the HF/6-31G*level of theory.A number of statistically-based parameters have been extracted.Linear relationship between gas-chromatographic retention index(RI)and the structural descriptors have been established by multiple linear regression.The result shows that two descriptors derived from positive electrostatic potential on molecular surface,σ+^2 andπ,together with the molecular volume(Vmc)and the energy of the lowest unoccupied molecular orbital(ELUMO)can be well used to express the quantitative structure-retention relationship(QSRR)of PCDTs and PCDTO2.Predictive capability of the two models has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient(RCV)of 0.996 and 0.997,respectively.Furthermore,the predictive power of the models is further examined for the external test set.Correlation coefficients(R)between the observed and predicted RI values for the external test set are 0.997 and0.998,respectively,validating the robustness and good prediction of our model.The QSRR model established may provide again a powerful method for predicting chromatographic properties of aromatic organosulfur compounds.
文摘A new aromatic thermotropic liquid crystalline polyester-ether sulfone(PEES)was prepared from 4,4-bis(4-hydroxyphenoxy)diphenyl sulfone(BHPDS),terephthalic acid(TPA)and p-hydroxybenzoic acid(P-HBA).Some factors that affected melting viscosity of polymer such as prepolymerization reaction medium and post-polymerization etc,were discussed.The liquid crystalline properties were characterized by DSC,polarizing microscope with a hot stage and WAXD measurements.
基金This project was supported by the National Ninth Five-Year-Plan Key Project "The pilot-scale production and the applied development of polyaryl ether concerning phthalazinone moiety" (No. 97-564-01-07).
文摘A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)- 1 (2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin in sulfolane in the presence of K2CO3 to produce high molecular weight polymers which can be dissolved in some polar solvents such as chloroform and nitrobenzene at room temperature and can be easily cast into flexible, yellowish and transparent films. PPESK is an amorphous polymer having a decomposition temperature above 400degreesC, which indicates that it has high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agent indicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (A-E) of the cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively. Therefore, the cross-linking reaction is approximately a first order reaction.
基金We are grateful to the National Natural Science Foundation of China (Nos. 20332060 and 2472072)
文摘One novel carbon-carbon bond insertion reaction of arynes has been developed. By this reaction β-keto sulfones can insert the triple bond of arynes to prepare polysubstituted ortho-keto benzyl sulfones.