Several new enediynes with long chain alkyl groups were synthesized through Sonogashira coupling reactions between long chain alkynes and（Z）-1,2-dichloroethene. These enediynes（1） were then subjected to thermal Be...Several new enediynes with long chain alkyl groups were synthesized through Sonogashira coupling reactions between long chain alkynes and（Z）-1,2-dichloroethene. These enediynes（1） were then subjected to thermal Bergman cyclization in a refluxing diphenyl ether bath under vacuum to obtain conjugated polyphenylenes with the weight-average molecular weights up to 4.9 × 103 g·mol·1. The occurrence of Bergman cyclization was confirmed by 1H-NMR, 13C-NMR, and IR spectroscopic analysis. These polyphenylenes are fully soluble in common organic solvents and exhibit good thermal stability. The optical properties of the polyphenylenes were investigated by UV-Vis absorption and photoluminescence（PL） spectroscopies. A blue emission was observed for all these polyphenylenes.展开更多
A fibrous strong base anion exchanger （QAPPS） was prepared for the first time via chloromethylation and quaternary amination reaction of polyphenylene sulfide fiber （PPS）, and its physical-chemical structure and a...A fibrous strong base anion exchanger （QAPPS） was prepared for the first time via chloromethylation and quaternary amination reaction of polyphenylene sulfide fiber （PPS）, and its physical-chemical structure and adsorption behavior for Cr（VI） were characterized by FT- IR, Energy Dispersive Spectrometry, TG-DTG, elemental analysis and batch adsorptive technique, respectively. The novel fibrous adsorbent could effectively adsorb Cr（VI） over the pH range 1-12, the maximum adsorption capacity was 166.39 mg/g at pH 3.5, and the adsorption behavior could be described well by Langmuir isotherm equation model. The adsorption kinetics was studied using pseudo first-order and pseudo second-order models, and the 4/2 and equilibrium adsorption time were 5 and 20 min respectively when initial Cr（VI） concentration was 100 mg/L. The saturated fibers could be regenerated rapidly by a mixed solution of 0.5 mol/L NaOH and 0.5 mol/L NaCl, and the adsorption capacity was well maintained after six adsorption-desorption cycles.展开更多
A series of novel chelating fibers containing sulfur, nitrogen, oxygen heteroatoms were prepared via the functionalization of chloromethylated polyphenylene sulfide （CMPPS）. The structures, micromorpholo- gy and phy...A series of novel chelating fibers containing sulfur, nitrogen, oxygen heteroatoms were prepared via the functionalization of chloromethylated polyphenylene sulfide （CMPPS）. The structures, micromorpholo- gy and physicochemical properties of these fibrous adsorptive materials were characterized by FT-IR, elementary analysis, TG and SEM-EDS. The results show that chelating fibers had high functional group contents （3.94 mmol/g for thiourea, 3.85 mmol/g for mercapto, 5.00 mmol/g for methylamine and 6.07 mmol/g for ethylenediamine, respectively）. Owing to the unique matrix of polyphenylene sulfide fiber, these fibrous adsorbents possess excellent thermostability. This synthetic method proved a simple and efficient way for the preparation of chelating fibers.展开更多
The effect of pressure-induced flow（PIF） processing on the mechanical properties of noncontinuous carbon fiber（CF） reinforced polyphenylene sulfide（PPS） composites was investigated. A series of CF/PPS composites...The effect of pressure-induced flow（PIF） processing on the mechanical properties of noncontinuous carbon fiber（CF） reinforced polyphenylene sulfide（PPS） composites was investigated. A series of CF/PPS composites under different processing conditions were prepared through PIF-processing. SEM observations showed that the interfaces adhesion between CFs and PPS became stronger and ductile fracture mainly occurred in PPS matrix. This brought to a great increase of both strength and toughness by about 2 folds, when the composites were processed at 240 ℃ and under 263 MPa. The results in differential scanning calorimetry（DSC） and X-ray diffraction（XRD） measurements indicated more regular crystalline structures and orientation of lamellae formed during PIF-processing.展开更多
Blends of polyphenylene sulfide (PPS) containing trace amounts of branching and/or cross-linking in chain and Polyamide-66 (PA-66) have been prepared by melt blending. The rheological behavior of PPS/PA-66 blends has ...Blends of polyphenylene sulfide (PPS) containing trace amounts of branching and/or cross-linking in chain and Polyamide-66 (PA-66) have been prepared by melt blending. The rheological behavior of PPS/PA-66 blends has been studied by means of capillary rheometer, and compared with PPS. The effects of shear rate, shear stress and temperature on the how of PPS/PA-66 blends and PPS are discussed. The non-Newtonian indexes and the activation energies of viscous how are obtained. The results show that the apparent viscosity of PPS/PA-66 blends is not sensitive to shear rate and stress, but decreases with the elevation of temperature. On the contrary, the apparent viscosity of the PPS decreases obviously with the increasing of shear rate and shear stress, but it is increased by the elevation of temperature.展开更多
Self-lubricating polyphenylene sulfide(PPS)composites were fabricated by constructing a segregated network structure using the co-deposition method.Both carboxyl-functionalized multi-walled carbon nanotubes(CNTs)and s...Self-lubricating polyphenylene sulfide(PPS)composites were fabricated by constructing a segregated network structure using the co-deposition method.Both carboxyl-functionalized multi-walled carbon nanotubes(CNTs)and silicon carbide(SiC)were successfully coated on the surface of PPS powders with the aid of self-polymerization of dopamine(PDA)and co-polymerization between PDA and polyethyleneimine(PEI),thereby forming PPS@PDA-CNTs-SiC hierarchical reinforcing hybrids.Results showed that the thermal conductivity of PPS@PDA-CNTs-SiC(0.97 W/(m K))is about 120%higher than that of PPS/CNTs/SiC.The friction coefficient(0.193)and specific wear rate(2.50×10^(-5)mm^(3)/(N m))of PPS@PDA-CNTs-SiC are 18.9%and 50%lower than those of PPS/CNTs/SiC,respectively.The enhanced thermal conductivity of PPS@PDA-CNTs-SiC contributes to rapid dissipation of frictional heat at the sliding interface which protects the polymer substrate from being destroyed or peeled,thereby improving the tribological performance.This work provides new insights into expanding the application of self-lubricating polymer composites in the fields where efficient heat dissipation is also a primary concern.展开更多
New hyperbranched polyphenylenes with high molecular weights are synthesized by the copolycyclotrimerizations of 1,4-diethynylbenzene (I) with phenylacetylene (A), 1-octyne (B), and 1-dodecyne (C) catalyzed by TaCl5-P...New hyperbranched polyphenylenes with high molecular weights are synthesized by the copolycyclotrimerizations of 1,4-diethynylbenzene (I) with phenylacetylene (A), 1-octyne (B), and 1-dodecyne (C) catalyzed by TaCl5-Ph4Sn. The polymers are completely soluble in common solvents such as toluene, THF, chloroform, and dichloromethane. The polymers are characterized by spectroscopic methods and all of the polymers give satisfactory analysis data corresponding to their expected molecular structures.展开更多
Fluororesin-based anti-corrosive coatings including graded FEP/PPS were prepared on carbon steel by melt powder coating, the bonding strength of all coating systems was determined by the pull-off test. It is found tha...Fluororesin-based anti-corrosive coatings including graded FEP/PPS were prepared on carbon steel by melt powder coating, the bonding strength of all coating systems was determined by the pull-off test. It is found that the poor adhesion of fluororesin coatings to metallic substrates is improved obviously by the graded coating structure of FEP/PPS, and the bonding strength reaches up to 11.8 MPa for the five-layer system. Examination by electron probe microanalysis （EPMA） verifies that the distribution of main components is graded in the five-layer system, which is responsible for the enhancement of the interfacial bonding.展开更多
Chiral enediynes with pendant chiral amino ester groups are synthesized through Sonogashira reactions and subjected to thermal triggered Bergman cyclization at elevated temperatures either in bulk or in solvents to pr...Chiral enediynes with pendant chiral amino ester groups are synthesized through Sonogashira reactions and subjected to thermal triggered Bergman cyclization at elevated temperatures either in bulk or in solvents to produce chiral polyphenylenes. The disappearance of enediyne monomers are evidenced by FTIR and NMR spectroscopies. The formation of polyphenylenes is further confirmed by UV-Vis and MALDI-TOF mass spectroscopies（MS）. Isotope pattern analysis of the MS spectra shows that the polymers prepared in solvents are terminated by the solvent molecules, whereas the chain ends of the polymers prepared in bulk consist of considerable amount of unmasked free radicals, which is further confirmed by EPR analysis. Circular dichroism（CD） spectra of the chiral polymers show blue shifts of the Cotton peaks, indicating the occurrence of the cycloaromatization reaction. A new set of peaks mirrored at the horizontal axis show up in the long wavelength range, which are assigned to main chain chirality of the polyphenylenes.展开更多
To date,there is no research that deals with biological waste as fillers in polyphenylene sulfide(PPS).In this study,oyster shells were recycled and treated to prepare thermally-treated oyster shells(TOS),which were u...To date,there is no research that deals with biological waste as fillers in polyphenylene sulfide(PPS).In this study,oyster shells were recycled and treated to prepare thermally-treated oyster shells(TOS),which were used as PPS fillers to make new bio-based antibacterial composite materials.The effect of varying the content of TOS was studied by means of structure and performance characterization.PPS/TOS composites were demonstrated to have an antibacterial effect on the growth of E coli and S.aureus.Qualitative analysis showed that when the TOS content was≥30%and 40%,the composite materials had an apparent inhibition zone.Quantitative analysis showed that the antibacterial activity increased with the TOS content.Fourier transform infrared spectroscopy indicated the formation of hydrogen bonds between the molecular chains of TOS and PPS and the occurrence of a coordination reaction.At 10%TOS,the composite tensile strength reached a maximum value of 72.5 MPa,which is 9.65%higher than that of pure PPS.The trend of bending properties is the same as that of tensile properties,showing that the maximum property was reached for the composite with 10%TOS.At the same time,the crystallinity and contact angle were the highest,and the permeability coefficient was the lowest.The fatigue test results indicated that for the composite with 10%TOS,the tensile strength was 23%lower than static tensile strength,and the yield strength was 10%lower than the static yield strength.The results of the study showed that TOS not only could reduce the cost of PPS,but also could impart antibacterial properties and enhance the mechanical and,barrier properties,the thermostability,as well as the crystallinity.展开更多
NiCl2(bpy) catalyzed polycondensation between p-dibromobenzene and m-dibromobenzene has been carried out under various conditions. The polycondensation endows the copolymer with an M-n of 2300 (by GPC, polystyrene sta...NiCl2(bpy) catalyzed polycondensation between p-dibromobenzene and m-dibromobenzene has been carried out under various conditions. The polycondensation endows the copolymer with an M-n of 2300 (by GPC, polystyrene standards) and good solubility in organic solvents. The fluorescence spectra of the copolymer measured with tetrahydrofuran solution shows an emission maximum (lambda(max)) at 372.8 nm, whereas for the film the maximum shifts to 436.6 nm.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.20874026 and 91023008)Ph.D.Programs Foundation of Ministry of Education of China(20100074110002)+1 种基金the Fundamental Research Funds for the Central Universities,Shanghai Leading Academic Discipline Project(B502)AH thanks the"Eastern Scholar Professorship"support from Shanghai local government
文摘Several new enediynes with long chain alkyl groups were synthesized through Sonogashira coupling reactions between long chain alkynes and（Z）-1,2-dichloroethene. These enediynes（1） were then subjected to thermal Bergman cyclization in a refluxing diphenyl ether bath under vacuum to obtain conjugated polyphenylenes with the weight-average molecular weights up to 4.9 × 103 g·mol·1. The occurrence of Bergman cyclization was confirmed by 1H-NMR, 13C-NMR, and IR spectroscopic analysis. These polyphenylenes are fully soluble in common organic solvents and exhibit good thermal stability. The optical properties of the polyphenylenes were investigated by UV-Vis absorption and photoluminescence（PL） spectroscopies. A blue emission was observed for all these polyphenylenes.
基金support of the National Natural Science Foundation of China (No. 20574063,21004055)
文摘A fibrous strong base anion exchanger （QAPPS） was prepared for the first time via chloromethylation and quaternary amination reaction of polyphenylene sulfide fiber （PPS）, and its physical-chemical structure and adsorption behavior for Cr（VI） were characterized by FT- IR, Energy Dispersive Spectrometry, TG-DTG, elemental analysis and batch adsorptive technique, respectively. The novel fibrous adsorbent could effectively adsorb Cr（VI） over the pH range 1-12, the maximum adsorption capacity was 166.39 mg/g at pH 3.5, and the adsorption behavior could be described well by Langmuir isotherm equation model. The adsorption kinetics was studied using pseudo first-order and pseudo second-order models, and the 4/2 and equilibrium adsorption time were 5 and 20 min respectively when initial Cr（VI） concentration was 100 mg/L. The saturated fibers could be regenerated rapidly by a mixed solution of 0.5 mol/L NaOH and 0.5 mol/L NaCl, and the adsorption capacity was well maintained after six adsorption-desorption cycles.
基金support by the National Natural Science Foundation of China(No.20574063)Doctoral Foundation of Ministry of Education of China(No. 20104101110005)
文摘A series of novel chelating fibers containing sulfur, nitrogen, oxygen heteroatoms were prepared via the functionalization of chloromethylated polyphenylene sulfide （CMPPS）. The structures, micromorpholo- gy and physicochemical properties of these fibrous adsorptive materials were characterized by FT-IR, elementary analysis, TG and SEM-EDS. The results show that chelating fibers had high functional group contents （3.94 mmol/g for thiourea, 3.85 mmol/g for mercapto, 5.00 mmol/g for methylamine and 6.07 mmol/g for ethylenediamine, respectively）. Owing to the unique matrix of polyphenylene sulfide fiber, these fibrous adsorbents possess excellent thermostability. This synthetic method proved a simple and efficient way for the preparation of chelating fibers.
基金Funded by the National Natural Science Foundation of China(No.21404023)the Foundation of State Key Laboratory for Modification of Chemical Fibers and Polymer Materials(No.LK1417)the Fundamental Research Funds for the Central Universities(2232015D-10)
文摘The effect of pressure-induced flow（PIF） processing on the mechanical properties of noncontinuous carbon fiber（CF） reinforced polyphenylene sulfide（PPS） composites was investigated. A series of CF/PPS composites under different processing conditions were prepared through PIF-processing. SEM observations showed that the interfaces adhesion between CFs and PPS became stronger and ductile fracture mainly occurred in PPS matrix. This brought to a great increase of both strength and toughness by about 2 folds, when the composites were processed at 240 ℃ and under 263 MPa. The results in differential scanning calorimetry（DSC） and X-ray diffraction（XRD） measurements indicated more regular crystalline structures and orientation of lamellae formed during PIF-processing.
基金This work was supported by the National High Technology Program Fund(863)of China.
文摘Blends of polyphenylene sulfide (PPS) containing trace amounts of branching and/or cross-linking in chain and Polyamide-66 (PA-66) have been prepared by melt blending. The rheological behavior of PPS/PA-66 blends has been studied by means of capillary rheometer, and compared with PPS. The effects of shear rate, shear stress and temperature on the how of PPS/PA-66 blends and PPS are discussed. The non-Newtonian indexes and the activation energies of viscous how are obtained. The results show that the apparent viscosity of PPS/PA-66 blends is not sensitive to shear rate and stress, but decreases with the elevation of temperature. On the contrary, the apparent viscosity of the PPS decreases obviously with the increasing of shear rate and shear stress, but it is increased by the elevation of temperature.
基金financially supported by the China Postdoctoral Science Foundation(No.2020M673217)the National Natural Science Foundation of China(No.51703137)the Fundamental Research Funds for the Central Universities
文摘Self-lubricating polyphenylene sulfide(PPS)composites were fabricated by constructing a segregated network structure using the co-deposition method.Both carboxyl-functionalized multi-walled carbon nanotubes(CNTs)and silicon carbide(SiC)were successfully coated on the surface of PPS powders with the aid of self-polymerization of dopamine(PDA)and co-polymerization between PDA and polyethyleneimine(PEI),thereby forming PPS@PDA-CNTs-SiC hierarchical reinforcing hybrids.Results showed that the thermal conductivity of PPS@PDA-CNTs-SiC(0.97 W/(m K))is about 120%higher than that of PPS/CNTs/SiC.The friction coefficient(0.193)and specific wear rate(2.50×10^(-5)mm^(3)/(N m))of PPS@PDA-CNTs-SiC are 18.9%and 50%lower than those of PPS/CNTs/SiC,respectively.The enhanced thermal conductivity of PPS@PDA-CNTs-SiC contributes to rapid dissipation of frictional heat at the sliding interface which protects the polymer substrate from being destroyed or peeled,thereby improving the tribological performance.This work provides new insights into expanding the application of self-lubricating polymer composites in the fields where efficient heat dissipation is also a primary concern.
基金This work was supported by the Research Grants Council of Hong Kong (Nos. 603304, 604903 and HKUST6085/02P).
文摘New hyperbranched polyphenylenes with high molecular weights are synthesized by the copolycyclotrimerizations of 1,4-diethynylbenzene (I) with phenylacetylene (A), 1-octyne (B), and 1-dodecyne (C) catalyzed by TaCl5-Ph4Sn. The polymers are completely soluble in common solvents such as toluene, THF, chloroform, and dichloromethane. The polymers are characterized by spectroscopic methods and all of the polymers give satisfactory analysis data corresponding to their expected molecular structures.
文摘Fluororesin-based anti-corrosive coatings including graded FEP/PPS were prepared on carbon steel by melt powder coating, the bonding strength of all coating systems was determined by the pull-off test. It is found that the poor adhesion of fluororesin coatings to metallic substrates is improved obviously by the graded coating structure of FEP/PPS, and the bonding strength reaches up to 11.8 MPa for the five-layer system. Examination by electron probe microanalysis （EPMA） verifies that the distribution of main components is graded in the five-layer system, which is responsible for the enhancement of the interfacial bonding.
基金financially supported by the National Natural Science Foundation of China(Nos.21474027,91023008)Ph.D.Programs Foundation of Ministry of Education of China(No.20100074110002)the Fundamental Research Funds for the Central Universities,and Shanghai Leading Academic Discipline Project(No.B502)
文摘Chiral enediynes with pendant chiral amino ester groups are synthesized through Sonogashira reactions and subjected to thermal triggered Bergman cyclization at elevated temperatures either in bulk or in solvents to produce chiral polyphenylenes. The disappearance of enediyne monomers are evidenced by FTIR and NMR spectroscopies. The formation of polyphenylenes is further confirmed by UV-Vis and MALDI-TOF mass spectroscopies（MS）. Isotope pattern analysis of the MS spectra shows that the polymers prepared in solvents are terminated by the solvent molecules, whereas the chain ends of the polymers prepared in bulk consist of considerable amount of unmasked free radicals, which is further confirmed by EPR analysis. Circular dichroism（CD） spectra of the chiral polymers show blue shifts of the Cotton peaks, indicating the occurrence of the cycloaromatization reaction. A new set of peaks mirrored at the horizontal axis show up in the long wavelength range, which are assigned to main chain chirality of the polyphenylenes.
基金Sichuan Province Science and Technology Support Program(2022JDTD0016,2020YFG0176)Chengdu Science and Technology(2021-RC02-00005-CG)+5 种基金Sichuan Golden-Elephant Sincerity Chemical Co.,Ltd(HX2020019)Zigong City Science and Technology(2019CXRC01,2020YGJC13)Opening Project of Material Corrosion and Protection Key Laboratory of Sichuan Province(2019CL05,2020CL19,2018CL07)Opening Project of Sichuan Province,the Foundation of Introduced Talent of Sichuan University of Science and Engineering(2017RCL16,2019RC05,2019RC07,2020RC16)the Opening Project of Key Laboratories of Fine Chemicals and Surfactants in Sichuan Provincial Universities(2020JXY04)Xi’an Weijingyi Art and Culture Communication Co.,Ltd(HX2021385)。
文摘To date,there is no research that deals with biological waste as fillers in polyphenylene sulfide(PPS).In this study,oyster shells were recycled and treated to prepare thermally-treated oyster shells(TOS),which were used as PPS fillers to make new bio-based antibacterial composite materials.The effect of varying the content of TOS was studied by means of structure and performance characterization.PPS/TOS composites were demonstrated to have an antibacterial effect on the growth of E coli and S.aureus.Qualitative analysis showed that when the TOS content was≥30%and 40%,the composite materials had an apparent inhibition zone.Quantitative analysis showed that the antibacterial activity increased with the TOS content.Fourier transform infrared spectroscopy indicated the formation of hydrogen bonds between the molecular chains of TOS and PPS and the occurrence of a coordination reaction.At 10%TOS,the composite tensile strength reached a maximum value of 72.5 MPa,which is 9.65%higher than that of pure PPS.The trend of bending properties is the same as that of tensile properties,showing that the maximum property was reached for the composite with 10%TOS.At the same time,the crystallinity and contact angle were the highest,and the permeability coefficient was the lowest.The fatigue test results indicated that for the composite with 10%TOS,the tensile strength was 23%lower than static tensile strength,and the yield strength was 10%lower than the static yield strength.The results of the study showed that TOS not only could reduce the cost of PPS,but also could impart antibacterial properties and enhance the mechanical and,barrier properties,the thermostability,as well as the crystallinity.
文摘NiCl2(bpy) catalyzed polycondensation between p-dibromobenzene and m-dibromobenzene has been carried out under various conditions. The polycondensation endows the copolymer with an M-n of 2300 (by GPC, polystyrene standards) and good solubility in organic solvents. The fluorescence spectra of the copolymer measured with tetrahydrofuran solution shows an emission maximum (lambda(max)) at 372.8 nm, whereas for the film the maximum shifts to 436.6 nm.
