Oxidative stress is a critical risk factor for various disease complications in patients with end-stage renal disease,which may be further aggravated during hemodialysis.Herein,we prepared a hemodialysis membrane by i...Oxidative stress is a critical risk factor for various disease complications in patients with end-stage renal disease,which may be further aggravated during hemodialysis.Herein,we prepared a hemodialysis membrane by introducing poly(2-Acrylamide-2-methylpropanesulfonic acid-N-vinylpyrrolidone)(P(AMPS-VP))into the polyethersulfone(PES)membrane by simple in-situ polymerization and non-solvent phase sepa-ration(NIPS)method,followed by tannic acid(TA)coating construction through hydrogen bonding interaction,termed PES/P(AMPS-VP)-TA.The membrane can efficiently remove reactive nitrogen radicals(RNS)(DPPH•,89.96%;ABTS•+,90.49%)and reactive oxygen species(ROS)(O_(2)•^(−),90.45%),and has a very sta-ble antioxidant property.Meanwhile,the membrane does not cause hemolysis and coagulation,and has superior blood compatibility required by hemodialysis membrane.In addition,the dialysis performance of the membrane is improved compared with unmodified PES,which is beneficial for practical hemodialysis applications.This work provides a reference for industrial preparation of hemodialysis membranes,which is expected to be applied to reduce oxidative stress in hemodialysis patients.展开更多
Biodegradable poly （D,L-lactide） （PLA）/carboxyl-functionalized multi-walled carbon nanotubes （c-MWCNTs） composites were achieved via in-situ polymerization. These as-prepared composite materials were characteriz...Biodegradable poly （D,L-lactide） （PLA）/carboxyl-functionalized multi-walled carbon nanotubes （c-MWCNTs） composites were achieved via in-situ polymerization. These as-prepared composite materials were characterized with FT-IR, XRD, TG, DSC, SEM, and high insulation resistance meter. The results demonstrate that the multi-walled carbon nanotube was carboxyl functionalized, which improved the collection between c-MWCNTs and PLA, and further realized the graft copolymerization of c-MWCNTs and PLA. There is a higher glass transition temperature and a lower pyrolysis temperature of PLA/c-MWCNTs composites than pure PLA. The c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLA matrix, and an even coating of PLA on the surface of c-MWCNTs was obtained, which increased the interfacial interaction. High insulation resistance analysis showed that the addition of c-MWCNTs increased the electric conductivity, and c-MWCNTs performed against the large dielectric coefficient and electrostatic state of PLA. These results demonstrated that c-MWCNTs modified PLA composites were beneficial for potential application in the development of heat-resisting and conductivity plastic engineering.展开更多
Gel polymer electrolytes(GPEs) are promising alternatives to liquid electrolytes applied in high-energydensity batteries.Here superior SiO_(2) nanofiber composite gel polymer electrolytes(SNCGPEs) are developed via in...Gel polymer electrolytes(GPEs) are promising alternatives to liquid electrolytes applied in high-energydensity batteries.Here superior SiO_(2) nanofiber composite gel polymer electrolytes(SNCGPEs) are developed via in-situ ionic ring-opening polymerization of 1,3-dioxolane(DOL) monomers in SiO_(2) nanofiber membrane(PDOL-SiO_(2)) for lithium metal batteries.The oxygen atoms of PDOL together with Si-O of SiO_(2) construct a more efficient channel for Li^(+) migration.Consequently,the lithium ion transference number(t_(Li^(+)) and ionic conductivity(σ) at 30℃ of PDOL-SiO_(2) are 0.80 and 1.68×10^(-4)S/cm separately.PDOL-SiO_(2) manifests the electrochemical decomposition potentials of 4.90 V.At 0.5 mA/cm^(2),Li|PDOL-SiO_(2) |Li cell shows a steady cycling performance for nearly 1400 h.LFP|PDOL-SiO_(2) |Li battery can steadily cycle at 0.5 C with a capacity retention rate of 89% after 200 cycles.While cycling at 2 C,the capacity retention rate can maintain at 78% after 300 cycles.This contribution provides a innovative strategy for accelerating Li^(+)transportation via designing PDOL molecular chains throughout the SiO_(2) nanofiber framework,which is crucial for high-energy-density LMBs.展开更多
Nano zinc oxide （ZnO） is a very useful and important material in many industrial and biological applications. In the present work, ZnO was synthesized by post thermal degradation of the precursor ＂zinc acetate di-h...Nano zinc oxide （ZnO） is a very useful and important material in many industrial and biological applications. In the present work, ZnO was synthesized by post thermal degradation of the precursor ＂zinc acetate di-hydrate＂ templated in crosslinked polyacrylic acid （PAA）. The crosslinked PAA template was prepared through an in-situ polymerization process adopted in presence of ammonium per sulphate, as an initiator, and N, Nt- methylene bis-acrylamide as the crosslinker. Variation of preparation parameters and their impact on the oxide stoichiometry, crystal structure, crystallite size and surface texture of the oxide were investigated. Energy dispersive X-ray technique （EDX）, X-ray diffraction （XRD） and scanning electron microscopy （SEM） were convincingly used to reveal the oxide structural features and characteristics. The performed bioassay tests indicated the efficacy of this method of preparation to produce nano ZnO with novel insecticidal activity against the greater wax moth, Galleria rnellonella.展开更多
Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support...Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support and keep cells.An in-situ polymerization-modification process with esterification and polycondensation stages was performed in a 2 L batch stirred reactor using pyromellitic dianhydride(PMDA)or pentaerythritol(PENTA)as modifying monomers to obtain PETs with high melt strength.The influence of amounts of modifying monomers on the properties of modified PET was investigated.It was found that the selected modifying monomers could effectively introduce branched structures into the modified PETs and improve their melt strength.With increasing the amount of the modifying monomer,the melt strength of the modified PET increased.But when the amount of PENTA reached 0.35%or PMDA reached 0.9%,crosslinking phenomenon was observed in the modified PET.Supercritical carbon dioxide(ScCO2)was employed as physical foaming agent to evaluate the foaming ability of modified PETs.The modified PETs had good foaming properties at 14 MPa of CO2pressure with foaming temperature ranging from 265°C to 280°C.SEM micrographs demonstrated that both modified PET foams had homogeneous cellular structures,with cell diameter ranging from 35μm to 49μm for PENTA modified PETs and38μm to 57μm for PMDA modified ones.Correspondingly,the cell density had a range of 3.5×107cells·cm 3to 7×106cells·cm 3for the former and 2.8×107cells·cm 3to 5.8×106cells·cm 3for the latter.展开更多
Conductive polymer composites based on crystalline polymer matrix have been prepared by using an in-situ polymerization process of pyrrole in amorphous poly （ethylene terephthalate） （PET） film. The DSC and WAXD me...Conductive polymer composites based on crystalline polymer matrix have been prepared by using an in-situ polymerization process of pyrrole in amorphous poly （ethylene terephthalate） （PET） film. The DSC and WAXD measurement and SEM observation show that liquid-induced crystallization of PET matrix has occurred during the preparation of composite films. Depending upon the equilibrium degree of swelling and crystallinity, the limited depth of penetration of pyrrole molecules results in a skin-core structure of the composite film. The skin layer containing charge transfer intercalated polypyrrole has a surface resistance of 3.5×10;Ω. Rigid and heat-resistant polypyrrole molecules formed in PET film increase the tensile modulus and, especially, the rigidity of PET at elevated temperatures. However, they decrease the tensile strength and elongation at break, and impair the thermal ductility of PET.展开更多
Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT was...Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).展开更多
A kind of new nano composite with ultraviolet （UV） ray resistance and high temperature stability was prepared by in-situ polymerization in low temperature. Polysulfonamide （PSA） was synthesized with 4, 4＇-diamin...A kind of new nano composite with ultraviolet （UV） ray resistance and high temperature stability was prepared by in-situ polymerization in low temperature. Polysulfonamide （PSA） was synthesized with 4, 4＇-diaminodiphenyl sulfone （DDS） and terephthaloyl chloride （TPC） in the common solvent N, N-Dimethyl- -acetamide （DMAc）. Nano filler is a certain nano titanium oxide modified by silicon oxide （TMS）, which plays the role of UV resistance additives. Properties of the novel composite materials were characterized by Atomic Force microscopy （AFM）, thermal gravimetric Analysis （TGA） and Ultraviolet Spectroscopy. AFM had showed the sizes and distributions of TMS particles in the nanocomposite. Ultraviolet Spectroscopy for the nanocomposites showed a large absorption in UV band. TGA showed the decomposition temperature was increased over ten degrees with 0.5% wt TMS for this nanocomposite compared with pure PSA.展开更多
Polypyrrole‐modified graphitic carbon nitride composites(PPy/g‐C3N4)are fabricated using an in‐situ polymerization method to improve the visible light photocatalytic activity of g‐C3N4.The PPy/g‐C3N4 is applied t...Polypyrrole‐modified graphitic carbon nitride composites(PPy/g‐C3N4)are fabricated using an in‐situ polymerization method to improve the visible light photocatalytic activity of g‐C3N4.The PPy/g‐C3N4 is applied to the photocatalytic degradation of methylene blue(MB)under visible light irradiation.Various characterization techniques are employed to investigate the relationship between the structural properties and photoactivities of the as‐prepared composites.Results show that the specific surface area of the PPy/g‐C3N4 composites increases upon assembly of the amorphous PPy nanoparticles on the g‐C3N4 surface.Owing to the strong conductivity,the PPy can be used as a transition channel for electrons to move onto the g‐C3N4 surface,thus inhibiting the recombination of photogenerated carriers of g‐C3N4 and improving the photocatalytic performance.The elevated light adsorption of PPy/g‐C3N4 composites is attributed to the strong absorption coefficient of PPy.The composite containing 0.75 wt%PPy exhibits a photocatalytic efficiency that is 3 times higher than that of g‐C3N4 in 2 h.Moreover,the degradation kinetics follow a pseudo‐first‐order model.A detailed photocatalytic mechanism is proposed with·OH and·O2-radicals as the main reactive species.The present work provides new insights into the mechanistic understanding of PPy in PPy/g‐C3N4 composites for environmental applications.展开更多
Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylaceta...Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylacetamide(DMAc). Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA and mechanical property was characterized by DXLL-1000 electromechanical material testing machine. The results showed that the breaking strength of the film containing 0.5% ZnO was great enhanced. The average size of ZnO particles was below 100 nm. The introduction of ZnO as nano filler in PSA react as UV shield effect and make the composite mechanical property improved.展开更多
Bi 0.5 Sb 1.5 Te 3/polyaniline composites were prepared by mechanical blending and in situ polymerization, and their transport properties were measured. It was found that for the composites with 1%, 3%, 5% and 7% poly...Bi 0.5 Sb 1.5 Te 3/polyaniline composites were prepared by mechanical blending and in situ polymerization, and their transport properties were measured. It was found that for the composites with 1%, 3%, 5% and 7% polyaniline (mass fraction) respectively, which were prepared by mechanical blending, the power factors decrease by about 30%, 50%, 55% and 65% compared with the Bi 0.5 Sb 1.5 Te 3 samples, which is mainly due to the remarkable decreases of the electrical conductivity. The electrical conductivity and power factor of the composites samples with 7% polyaniline prepared by in situ polymerization are higher by about 65% and 60%, respectively, than that of the corresponding samples prepared by mechanical blending.展开更多
The morphology of PE in the in-situ CB/PE composites prepared from in-situ polymerization via a catalyst-supported approach was studied by DSC. It is found that both the melting peak temperature and crystallinity of t...The morphology of PE in the in-situ CB/PE composites prepared from in-situ polymerization via a catalyst-supported approach was studied by DSC. It is found that both the melting peak temperature and crystallinity of the PE shelldecrease as filler level increases. The unexpected phenomena are ascribed to the strong interaction between PE and CB andthe very high specific area of CB. It is suggested that the lamellar thickness should be well correlated to the PE shell thickness. A two-layer PE model is successfully used to explain the experiment results.展开更多
The dispersion of functional nanometer materials in polyolefin/clay nanocomposites is a key factor to determine the performances of mate-rials[1].In this research,the sepiolite with high specific surface area and good...The dispersion of functional nanometer materials in polyolefin/clay nanocomposites is a key factor to determine the performances of mate-rials[1].In this research,the sepiolite with high specific surface area and good adsorption was introduced into the molybdenum-based butadiene polymerization system.Sepiolite-supporting MoCl5(Mo)function as the main catalysts,together with the alkyl aluminum(Al)substituted by m-cresol to form the butadiene coordination polymerization catalyst system to prepare high vinyl polybutadiene(HVPB)/sepiolite(Sep)nanocomposite.展开更多
High-energy lithium-sulfur(Li-S)batteries are anticipated to be pivotal in next-generation energy storage systems.However,their practical implementation is severely hindered by the shuttling of polysulfides between th...High-energy lithium-sulfur(Li-S)batteries are anticipated to be pivotal in next-generation energy storage systems.However,their practical implementation is severely hindered by the shuttling of polysulfides between the sulfur cathode and the lithium metal anode,as well as the safety hazards introduced using liquid electrolytes.To address these challenges,we apply molybdenum disulfide(MoS_(2))interlayer onto a polypropylene(PP)separator via electrostatic spraying,leveraging the Lewis acidity of MoS_(2) to initiate the ringopening polymerization of 1,3-dioxolane.This process effortlessly converts a commercial liquid electrolyte into a gel polymer electrolyte(GPE)before cycling,enhancing battery safety and effectively protecting lithium anodes.Furthermore,the MoS_(2) interlayer serves as a critical component in capturing lithium polysulfides during cycling.The GPE demonstrates exceptional performance characteristics:it maintains an ionic conductivity of 7.2×10^(−4) S cm^(−1) at 30℃,extends an electrochemical window up to 4.7 V,and achieves a high lithiumion transference number of 0.7.Moreover,the MoS_(2)/PP composite separator with the GPE remains stable even at temperatures as high as 200℃.Consequently,Li-S batteries equipped with GPE display excellent cycle stability,with a capacity retention of 613 mAh g^(−1) after 500 cycles at 0.5 C and achieve a high coulombic efficiency of 98.5%.This research offers an effective approach to developing high-performance and safe Li-S batteries.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effectiv...Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.展开更多
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford prod...Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford products with fixed sequences and compositions.Herein,we report the triethylborane/1,8-diazabicyclo[5.4.0]undec-7-ene(Et_3B/DBU)pair-mediated four-component switchable polymerization of propylene oxide(PO),CO_(2),phthalic anhydride(PA),and racemic lactide(rac-LA),which enables the on-demand synthesis of four different block copolymers,i.e.,poly(propylene phthalate)-b-polylactide(PPE-b-PLA),PPE-b-PLA-b-poly(propylene carbonate)(PPC),PPE-b-PPC-b-PLA,and PPE-b-PPCb-poly(propylene oxide)(PPO),through rationally modulating the Lewis pair(LP)ratio.Core to this protocol is that increasing the loading of Et_(3)B accelerates the ring-opening of PO while impeding the reactivity of rac-LA,thus allowing for fine-tuning of the thermodynamic and kinetic of the switchable polymerization.Therefore,the four polymerization cycles involving PO/PA ring-opening copolymerization(ROCOP),PO/CO_(2) ROCOP,rac-LA ring-opening polymerization(ROP),and PO ROP can be connected and discriminated in precisely programmed manners.展开更多
In-situ polymerized solid-state lithium metal batteries have garnered significant attention due to their conformal interface contact and continuous pathways for lithium ion(Li^(+))conduction.However,their electrochemi...In-situ polymerized solid-state lithium metal batteries have garnered significant attention due to their conformal interface contact and continuous pathways for lithium ion(Li^(+))conduction.However,their electrochemical performance is often hindered by slow Li^(+)transport within high-area-loading cathodes.This study presents an in-situ poly(ε-caprolactone)electrolyte with gradient molar mass(iGPCE)through lithium metal anode(LMA)-induced anionic ring-opening polymerization.Our electrochemical and kinetic analyses reveal that the iGPCE,characterized by low molar mass(M),significantly enhances Li~+diffusion within high-area-loading cathodes and bulk electrolytes,thereby reducing concentration polarization and promoting uniform electrochemical reactions.Moreover,the high M region on LMA side acts as artificial solid electrolyte interphases,stabilizing the stripping and plating of lithium.Consequently,Li//LFP(20 mg cm^(-2))and Li//NCM622(7.4 mg cm^(-2))utilizing iGPCE exhibit stable charge/discharge behaviors.This study offers a fresh approach to accelerate Li~+diffusion kinetics of high-area-loading batteries and suggests broad applicability in other systems.展开更多
1 Introduction With the development of portable electric devices,polymer lithium ion batteries(PLiBs)have been widely used as the power sources because of their high energy density and safe property[1].P(AN-MMA)copoly...1 Introduction With the development of portable electric devices,polymer lithium ion batteries(PLiBs)have been widely used as the power sources because of their high energy density and safe property[1].P(AN-MMA)copolymer is a kind of cheap macromolecules easily dissolving in the polar solvents such as carbonate,it has been applied as gel polymer electrolyte in PLiBs.展开更多
基金financially sponsored by the State Key Research Development Program of China(Nos.2021YFB3800700 and 2021YFB3800703)the National Natural Science Foundation of China(Nos.52122306 and U21A2098)the Sichuan Province Science and Technology Program(No.2022NSFSC0382).
文摘Oxidative stress is a critical risk factor for various disease complications in patients with end-stage renal disease,which may be further aggravated during hemodialysis.Herein,we prepared a hemodialysis membrane by introducing poly(2-Acrylamide-2-methylpropanesulfonic acid-N-vinylpyrrolidone)(P(AMPS-VP))into the polyethersulfone(PES)membrane by simple in-situ polymerization and non-solvent phase sepa-ration(NIPS)method,followed by tannic acid(TA)coating construction through hydrogen bonding interaction,termed PES/P(AMPS-VP)-TA.The membrane can efficiently remove reactive nitrogen radicals(RNS)(DPPH•,89.96%;ABTS•+,90.49%)and reactive oxygen species(ROS)(O_(2)•^(−),90.45%),and has a very sta-ble antioxidant property.Meanwhile,the membrane does not cause hemolysis and coagulation,and has superior blood compatibility required by hemodialysis membrane.In addition,the dialysis performance of the membrane is improved compared with unmodified PES,which is beneficial for practical hemodialysis applications.This work provides a reference for industrial preparation of hemodialysis membranes,which is expected to be applied to reduce oxidative stress in hemodialysis patients.
基金Projects(21107032,51073072)supported by the National Natural Science Foundation of ChinaProjects(Y406469,Y4110555,Y4100745)supported by Natural Science Foundation of Zhejiang Province,ChinaProjects(2011AY1048-5,2011AY1030)supported by the Science Foundation of Jiaxing Science and Technology Bureau,China
文摘Biodegradable poly （D,L-lactide） （PLA）/carboxyl-functionalized multi-walled carbon nanotubes （c-MWCNTs） composites were achieved via in-situ polymerization. These as-prepared composite materials were characterized with FT-IR, XRD, TG, DSC, SEM, and high insulation resistance meter. The results demonstrate that the multi-walled carbon nanotube was carboxyl functionalized, which improved the collection between c-MWCNTs and PLA, and further realized the graft copolymerization of c-MWCNTs and PLA. There is a higher glass transition temperature and a lower pyrolysis temperature of PLA/c-MWCNTs composites than pure PLA. The c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLA matrix, and an even coating of PLA on the surface of c-MWCNTs was obtained, which increased the interfacial interaction. High insulation resistance analysis showed that the addition of c-MWCNTs increased the electric conductivity, and c-MWCNTs performed against the large dielectric coefficient and electrostatic state of PLA. These results demonstrated that c-MWCNTs modified PLA composites were beneficial for potential application in the development of heat-resisting and conductivity plastic engineering.
基金supported by the Department of Science and Technology of Zhuhai City(No.ZH22017001200059PWC)the Department of Science and Technology of Guangdong Province,China(No.2019A050510043)。
文摘Gel polymer electrolytes(GPEs) are promising alternatives to liquid electrolytes applied in high-energydensity batteries.Here superior SiO_(2) nanofiber composite gel polymer electrolytes(SNCGPEs) are developed via in-situ ionic ring-opening polymerization of 1,3-dioxolane(DOL) monomers in SiO_(2) nanofiber membrane(PDOL-SiO_(2)) for lithium metal batteries.The oxygen atoms of PDOL together with Si-O of SiO_(2) construct a more efficient channel for Li^(+) migration.Consequently,the lithium ion transference number(t_(Li^(+)) and ionic conductivity(σ) at 30℃ of PDOL-SiO_(2) are 0.80 and 1.68×10^(-4)S/cm separately.PDOL-SiO_(2) manifests the electrochemical decomposition potentials of 4.90 V.At 0.5 mA/cm^(2),Li|PDOL-SiO_(2) |Li cell shows a steady cycling performance for nearly 1400 h.LFP|PDOL-SiO_(2) |Li battery can steadily cycle at 0.5 C with a capacity retention rate of 89% after 200 cycles.While cycling at 2 C,the capacity retention rate can maintain at 78% after 300 cycles.This contribution provides a innovative strategy for accelerating Li^(+)transportation via designing PDOL molecular chains throughout the SiO_(2) nanofiber framework,which is crucial for high-energy-density LMBs.
文摘Nano zinc oxide （ZnO） is a very useful and important material in many industrial and biological applications. In the present work, ZnO was synthesized by post thermal degradation of the precursor ＂zinc acetate di-hydrate＂ templated in crosslinked polyacrylic acid （PAA）. The crosslinked PAA template was prepared through an in-situ polymerization process adopted in presence of ammonium per sulphate, as an initiator, and N, Nt- methylene bis-acrylamide as the crosslinker. Variation of preparation parameters and their impact on the oxide stoichiometry, crystal structure, crystallite size and surface texture of the oxide were investigated. Energy dispersive X-ray technique （EDX）, X-ray diffraction （XRD） and scanning electron microscopy （SEM） were convincingly used to reveal the oxide structural features and characteristics. The performed bioassay tests indicated the efficacy of this method of preparation to produce nano ZnO with novel insecticidal activity against the greater wax moth, Galleria rnellonella.
基金Supported by the National Natural Science Foundation of China（21176070） the National High Technology Research and Development Program of China（2012AA040211）+2 种基金 the Joint Research Project of Yangtze River Delta（12195810900） the Specialized Research Fund for the Doctoral Program of Higher Education（20120074120019） the Fundamental Research Funds for the Central Universities
文摘Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support and keep cells.An in-situ polymerization-modification process with esterification and polycondensation stages was performed in a 2 L batch stirred reactor using pyromellitic dianhydride(PMDA)or pentaerythritol(PENTA)as modifying monomers to obtain PETs with high melt strength.The influence of amounts of modifying monomers on the properties of modified PET was investigated.It was found that the selected modifying monomers could effectively introduce branched structures into the modified PETs and improve their melt strength.With increasing the amount of the modifying monomer,the melt strength of the modified PET increased.But when the amount of PENTA reached 0.35%or PMDA reached 0.9%,crosslinking phenomenon was observed in the modified PET.Supercritical carbon dioxide(ScCO2)was employed as physical foaming agent to evaluate the foaming ability of modified PETs.The modified PETs had good foaming properties at 14 MPa of CO2pressure with foaming temperature ranging from 265°C to 280°C.SEM micrographs demonstrated that both modified PET foams had homogeneous cellular structures,with cell diameter ranging from 35μm to 49μm for PENTA modified PETs and38μm to 57μm for PMDA modified ones.Correspondingly,the cell density had a range of 3.5×107cells·cm 3to 7×106cells·cm 3for the former and 2.8×107cells·cm 3to 5.8×106cells·cm 3for the latter.
文摘Conductive polymer composites based on crystalline polymer matrix have been prepared by using an in-situ polymerization process of pyrrole in amorphous poly （ethylene terephthalate） （PET） film. The DSC and WAXD measurement and SEM observation show that liquid-induced crystallization of PET matrix has occurred during the preparation of composite films. Depending upon the equilibrium degree of swelling and crystallinity, the limited depth of penetration of pyrrole molecules results in a skin-core structure of the composite film. The skin layer containing charge transfer intercalated polypyrrole has a surface resistance of 3.5×10;Ω. Rigid and heat-resistant polypyrrole molecules formed in PET film increase the tensile modulus and, especially, the rigidity of PET at elevated temperatures. However, they decrease the tensile strength and elongation at break, and impair the thermal ductility of PET.
文摘Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).
文摘A kind of new nano composite with ultraviolet （UV） ray resistance and high temperature stability was prepared by in-situ polymerization in low temperature. Polysulfonamide （PSA） was synthesized with 4, 4＇-diaminodiphenyl sulfone （DDS） and terephthaloyl chloride （TPC） in the common solvent N, N-Dimethyl- -acetamide （DMAc）. Nano filler is a certain nano titanium oxide modified by silicon oxide （TMS）, which plays the role of UV resistance additives. Properties of the novel composite materials were characterized by Atomic Force microscopy （AFM）, thermal gravimetric Analysis （TGA） and Ultraviolet Spectroscopy. AFM had showed the sizes and distributions of TMS particles in the nanocomposite. Ultraviolet Spectroscopy for the nanocomposites showed a large absorption in UV band. TGA showed the decomposition temperature was increased over ten degrees with 0.5% wt TMS for this nanocomposite compared with pure PSA.
文摘Polypyrrole‐modified graphitic carbon nitride composites(PPy/g‐C3N4)are fabricated using an in‐situ polymerization method to improve the visible light photocatalytic activity of g‐C3N4.The PPy/g‐C3N4 is applied to the photocatalytic degradation of methylene blue(MB)under visible light irradiation.Various characterization techniques are employed to investigate the relationship between the structural properties and photoactivities of the as‐prepared composites.Results show that the specific surface area of the PPy/g‐C3N4 composites increases upon assembly of the amorphous PPy nanoparticles on the g‐C3N4 surface.Owing to the strong conductivity,the PPy can be used as a transition channel for electrons to move onto the g‐C3N4 surface,thus inhibiting the recombination of photogenerated carriers of g‐C3N4 and improving the photocatalytic performance.The elevated light adsorption of PPy/g‐C3N4 composites is attributed to the strong absorption coefficient of PPy.The composite containing 0.75 wt%PPy exhibits a photocatalytic efficiency that is 3 times higher than that of g‐C3N4 in 2 h.Moreover,the degradation kinetics follow a pseudo‐first‐order model.A detailed photocatalytic mechanism is proposed with·OH and·O2-radicals as the main reactive species.The present work provides new insights into the mechanistic understanding of PPy in PPy/g‐C3N4 composites for environmental applications.
基金Education Commission of Shanghai (No04AB19)Science and Technology Commission of Shanghai Municipal Government(Nano Founds No 0452NM051)
文摘Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylacetamide(DMAc). Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA and mechanical property was characterized by DXLL-1000 electromechanical material testing machine. The results showed that the breaking strength of the film containing 0.5% ZnO was great enhanced. The average size of ZnO particles was below 100 nm. The introduction of ZnO as nano filler in PSA react as UV shield effect and make the composite mechanical property improved.
文摘Bi 0.5 Sb 1.5 Te 3/polyaniline composites were prepared by mechanical blending and in situ polymerization, and their transport properties were measured. It was found that for the composites with 1%, 3%, 5% and 7% polyaniline (mass fraction) respectively, which were prepared by mechanical blending, the power factors decrease by about 30%, 50%, 55% and 65% compared with the Bi 0.5 Sb 1.5 Te 3 samples, which is mainly due to the remarkable decreases of the electrical conductivity. The electrical conductivity and power factor of the composites samples with 7% polyaniline prepared by in situ polymerization are higher by about 65% and 60%, respectively, than that of the corresponding samples prepared by mechanical blending.
文摘The morphology of PE in the in-situ CB/PE composites prepared from in-situ polymerization via a catalyst-supported approach was studied by DSC. It is found that both the melting peak temperature and crystallinity of the PE shelldecrease as filler level increases. The unexpected phenomena are ascribed to the strong interaction between PE and CB andthe very high specific area of CB. It is suggested that the lamellar thickness should be well correlated to the PE shell thickness. A two-layer PE model is successfully used to explain the experiment results.
基金Supported by Shandong Provincial Natural Science Foundation(ZR 2020 ME 059).
文摘The dispersion of functional nanometer materials in polyolefin/clay nanocomposites is a key factor to determine the performances of mate-rials[1].In this research,the sepiolite with high specific surface area and good adsorption was introduced into the molybdenum-based butadiene polymerization system.Sepiolite-supporting MoCl5(Mo)function as the main catalysts,together with the alkyl aluminum(Al)substituted by m-cresol to form the butadiene coordination polymerization catalyst system to prepare high vinyl polybutadiene(HVPB)/sepiolite(Sep)nanocomposite.
基金supported by the National Natural Science Foundation of China(52262036)the Jiangxi Provincial Natural Science Foundation(20242BAB25229)the Science and Technology Project of Shenzhen(JCYJ20210324094206019)。
文摘High-energy lithium-sulfur(Li-S)batteries are anticipated to be pivotal in next-generation energy storage systems.However,their practical implementation is severely hindered by the shuttling of polysulfides between the sulfur cathode and the lithium metal anode,as well as the safety hazards introduced using liquid electrolytes.To address these challenges,we apply molybdenum disulfide(MoS_(2))interlayer onto a polypropylene(PP)separator via electrostatic spraying,leveraging the Lewis acidity of MoS_(2) to initiate the ringopening polymerization of 1,3-dioxolane.This process effortlessly converts a commercial liquid electrolyte into a gel polymer electrolyte(GPE)before cycling,enhancing battery safety and effectively protecting lithium anodes.Furthermore,the MoS_(2) interlayer serves as a critical component in capturing lithium polysulfides during cycling.The GPE demonstrates exceptional performance characteristics:it maintains an ionic conductivity of 7.2×10^(−4) S cm^(−1) at 30℃,extends an electrochemical window up to 4.7 V,and achieves a high lithiumion transference number of 0.7.Moreover,the MoS_(2)/PP composite separator with the GPE remains stable even at temperatures as high as 200℃.Consequently,Li-S batteries equipped with GPE display excellent cycle stability,with a capacity retention of 613 mAh g^(−1) after 500 cycles at 0.5 C and achieve a high coulombic efficiency of 98.5%.This research offers an effective approach to developing high-performance and safe Li-S batteries.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
基金financially supported by the National Natural Science Foundation of China(No.52473338)the National Natural Science Foundation of China(Nos.52173004 and 51873055)+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)Advanced Materials-National Science and Technology Major Project(No.2025ZD0614000)Hebei Natural Science Foundation(No.E2022202015)Anhui Province Science and Technology Innovation Tackling Key Project(No.202423i08050025)。
文摘Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金financially supported by National Key R&D Program Young Scientists Project(No.2023YFC3903100)the National Natural Science Foundation of China(No.22322503)analytical and testing assistance from the Analysis and Testing Center of HUST。
文摘Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford products with fixed sequences and compositions.Herein,we report the triethylborane/1,8-diazabicyclo[5.4.0]undec-7-ene(Et_3B/DBU)pair-mediated four-component switchable polymerization of propylene oxide(PO),CO_(2),phthalic anhydride(PA),and racemic lactide(rac-LA),which enables the on-demand synthesis of four different block copolymers,i.e.,poly(propylene phthalate)-b-polylactide(PPE-b-PLA),PPE-b-PLA-b-poly(propylene carbonate)(PPC),PPE-b-PPC-b-PLA,and PPE-b-PPCb-poly(propylene oxide)(PPO),through rationally modulating the Lewis pair(LP)ratio.Core to this protocol is that increasing the loading of Et_(3)B accelerates the ring-opening of PO while impeding the reactivity of rac-LA,thus allowing for fine-tuning of the thermodynamic and kinetic of the switchable polymerization.Therefore,the four polymerization cycles involving PO/PA ring-opening copolymerization(ROCOP),PO/CO_(2) ROCOP,rac-LA ring-opening polymerization(ROP),and PO ROP can be connected and discriminated in precisely programmed manners.
基金supported by the Key Scientific Research Project of Colleges and Universities in Henan(24A480006 and 24A530005)the Natural Science Foundation of Henan Province(242300420337)。
文摘In-situ polymerized solid-state lithium metal batteries have garnered significant attention due to their conformal interface contact and continuous pathways for lithium ion(Li^(+))conduction.However,their electrochemical performance is often hindered by slow Li^(+)transport within high-area-loading cathodes.This study presents an in-situ poly(ε-caprolactone)electrolyte with gradient molar mass(iGPCE)through lithium metal anode(LMA)-induced anionic ring-opening polymerization.Our electrochemical and kinetic analyses reveal that the iGPCE,characterized by low molar mass(M),significantly enhances Li~+diffusion within high-area-loading cathodes and bulk electrolytes,thereby reducing concentration polarization and promoting uniform electrochemical reactions.Moreover,the high M region on LMA side acts as artificial solid electrolyte interphases,stabilizing the stripping and plating of lithium.Consequently,Li//LFP(20 mg cm^(-2))and Li//NCM622(7.4 mg cm^(-2))utilizing iGPCE exhibit stable charge/discharge behaviors.This study offers a fresh approach to accelerate Li~+diffusion kinetics of high-area-loading batteries and suggests broad applicability in other systems.
文摘1 Introduction With the development of portable electric devices,polymer lithium ion batteries(PLiBs)have been widely used as the power sources because of their high energy density and safe property[1].P(AN-MMA)copolymer is a kind of cheap macromolecules easily dissolving in the polar solvents such as carbonate,it has been applied as gel polymer electrolyte in PLiBs.
