Poly(L-lactic acid)(PLLA)has been widely concerned because of its excellent biodegradability and biocompatibility.However,the poor crystallization ability of PLLA during the molding process not only leads to weak mech...Poly(L-lactic acid)(PLLA)has been widely concerned because of its excellent biodegradability and biocompatibility.However,the poor crystallization ability of PLLA during the molding process not only leads to weak mechanical properties but also reduces the processing efficiency,which limits the application of PLLA greatly.Enhancing crystallization ability of PLLA via introducing inorganic nanoparticles usually sacrifices biodegradability or transparency.Here,the microfine fibers with stereocomplex(SC)crystallites were incorporated into PLLA film to tailor the crystallization ability of PLLA as well as the mechanical properties.The results confirmed that the crystallization ability of PLLA matrix under different circumstances could be greatly enhanced by a few amounts of SC crystalline fibers,and synchronously enhanced tensile strength and ductility were also achieved,especially at relatively high temperature.Due to the relatively homogeneous dispersion of SC crystalline fibers and the similar refractive index between components,the PLLA-based film also exhibited high transparency,up to 85%-90%depending on the content of SC crystalline fibers.This work provides guidance for manufacturing transparent PLLA-based packaging materials with good crystallization capability and mechanical properties.展开更多
Poly(_(L)-lactide)(PLLA),a leading biodegradable polyester,has demonstrated potential as a sustainable alternative,owing to its excellent biodegradability and rigidity.However,their slow crystallization kinetics and p...Poly(_(L)-lactide)(PLLA),a leading biodegradable polyester,has demonstrated potential as a sustainable alternative,owing to its excellent biodegradability and rigidity.However,their slow crystallization kinetics and poor heat resistance limit their application scope.Recent advances have highlighted that the combination of extensional flow and thermal fields can achieve toughness–stiffness balance,high transparency,and good heat resistance.However,the effect of extensional flow on the post-non-isothermal crystallization of PLLA during heating and the resulting crystalline texture remains unclear.In this study,PLLA with a heterogeneous amorphous structure and oriented polymorph was prepared by extensional flow.The effect of heterogeneous amorphous structures on non-isothermal crystallization kinetics during the heating process was studied by thermal analysis,polarized optical microscopy,infrared spectroscopy,and ex situ/in situ X-ray characterization.These results clearly illustrate that extensional flow enhances the formation of oriented crystalline structures,accelerates non-isothermal crystallization,and modulates the polymorphic composition of PLLA.Moreover,an unexpected dual cold-crystallization behavior is identified in ordered PLLA samples upon extensional flow,which is from the extensional flow-induced heterogeneous amorphous phase into α' phase(low-temperature peak)and the pristine amorphous phase intoαphase(high-temperature peak).The extensional flow primarily promotes the formation of the more perfectαandα'phases,but has a negative effect on the final content ofαphase formed after cold crystallization andα'-to-αphase transformation.The findings of this work advance the understanding of PLLA non-isothermal crystallization after extensional flow and offer valuable guidance for high-performance PLLA upon heat treatment in practical processing.展开更多
Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport ...Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge‑discharge cycles.Electrochemical characterization under a three‑electrode system revealed exceptional rate capability:Mn@PN delivered an ultrahigh specific capacitance of 10318 F·g^(-1) at a low current density of 3 A·g^(-1) and retained 9415 F·g^(-1)(91.2%retention compared to the value at 3 A·g^(-1))even at an ultrahigh current density of 50 A·g^(-1).Moreover,the material exhibited 97.4%capacitance retention after 9000 cycles at 30 A·g^(-1),corresponding with a low capacitance decay rate of 0.003‰per cycle,significantly outperforming conventional conductive polymers like polyaniline(PANI).An asymmetric supercapacitor assembled with Mn@PN as the positive electrode(Mn@PN||AC)achieved an energy density of 328 Wh·kg^(-1) at 15 A·g^(-1) and retained 80.7%of its initial specific capacitance after 4000 cycles at 20 A·g^(-1).展开更多
Conductive polymers have recently drawn tremendous attention due to their promising applications in electronic and energy-related devices.While p-type conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(...Conductive polymers have recently drawn tremendous attention due to their promising applications in electronic and energy-related devices.While p-type conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)have achieved commercialization,the development of stable,high-performance n-type polymers has lagged.Recently,the discovery of n-type polymer poly(benzodifurandione)(PBFDO)has greatly promoted the development and application of n-type conductive polymers.However,the synthesis process involves cumbersome post-processing,which greatly increases the cost and difficulty of mass production.Herein,a novel synthesis method for PBFDO has been developed,which was promoted by the combination of solvent dimethyl sulfoxide(DMSO)and acetic anhydride(Ac_(2)O).This method exploits the oxidative capability of DMSO,activated by Ac_(2)O,which can promote the keto-enol tautomerism of 3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione(BFDO)and induce the rapid polymerization.The resulting PBFDO ink exhibits a high electronic conductivity of more than 2000 S cm^(-1)and excellent ambient stability.Significantly,the additives and by-products remain in a liquid state during the polymerization process and possess low boiling points,allowing for the production of pure PBFDO films through straightforward heating and drying.Furthermore,this approach holds considerable promise for in situ polymerization,as functional conductive films can be prepared by merely combining the monomers with the DMSO/Ac_(2)O mixture and applying heat.This efficient,purification-free strategy represents a significant step toward the industrial application of the highperformance n-type conductive polymer PBFDO.展开更多
In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still face...In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.展开更多
Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this stu...Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.展开更多
Poly(phenylene oxide)(PPO)exhibits excellent dielectric properties,making it an ideal substrate for high-frequency,high-speed copper-clad laminates.The phenolic hydroxyl group at the end of PPO plays a key role in its...Poly(phenylene oxide)(PPO)exhibits excellent dielectric properties,making it an ideal substrate for high-frequency,high-speed copper-clad laminates.The phenolic hydroxyl group at the end of PPO plays a key role in its reactivity.Accurately quantifying the phenolic hydroxyl content in PPO is essential but challenging.In this study,we proposed a method for measuring the phenolic hydroxyl content of PPO using differential UV absorption spectroscopy.In alkaline solutions,the phenolic hydroxyl in PPO completely ionizes to form phenoxide ions,leading to a significant increase in UV absorbance at approximately 250 and 300 nm.Notably,the differential UV absorbance at approximately 300 nm was directly proportional to the phenolic hydroxyl concentration.Using 2,6-dimethylphenol as a standard,a calibration curve was established to relate the phenolic hydroxyl concentration to differential UV absorbance at approximately 300 nm,providing a precise and straightforward method for phenolic hydroxyl quantification in PPO with distinct advantages over conventional techniques.展开更多
Although poly(urethane-urea)elastomers(PUEs)possess excellent mechanical properties and durability,their inherent flammability and inability to self-repair after damage significantly limits their applications in high-...Although poly(urethane-urea)elastomers(PUEs)possess excellent mechanical properties and durability,their inherent flammability and inability to self-repair after damage significantly limits their applications in high-end fields.To address this challenge,this study employs a supramolecular chemistry approach by simultaneously incorporating multiple hydrogen bonds as dynamic cross-linking points and a phosphorus-nitrogen synergistic flame-retardant structure into the poly(urethane-urea)network.The multiple hydrogen bonds endow the material with efficient intrinsic self-healing capability,while the phosphorus-nitrogen flame retardant ensures outstanding thermal stability and flame resistance,leading to the successful synthesis of a high-performance multifunctional poly(urethane-urea)elastomer.Experimental results demonstrated that when the content of the flame retardant diethyl(2-((2-aminoethyl)amino)ethyl)phosphoramidate(DEPTA)was 10 wt%,the resulting PUE/10%DEPTA achieved a V-0 rating in the vertical burning test,with a limiting oxygen index(LOI)of 30%.Concurrently,the elastomer maintained good toughness,exhibiting a tensile strength of 27.3 MPa,an elongation at break of 601%,and a self-healing efficiency of up to 94.46%.This breakthrough shows significant promise for advanced engineering applications that demand fire safety,structural durability,and extended service life through self-repair.展开更多
This study uses all-atom molecular dynamics simulations to investigate the dislocation propagation, stress transmission, and mechanical properties in poly(p-phenylene terephthalamide) fibers under uniaxial tension. Th...This study uses all-atom molecular dynamics simulations to investigate the dislocation propagation, stress transmission, and mechanical properties in poly(p-phenylene terephthalamide) fibers under uniaxial tension. The results indicate that the dislocation propagates and the stress transfers not only along the fiber axis but also between adjacent molecular chains through hydrogen bonds, demonstrating their influence on the yield behavior. As the degree of polymerization increases, breakage of covalent bonds and interchain slippage contribute to the yield of fibers together. This work provides theoretical guidance for the design and manufacturing of high-performance fibers.展开更多
Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardan...Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.展开更多
Poly(ester amide)s(PEAs)represent promising biomaterials because of their well-balanced mechanical properties,biodegradability,and biocompatibility.However,practical applications of PEAs are still limited by challenge...Poly(ester amide)s(PEAs)represent promising biomaterials because of their well-balanced mechanical properties,biodegradability,and biocompatibility.However,practical applications of PEAs are still limited by challenges in functional versatility and environmental adaptability.Here,we present the first synthesis of periodic selenium-incorporated PEAs(Se-PEAs)via a rapid,catalyst-free selenol-yne click polymerization process.By harnessing the versatility of selenium,we achieved precise modulation of material properties.The resulting Se-PEAs demonstrated tunable mechanical behavior,spanning rigid plastics to elastomers,alongside exceptional thermal stability and high optical clarity.Programmable degradation profiles ensure long-term stability in physiological environments while facilitating rapid oxidative degradation at the end of the lifecycle.Surface selenoniumization further conferred robust antibacterial efficacy without compromising mechanical integrity.This multifunctionality positions Se-PEAs as transformative materials for biomedical implants,sustainable packaging,and high-refractiveindex optics.Our work advanced functional polymer design and underscored the potential of selenium chemistry in addressing global challenges in terms of plastic waste and ecological sustainability.展开更多
Chemical upcycling of end-of-life poly(lactide) plastics to lactide,lactate ester and new poly(lactide)has been achieved by using magnesium bis[bis(trimethylsilyl)amide][Mg(HMDS)_(2)]as promoter.Mg(HMDS)2 showed high ...Chemical upcycling of end-of-life poly(lactide) plastics to lactide,lactate ester and new poly(lactide)has been achieved by using magnesium bis[bis(trimethylsilyl)amide][Mg(HMDS)_(2)]as promoter.Mg(HMDS)2 showed high efficiency in L-lactide polymerization and poly(lactide) depolymerization.Mg(HMDS)_(2)/Ph_(2) CHOH catalytic system displayed high ring-opening selectivity and the characteristic of immortal polymerization.Taking advantage of transesterification,depolymerizations of end-oflife poly(lactide) plastics to lactate ester (polymer to value-added chemicals) and lactide (polymer to monomer) were achieved with high yields.Besides,a new“depolymerization-repolymerization”strategy was proposed to directly transform poly(lactide) into new poly(lactide).This work provides a theoretical basis for the design of polymerization and depolymerization catalysts and promotes the development of degradable polymers.展开更多
The effects of the plasticizer poly(ethylene glycol)(PEG)on crystallization properties of equimolar poly(L-lactide)(PLLA)/poly(D-lactide)(PDLA)blends were investigated.Forma-tion of the stereocomplex-type poly(lactide...The effects of the plasticizer poly(ethylene glycol)(PEG)on crystallization properties of equimolar poly(L-lactide)(PLLA)/poly(D-lactide)(PDLA)blends were investigated.Forma-tion of the stereocomplex-type poly(lactide acid)(sc-PLA)crystallites was confirmed by Wide-angle X-ray diffraction(WAXD)and differential scanning calorimetry(DSC)analyses.Sc-PLA crystallites without any homochiral poly(lactide acid)(hc-PLA)formed,as the result of the incorporation of the plasticizer PEG(more than or equal to 10%(wt))at a processing temperature(240℃).More-over,when the Mw of PEG reached 1000 g·mol^(-1),the crystal-lizability of stereocomplex crystallites was the best.Isothermal crystallization kinetics further revealed that PEG could accelerate the crystallization rate of sc-PLA,with the optimum crystallization kinetic parameters being obtained at 10%(wt)PEG.Several crys-tallization kinetics equations were applied to describe the effect of PEG on the crystallization behavior of sc-PLA.The influence of PEG on the spherocrystal morphologies of sc-PLA was also inves-tigated using polarized optical microscopy.展开更多
Structure and properties of bioabsorbable polyglycolide (PGA) and poly(glycolide-co-lactide) (PGA-co-PLA)fibers were investigated during several industrial processing stages and in vitro degradation by means of wide-a...Structure and properties of bioabsorbable polyglycolide (PGA) and poly(glycolide-co-lactide) (PGA-co-PLA)fibers were investigated during several industrial processing stages and in vitro degradation by means of wide-angle X-raydiffraction (WAXD), dynamic mechanical analysis (DMA) and mechanical property tests. In the orientation stage, the PGAfibers were found to have higher degrees of crystallinity than corresponding PGA-co-PLA samples produced under similarconditions. In the hot-stretching and post-annealing stages, after fibers were braided, PGA samples were found to gain morecrystallinity and higher T_g than PGA-co-PLA samples. The higher crystallinity in PGA fibers resulted in a slower rate ofdegradation. DMA results showed that a great deal of internal stress that was built during orientation and hot-stretchingstages was released in the post-annealing stage for a1l PGA and PGA-co-PLA samples. During earlier stages of in vitrodegradation, both PGA and PGA-co-PLA samples exhibited the typical cleavage-induced crystallization mechanism. Theheat shrinkage in the glass transition area was found to disappear after 6-8 days of degradation for all PGA and PGA-co-PLAsamples, indicating the amorphous portions of the polymers lost orientation after a short period in the buffer solution, mostlikely due to relaxation of the cleaved chains.展开更多
Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolym...Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolymers and electrospun ultrafine fibers were investigated and compared with those of PLLA and PA4 blends. PLLA and PA4 were found incompatible and formed individual crystalline regions, along with reciprocal inhibition in crystallization. Electrospun fibers were highly hydrophobic, even if hydrophilic PA4 was the rich component. The crystallinity of either PLLA or PA4 decreased after electrospinning and PLLA-rich as-spun fibers were almost amorphous. Immersion tests proved that fibers of block copolymers were relatively homogeneous with micro-phase separation between PLLA and PA4. The fibrous structures of copolymers were different from those of the fibers electrospun from blends, for which sheath-core structure induced by macro-phase separation between homopolymers of PLLA and PA4 was confirmed by TEM, EDS, and XPS.展开更多
Polyester-based biodegradable polyurethane （PU） with different hard segment ratios was selected to modify the impact toughness of poly（L-lactide） （PLLA）. The influence of blending composition and hard segment ra...Polyester-based biodegradable polyurethane （PU） with different hard segment ratios was selected to modify the impact toughness of poly（L-lactide） （PLLA）. The influence of blending composition and hard segment ratio of PU on the phase morphology, crystallization behavior and mechanical properties of PLLA/PU blends has been investigated systematically. The results showed that the PU particles were uniformly dispersed in PLLA matrix at a scale from sub- microns to several microns. The glass transition temperature of PU within these blends decreased compared to that of neat PU, but rose slightly with its content and hard segment ratio. The presence of PU retarded the crystallization ability of PLLA, whereas enhanced its elongation at break and impact resistance effectively. As the PU content reaches up to 30 wt%, the phenomenon of brittle-ductile transition occurred, resulting in a rougher fracture surface with the formation of fibril-like structure. Moreover, under the same concentrations, the elongation at break and impact strength of PLLA blends decreased slightly with the increase of hard segment ratio of PU.展开更多
In the present investigation, the novel copper Schiff base complex was synthesized and its catalytic activity was evaluated for the ring-opening polymerization （ROP） of lactide and block polymerization of poly（lact...In the present investigation, the novel copper Schiff base complex was synthesized and its catalytic activity was evaluated for the ring-opening polymerization （ROP） of lactide and block polymerization of poly（lactide） with po/y（ethylene glycol）methyl ether,展开更多
Poly（propylene carbonate） （PPC） was blended with polylactide （PLA） and poly（1,2-propylene glycol adipate） （PPA） using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film tech...Poly（propylene carbonate） （PPC） was blended with polylactide （PLA） and poly（1,2-propylene glycol adipate） （PPA） using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film technique. DMA results showed that PPA could act as a plasticizer and improve the miscibility between PPC and PLA. Crystal morphology displayed that blending PLA with the amorphous PPC led to a decrease of the spherulite size of PLA. The results of mechanical tests indicated that PPC-rich films showed high elongation at break and PLA-rich films showed high tear strength and good optical properties. The content of PPC and PLA significantly affected the physical properties of the films. With increasing PPC content, the melt strengths of the PPC/PLA/PPA films were enhanced. These findings contributed to the biodegradable materials application for designing and manufacturing polymer packaging.展开更多
Poly (L-lactide) was prepared by bulk polymerization ofL-lactide at 140°C in the presence of stannous octoate. The polymer products were characterized by number average molecular weight Mn, weight average molecul...Poly (L-lactide) was prepared by bulk polymerization ofL-lactide at 140°C in the presence of stannous octoate. The polymer products were characterized by number average molecular weight Mn, weight average molecular weight Mw and molecular weight distribution MWD (M w/M n) respectively. The results showed that stannous octoate was a high effective catalyst, and coordinated insertion mechanism of the reaction was proposed.展开更多
Polylactide （PLA） was successfully toughened by blending with bio-based poly（ester）urethane （TPU） elastomers which contained bio-based polyester soft segments synthesized from biomass diols and diacids. The misc...Polylactide （PLA） was successfully toughened by blending with bio-based poly（ester）urethane （TPU） elastomers which contained bio-based polyester soft segments synthesized from biomass diols and diacids. The miscibility, mechanical properties, phase morphology and toughening mechanism of the blend were investigated. Both DSC and DMTA results manifested that the addition of TPU elastomer not only accelerated the crystallization rate, but also increased the final degree of crystallinity, which proved that TPU has limited miscibility with PLA and has functioned as a plasticizer. All the blend samples showed distinct phase separation phenomenon with sea-island structure under SEM observation and the rubber particle size in the PLA matrix increased with the increased contents of TPU. The mechanical property variation of PLA/TPU blends could be quantitatively explained by Wu＇s model. With the variation of TPU, a brittle-ductile transition has been observed for the TPU/PLA blends. When these blends were under tensile stress conditions, the TPU particles could be debonded from the PLA matrix and the blends showed a high ability to induce large area plastic deformation before break, which was important for the dissipation of the breaking energy. Such mechanism was demonstrated by tensile tests and scanning electron microcopy （SEM） observations.展开更多
基金supported by the Sichuan Science and Technology Program(No.2023ZHCG0050)the China Postdoctoral Science Foundation(No.2023M742883)+2 种基金the Science and Technology Innovation Fund for Basic Scientific Research Operating Expenses of Central Universities(No.2682023CX002)the New Interdisciplinary Cultivation Fund of SWJTU(No.2682022KJ040)SEM characterizations were supported by the Analytical and Testing Center of Southwest Jiaotong University。
文摘Poly(L-lactic acid)(PLLA)has been widely concerned because of its excellent biodegradability and biocompatibility.However,the poor crystallization ability of PLLA during the molding process not only leads to weak mechanical properties but also reduces the processing efficiency,which limits the application of PLLA greatly.Enhancing crystallization ability of PLLA via introducing inorganic nanoparticles usually sacrifices biodegradability or transparency.Here,the microfine fibers with stereocomplex(SC)crystallites were incorporated into PLLA film to tailor the crystallization ability of PLLA as well as the mechanical properties.The results confirmed that the crystallization ability of PLLA matrix under different circumstances could be greatly enhanced by a few amounts of SC crystalline fibers,and synchronously enhanced tensile strength and ductility were also achieved,especially at relatively high temperature.Due to the relatively homogeneous dispersion of SC crystalline fibers and the similar refractive index between components,the PLLA-based film also exhibited high transparency,up to 85%-90%depending on the content of SC crystalline fibers.This work provides guidance for manufacturing transparent PLLA-based packaging materials with good crystallization capability and mechanical properties.
基金supported by the National Natural Science Foundation of China(Nos.U23A20583,52033005,U21A2090,and 52173040)Department of Science and Technology of Sichuan Province(No.2024NSFTD0003)。
文摘Poly(_(L)-lactide)(PLLA),a leading biodegradable polyester,has demonstrated potential as a sustainable alternative,owing to its excellent biodegradability and rigidity.However,their slow crystallization kinetics and poor heat resistance limit their application scope.Recent advances have highlighted that the combination of extensional flow and thermal fields can achieve toughness–stiffness balance,high transparency,and good heat resistance.However,the effect of extensional flow on the post-non-isothermal crystallization of PLLA during heating and the resulting crystalline texture remains unclear.In this study,PLLA with a heterogeneous amorphous structure and oriented polymorph was prepared by extensional flow.The effect of heterogeneous amorphous structures on non-isothermal crystallization kinetics during the heating process was studied by thermal analysis,polarized optical microscopy,infrared spectroscopy,and ex situ/in situ X-ray characterization.These results clearly illustrate that extensional flow enhances the formation of oriented crystalline structures,accelerates non-isothermal crystallization,and modulates the polymorphic composition of PLLA.Moreover,an unexpected dual cold-crystallization behavior is identified in ordered PLLA samples upon extensional flow,which is from the extensional flow-induced heterogeneous amorphous phase into α' phase(low-temperature peak)and the pristine amorphous phase intoαphase(high-temperature peak).The extensional flow primarily promotes the formation of the more perfectαandα'phases,but has a negative effect on the final content ofαphase formed after cold crystallization andα'-to-αphase transformation.The findings of this work advance the understanding of PLLA non-isothermal crystallization after extensional flow and offer valuable guidance for high-performance PLLA upon heat treatment in practical processing.
文摘Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge‑discharge cycles.Electrochemical characterization under a three‑electrode system revealed exceptional rate capability:Mn@PN delivered an ultrahigh specific capacitance of 10318 F·g^(-1) at a low current density of 3 A·g^(-1) and retained 9415 F·g^(-1)(91.2%retention compared to the value at 3 A·g^(-1))even at an ultrahigh current density of 50 A·g^(-1).Moreover,the material exhibited 97.4%capacitance retention after 9000 cycles at 30 A·g^(-1),corresponding with a low capacitance decay rate of 0.003‰per cycle,significantly outperforming conventional conductive polymers like polyaniline(PANI).An asymmetric supercapacitor assembled with Mn@PN as the positive electrode(Mn@PN||AC)achieved an energy density of 328 Wh·kg^(-1) at 15 A·g^(-1) and retained 80.7%of its initial specific capacitance after 4000 cycles at 20 A·g^(-1).
基金supported by the National Natural Science Foundation of China(52433012)the National Key R&D Program of China(2024YFF1500300)the China Postdoctoral Science Foundation(2023M741201,2024T170286)。
文摘Conductive polymers have recently drawn tremendous attention due to their promising applications in electronic and energy-related devices.While p-type conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)have achieved commercialization,the development of stable,high-performance n-type polymers has lagged.Recently,the discovery of n-type polymer poly(benzodifurandione)(PBFDO)has greatly promoted the development and application of n-type conductive polymers.However,the synthesis process involves cumbersome post-processing,which greatly increases the cost and difficulty of mass production.Herein,a novel synthesis method for PBFDO has been developed,which was promoted by the combination of solvent dimethyl sulfoxide(DMSO)and acetic anhydride(Ac_(2)O).This method exploits the oxidative capability of DMSO,activated by Ac_(2)O,which can promote the keto-enol tautomerism of 3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione(BFDO)and induce the rapid polymerization.The resulting PBFDO ink exhibits a high electronic conductivity of more than 2000 S cm^(-1)and excellent ambient stability.Significantly,the additives and by-products remain in a liquid state during the polymerization process and possess low boiling points,allowing for the production of pure PBFDO films through straightforward heating and drying.Furthermore,this approach holds considerable promise for in situ polymerization,as functional conductive films can be prepared by merely combining the monomers with the DMSO/Ac_(2)O mixture and applying heat.This efficient,purification-free strategy represents a significant step toward the industrial application of the highperformance n-type conductive polymer PBFDO.
基金the financial support from the National Natural Science Foundation of China (No. 52072390)the National High-Level Talents Special Support Program (Leading Talent of Technological Innovation)+2 种基金the China Postdoctoral Science Foundation (No. 2023M743648)the Young Scientists Fund of the National Natural Science Foundation of China (No. 52302330)the support from the Shanghai Emperor of Cleaning Hi-Tech Co.,LTD
文摘In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.
基金financially supported by the Jiangsu Forestry Science and Technology Innovation and Promotion Project(No.LYKJ-Nanjing[2022]02)the Jiangsu Agricultural Science and Technology Innovation Fund(No.CX(23)3090)。
文摘Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.
基金the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C01072)the Institute of Zhejiang University-Quzhou for their financial support。
文摘Poly(phenylene oxide)(PPO)exhibits excellent dielectric properties,making it an ideal substrate for high-frequency,high-speed copper-clad laminates.The phenolic hydroxyl group at the end of PPO plays a key role in its reactivity.Accurately quantifying the phenolic hydroxyl content in PPO is essential but challenging.In this study,we proposed a method for measuring the phenolic hydroxyl content of PPO using differential UV absorption spectroscopy.In alkaline solutions,the phenolic hydroxyl in PPO completely ionizes to form phenoxide ions,leading to a significant increase in UV absorbance at approximately 250 and 300 nm.Notably,the differential UV absorbance at approximately 300 nm was directly proportional to the phenolic hydroxyl concentration.Using 2,6-dimethylphenol as a standard,a calibration curve was established to relate the phenolic hydroxyl concentration to differential UV absorbance at approximately 300 nm,providing a precise and straightforward method for phenolic hydroxyl quantification in PPO with distinct advantages over conventional techniques.
文摘Although poly(urethane-urea)elastomers(PUEs)possess excellent mechanical properties and durability,their inherent flammability and inability to self-repair after damage significantly limits their applications in high-end fields.To address this challenge,this study employs a supramolecular chemistry approach by simultaneously incorporating multiple hydrogen bonds as dynamic cross-linking points and a phosphorus-nitrogen synergistic flame-retardant structure into the poly(urethane-urea)network.The multiple hydrogen bonds endow the material with efficient intrinsic self-healing capability,while the phosphorus-nitrogen flame retardant ensures outstanding thermal stability and flame resistance,leading to the successful synthesis of a high-performance multifunctional poly(urethane-urea)elastomer.Experimental results demonstrated that when the content of the flame retardant diethyl(2-((2-aminoethyl)amino)ethyl)phosphoramidate(DEPTA)was 10 wt%,the resulting PUE/10%DEPTA achieved a V-0 rating in the vertical burning test,with a limiting oxygen index(LOI)of 30%.Concurrently,the elastomer maintained good toughness,exhibiting a tensile strength of 27.3 MPa,an elongation at break of 601%,and a self-healing efficiency of up to 94.46%.This breakthrough shows significant promise for advanced engineering applications that demand fire safety,structural durability,and extended service life through self-repair.
基金financially supported by the National Natural Science Foundation of China(Nos.22473105 and 22341302).
文摘This study uses all-atom molecular dynamics simulations to investigate the dislocation propagation, stress transmission, and mechanical properties in poly(p-phenylene terephthalamide) fibers under uniaxial tension. The results indicate that the dislocation propagates and the stress transfers not only along the fiber axis but also between adjacent molecular chains through hydrogen bonds, demonstrating their influence on the yield behavior. As the degree of polymerization increases, breakage of covalent bonds and interchain slippage contribute to the yield of fibers together. This work provides theoretical guidance for the design and manufacturing of high-performance fibers.
基金financially supported by the National Key Research and Development Program of China(No.2021YFB3700300)the National Natural Science Foundation of China(Nos.52573017 and U21B2093)+1 种基金Key Research and Development Program of Ningbo(No.2022Z200)the Zhejiang Provincial Natural Science Foundation(No.LY23E030005)。
文摘Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.
基金supported by the National Natural Science Foundation of China(21971177)the Natural Science Foundation of the Jiangsu Higher Education Institution of China(22KJA150004)+3 种基金the Suzhou Science and Technology Bureau(SZM2021008)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutionsthe Jiangsu Key Laboratory of Advanced Functional Polymers Design and Application,Soochow University,Suzhou Medical and Industrial Cooperation Innovation Project(SZM2022011)the Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis and the Program of Innovative Research Team of Soochow University。
文摘Poly(ester amide)s(PEAs)represent promising biomaterials because of their well-balanced mechanical properties,biodegradability,and biocompatibility.However,practical applications of PEAs are still limited by challenges in functional versatility and environmental adaptability.Here,we present the first synthesis of periodic selenium-incorporated PEAs(Se-PEAs)via a rapid,catalyst-free selenol-yne click polymerization process.By harnessing the versatility of selenium,we achieved precise modulation of material properties.The resulting Se-PEAs demonstrated tunable mechanical behavior,spanning rigid plastics to elastomers,alongside exceptional thermal stability and high optical clarity.Programmable degradation profiles ensure long-term stability in physiological environments while facilitating rapid oxidative degradation at the end of the lifecycle.Surface selenoniumization further conferred robust antibacterial efficacy without compromising mechanical integrity.This multifunctionality positions Se-PEAs as transformative materials for biomedical implants,sustainable packaging,and high-refractiveindex optics.Our work advanced functional polymer design and underscored the potential of selenium chemistry in addressing global challenges in terms of plastic waste and ecological sustainability.
基金support by the National Natural Science Foundation of China (No. 21901249)Taishan Scholars Program of Shandong Province (No. tsqn201812112)the Scientific Research and Innovation Fund Project of Shandong Energy Research Institute (No. SEI I202004)。
文摘Chemical upcycling of end-of-life poly(lactide) plastics to lactide,lactate ester and new poly(lactide)has been achieved by using magnesium bis[bis(trimethylsilyl)amide][Mg(HMDS)_(2)]as promoter.Mg(HMDS)2 showed high efficiency in L-lactide polymerization and poly(lactide) depolymerization.Mg(HMDS)_(2)/Ph_(2) CHOH catalytic system displayed high ring-opening selectivity and the characteristic of immortal polymerization.Taking advantage of transesterification,depolymerizations of end-oflife poly(lactide) plastics to lactate ester (polymer to value-added chemicals) and lactide (polymer to monomer) were achieved with high yields.Besides,a new“depolymerization-repolymerization”strategy was proposed to directly transform poly(lactide) into new poly(lactide).This work provides a theoretical basis for the design of polymerization and depolymerization catalysts and promotes the development of degradable polymers.
基金Supported by the National Natural Science Foundation of China(51403160)the Opening Project of Hubei Key Laboratory Biomass Fibers and Eco-dyeing&Finishing(STRZ2017009)
文摘The effects of the plasticizer poly(ethylene glycol)(PEG)on crystallization properties of equimolar poly(L-lactide)(PLLA)/poly(D-lactide)(PDLA)blends were investigated.Forma-tion of the stereocomplex-type poly(lactide acid)(sc-PLA)crystallites was confirmed by Wide-angle X-ray diffraction(WAXD)and differential scanning calorimetry(DSC)analyses.Sc-PLA crystallites without any homochiral poly(lactide acid)(hc-PLA)formed,as the result of the incorporation of the plasticizer PEG(more than or equal to 10%(wt))at a processing temperature(240℃).More-over,when the Mw of PEG reached 1000 g·mol^(-1),the crystal-lizability of stereocomplex crystallites was the best.Isothermal crystallization kinetics further revealed that PEG could accelerate the crystallization rate of sc-PLA,with the optimum crystallization kinetic parameters being obtained at 10%(wt)PEG.Several crys-tallization kinetics equations were applied to describe the effect of PEG on the crystallization behavior of sc-PLA.The influence of PEG on the spherocrystal morphologies of sc-PLA was also inves-tigated using polarized optical microscopy.
基金This research was made possible by a Johnson & Johnson CORD Internship Award funded by Ethicon. BH and BF thank the National Science Foundation for partial financial support (DMR-0098104).
文摘Structure and properties of bioabsorbable polyglycolide (PGA) and poly(glycolide-co-lactide) (PGA-co-PLA)fibers were investigated during several industrial processing stages and in vitro degradation by means of wide-angle X-raydiffraction (WAXD), dynamic mechanical analysis (DMA) and mechanical property tests. In the orientation stage, the PGAfibers were found to have higher degrees of crystallinity than corresponding PGA-co-PLA samples produced under similarconditions. In the hot-stretching and post-annealing stages, after fibers were braided, PGA samples were found to gain morecrystallinity and higher T_g than PGA-co-PLA samples. The higher crystallinity in PGA fibers resulted in a slower rate ofdegradation. DMA results showed that a great deal of internal stress that was built during orientation and hot-stretchingstages was released in the post-annealing stage for a1l PGA and PGA-co-PLA samples. During earlier stages of in vitrodegradation, both PGA and PGA-co-PLA samples exhibited the typical cleavage-induced crystallization mechanism. Theheat shrinkage in the glass transition area was found to disappear after 6-8 days of degradation for all PGA and PGA-co-PLAsamples, indicating the amorphous portions of the polymers lost orientation after a short period in the buffer solution, mostlikely due to relaxation of the cleaved chains.
基金financially supported by the National Key Research and Development Program of China (Nos. 2017YFB0309301 and 2017YFB0309302)the Natural Science Foundation of Shanghai, China (No. 17ZR1407200)
文摘Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolymers and electrospun ultrafine fibers were investigated and compared with those of PLLA and PA4 blends. PLLA and PA4 were found incompatible and formed individual crystalline regions, along with reciprocal inhibition in crystallization. Electrospun fibers were highly hydrophobic, even if hydrophilic PA4 was the rich component. The crystallinity of either PLLA or PA4 decreased after electrospinning and PLLA-rich as-spun fibers were almost amorphous. Immersion tests proved that fibers of block copolymers were relatively homogeneous with micro-phase separation between PLLA and PA4. The fibrous structures of copolymers were different from those of the fibers electrospun from blends, for which sheath-core structure induced by macro-phase separation between homopolymers of PLLA and PA4 was confirmed by TEM, EDS, and XPS.
基金financially supported by the National Natural Science Foundation of China(No.51403210)China Postdoctoral Science Foundation(No.2014M550801)President Fund of University of Chinese Academy of Sciences(No.Y35102CN00)
文摘Polyester-based biodegradable polyurethane （PU） with different hard segment ratios was selected to modify the impact toughness of poly（L-lactide） （PLLA）. The influence of blending composition and hard segment ratio of PU on the phase morphology, crystallization behavior and mechanical properties of PLLA/PU blends has been investigated systematically. The results showed that the PU particles were uniformly dispersed in PLLA matrix at a scale from sub- microns to several microns. The glass transition temperature of PU within these blends decreased compared to that of neat PU, but rose slightly with its content and hard segment ratio. The presence of PU retarded the crystallization ability of PLLA, whereas enhanced its elongation at break and impact resistance effectively. As the PU content reaches up to 30 wt%, the phenomenon of brittle-ductile transition occurred, resulting in a rougher fracture surface with the formation of fibril-like structure. Moreover, under the same concentrations, the elongation at break and impact strength of PLLA blends decreased slightly with the increase of hard segment ratio of PU.
文摘In the present investigation, the novel copper Schiff base complex was synthesized and its catalytic activity was evaluated for the ring-opening polymerization （ROP） of lactide and block polymerization of poly（lactide） with po/y（ethylene glycol）methyl ether,
基金financially supported by the fund of Science&Technology Bureau of Jilin Province of China(No.20130305028NY)Chinese Science Academy(Changchun Branch)(No.2014SYHZ0019)+1 种基金the National High Technology Research and Development Program of China(863 Program)(No.2012AA062904)the National Natural Science Foundation of China(No.51021003)
文摘Poly（propylene carbonate） （PPC） was blended with polylactide （PLA） and poly（1,2-propylene glycol adipate） （PPA） using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film technique. DMA results showed that PPA could act as a plasticizer and improve the miscibility between PPC and PLA. Crystal morphology displayed that blending PLA with the amorphous PPC led to a decrease of the spherulite size of PLA. The results of mechanical tests indicated that PPC-rich films showed high elongation at break and PLA-rich films showed high tear strength and good optical properties. The content of PPC and PLA significantly affected the physical properties of the films. With increasing PPC content, the melt strengths of the PPC/PLA/PPA films were enhanced. These findings contributed to the biodegradable materials application for designing and manufacturing polymer packaging.
文摘Poly (L-lactide) was prepared by bulk polymerization ofL-lactide at 140°C in the presence of stannous octoate. The polymer products were characterized by number average molecular weight Mn, weight average molecular weight Mw and molecular weight distribution MWD (M w/M n) respectively. The results showed that stannous octoate was a high effective catalyst, and coordinated insertion mechanism of the reaction was proposed.
文摘Polylactide （PLA） was successfully toughened by blending with bio-based poly（ester）urethane （TPU） elastomers which contained bio-based polyester soft segments synthesized from biomass diols and diacids. The miscibility, mechanical properties, phase morphology and toughening mechanism of the blend were investigated. Both DSC and DMTA results manifested that the addition of TPU elastomer not only accelerated the crystallization rate, but also increased the final degree of crystallinity, which proved that TPU has limited miscibility with PLA and has functioned as a plasticizer. All the blend samples showed distinct phase separation phenomenon with sea-island structure under SEM observation and the rubber particle size in the PLA matrix increased with the increased contents of TPU. The mechanical property variation of PLA/TPU blends could be quantitatively explained by Wu＇s model. With the variation of TPU, a brittle-ductile transition has been observed for the TPU/PLA blends. When these blends were under tensile stress conditions, the TPU particles could be debonded from the PLA matrix and the blends showed a high ability to induce large area plastic deformation before break, which was important for the dissipation of the breaking energy. Such mechanism was demonstrated by tensile tests and scanning electron microcopy （SEM） observations.
