The incorporation of molecular switches into polymer networks has been a powerful approach for the development of functional polymer materials that display macroscopic actuation and function enabled directly by molecu...The incorporation of molecular switches into polymer networks has been a powerful approach for the development of functional polymer materials that display macroscopic actuation and function enabled directly by molecular changes.However,such materials sometimes require harsh conditions to perform their functions,and the design of new molecular photoswitches that can function under physiological conditions is highly needed.Here,we report the design and synthesis of a spiropyridine-based photoswitchable hydrogel that exhibits light-driven actuation at physiological pH.Owing to its high p Ka,spiropyridine maintains its ring-open protonated form at neutral pH,and the resulting hydrogel remains in a swollen state.Upon irradiation with visible light,the ring closure of spiropyridine leads to a decrease in the charge and a reduction in the volume of the hydrogel.The contracted gel could spontaneously recover to its expanding state in the dark,and this process is highly dynamic and reversible when the light is switched on and off.Furthermore,the hydrogel shows switchable fluorescence in response to visible light.Bending deformation is observed in the hydrogel thin films upon irradiation from one side.Importantly,the independence of this spiropyridine hydrogel from the acidic environment makes it biotolerant and shows excellent biocompatibility.This biocompatible spiropyridine hydrogel might have important biorelated applications in the future.展开更多
Cyclic polymers are a class of polymers that feature endless topology,and the synthesis of cyclic polymers has attracted the attention of many researchers.Herein,cyclic polymers were efficiently constructed by self-fo...Cyclic polymers are a class of polymers that feature endless topology,and the synthesis of cyclic polymers has attracted the attention of many researchers.Herein,cyclic polymers were efficiently constructed by self-folding cyclization technique at high concentrations.Linear poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate))(P(OEGA-co-DDA))precursors with different ratios of hydrophilic and hydrophobic moieties were synthesized by reversible addition-fragmentation chain transfer(RAFT)polymerization using a bifunctional chain transfer agent with two anthryl end groups.The amphiphilic linear precursors underwent the self-folding process to generate polymeric nanoparticles in water.By irradiating the aqueous solution of the nanoparticles with 365 nm UV light,cyclic polymers were synthesized successfully via coupling of anthryl groups.The effects of the ratios of hydrophilic and hydrophobic moieties in linear P(OEGA-co-DDA)copolymers and polymer concentration on the purity of the obtained cyclic polymers were explored in detail via ^(1)H nuclear magnetic resonance(^(1)H NMR),dynamic light scattering(DLS),UV‒visible(vis)analysis,three-detection size exclusion chromatography(TD-SEC)and transmission electron microscopy(TEM).It was found that by adjusting the content of the hydrophilic segments in linear precursors,single chain polymeric nanoparticles(SCPNs)can be generated at high polymer concentrations.Therefore,cyclic polymers with high purity can be constructed efficiently.This method overcomes the limitation of traditional ring-closure method,which is typically conducted in highly dilute conditions,providing an efficient method for the scalable preparation of cyclic polymers.展开更多
With the blooming development of electronic technology,the use of electron conductive gel or ionic conductive gel in preparing flexible electronic devices is drawing more and more attention.Deep eutectic solvents are ...With the blooming development of electronic technology,the use of electron conductive gel or ionic conductive gel in preparing flexible electronic devices is drawing more and more attention.Deep eutectic solvents are excellent substitutes for ionic liquids because of their good biocompatibility,low cost,and easy preparation,except for good conductivity.In this work,we synthesized a reactive quaternary ammonium monomer(3-acrylamidopropyl)octadecyldimethyl ammonium bromide with a hydrophobic chain of 18 carbons via the quaternization of 1-bromooctadecane and N-dimethylaminopropyl acrylamide at first,then we mixed quaternary ammonium with choline chloride,acrylic acid and glycerol to obtain a hydrophobic deep eutectic solvent,and initialized polymerization in UV light of 365 nm to obtain the ionic conductive eutectogel based on polyacrylamide copolymer with long hydrophobic chain.The obtained eutectogel exibits good stretchability(1200%),Young's modulus(0.185 MPa),toughness(4.2 MJ/m^(3)),conductivity(0.315 S/m).The eutectogel also shows desireable moisture resistance with the maximum water absorption of 11.7 wt%after one week at 25℃ and 60% humidity,while the water absorption of eutectogel without hydrophobic long chains is 24.0 wt%.The introduction of long-chain hydrophobic groups not only improves the mechanical strength of the gels,but also significantly improves moisture resistance of the eutectogel.This work provides a simpler and more effective method for the preparation of ionic conductive eutectogels,which can further provide a reference for the applications of ionic conductive eutectogels in the field of flexible electronic devices.展开更多
Due to the structure characteristics of huge macromolecular size and the very low motion feature of the polymer chain which is very difficult to arrange regularly their long chain into the three dimensional space,thus...Due to the structure characteristics of huge macromolecular size and the very low motion feature of the polymer chain which is very difficult to arrange regularly their long chain into the three dimensional space,thus the polymer will incompletely crystallize except for the macroscopic single crystal of polydiacetylene polymerized by means of solid state crystalline polymerization.展开更多
Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to p...Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.展开更多
In recent years,renewable energy sources,which aim to replace rapidly depleting fossil fuels,face challenges due to limited energy storage and conversion technologies.To enhance energy storage and conversion efficienc...In recent years,renewable energy sources,which aim to replace rapidly depleting fossil fuels,face challenges due to limited energy storage and conversion technologies.To enhance energy storage and conversion efficiency,extensive research has been conducted in the academic community on numerous potential materials.Among these materials,metal fluorides have attracted significant attention due to their ionic metal-fluorine bonds and tunable electronic structures,attributed to the highest electronegativity of fluorine in their chemical composition.This makes them promising candidates for future electrochemical applications in various fields.However,metal fluorides encounter various challenges in different application directions.Therefore,we comprehensively review the applications of metal fluorides in the field of energy storage and conversion,aiming to deepen our understanding of their exhibited characteristics in different electrochemical processes.In this paper,we summarize the difficulties and improvement methods encountered in different types of battery applications and several typical electrode optimization strategies in the field of supercapacitors.In the field of water electrolysis,we focus on surface reconstruction and the critical role of fluorine,demonstrating the catalytic performance of metal fluorides from the perspectives of reconstruction mechanism and process analysis.Finally,we provide a summary and outlook for this field,aiming to offer guidance for future breakthroughs in the energy storage and conversion applications of metal fluorides.展开更多
The facile synthesis of high-valued polymers from waste molecules or low-cost common chemicals presents a significant challenge.Here,we develop a series of degradable poly(thiocarbonate)s from the new step-growth poly...The facile synthesis of high-valued polymers from waste molecules or low-cost common chemicals presents a significant challenge.Here,we develop a series of degradable poly(thiocarbonate)s from the new step-growth polymerization of diols,carbonyl sulfide(CoS,or carbon disulfide,CS_(2)),and dichlorides.Diols and dichlorides are common chemicals,and CoS(CS_(2))is released as industrial waste.In addition to abun-dant feedstocks,the method is efficient and performed under mild conditions,using common organic bases as catalysts,and affording unprece-dented polymers.When cos,diols,and dihalides were used as monomers,optimized conditions could completely suppress the oxygen-sulfur exchange reaction,enabling the efficient synthesis of well-defined poly(monothiocarbonate)s with melting points ranging from 48°C to 101°C.These polymers,which have a structure similar to polyethylene with low-density in-chain polar groups,exhibit remarkable toughness and ductili-ty that rival those of high-density polyethylene(melting point:90°C,tensile strength:21.6±0.7 MPa,and elongation at break:576%).Moreover,the obtained poly(monothiocarbonate)s can be chemically degraded by alcoholysis to yield small-molecule diols and dithiols.When CS_(2)was used in place of cos,a pronounced oxygen-sulfur exchange reaction occurred.By optimizing reaction condition,it was found that polymers with-S(C=O)S-and-S(C=S)S-as the main repeating units exhibited high thermal stability and crystallinity.Thus,a new approach for regulat-ing the structure of polythiocarbonates via the oxygen-sulfur exchange reaction is developed.Overall,the polymers hold great potential for green materials due to their facile synthesis,readily available feedstocks,excellent performance,and chemical degradability.展开更多
The toughness of thermoplastic polymers such as polypropylene(PP)can be improved by adding elastomers-based toughening agents,and the phase morphology of these toughening agents is very important for the strength and ...The toughness of thermoplastic polymers such as polypropylene(PP)can be improved by adding elastomers-based toughening agents,and the phase morphology of these toughening agents is very important for the strength and toughness of PP.The low-temperature toughness of PP was improved by inserting high-density polyethylene(HDPE)between PP and polystyrene-b-ethylene-co-propyleneb-polystyrene(SEPS)to form an unusual SEPS@HDPE core–shell structure,with SEPS as the core and HDPE as the shell.Based on the microtopography and rheological behavior characterization,HDPE in PP/SEPS/HDPE composites was found to serve as an emulsifier,decrease the size of SEPS particles,and promote the homogeneous dispersion of dispersed phase particles in the matrix.An increase in the HDPE content shifted the toughening mechanism of PP composites from cavitation to matrix shear yielding.The reduction in the distance between the dispersed core–shell structure particles promoted shear yielding in the PP composites,leading to increased toughness.The creation of an intermediate HDPE layer with a moderate modulus was crucial for dispersing stress concentrations and significantly improving toughness without compromising the tensile strength.These findings will facilitate the fabrication of high-toughness PP products at low temperatures.展开更多
Electromagnetic interference shielding materials are inevitably damaged during service,causing a serious decline in their shielding performance.Therefore,it is urgent to develop polymer-based composites with excellent...Electromagnetic interference shielding materials are inevitably damaged during service,causing a serious decline in their shielding performance.Therefore,it is urgent to develop polymer-based composites with excellent electromagnetic shielding and self-healing properties.In this study,a layered foam/film structure polycaprolactone composite characterized by electric/magnetic bifunctionality was constructed by a hot-pressing process and supercritical carbon dioxide foaming.The microcellular framework offers rich heterogeneous interfaces and improves electromagnetic attenuation capabilities.Such a reasonable construction of asymmetric shielding networks optimizes the impedance matching,while the incident electromagnetic waves form a special attenuation mode of“absorption-reflection-reabsorption”.The polycaprolactone composite foam exhibits an excellent electromagnetic interference shielding effectiveness of 53.6 dB in the X-band and a low reflection value of only 0.36,effectively reducing secondary pollution.In addition,the damaged polycaprolactone composite foam exhibits over 93%electromagnetic interference shielding effectiveness and healing efficiency,ensuring the long-term stability of the material in practical applications.展开更多
Flexible and stretchable energy storage devices are highly desirable for wearable electronics,particularly in the emerging fields of smart clothes,medical instruments,and stretchable skin.Lithium metal batteries(LMBs)...Flexible and stretchable energy storage devices are highly desirable for wearable electronics,particularly in the emerging fields of smart clothes,medical instruments,and stretchable skin.Lithium metal batteries(LMBs) with high power density and long cycle life are one of the ideal power sources for flexible and stretchable energy storage devices.However,the current LMBs are usually too rigid and bulky to meet the requirements of these devices.The electrolyte is the critical component that determines the energy density and security of flexible and stretchable LMBs.Among various electrolytes,gel polymer electrolytes(GPEs) perform excellent flexibility,safety,and high ionic conductivity compared with traditional liquid electrolytes and solid electrolytes,fulfilling the next generation deformable LMBs.This essay mainly reviews and highlights the recent progress in GPEs for flexible/stretchable LMBs and provides some useful insights for people interested in this field.Additionally,the multifunctional GPEs with self-healing,flame retardant,and temperature tolerance abilities are summarized.Finally,the perspectives and opportunities for flexible and stretchable GPEs are discussed.展开更多
As a highly promising conductive polymer material,the synthesis method,structure regulation,and performance improvement of polyaniline(PANI)are hot research topics.In this work,the radiation-induced polymerization of ...As a highly promising conductive polymer material,the synthesis method,structure regulation,and performance improvement of polyaniline(PANI)are hot research topics.In this work,the radiation-induced polymerization of aniline in HNO_(3)solution was successfully achieved at room temperature without the use of chemical oxidants.Through the analysis of the radiation chemical reactions of inorganic acids and nitrate salt solutions,the characterization of the intermediate free radicals in the irradiated systems,and the influence of the pH of the solutions on the polymerization activity and product morphologies,the radiation-induced polymerization mechanism of aniline is discussed in detail and proposed.Only at a condition of[HNO_(3)]>[aniline],i.e.,pH<2.5,PANI can be successfully obtained underγ-ray radiation.The polymerization begins with the oxidation of aniline cations to aniline cation radicals by·NO_(3)generated by radiolysis reactions,and undergoes repeated three steps of monomer free radical recombination,deprotonation,and oxidation reaction of·NO_(3),thus forming a PANI macromolecule.In addition to the polymerization reaction,the aniline units are protonated and oxidized because of the strongly acidity and oxidation of the reaction system under γ-ray irradiation,which means that the molecular chain structure of the radiation-synthesized PANI can be regulated by pH,nitrate concentration,and irradiation conditions.Radiation-synthesized PANI has a moderate protonation and oxidation state,which can be used for the preparation of PANI supercapacitors with better electrochemical properties than those prepared by chemical oxidation under the same conditions.This work presents a new radiation-synthesis method and polymerization mechanism of PANI,which not only expands the application of radiation technique in the field of polymer synthesis,but also provides a new idea for the structural regulation and electrochemical property optimization of PANI.展开更多
As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of t...As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.展开更多
Recently circularly polarized luminescence(CPL)materials have attracted significant interest.Introducing reversible dynamic property to these materials has been a key focus in cutting-edge fields,such as in high-level...Recently circularly polarized luminescence(CPL)materials have attracted significant interest.Introducing reversible dynamic property to these materials has been a key focus in cutting-edge fields,such as in high-level information encryption.Here,we provided a novel and general strategy involving handednessselective filtration and ground-state chiral self-recovery(CSR)in double film system to address this issue.Based on this strategy,we achieved CPL switch through the reversible modulation of ground-state chirality including absorption and scattering circular dichroism(CD)signals over the full UV-visible wavelength range(365-700 nm)in a single azobenzene polymer(PAzo)film.More importantly,by flexibly changing the type of fluorescent films,it is convenient to achieve general excited-state CSR,that is reversible switching of full-color including ideal white(CIE coordinate(0.33,0.33)),as well as room-temperature phosphorescent CPL.All these CPL signals without almost any intensity decay after three cycles of onand-off switching.Experimental results indicated that the trans-cis isomerization and ordered rearrangement of azobenzene units in PAzo film were the fundamental reasons for realizing CPL switching.Finally,based on this system we achieved dynamic visual encryption and decryption process including multiple decryption methods.This study provides an effective method for constructing a universally applicable chiroptical switch in excited state.展开更多
The recovery of ionic liquids(ILs)has attracted growing attention as an indispensable process in“green”industrial applications.Forward osmosis(FO)has proven to be a sustainable method for concentrating the very dilu...The recovery of ionic liquids(ILs)has attracted growing attention as an indispensable process in“green”industrial applications.Forward osmosis(FO)has proven to be a sustainable method for concentrating the very dilute aqueous solutions of ILs at ambient temperature,in which semi-permeable membranes play a vital role in determining the recovery efficiency.Herein,we use interfacial polymerization method to prepare thin-film composite membranes consisting of polyamide skin layer and electrospun nanofibrous substrate with tunable water permeability and IL selectivity for osmotic enrichment of imidazolium ILs from their dilute aqueous solutions through FO process.The resulting FO membrane shows a compact polyamide layer with a thickness of 30-200 nm,guranteeing a high selectivity to ILs and water.Meanwhile,the nanofibrous substrate with large and interconnect pores as well as low tortuosity,providing mechanical and permeable support for the composite membranes.IL structure influences the osmotic pressure difference as well as the interactions with polyamide layer of the membrane and thus determines the whole concentration process.First,the alkyl chain growth augments the osmosis pressure difference between the ILs solution and draw solution,resulting in an enhancement in driving force of water osmosis and IL enrichment.Moreover,alkyl length aggravates external concentration polarization caused by the enhanced adsorption of ILs onto the skin layer via electrostatic and alkyl-πinteractions.Meanwhile,such adsorbed ILs further enhance the IL retention but decrease the reverse salt diffusion.Therefore,imidazolium ILs with varied alkyl lengths are ultimately enriched with a 100-fold increase in concentration from their dilute aqueous solutions with high IL/NaCl rejection and low IL loss.Remarkably,the final concentration of IL with longest alkyl length reaches the highest(6.4 mol·L^(-1)).This work provides the insights in respect to material preparation and process amelioration for IL recovery with high scalability at mild conditions.展开更多
The designing and manufacturing of micro/nanoscale tools for delivery,diagnostic,and therapeutic are essential for their multiscale integration in the precision medicine field.Conventional three-dimensional(3D)printin...The designing and manufacturing of micro/nanoscale tools for delivery,diagnostic,and therapeutic are essential for their multiscale integration in the precision medicine field.Conventional three-dimensional(3D)printing approaches are not suitable for such kind of tools due to the accuracy limitation.Multiphoton polymerization(MPP)-based micro/nanomanufacturing is a noncontact,high-precision molding technology that has been widely used in the micro/nano field is a promising tool for micro/nanoscale related precision medicine.In this article the fundamentals of MPP-based technology and the required materials in precision medicine are overviewed.The biomedical applications in various scenarios are then summarized and categorized as delivery systems,microtissue modeling,surgery,and diagnosis.Finally,the existing challenges and future perspectives on MPP-based micro/nanomanufacturing for precision medicine are discussed,focusing on material design,process optimization,and practical applications to overcome its current limitations.展开更多
Achieving continuous motions typically requires dynamic external stimuli for cyclic deformation,or crafted geometries with intricate modules to form a self-regulated feedback loop upon static stimulation.It is still a...Achieving continuous motions typically requires dynamic external stimuli for cyclic deformation,or crafted geometries with intricate modules to form a self-regulated feedback loop upon static stimulation.It is still a grand challenge to realize self-sustained motion in soft robots subject to unchanging environment,without complex geometry or a control module.In this work,we report soft robots based on an anisotropic cylindrical hydrogel showing self-regulated,continuous rolling motions under constant light irradiation.The robots are animated by mirror-symmetry-breaking induced by photothermal strain gradient.The self-sustained motion is attributed to the fast and reversible deformation of the gel and the autonomous refresh of the irradiated region during the rolling motion.The hydrogel robots can reach a rolling speed of 1.27 mm·s^(-1)on a horizonal surface and even climb a ramp of 18°at a speed of 0.57 mm·s^(-1)in an aqueous environment.Furthermore,the hydrogel robots can overcome an obstacle,with rolling direction controllable through irradiation angle of the light and local irradiation on selective regions.This work suggests a facile strategy to develop hydrogel robots and may provide unforeseen inspirations for the design of self-regulated soft robots by using other intelligent materials.展开更多
Given the increasing demand for distributed electricity,there is a burning desire to harvest electricity from renewable sources using environmentally friendly methods.Thermoelectric (TE) materials can meet this requir...Given the increasing demand for distributed electricity,there is a burning desire to harvest electricity from renewable sources using environmentally friendly methods.Thermoelectric (TE) materials can meet this requirement not only because of their ability to convert heat directly into electricity,enabling energy harvesting from waste heat and natural heat resources,but also because more than 60%of the energy is lost as waste heat [1].The discovery of the TE effect dates back to the 1820s when T.M.Seebeck observed electricity generation at the junction of two conductors with different temperatures.Additionally,when a voltage is applied to TE materials,they can create a temperature difference to enable solid-state cooling (known as the Peltier effect).Therefore,the TE effect promises both sustainable energy solutions and temperature control technologies.Over the past two decades,the urgent demand for powering ubiquitous Internet of Things devices has sparked significant interest in flexible thermoelectrics(F-TEs),which raises an intriguing question:Is the intrinsically flexible polymer an important candidate for state-of-the-art F-TEs applications?展开更多
In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especia...In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.展开更多
Inspired by the self-polymerization and strong adhesion characteristics of dopamine in aqueous conditions, a novel hydrophilic nanofiltration （NF） membrane was fabricated by simply dipping polysulfone （PSf） ultraf...Inspired by the self-polymerization and strong adhesion characteristics of dopamine in aqueous conditions, a novel hydrophilic nanofiltration （NF） membrane was fabricated by simply dipping polysulfone （PSf） ultrafiltration （UF） substrate in dopamine solution. The changes in surface chemical composition and morphology of membranes were determined by Fourier transform infrared spectroscopy （FTIR-ATR）, X-ray photoelectron spectroscopy （XPS）, scanning electron microscopy （SEM） and atomic force microscopy （AFM）. The experimental results indicated that the self-polymerized dopamine formed an ultrathin and defect-free barrier layer on the PSf UF membrane. The surface hydrophilicity of membranes was evaluated through water contact angle measurements. It was found that membrane hydrophilicity was significantly improved after coating a polydopamine （pDA） layer, especially after double coating. The dyes filtration experiments showed that the double-coated membranes were able to reject completely the dyes of brilliant blue, congo red and methyl orange with a pure water flux of 83.7 L/（mE.h） under 0.6 MPa. The zeta potential determination revealed the positively-charged characteristics of PSf/pDA composite membrane in NF process. The salt rejection of the membranes was characterized by 0.01 mmol/L of salts filtration experiment. It was demonstrated that the salts rejections followed the sequence： NaC1 〈 NaaSO4 〈 MgSO4 〈 MgC12 〈 CaCl2, and the rejection to CaC12 reached 68.7%. Moreover, the composite NF membranes showed a good stability in water-phase filtration process.展开更多
A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluen...A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluene diisocyanate. Meanwhile, NS with different molecular weights was synthesized and used as the soft co-segment. Effects of types and contents of soft co-segments as well as chain extenders on the thermal degradation and stability for WPSUR films were examined. Results reveal that WPSUR films exhibit excellent water resistance and mechanical properties as compared with pure polyurethane （PU） films, and the NS soft co-segment possesses a remarkable effect on the second stage （stage Ⅱ）, while the content of the hard segment is propitious to the initial stage （stage Ⅰ）. Moreover, the highest temperature of stage Ⅱ （T2m） for WPSUR films using NS as soft co-segment is 413℃, approximately being 30℃ higher than that of those typical PUs using HDA and APDMS as the chain extenders, respectively.展开更多
基金supported by the National Natural Science Foundation of China(No.52373121)the National Key R&D Program of China(No.2022YFA1305100)the Natural Science Foundation of Anhui Province(No.2208085MB27)。
文摘The incorporation of molecular switches into polymer networks has been a powerful approach for the development of functional polymer materials that display macroscopic actuation and function enabled directly by molecular changes.However,such materials sometimes require harsh conditions to perform their functions,and the design of new molecular photoswitches that can function under physiological conditions is highly needed.Here,we report the design and synthesis of a spiropyridine-based photoswitchable hydrogel that exhibits light-driven actuation at physiological pH.Owing to its high p Ka,spiropyridine maintains its ring-open protonated form at neutral pH,and the resulting hydrogel remains in a swollen state.Upon irradiation with visible light,the ring closure of spiropyridine leads to a decrease in the charge and a reduction in the volume of the hydrogel.The contracted gel could spontaneously recover to its expanding state in the dark,and this process is highly dynamic and reversible when the light is switched on and off.Furthermore,the hydrogel shows switchable fluorescence in response to visible light.Bending deformation is observed in the hydrogel thin films upon irradiation from one side.Importantly,the independence of this spiropyridine hydrogel from the acidic environment makes it biotolerant and shows excellent biocompatibility.This biocompatible spiropyridine hydrogel might have important biorelated applications in the future.
基金The financial support from the National Natural Science Foundation of China(Nos.22201276,22131010,52021002)the Fundamental Research Funds for the Central Universities(No.WK2060000012)is gratefully acknowledged.
文摘Cyclic polymers are a class of polymers that feature endless topology,and the synthesis of cyclic polymers has attracted the attention of many researchers.Herein,cyclic polymers were efficiently constructed by self-folding cyclization technique at high concentrations.Linear poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate))(P(OEGA-co-DDA))precursors with different ratios of hydrophilic and hydrophobic moieties were synthesized by reversible addition-fragmentation chain transfer(RAFT)polymerization using a bifunctional chain transfer agent with two anthryl end groups.The amphiphilic linear precursors underwent the self-folding process to generate polymeric nanoparticles in water.By irradiating the aqueous solution of the nanoparticles with 365 nm UV light,cyclic polymers were synthesized successfully via coupling of anthryl groups.The effects of the ratios of hydrophilic and hydrophobic moieties in linear P(OEGA-co-DDA)copolymers and polymer concentration on the purity of the obtained cyclic polymers were explored in detail via ^(1)H nuclear magnetic resonance(^(1)H NMR),dynamic light scattering(DLS),UV‒visible(vis)analysis,three-detection size exclusion chromatography(TD-SEC)and transmission electron microscopy(TEM).It was found that by adjusting the content of the hydrophilic segments in linear precursors,single chain polymeric nanoparticles(SCPNs)can be generated at high polymer concentrations.Therefore,cyclic polymers with high purity can be constructed efficiently.This method overcomes the limitation of traditional ring-closure method,which is typically conducted in highly dilute conditions,providing an efficient method for the scalable preparation of cyclic polymers.
基金This work was supported by the National Science and Technology Major Project of the Ministry of Science and Technology of China(No.2016ZX05016 and No.2016ZX05046).
文摘With the blooming development of electronic technology,the use of electron conductive gel or ionic conductive gel in preparing flexible electronic devices is drawing more and more attention.Deep eutectic solvents are excellent substitutes for ionic liquids because of their good biocompatibility,low cost,and easy preparation,except for good conductivity.In this work,we synthesized a reactive quaternary ammonium monomer(3-acrylamidopropyl)octadecyldimethyl ammonium bromide with a hydrophobic chain of 18 carbons via the quaternization of 1-bromooctadecane and N-dimethylaminopropyl acrylamide at first,then we mixed quaternary ammonium with choline chloride,acrylic acid and glycerol to obtain a hydrophobic deep eutectic solvent,and initialized polymerization in UV light of 365 nm to obtain the ionic conductive eutectogel based on polyacrylamide copolymer with long hydrophobic chain.The obtained eutectogel exibits good stretchability(1200%),Young's modulus(0.185 MPa),toughness(4.2 MJ/m^(3)),conductivity(0.315 S/m).The eutectogel also shows desireable moisture resistance with the maximum water absorption of 11.7 wt%after one week at 25℃ and 60% humidity,while the water absorption of eutectogel without hydrophobic long chains is 24.0 wt%.The introduction of long-chain hydrophobic groups not only improves the mechanical strength of the gels,but also significantly improves moisture resistance of the eutectogel.This work provides a simpler and more effective method for the preparation of ionic conductive eutectogels,which can further provide a reference for the applications of ionic conductive eutectogels in the field of flexible electronic devices.
文摘Due to the structure characteristics of huge macromolecular size and the very low motion feature of the polymer chain which is very difficult to arrange regularly their long chain into the three dimensional space,thus the polymer will incompletely crystallize except for the macroscopic single crystal of polydiacetylene polymerized by means of solid state crystalline polymerization.
基金financially supported by the National Natural Science Foundation of China(Nos.22271252 and 22201105)。
文摘Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.
基金National Natural Science Foundation of China,Grant/Award Number:51073067Scientific and Technological Development Program of Jilin Province,Grant/Award Number:20220201138GX.
文摘In recent years,renewable energy sources,which aim to replace rapidly depleting fossil fuels,face challenges due to limited energy storage and conversion technologies.To enhance energy storage and conversion efficiency,extensive research has been conducted in the academic community on numerous potential materials.Among these materials,metal fluorides have attracted significant attention due to their ionic metal-fluorine bonds and tunable electronic structures,attributed to the highest electronegativity of fluorine in their chemical composition.This makes them promising candidates for future electrochemical applications in various fields.However,metal fluorides encounter various challenges in different application directions.Therefore,we comprehensively review the applications of metal fluorides in the field of energy storage and conversion,aiming to deepen our understanding of their exhibited characteristics in different electrochemical processes.In this paper,we summarize the difficulties and improvement methods encountered in different types of battery applications and several typical electrode optimization strategies in the field of supercapacitors.In the field of water electrolysis,we focus on surface reconstruction and the critical role of fluorine,demonstrating the catalytic performance of metal fluorides from the perspectives of reconstruction mechanism and process analysis.Finally,we provide a summary and outlook for this field,aiming to offer guidance for future breakthroughs in the energy storage and conversion applications of metal fluorides.
基金supported by the National Natural Science Foundation of China(Nos.223B2119,U23A2083,52373014,52203129).
文摘The facile synthesis of high-valued polymers from waste molecules or low-cost common chemicals presents a significant challenge.Here,we develop a series of degradable poly(thiocarbonate)s from the new step-growth polymerization of diols,carbonyl sulfide(CoS,or carbon disulfide,CS_(2)),and dichlorides.Diols and dichlorides are common chemicals,and CoS(CS_(2))is released as industrial waste.In addition to abun-dant feedstocks,the method is efficient and performed under mild conditions,using common organic bases as catalysts,and affording unprece-dented polymers.When cos,diols,and dihalides were used as monomers,optimized conditions could completely suppress the oxygen-sulfur exchange reaction,enabling the efficient synthesis of well-defined poly(monothiocarbonate)s with melting points ranging from 48°C to 101°C.These polymers,which have a structure similar to polyethylene with low-density in-chain polar groups,exhibit remarkable toughness and ductili-ty that rival those of high-density polyethylene(melting point:90°C,tensile strength:21.6±0.7 MPa,and elongation at break:576%).Moreover,the obtained poly(monothiocarbonate)s can be chemically degraded by alcoholysis to yield small-molecule diols and dithiols.When CS_(2)was used in place of cos,a pronounced oxygen-sulfur exchange reaction occurred.By optimizing reaction condition,it was found that polymers with-S(C=O)S-and-S(C=S)S-as the main repeating units exhibited high thermal stability and crystallinity.Thus,a new approach for regulat-ing the structure of polythiocarbonates via the oxygen-sulfur exchange reaction is developed.Overall,the polymers hold great potential for green materials due to their facile synthesis,readily available feedstocks,excellent performance,and chemical degradability.
基金supported by the Taiyuan Major Science and Technology Project Fund in 2021,Fund for Shanxi“1331 Project,”Key Research and Development Program of Shanxi Province(202102040201011)the Zhanjiang Marine Equipment and Marine Biological Industry Unveiled the Talent Team Project(2021E05034).
文摘The toughness of thermoplastic polymers such as polypropylene(PP)can be improved by adding elastomers-based toughening agents,and the phase morphology of these toughening agents is very important for the strength and toughness of PP.The low-temperature toughness of PP was improved by inserting high-density polyethylene(HDPE)between PP and polystyrene-b-ethylene-co-propyleneb-polystyrene(SEPS)to form an unusual SEPS@HDPE core–shell structure,with SEPS as the core and HDPE as the shell.Based on the microtopography and rheological behavior characterization,HDPE in PP/SEPS/HDPE composites was found to serve as an emulsifier,decrease the size of SEPS particles,and promote the homogeneous dispersion of dispersed phase particles in the matrix.An increase in the HDPE content shifted the toughening mechanism of PP composites from cavitation to matrix shear yielding.The reduction in the distance between the dispersed core–shell structure particles promoted shear yielding in the PP composites,leading to increased toughness.The creation of an intermediate HDPE layer with a moderate modulus was crucial for dispersing stress concentrations and significantly improving toughness without compromising the tensile strength.These findings will facilitate the fabrication of high-toughness PP products at low temperatures.
基金Financial support from the National Research Foundation of Korea grant funded by the Korean government(No.2022R1F1A1074210)the University Natural Science Research Projects of Anhui Province(No.2024AH050145)is gratefully acknowledged.
文摘Electromagnetic interference shielding materials are inevitably damaged during service,causing a serious decline in their shielding performance.Therefore,it is urgent to develop polymer-based composites with excellent electromagnetic shielding and self-healing properties.In this study,a layered foam/film structure polycaprolactone composite characterized by electric/magnetic bifunctionality was constructed by a hot-pressing process and supercritical carbon dioxide foaming.The microcellular framework offers rich heterogeneous interfaces and improves electromagnetic attenuation capabilities.Such a reasonable construction of asymmetric shielding networks optimizes the impedance matching,while the incident electromagnetic waves form a special attenuation mode of“absorption-reflection-reabsorption”.The polycaprolactone composite foam exhibits an excellent electromagnetic interference shielding effectiveness of 53.6 dB in the X-band and a low reflection value of only 0.36,effectively reducing secondary pollution.In addition,the damaged polycaprolactone composite foam exhibits over 93%electromagnetic interference shielding effectiveness and healing efficiency,ensuring the long-term stability of the material in practical applications.
基金financial support from National Natural Science Foundation of China(Nos.22005186 and 51877132) was acknowledged。
文摘Flexible and stretchable energy storage devices are highly desirable for wearable electronics,particularly in the emerging fields of smart clothes,medical instruments,and stretchable skin.Lithium metal batteries(LMBs) with high power density and long cycle life are one of the ideal power sources for flexible and stretchable energy storage devices.However,the current LMBs are usually too rigid and bulky to meet the requirements of these devices.The electrolyte is the critical component that determines the energy density and security of flexible and stretchable LMBs.Among various electrolytes,gel polymer electrolytes(GPEs) perform excellent flexibility,safety,and high ionic conductivity compared with traditional liquid electrolytes and solid electrolytes,fulfilling the next generation deformable LMBs.This essay mainly reviews and highlights the recent progress in GPEs for flexible/stretchable LMBs and provides some useful insights for people interested in this field.Additionally,the multifunctional GPEs with self-healing,flame retardant,and temperature tolerance abilities are summarized.Finally,the perspectives and opportunities for flexible and stretchable GPEs are discussed.
基金financially supported by the National Natural Science Foundation of China(Nos.51973205 and 51773189)the Fundamental Research Funds for the Central Universities(Nos.WK9110000066,WK345000005 and WK345000006).
文摘As a highly promising conductive polymer material,the synthesis method,structure regulation,and performance improvement of polyaniline(PANI)are hot research topics.In this work,the radiation-induced polymerization of aniline in HNO_(3)solution was successfully achieved at room temperature without the use of chemical oxidants.Through the analysis of the radiation chemical reactions of inorganic acids and nitrate salt solutions,the characterization of the intermediate free radicals in the irradiated systems,and the influence of the pH of the solutions on the polymerization activity and product morphologies,the radiation-induced polymerization mechanism of aniline is discussed in detail and proposed.Only at a condition of[HNO_(3)]>[aniline],i.e.,pH<2.5,PANI can be successfully obtained underγ-ray radiation.The polymerization begins with the oxidation of aniline cations to aniline cation radicals by·NO_(3)generated by radiolysis reactions,and undergoes repeated three steps of monomer free radical recombination,deprotonation,and oxidation reaction of·NO_(3),thus forming a PANI macromolecule.In addition to the polymerization reaction,the aniline units are protonated and oxidized because of the strongly acidity and oxidation of the reaction system under γ-ray irradiation,which means that the molecular chain structure of the radiation-synthesized PANI can be regulated by pH,nitrate concentration,and irradiation conditions.Radiation-synthesized PANI has a moderate protonation and oxidation state,which can be used for the preparation of PANI supercapacitors with better electrochemical properties than those prepared by chemical oxidation under the same conditions.This work presents a new radiation-synthesis method and polymerization mechanism of PANI,which not only expands the application of radiation technique in the field of polymer synthesis,but also provides a new idea for the structural regulation and electrochemical property optimization of PANI.
基金financially supported by National Key R&D Program of China(No.2021YFA1501700)CAS Project for Young Scientists in Basic Research(No.YSBR-094)+1 种基金Natural Science Foundation of Anhui Province(Nos.2308085Y35 and 2023AH030002)Hefei Natural Science Foundation(No.202304)。
文摘As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.
基金the financial support from the National Natural Science Foundation of China(Nos.22301206,92356305 and 22301208)Natural Science Foundation of Anhui Province(No.2308085J15)+5 种基金Natural Science Foundation of Anhui Provincial Higher Education Institutions(No.2023AH010012)China Post-doctoral Science Foundation(No.2022M722312)the Key Laboratory of Polymeric Material Design and Synthesis for Biomedical Functionthe Priority Academic Program Development(PAPD)of Jiangsu Higher Education InstitutionsJiangsu Funding Program for Excellent Postdoctoral Talentthe Program of Innovative Research Team of Soochow University。
文摘Recently circularly polarized luminescence(CPL)materials have attracted significant interest.Introducing reversible dynamic property to these materials has been a key focus in cutting-edge fields,such as in high-level information encryption.Here,we provided a novel and general strategy involving handednessselective filtration and ground-state chiral self-recovery(CSR)in double film system to address this issue.Based on this strategy,we achieved CPL switch through the reversible modulation of ground-state chirality including absorption and scattering circular dichroism(CD)signals over the full UV-visible wavelength range(365-700 nm)in a single azobenzene polymer(PAzo)film.More importantly,by flexibly changing the type of fluorescent films,it is convenient to achieve general excited-state CSR,that is reversible switching of full-color including ideal white(CIE coordinate(0.33,0.33)),as well as room-temperature phosphorescent CPL.All these CPL signals without almost any intensity decay after three cycles of onand-off switching.Experimental results indicated that the trans-cis isomerization and ordered rearrangement of azobenzene units in PAzo film were the fundamental reasons for realizing CPL switching.Finally,based on this system we achieved dynamic visual encryption and decryption process including multiple decryption methods.This study provides an effective method for constructing a universally applicable chiroptical switch in excited state.
基金supported by the National Natural Science Foundation of China(No.52173095)the MOE Key Laboratory of Macromolecular Synthesis and Functionalization,Zhejiang University(No.2023MSF05)。
文摘The recovery of ionic liquids(ILs)has attracted growing attention as an indispensable process in“green”industrial applications.Forward osmosis(FO)has proven to be a sustainable method for concentrating the very dilute aqueous solutions of ILs at ambient temperature,in which semi-permeable membranes play a vital role in determining the recovery efficiency.Herein,we use interfacial polymerization method to prepare thin-film composite membranes consisting of polyamide skin layer and electrospun nanofibrous substrate with tunable water permeability and IL selectivity for osmotic enrichment of imidazolium ILs from their dilute aqueous solutions through FO process.The resulting FO membrane shows a compact polyamide layer with a thickness of 30-200 nm,guranteeing a high selectivity to ILs and water.Meanwhile,the nanofibrous substrate with large and interconnect pores as well as low tortuosity,providing mechanical and permeable support for the composite membranes.IL structure influences the osmotic pressure difference as well as the interactions with polyamide layer of the membrane and thus determines the whole concentration process.First,the alkyl chain growth augments the osmosis pressure difference between the ILs solution and draw solution,resulting in an enhancement in driving force of water osmosis and IL enrichment.Moreover,alkyl length aggravates external concentration polarization caused by the enhanced adsorption of ILs onto the skin layer via electrostatic and alkyl-πinteractions.Meanwhile,such adsorbed ILs further enhance the IL retention but decrease the reverse salt diffusion.Therefore,imidazolium ILs with varied alkyl lengths are ultimately enriched with a 100-fold increase in concentration from their dilute aqueous solutions with high IL/NaCl rejection and low IL loss.Remarkably,the final concentration of IL with longest alkyl length reaches the highest(6.4 mol·L^(-1)).This work provides the insights in respect to material preparation and process amelioration for IL recovery with high scalability at mild conditions.
基金the National Natural Science Foundation of China(52275294)the National Key Research and Development Program of China(2018YFA0703000).
文摘The designing and manufacturing of micro/nanoscale tools for delivery,diagnostic,and therapeutic are essential for their multiscale integration in the precision medicine field.Conventional three-dimensional(3D)printing approaches are not suitable for such kind of tools due to the accuracy limitation.Multiphoton polymerization(MPP)-based micro/nanomanufacturing is a noncontact,high-precision molding technology that has been widely used in the micro/nano field is a promising tool for micro/nanoscale related precision medicine.In this article the fundamentals of MPP-based technology and the required materials in precision medicine are overviewed.The biomedical applications in various scenarios are then summarized and categorized as delivery systems,microtissue modeling,surgery,and diagnosis.Finally,the existing challenges and future perspectives on MPP-based micro/nanomanufacturing for precision medicine are discussed,focusing on material design,process optimization,and practical applications to overcome its current limitations.
基金supported by the National Natural Science Foundation of China(Nos.52325302 and 52173012)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(No.2022SZ-FR005)。
文摘Achieving continuous motions typically requires dynamic external stimuli for cyclic deformation,or crafted geometries with intricate modules to form a self-regulated feedback loop upon static stimulation.It is still a grand challenge to realize self-sustained motion in soft robots subject to unchanging environment,without complex geometry or a control module.In this work,we report soft robots based on an anisotropic cylindrical hydrogel showing self-regulated,continuous rolling motions under constant light irradiation.The robots are animated by mirror-symmetry-breaking induced by photothermal strain gradient.The self-sustained motion is attributed to the fast and reversible deformation of the gel and the autonomous refresh of the irradiated region during the rolling motion.The hydrogel robots can reach a rolling speed of 1.27 mm·s^(-1)on a horizonal surface and even climb a ramp of 18°at a speed of 0.57 mm·s^(-1)in an aqueous environment.Furthermore,the hydrogel robots can overcome an obstacle,with rolling direction controllable through irradiation angle of the light and local irradiation on selective regions.This work suggests a facile strategy to develop hydrogel robots and may provide unforeseen inspirations for the design of self-regulated soft robots by using other intelligent materials.
文摘Given the increasing demand for distributed electricity,there is a burning desire to harvest electricity from renewable sources using environmentally friendly methods.Thermoelectric (TE) materials can meet this requirement not only because of their ability to convert heat directly into electricity,enabling energy harvesting from waste heat and natural heat resources,but also because more than 60%of the energy is lost as waste heat [1].The discovery of the TE effect dates back to the 1820s when T.M.Seebeck observed electricity generation at the junction of two conductors with different temperatures.Additionally,when a voltage is applied to TE materials,they can create a temperature difference to enable solid-state cooling (known as the Peltier effect).Therefore,the TE effect promises both sustainable energy solutions and temperature control technologies.Over the past two decades,the urgent demand for powering ubiquitous Internet of Things devices has sparked significant interest in flexible thermoelectrics(F-TEs),which raises an intriguing question:Is the intrinsically flexible polymer an important candidate for state-of-the-art F-TEs applications?
文摘In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.
基金financially supported by the National Natural Science Foundation of China(No.50803054)Zhejiang Provincial Nature Science Foundation of China(No.Y4100204)
文摘Inspired by the self-polymerization and strong adhesion characteristics of dopamine in aqueous conditions, a novel hydrophilic nanofiltration （NF） membrane was fabricated by simply dipping polysulfone （PSf） ultrafiltration （UF） substrate in dopamine solution. The changes in surface chemical composition and morphology of membranes were determined by Fourier transform infrared spectroscopy （FTIR-ATR）, X-ray photoelectron spectroscopy （XPS）, scanning electron microscopy （SEM） and atomic force microscopy （AFM）. The experimental results indicated that the self-polymerized dopamine formed an ultrathin and defect-free barrier layer on the PSf UF membrane. The surface hydrophilicity of membranes was evaluated through water contact angle measurements. It was found that membrane hydrophilicity was significantly improved after coating a polydopamine （pDA） layer, especially after double coating. The dyes filtration experiments showed that the double-coated membranes were able to reject completely the dyes of brilliant blue, congo red and methyl orange with a pure water flux of 83.7 L/（mE.h） under 0.6 MPa. The zeta potential determination revealed the positively-charged characteristics of PSf/pDA composite membrane in NF process. The salt rejection of the membranes was characterized by 0.01 mmol/L of salts filtration experiment. It was demonstrated that the salts rejections followed the sequence： NaC1 〈 NaaSO4 〈 MgSO4 〈 MgC12 〈 CaCl2, and the rejection to CaC12 reached 68.7%. Moreover, the composite NF membranes showed a good stability in water-phase filtration process.
基金supported by the Science and Technology Department of Zhejiang Province(No.2006C11050)
文摘A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluene diisocyanate. Meanwhile, NS with different molecular weights was synthesized and used as the soft co-segment. Effects of types and contents of soft co-segments as well as chain extenders on the thermal degradation and stability for WPSUR films were examined. Results reveal that WPSUR films exhibit excellent water resistance and mechanical properties as compared with pure polyurethane （PU） films, and the NS soft co-segment possesses a remarkable effect on the second stage （stage Ⅱ）, while the content of the hard segment is propitious to the initial stage （stage Ⅰ）. Moreover, the highest temperature of stage Ⅱ （T2m） for WPSUR films using NS as soft co-segment is 413℃, approximately being 30℃ higher than that of those typical PUs using HDA and APDMS as the chain extenders, respectively.
