The emulsion copolymerization of vinylidene chloride (VDC) with methyl-methacrylate(MMA) and acrylonitrile (AN) was carried out by batch, seeded batch and semicontinuous pro-cesses,respectively. Significant difference...The emulsion copolymerization of vinylidene chloride (VDC) with methyl-methacrylate(MMA) and acrylonitrile (AN) was carried out by batch, seeded batch and semicontinuous pro-cesses,respectively. Significant differences were found in the physical and mechanical propertiesof the latexes and films, depending on the methods of monomer feeding. The results both intheory and experiments demonstrated that the copolymer composition and the length of the VDC sequences in the copolymer could be controlled by the modes of monomer feeding process.展开更多
The gradient copolymers of acrylic acid and trifluoroethyl methacrylate（coded as P（TFEMAgrad-AA）） were synthesized via reversible addition-fragmentation transfer（RAFT） emulsifier-free emulsion polymerization. Th...The gradient copolymers of acrylic acid and trifluoroethyl methacrylate（coded as P（TFEMAgrad-AA）） were synthesized via reversible addition-fragmentation transfer（RAFT） emulsifier-free emulsion polymerization. The spontaneous batch feeding approach was used to control the gradient chain sequence. Transmission electron microscopy（TEM） analysis revealed that the P（TFEMA-grad-AA） can self-assemble to form spherical micelles, rodlike micelles or vesicles in selective solvents. Morphological transition of the P（TFEMA-grad-AA） micelles was sensitive to the water content of the dioxane/water mixed solvent. More interestingly, Ag nanoparticles（NPs） were encapsulated by the P（TFEMA-grad-AA） micelles during the selfassembly process. The gradient chain sequence made the Ag NPs easily enter the core of the micelles, even when P（TFEMA-grad-AA） had less hydrophobic fluoro-units and more hydrophilic units. TEM images with energy dispersive spectrometer indicated that the nanocomposite micelles consisted of a Ag NPs core and a gradient copolymer shell.展开更多
The emulsion polymerization of N-phenylmaleimide, Styrene and acrylonitrile was studied. The thermal property of this copolymer was measures by dynamic thermomechanical analysis(DMA). The mechanical properties, such a...The emulsion polymerization of N-phenylmaleimide, Styrene and acrylonitrile was studied. The thermal property of this copolymer was measures by dynamic thermomechanical analysis(DMA). The mechanical properties, such as tensile strength, hardness and fie-cural Strength were StUdied experimentally. The results indicated that not only the monomer component but also the polymerization technologies have effect on the properties of the copolymer. The optimum monomer content and suitable polymerization method were obtained.展开更多
Comprehensive Summary Metal nanoparticles(NPs)decorated block copolymer(BCP)hybrid nanoparticles have attracted enormous attention for their actual value in catalysis,medical therapy,and bioengineering.The confined as...Comprehensive Summary Metal nanoparticles(NPs)decorated block copolymer(BCP)hybrid nanoparticles have attracted enormous attention for their actual value in catalysis,medical therapy,and bioengineering.The confined assembly of BCPs within evaporative emulsion droplet is verified as an effective method to provide polymeric scaffolds to load metal NPs.However,to date,it remains challenging to generate different types of metal NPs decorated BCP hybrid nanoparticles.Herein,we employed the emulsion confined self-assembly of poly(styrene-b-2-vinylpyridine)(PS-b-P2VP)and the followed seed-mediated growth of Au and palladium(Pd)NPs onto well-defined BCP particles to design a series of Au/Pd decorated BCP hybrid nanoparticles,which exhibited excellent catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol with the reductant of NaBH4.This work may inspire more researchers to investigate the selective decoration of different metal NPs onto the polymeric scaffolds,broadening the potential applications of the inorganic/organic hybrid nanoparticles.展开更多
Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl...Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizationsof MMA and BA were obtained. The stabilizing effect was found to be dependent on themolecular weight and the feed amount of the macromonomer.展开更多
Stimulus-responsive vesicles have broad applications in a variety of areas. Herein, oxidation-responsive framboidal triblock copolymer vesicles are prepared by photoinitiated RAFT seeded emulsion polymerization of a t...Stimulus-responsive vesicles have broad applications in a variety of areas. Herein, oxidation-responsive framboidal triblock copolymer vesicles are prepared by photoinitiated RAFT seeded emulsion polymerization of a thioether-functionalized monomer using diblock copolymer vesicles as seeds. The obtained framboidal vesicles can transform into worms or spheres in the presence of reactive oxygen species,which can be further used for controlled release of cargos(e.g., silica nanoparticles).展开更多
Soap-free poly（methyl methacrylate-ethyl acrylate-methacrylic acid） latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwi...Soap-free poly（methyl methacrylate-ethyl acrylate-methacrylic acid） latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase of initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.展开更多
Block copolymers(BCPs)can automatically assemble into various regulated nanoparticles when they are confined within the emulsion droplet be-cause of the structural frustration of polymer chains and the soft template e...Block copolymers(BCPs)can automatically assemble into various regulated nanoparticles when they are confined within the emulsion droplet be-cause of the structural frustration of polymer chains and the soft template effect of the oil/water interface.In the past few years,great efforts have been made to regulate the morphologies of the resulting BCP particles.In this review article,various strategies for tuning oil/water interfacial prop-erties to engineer the as-formed BCP particles were summarized.Then,the comprehensive scenarios of the applications of the resulting BCP parti-cles were discussed.Finally,the future tendency and challenge of the self-assembly of BCPs confined in emulsion droplet were suggested.展开更多
Chitosan （CS） was successfully modified in supercritical carbon dioxide （ scCOz ） by grafting method to enhance its water solubility. In this work, a three.arm star-like fluorinated polymer was synthesized by atom...Chitosan （CS） was successfully modified in supercritical carbon dioxide （ scCOz ） by grafting method to enhance its water solubility. In this work, a three.arm star-like fluorinated polymer was synthesized by atom transfer radical polymerization （ ATRP ） method and applied as a surfactant in supereriticul carbon dioxide （scCO2 ）. Then 2-acrylamido-2-methyl propane sulfonie acid （AMPS） was grafted onto CS （CS-g-PAMPS） in H2O/scCO2 inverse emulsion. The effects of mass ratio of water and surfactants （Rw/s ） and pressure of scCO2 on the grafting reaction were investigated. The grafting rate, partide size, and dispersity in water of CS-g-PAMPS varied greatly as Rw/s and pressure of scCO2 changed. It could be found that the value of Rw/s at 12 and the pressure of scCO2 at 30 MPa were the optimum conditions for the grafting reaction. CS-g-PAMPS prepared in this reaction system has higher grafting rate, smaller particle sizes, and better dispersity in water than those prepared via conventional methods.展开更多
In the past few decades,significant progress in block copolymer self-assembly has been achieved in many fields,and with the development of nanoscience and nanotechnology,more and more complex situations need block cop...In the past few decades,significant progress in block copolymer self-assembly has been achieved in many fields,and with the development of nanoscience and nanotechnology,more and more complex situations need block copolymer self-assembly based nanoplatforms having more complex structures for specific multimodal or multiplexed applications.Through the combination of emulsification and self-assembly of the block copolymer,different materials with exotic architectures and functions could be combined within an entity,such as controlled vesicles,Janus particles,and composite particles which are more like ideal nanoplatforms.Various designs can show their different desired properties depending upon the application situation,including molecular delivery,surfactants,and multicolor encoding.This review will provide a complete summary of the optimization and the synthesis method for the recently designed emulsion confined block copolymer assemblies,and also the challenges and limitations this method faces,and the potential solutions in this field.展开更多
Lithium-sulfur batteries suffer a lot from the huge volume change and the shuttle effect. However, conventional poly(vinylidene fluoride) binder has intrinsic drawbacks, such as low ion conductivity, weak polysulfide-...Lithium-sulfur batteries suffer a lot from the huge volume change and the shuttle effect. However, conventional poly(vinylidene fluoride) binder has intrinsic drawbacks, such as low ion conductivity, weak polysulfide-trapping ability, poor mechanical properties, and requirement of organic solvents. Herein, we designed a functional emulsion binder with multi crosslinked structure. Such a structure was formed by the covalent crosslinking within and between the emulsion particles, which facilitates the adapting of the volume expansion of sulfur cathode, thereby ensuring the integrity of electrodes. Besides, the polar functional groups endow the binder with strong chemisorption of lithium polysulfide and fast lithium-ion migration ability. Thus, the assembled lithium-sulfur battery displayed a high initial discharge capacity of 1246 mAh·g^(−1) at 0.1 C, and a capacity fading rate of 0.04% per cycle after 500 cycles at 0.5 C. Even at a high sulfur mass loading of 4.8 mg·cm^(−2), a high capacity of 956 mAh·g^(−1) was still obtained at 0.2 C.展开更多
基金The project is supported by Beijing Natural Science Fund.
文摘The emulsion copolymerization of vinylidene chloride (VDC) with methyl-methacrylate(MMA) and acrylonitrile (AN) was carried out by batch, seeded batch and semicontinuous pro-cesses,respectively. Significant differences were found in the physical and mechanical propertiesof the latexes and films, depending on the methods of monomer feeding. The results both intheory and experiments demonstrated that the copolymer composition and the length of the VDC sequences in the copolymer could be controlled by the modes of monomer feeding process.
基金the National Natural Science Foundation of China(Nos.50803048 and 50703030)
文摘The gradient copolymers of acrylic acid and trifluoroethyl methacrylate（coded as P（TFEMAgrad-AA）） were synthesized via reversible addition-fragmentation transfer（RAFT） emulsifier-free emulsion polymerization. The spontaneous batch feeding approach was used to control the gradient chain sequence. Transmission electron microscopy（TEM） analysis revealed that the P（TFEMA-grad-AA） can self-assemble to form spherical micelles, rodlike micelles or vesicles in selective solvents. Morphological transition of the P（TFEMA-grad-AA） micelles was sensitive to the water content of the dioxane/water mixed solvent. More interestingly, Ag nanoparticles（NPs） were encapsulated by the P（TFEMA-grad-AA） micelles during the selfassembly process. The gradient chain sequence made the Ag NPs easily enter the core of the micelles, even when P（TFEMA-grad-AA） had less hydrophobic fluoro-units and more hydrophilic units. TEM images with energy dispersive spectrometer indicated that the nanocomposite micelles consisted of a Ag NPs core and a gradient copolymer shell.
文摘The emulsion polymerization of N-phenylmaleimide, Styrene and acrylonitrile was studied. The thermal property of this copolymer was measures by dynamic thermomechanical analysis(DMA). The mechanical properties, such as tensile strength, hardness and fie-cural Strength were StUdied experimentally. The results indicated that not only the monomer component but also the polymerization technologies have effect on the properties of the copolymer. The optimum monomer content and suitable polymerization method were obtained.
基金the financial support of the Natural Science Foundation of China(52003070)Zhejiang Provincial Natural Science Foundation of China(LR20E030003).
文摘Comprehensive Summary Metal nanoparticles(NPs)decorated block copolymer(BCP)hybrid nanoparticles have attracted enormous attention for their actual value in catalysis,medical therapy,and bioengineering.The confined assembly of BCPs within evaporative emulsion droplet is verified as an effective method to provide polymeric scaffolds to load metal NPs.However,to date,it remains challenging to generate different types of metal NPs decorated BCP hybrid nanoparticles.Herein,we employed the emulsion confined self-assembly of poly(styrene-b-2-vinylpyridine)(PS-b-P2VP)and the followed seed-mediated growth of Au and palladium(Pd)NPs onto well-defined BCP particles to design a series of Au/Pd decorated BCP hybrid nanoparticles,which exhibited excellent catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol with the reductant of NaBH4.This work may inspire more researchers to investigate the selective decoration of different metal NPs onto the polymeric scaffolds,broadening the potential applications of the inorganic/organic hybrid nanoparticles.
文摘Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizationsof MMA and BA were obtained. The stabilizing effect was found to be dependent on themolecular weight and the feed amount of the macromonomer.
基金support from the Science and Technology Program of Guangzhou(No.202102020631)the National Natural Science Foundation of China(Nos.22171055 and 21971047)+1 种基金Innovation Project of Education Department in Guangdong(No.2018KTSCX053)support from Guangdong Special Support Program(No.2017TX04N371)。
文摘Stimulus-responsive vesicles have broad applications in a variety of areas. Herein, oxidation-responsive framboidal triblock copolymer vesicles are prepared by photoinitiated RAFT seeded emulsion polymerization of a thioether-functionalized monomer using diblock copolymer vesicles as seeds. The obtained framboidal vesicles can transform into worms or spheres in the presence of reactive oxygen species,which can be further used for controlled release of cargos(e.g., silica nanoparticles).
基金The research was supported by the National 863 Project of China(No.2001AA242041).
文摘Soap-free poly（methyl methacrylate-ethyl acrylate-methacrylic acid） latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase of initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.
基金Y.Z acknowledges the financial support of Zhejiang Provincial Natural Science Foundation of China(LR20E030003)X.C acknowledges the financial support of National Natural Science FoundationofChina(52003070).
文摘Block copolymers(BCPs)can automatically assemble into various regulated nanoparticles when they are confined within the emulsion droplet be-cause of the structural frustration of polymer chains and the soft template effect of the oil/water interface.In the past few years,great efforts have been made to regulate the morphologies of the resulting BCP particles.In this review article,various strategies for tuning oil/water interfacial prop-erties to engineer the as-formed BCP particles were summarized.Then,the comprehensive scenarios of the applications of the resulting BCP parti-cles were discussed.Finally,the future tendency and challenge of the self-assembly of BCPs confined in emulsion droplet were suggested.
基金National Natural Science Foundation of China(No.20674017)Shanghai Key Laboratory Project of China(No.08DZ2230500)
文摘Chitosan （CS） was successfully modified in supercritical carbon dioxide （ scCOz ） by grafting method to enhance its water solubility. In this work, a three.arm star-like fluorinated polymer was synthesized by atom transfer radical polymerization （ ATRP ） method and applied as a surfactant in supereriticul carbon dioxide （scCO2 ）. Then 2-acrylamido-2-methyl propane sulfonie acid （AMPS） was grafted onto CS （CS-g-PAMPS） in H2O/scCO2 inverse emulsion. The effects of mass ratio of water and surfactants （Rw/s ） and pressure of scCO2 on the grafting reaction were investigated. The grafting rate, partide size, and dispersity in water of CS-g-PAMPS varied greatly as Rw/s and pressure of scCO2 changed. It could be found that the value of Rw/s at 12 and the pressure of scCO2 at 30 MPa were the optimum conditions for the grafting reaction. CS-g-PAMPS prepared in this reaction system has higher grafting rate, smaller particle sizes, and better dispersity in water than those prepared via conventional methods.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China(Nos.52103276,51533009,and 22071271)the Natural Science Foundation of Guangdong Province of China(No.2022A1515010947)+2 种基金Guangzhou Basic and Applied Basic Research Foundation(No.202201011343)the Key Areas Research and Development Program of Guangzhou(202007020006)the Hundred Talents Program Startup Grant of Sun Yat-sen University.
文摘In the past few decades,significant progress in block copolymer self-assembly has been achieved in many fields,and with the development of nanoscience and nanotechnology,more and more complex situations need block copolymer self-assembly based nanoplatforms having more complex structures for specific multimodal or multiplexed applications.Through the combination of emulsification and self-assembly of the block copolymer,different materials with exotic architectures and functions could be combined within an entity,such as controlled vesicles,Janus particles,and composite particles which are more like ideal nanoplatforms.Various designs can show their different desired properties depending upon the application situation,including molecular delivery,surfactants,and multicolor encoding.This review will provide a complete summary of the optimization and the synthesis method for the recently designed emulsion confined block copolymer assemblies,and also the challenges and limitations this method faces,and the potential solutions in this field.
基金supported by the National Natural Science Foundation of China(Nos.21875065 and 22109045)China Postdoctoral Science Foundation(No.2021M701191).
文摘Lithium-sulfur batteries suffer a lot from the huge volume change and the shuttle effect. However, conventional poly(vinylidene fluoride) binder has intrinsic drawbacks, such as low ion conductivity, weak polysulfide-trapping ability, poor mechanical properties, and requirement of organic solvents. Herein, we designed a functional emulsion binder with multi crosslinked structure. Such a structure was formed by the covalent crosslinking within and between the emulsion particles, which facilitates the adapting of the volume expansion of sulfur cathode, thereby ensuring the integrity of electrodes. Besides, the polar functional groups endow the binder with strong chemisorption of lithium polysulfide and fast lithium-ion migration ability. Thus, the assembled lithium-sulfur battery displayed a high initial discharge capacity of 1246 mAh·g^(−1) at 0.1 C, and a capacity fading rate of 0.04% per cycle after 500 cycles at 0.5 C. Even at a high sulfur mass loading of 4.8 mg·cm^(−2), a high capacity of 956 mAh·g^(−1) was still obtained at 0.2 C.
