Monodisperse hollow polymer microspheres having various functional groups on the shell-layer, such as carboxylic acid, pyridyl and amide, were prepared by two-stage distillation precipitation polymerization in neat ac...Monodisperse hollow polymer microspheres having various functional groups on the shell-layer, such as carboxylic acid, pyridyl and amide, were prepared by two-stage distillation precipitation polymerization in neat acetonitrile in the absence of any stabilizer or additive, during which monodisperse poly（methacrylic acid） （PMAA） afforded from the first-stage polymerization was utilized as the seeds for the second-stage polymerization. The shell layer with different functional groups was formed during the second-stage copolymerization of either divinylbenzene （DVB） or ethyleneglycol dimethacrylate （EGDMA） as crosslinker and the functional comonomers, in which the hydrogen-bonding interaction between the carboxylic acid group of PMAA core and the functional groups of the corresponding comonomers, including carboxylic acid, amide and pyridyl, played an essential role for the formation of monodisperse core-shell functional microspheres. The hollow polymer microspheres were then developed after the subsequent removal of PMAA cores by dissolution in ethanol under basic condition. Transmission electron microscopy （TEM） and scanning electron microscopy （SEM） were used to determine the morphology of the resultant PMAA core, functional core-shell microspheres and the corresponding hollow polymer microspheres with different functional groups. FT-IR spectra confirmed the successful incorporation of the various functional groups on the shell layer of the hollow polymer microspheres.展开更多
Monodisperse crosslinked poly(chloromethylstyrene-co-divinylbenzene)(poly(CMSt-co-DVB))microsphereswere prepared by distillation-precipitation copolymerization of chloromethylstyrene(CMSt)and divinylbenzene(DVB)inneat...Monodisperse crosslinked poly(chloromethylstyrene-co-divinylbenzene)(poly(CMSt-co-DVB))microsphereswere prepared by distillation-precipitation copolymerization of chloromethylstyrene(CMSt)and divinylbenzene(DVB)inneat acetonitrile.The polymer particles had clean surfaces due to the absence of any added stabilizer.The size of the particlesranges from 2.59 μm to 3.19 μm and with mono-dispersity around 1.002-1.014.The effects of monomer feed incopolymerization on the microsphere formation were described.The polymer microspheres were characterized by SEM andchlorinity elemental analysis.展开更多
Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslin...Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.展开更多
High selective molecularly imprinted polymers （MIPs） for tetracycline have been prepared by precipitation polymerization. Effects of monomer and solvent, the ratio of monomer and template and the characterization of...High selective molecularly imprinted polymers （MIPs） for tetracycline have been prepared by precipitation polymerization. Effects of monomer and solvent, the ratio of monomer and template and the characterization of the polymer were investigated by frontal chromatography and selectivity experiment. The results clearly indicated that the polymer, which had the highest molecular recognition abilities for tetracycline antibiotics, had been received.展开更多
Molecularly imprinted microspheres (MIP) for monocrotophos have been prepared by precipitation polymerization in acetonitrile (ACN) 60℃,24 h,using methacrylic acid (MAA),ethylene glycol dimethacrylate (EGDMA) and 2, ...Molecularly imprinted microspheres (MIP) for monocrotophos have been prepared by precipitation polymerization in acetonitrile (ACN) 60℃,24 h,using methacrylic acid (MAA),ethylene glycol dimethacrylate (EGDMA) and 2, 2-azobisiobutyronitrile (AIBN) as functional monomer,cross-linker and initiator,respectively.The recognition mechanism was elucidated by UV-vis spectra and computer modeling.Equilibrium binding experiment was employed to investigate the rebinding properties,Scatchard analysis showed that specific binding sites formed in the imprinted microspheres,and there were two kinds of binding sites,one was high binding sites,the other was low binding sites.This microspheres can be useful affinity absorbent used for organophosphorus pesticides separation and purification in food and environmental analysis.展开更多
Simultaneous achievement in high solid content and high microsphere yield is deemed a challenge in the fabrication of monodisperse microspheres by precipitation polymerization.We herein demonstrate that micro-sized mo...Simultaneous achievement in high solid content and high microsphere yield is deemed a challenge in the fabrication of monodisperse microspheres by precipitation polymerization.We herein demonstrate that micro-sized monodisperse poly(methacrylic monomer-divinylbenzene)microspheres containing epoxy,lauyl,carboxyl and hydroxyl functions can be fabricated by solvothermal precipitation copolymerization at 20%(mass)monomer loading with over 94%microsphere yield.The morphology and porosity of the obtained particles can be readily tuned by cosolvent-acetonitrile binary solvents.Addition of a small amount of cosolvent that has similar solubility parameter to that of the functional monomer can significantly improve the monodispersity of the obtained microspheres.When tetrahydrofuran was used as the co-solvent,the surface area of the highly porous microspheres achieved higher than 400 m^(2)·g^(-1).Solvothermal precipitation co-polymerization can be expected in scale-up fabrication of various monodisperse functional microspheres free of any surfactant and additive.展开更多
Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobu...Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.展开更多
The synthesis of Nd3＋,Y3＋：CaF2 nanopowder was conducted by azeotropic distillation method,which effectively dehydrated hydrous CaF2 and prevented forming hard agglomerates.X-ray diffraction（XRD）,scanning electron...The synthesis of Nd3＋,Y3＋：CaF2 nanopowder was conducted by azeotropic distillation method,which effectively dehydrated hydrous CaF2 and prevented forming hard agglomerates.X-ray diffraction（XRD）,scanning electron microscopy（SEM）,scanning calorimetries-thermalgravimetry（DSC-TG）,Fourier transform infrared spectroscopy（FT-IR） and absorption spectroscopy were performed to characterize the powder properties.The experimental results showed that products obtained by azeotropic distillation were single phased,rather monodispersed,successfully prevented the hard agglomerate formation and effectively removed the residual water inside the as-prepared precipitate than that of the direct drying.The absorption spectra showed a wider and stronger absorption bands around 792 nm,which should be profitable for LD pumping.展开更多
Ultra-high-molecular-weight polyethylene(UHMWPE)plays an important role in many important fields as engineering plastics.In this contribution,a precipitation polymerization strategy is developed by combination of high...Ultra-high-molecular-weight polyethylene(UHMWPE)plays an important role in many important fields as engineering plastics.In this contribution,a precipitation polymerization strategy is developed by combination of highly active phosphino-phenolate nickel catalysts with polymer-insoluble solvent(heptane)to access UHMWPE(Mn up to 8.3×10^(6)g mol^(-1))with good product morphology,free-flowing characteristics,and great mechanical properties.Compared with the academically commonly used aromatic solvent(toluene),the utilization of heptane offers simultaneous enhancement in important parameters including activity,polymer molecular weight,and catalyst thermal stability.This system can also generate polar functionalized UHMWPE with molecular weight of up to 1.6×10^(6)g mol^(-1)in the copolymerization of ethylene with polar comonomers.More importantly,this precipitation polymerization strategy is generally applicable to several representative transition metal catalyst systems,leading to UHMWPE synthesis with good product morphology control.展开更多
基金supported by the National Natural Science Foundation of China(No.20874049)
文摘Monodisperse hollow polymer microspheres having various functional groups on the shell-layer, such as carboxylic acid, pyridyl and amide, were prepared by two-stage distillation precipitation polymerization in neat acetonitrile in the absence of any stabilizer or additive, during which monodisperse poly（methacrylic acid） （PMAA） afforded from the first-stage polymerization was utilized as the seeds for the second-stage polymerization. The shell layer with different functional groups was formed during the second-stage copolymerization of either divinylbenzene （DVB） or ethyleneglycol dimethacrylate （EGDMA） as crosslinker and the functional comonomers, in which the hydrogen-bonding interaction between the carboxylic acid group of PMAA core and the functional groups of the corresponding comonomers, including carboxylic acid, amide and pyridyl, played an essential role for the formation of monodisperse core-shell functional microspheres. The hollow polymer microspheres were then developed after the subsequent removal of PMAA cores by dissolution in ethanol under basic condition. Transmission electron microscopy （TEM） and scanning electron microscopy （SEM） were used to determine the morphology of the resultant PMAA core, functional core-shell microspheres and the corresponding hollow polymer microspheres with different functional groups. FT-IR spectra confirmed the successful incorporation of the various functional groups on the shell layer of the hollow polymer microspheres.
基金This work was funded by the financial support of the National Natural Science Foundation of China(Project No.20274018)Nankai University.
文摘Monodisperse crosslinked poly(chloromethylstyrene-co-divinylbenzene)(poly(CMSt-co-DVB))microsphereswere prepared by distillation-precipitation copolymerization of chloromethylstyrene(CMSt)and divinylbenzene(DVB)inneat acetonitrile.The polymer particles had clean surfaces due to the absence of any added stabilizer.The size of the particlesranges from 2.59 μm to 3.19 μm and with mono-dispersity around 1.002-1.014.The effects of monomer feed incopolymerization on the microsphere formation were described.The polymer microspheres were characterized by SEM andchlorinity elemental analysis.
基金This work was supported in part by the National Science Foundation of China (No. 20504015)the starting project for young teachers from the Ministry of Education, China.
文摘Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.
文摘High selective molecularly imprinted polymers （MIPs） for tetracycline have been prepared by precipitation polymerization. Effects of monomer and solvent, the ratio of monomer and template and the characterization of the polymer were investigated by frontal chromatography and selectivity experiment. The results clearly indicated that the polymer, which had the highest molecular recognition abilities for tetracycline antibiotics, had been received.
基金support by the National Natural Science Foundation of China(No.30371218)High Technology Research and Development Program of China(863 Project No.2004AA649110)
文摘Molecularly imprinted microspheres (MIP) for monocrotophos have been prepared by precipitation polymerization in acetonitrile (ACN) 60℃,24 h,using methacrylic acid (MAA),ethylene glycol dimethacrylate (EGDMA) and 2, 2-azobisiobutyronitrile (AIBN) as functional monomer,cross-linker and initiator,respectively.The recognition mechanism was elucidated by UV-vis spectra and computer modeling.Equilibrium binding experiment was employed to investigate the rebinding properties,Scatchard analysis showed that specific binding sites formed in the imprinted microspheres,and there were two kinds of binding sites,one was high binding sites,the other was low binding sites.This microspheres can be useful affinity absorbent used for organophosphorus pesticides separation and purification in food and environmental analysis.
基金National Natural Science Foundation of China(51873079)for financial support。
文摘Simultaneous achievement in high solid content and high microsphere yield is deemed a challenge in the fabrication of monodisperse microspheres by precipitation polymerization.We herein demonstrate that micro-sized monodisperse poly(methacrylic monomer-divinylbenzene)microspheres containing epoxy,lauyl,carboxyl and hydroxyl functions can be fabricated by solvothermal precipitation copolymerization at 20%(mass)monomer loading with over 94%microsphere yield.The morphology and porosity of the obtained particles can be readily tuned by cosolvent-acetonitrile binary solvents.Addition of a small amount of cosolvent that has similar solubility parameter to that of the functional monomer can significantly improve the monodispersity of the obtained microspheres.When tetrahydrofuran was used as the co-solvent,the surface area of the highly porous microspheres achieved higher than 400 m^(2)·g^(-1).Solvothermal precipitation co-polymerization can be expected in scale-up fabrication of various monodisperse functional microspheres free of any surfactant and additive.
基金The work was supported by the National Natural Science Foundation of China (Nos. 20274018 and 20504015)the starting-up foundation from Nankai University and Ministry of Education, China.
文摘Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.
基金Funded by the National Natural Science Foundation of China(No.51072144)the State Key Program of National Science Foundation of China(No.51432007)the Project for Science and Technology Plan of Wuhan City(No.201210231092)
文摘The synthesis of Nd3＋,Y3＋：CaF2 nanopowder was conducted by azeotropic distillation method,which effectively dehydrated hydrous CaF2 and prevented forming hard agglomerates.X-ray diffraction（XRD）,scanning electron microscopy（SEM）,scanning calorimetries-thermalgravimetry（DSC-TG）,Fourier transform infrared spectroscopy（FT-IR） and absorption spectroscopy were performed to characterize the powder properties.The experimental results showed that products obtained by azeotropic distillation were single phased,rather monodispersed,successfully prevented the hard agglomerate formation and effectively removed the residual water inside the as-prepared precipitate than that of the direct drying.The absorption spectra showed a wider and stronger absorption bands around 792 nm,which should be profitable for LD pumping.
基金This work was supported by National Key R&D Program of China(No.2021YFA1501700)National Natural Science Foundation of China(No.52025031,52203016,and 22261142664)USTC Research Funds of the Double First-Class Initiative(YD9990002018).
文摘Ultra-high-molecular-weight polyethylene(UHMWPE)plays an important role in many important fields as engineering plastics.In this contribution,a precipitation polymerization strategy is developed by combination of highly active phosphino-phenolate nickel catalysts with polymer-insoluble solvent(heptane)to access UHMWPE(Mn up to 8.3×10^(6)g mol^(-1))with good product morphology,free-flowing characteristics,and great mechanical properties.Compared with the academically commonly used aromatic solvent(toluene),the utilization of heptane offers simultaneous enhancement in important parameters including activity,polymer molecular weight,and catalyst thermal stability.This system can also generate polar functionalized UHMWPE with molecular weight of up to 1.6×10^(6)g mol^(-1)in the copolymerization of ethylene with polar comonomers.More importantly,this precipitation polymerization strategy is generally applicable to several representative transition metal catalyst systems,leading to UHMWPE synthesis with good product morphology control.
