Poly(vinyl chloride), with ultralow molecular weight, produced by free radical polymerization either at high temperature or in the presence of chain transfer agents, is widely used as special resins and polymer proces...Poly(vinyl chloride), with ultralow molecular weight, produced by free radical polymerization either at high temperature or in the presence of chain transfer agents, is widely used as special resins and polymer process additives. This paper reports a new process, called self-stabilized precipitation polymerization, in which the polymerization of vinyl chloride monomer (VCM) is conducted in hydrocarbon diluents without addition of any suspending agent or emulsifier. The merits of this novel strategy include:(1) PVC resins with ultra-low number-average molecular weight (Mn) from 4000 to 15000, which is much lower than Mn of those prepared by conventional suspension and emulsion polymerizations,(2) sub-micrometer PVC particles with near spherical morphology, and (3) the very simple post-polymerization separation process. Under mild stirring, polymerization proceeds stably and smoothly. The influences of main process factors, such as solvents, initiator and monomer concentrations, polymerization time, and temperature on both particle morphology and Mn of the polymer products are investigated systematically. The molar ratio of-CH2-CHCl-/-CH=CH-CH2CHCl, a good indicator of structural defects, is about 1000/0.1 which means the low molecular weights do not result from chain transfer to the monomers. Then the mechanism of this polymerization is proposed. In summary, this novel polymerization technology provides a straightforward method for preparing PVC particulate products with low Mn.展开更多
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
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
In order to investigate the partition of initiators for quasi-static precipitation polymerization of acrylamide （AAm） and methacrylic acid （MAc） in ethanol, azo-initiators were employed with various functional gro...In order to investigate the partition of initiators for quasi-static precipitation polymerization of acrylamide （AAm） and methacrylic acid （MAc） in ethanol, azo-initiators were employed with various functional groups such as --COOCH3 （V- 601, dimethyl 2,2＇-azobis（isobutyrate））, --CN （V-65, 2,2＇-Azobis（2,4-diemthylvaleronitrile））, --COOH （V-501, 4,4＇-azobis（4-cyanovaleric acid）） and --NH-（VA-061, 2,2＇-azobis[2-（2-imidazolin-2-yl）propane]）, respectively. Particle size, induction time and kinetics of polymerization were investigated by the scanning electron microscopy （SEM） and gravimetry. It was observed that the polymerization parameters, such as the particle size, induction time and polymerization rate, were considerably affected by the functional groups of initiators. Besides, the monomer concentration also played important roles in the particle formation. By using V-601, the polymerization rate was strongly correlated with the total surface area of particles and the concentration of initiators. However, by using V-50 l, the polymerization rate was strongly related to WoQo, where W0 is the initial concentration of monomers and Ci,0, the initial concentration of initiators. The results indicated that the different functional groups determined the different partition types of initiators between the minimonomer droplets and the continuous phase due to the molecular interactions of initiator and monomers. V-601 was all partitioned in the continuous phase, but a part of V-65 was partitioned in the minimonomer droplets. Besides the V-501 dissolved in the continuous phase, a part of V-501 was adsorbed on the surface of minimonomer droplets. VA-061 destroyed the stability of minimonomer droplets by the formation of zwitterions with MAA.展开更多
Narrow-disperse, surface-functionalized ＂living＂ polymer microspheres with uniformly cross-linked structures were prepared by two-stage precipitation copolymerization of styrene and divinylbenzene. The two-stage pre...Narrow-disperse, surface-functionalized ＂living＂ polymer microspheres with uniformly cross-linked structures were prepared by two-stage precipitation copolymerization of styrene and divinylbenzene. The two-stage precipitation polymerization is composed of an initial conventional precipitation polymerization for the nucleation followed by a reverse atom transfer radical polymerization （reverse ATRP） for the controlled polymerization process. The polymerization parameters （including reaction time for the first stage, AIBN amount and monomer loading） have been studied to show significant influences on the morphologies. Moreover, narrower size distribution and an ATRP initiator-functional surface of resulting particles can be obtained by applying reverse ATRP to conventional precipitation polymerization in the second stage. Furthermore, the ＂livingness＂ of the resulting polymer microspheres was testified by their surface modification of poly[2-（dimethylamino） ethyl methacrylate] （PDMAEMA） brushes via surface-initiated ATRP （SI-ATRP）.展开更多
Precipitation polymerizations of divinylbenzene（DVB） in pure supercritical carbon dioxide,and parallel runs with presence of a cosolvent were carried out.The results showed that use of acetone as the cosolvent contr...Precipitation polymerizations of divinylbenzene（DVB） in pure supercritical carbon dioxide,and parallel runs with presence of a cosolvent were carried out.The results showed that use of acetone as the cosolvent contributed greatly to the formation of the monodisperse microspheres.PDVB microspheres,with obviously higher uniformity than reported up to date,were achieved using 6-7 mL of acetone in a reactor of 50 mL with DVB concentration of 0.4 mol/L under 16 MPa,a much lower pressure than previously reported without use of cosolvent.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
Without any type of su rfactant or dispersing agent,precipitation polymerization has great superiorities in both polymer synthesis and applications.In the present work,the polymerization of vinyl chloride(VC),n-butyl ...Without any type of su rfactant or dispersing agent,precipitation polymerization has great superiorities in both polymer synthesis and applications.In the present work,the polymerization of vinyl chloride(VC),n-butyl acrylate(BA),and vinyl acetate(VAc)are conducted in the precipitation polymerization system and series of their random terpolymers poly(vinyl chloride-co-n-butyl acrylate-co-vinyl acetate)(PCBV)are synthesized successfully.The effects of various polymerization conditions,including solvent polarity,temperature,initiator concentration,and monomer feed ratios on the polymerization kinetics,number-average molecular weight(M_(n)),and terpolymer composition are investigated systematically.The solvent and the monomer feed ratio are crucial factors not only for the polymer morphology,but also for the reaction kinetic.In the non-polar solvent such as n-hexane,the PCBV displays particle morphology when the composition of BA ratio lower than 10 wt%.Otherwise,the PCBV forms a uniform polymer phase and precipitates out from the mixture.In the polar solvent,e.g.,dimethyl carbonate(DMC)and ethanol,the PCBV polymer maintains a slurry state either in low or in high monomer feed ratio.Impressively,VC based ternary copolymer that obtained in n-hexane has much lower M_(n)(<20 kDa)and much higher BA units mass fraction(>40 wt%)compared with emulsion and suspension polymerization.Additionally,the terpolymer can be easily sepa rated by simple centrifugation.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
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
Poly（methyl methacrylate）/poly（N-isopropylacrylamide） （PMMA/PNIPAM） core-shell particles were synthesized by seeded precipitation polymerization of N-isopropylacrylamide （NIPAM） in the presence of PMMA seed pa...Poly（methyl methacrylate）/poly（N-isopropylacrylamide） （PMMA/PNIPAM） core-shell particles were synthesized by seeded precipitation polymerization of N-isopropylacrylamide （NIPAM） in the presence of PMMA seed particles. The anionic potassium persulfate was used as initiator, and acrylic acid as functional comonomer. It was shown that the weight ratio of the PNIPAM shell to the PMMA core can be greatly increased through continuous addition of NIPAM monomer at a relatively slow rate. PMMA/PNIPAM particles with different shell thickness were obtained by varying the amount of charged NIPAM monomers. These particles exhibited unique nonspherical core-shell morphology. PMMA core was partially coated by dense hair-like or antler-like PNIPAM shell depending on the shell thickness. The measurement of these particles＇ zeta potential at different temperatures showed that the absolute value of zeta potential unusually decreased as the particle size decreased with temperature.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
The burgeoning ethylene production in the Asia-Pacific region has led to a substantial oversupply of butadiene as a byproduct,and it is highly important to develop new butadiene-based materials.Butadiene-maleic anhydr...The burgeoning ethylene production in the Asia-Pacific region has led to a substantial oversupply of butadiene as a byproduct,and it is highly important to develop new butadiene-based materials.Butadiene-maleic anhydride copolymer,characterized by its amphiphilic nature,shows potential applications in adhesives,emulsifiers,etc.However,the Diels-Alder(DA)reaction of butadiene and maleic anhydride competes with the polymerization,limiting the copolymer yield.In this study,the kinetics of the DA reaction and copolymerization between butadiene and maleic anhydride were examined,and the influence of various reaction conditions on the copolymer yield was investigated.We found that the DA reaction in the induction period of the radical polymerization was the critical factor in limiting copolymer yield.Therefore,we proposed the two-step method to suppress the DA reaction and achieve high-yield production(~85%)of cross-linked microspheres with controllable particle size(175-800 nm)by self-stabilized precipitation polymerization.This work enables an efficient synthesis of conjugated diolefin-maleic anhydride cross-linked microspheres,offering a novel approach to address the issue of butadiene overcapacity.展开更多
Organic luminophores with superior solid-state luminescence are urgently required in various fields,such as lighting,display,sensing,and solar energy conversion.However,to achieve their highly efficient luminescence s...Organic luminophores with superior solid-state luminescence are urgently required in various fields,such as lighting,display,sensing,and solar energy conversion.However,to achieve their highly efficient luminescence still remains a challenge.Herein,a newly designed Nile red derivative,Nile-DPA-VB,is successfully obtained to exhibit aggregation-induced emission characteristics with the photoluminescent quantum yield(PLQY)of 11.45%.Such PLQY could be further promoted to 53.45%when Nile-DPA-VB is polymerized undergoing precipitation polymerization process,where the confined aggregation microenvironment severely restricts the intramolecular motions of Nile-DPA-VB.Remarkably,Nile-DPA-VB is ultrasensitive to the polarity and steric effect,enabling the real-time monitoring of aggregation microenvironment evolution for precipitation polymerization.The microphase separation and dynamic hardening for the nucleation and growth processes are visually demonstrated,which contribute dominantly to the high-efficiency luminescence.Finally,by doping the as-prepared fluorescent polymeric particles into polymethyl methacrylate,functional films with high luminescence and high haze are achieved to show the potential in lighting.These findings clearly demonstrate the significant role of polymerization in constructing high-efficiency solid-state luminescent materials for practice.展开更多
Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this stu...Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.展开更多
A facile approach has been adopted for coating cross-linked polystyrene(PS) shells on the surface of Fe304 magnetic clusters using reflux-precipitation polymerization(RPP).Treating the PS shell with chlorosulfonic aci...A facile approach has been adopted for coating cross-linked polystyrene(PS) shells on the surface of Fe304 magnetic clusters using reflux-precipitation polymerization(RPP).Treating the PS shell with chlorosulfonic acid yields magnetic composite particles with acid functionality.By adjusting the amount and proportion of monomers(styrene and divinylbenzene),the obtained magnetic composite particle solid acid(MPM-5 S) exhibits a saturation magnetization value of 18 emu/g,a specific surface area of 243 m^2/g and an acid density of 2.113 mmol/g.The MPM-5 S magnetic solid acid catalyst was evaluated for esterification of oleic acid with methanol to prepare biodiesel.Under mild conditions,the conversion of oleic acid reached 91%,which was much higher than the catalytic activity of Amberlyst-15 and close to the catalytic activity of concentrated H2 SO4.The solid acid catalyst can be recovered by magnetic separation and reused three times maintaining over 95% of its initial catalytic activity.Additionally,the solid acid can be used to catalyze the dehydration of fructose to 5-hydroxymethylfurfural.展开更多
A new biomimetic bulk acoustic wave sensor based on molecularly imprinted microspheres (MUM) technique was described. The sensing materials were synthesized by precipitation polymerization. By using the Scatchard anal...A new biomimetic bulk acoustic wave sensor based on molecularly imprinted microspheres (MUM) technique was described. The sensing materials were synthesized by precipitation polymerization. By using the Scatchard analysis, the equilibrium dissociation constant K-D and the apparent maximum number Q(max) of the binding sites were calculated to be 3.70 mmol (.) L-1 and 9.11 mumol (.) g(-1), respectively. The sensor exhibited a sensitive response to the template compound (dipyridamole) in liquid phase with a detection Unfit of 2 x 10(-9) mol (.) L-1. The recoveries of the sensor were 95.1%-105.4%. Studies presented in this paper show that the stability of this sensor is excellent. The sensor has been applied successfully to the determination of dipyridamole in human urine.展开更多
基金financially supported by the National Natural Science Foundation of China (No. 51521062)
文摘Poly(vinyl chloride), with ultralow molecular weight, produced by free radical polymerization either at high temperature or in the presence of chain transfer agents, is widely used as special resins and polymer process additives. This paper reports a new process, called self-stabilized precipitation polymerization, in which the polymerization of vinyl chloride monomer (VCM) is conducted in hydrocarbon diluents without addition of any suspending agent or emulsifier. The merits of this novel strategy include:(1) PVC resins with ultra-low number-average molecular weight (Mn) from 4000 to 15000, which is much lower than Mn of those prepared by conventional suspension and emulsion polymerizations,(2) sub-micrometer PVC particles with near spherical morphology, and (3) the very simple post-polymerization separation process. Under mild stirring, polymerization proceeds stably and smoothly. The influences of main process factors, such as solvents, initiator and monomer concentrations, polymerization time, and temperature on both particle morphology and Mn of the polymer products are investigated systematically. The molar ratio of-CH2-CHCl-/-CH=CH-CH2CHCl, a good indicator of structural defects, is about 1000/0.1 which means the low molecular weights do not result from chain transfer to the monomers. Then the mechanism of this polymerization is proposed. In summary, this novel polymerization technology provides a straightforward method for preparing PVC particulate products with low Mn.
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.
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financially supported by the National Natural Science Foundation of China(No.51073035)
文摘In order to investigate the partition of initiators for quasi-static precipitation polymerization of acrylamide （AAm） and methacrylic acid （MAc） in ethanol, azo-initiators were employed with various functional groups such as --COOCH3 （V- 601, dimethyl 2,2＇-azobis（isobutyrate））, --CN （V-65, 2,2＇-Azobis（2,4-diemthylvaleronitrile））, --COOH （V-501, 4,4＇-azobis（4-cyanovaleric acid）） and --NH-（VA-061, 2,2＇-azobis[2-（2-imidazolin-2-yl）propane]）, respectively. Particle size, induction time and kinetics of polymerization were investigated by the scanning electron microscopy （SEM） and gravimetry. It was observed that the polymerization parameters, such as the particle size, induction time and polymerization rate, were considerably affected by the functional groups of initiators. Besides, the monomer concentration also played important roles in the particle formation. By using V-601, the polymerization rate was strongly correlated with the total surface area of particles and the concentration of initiators. However, by using V-50 l, the polymerization rate was strongly related to WoQo, where W0 is the initial concentration of monomers and Ci,0, the initial concentration of initiators. The results indicated that the different functional groups determined the different partition types of initiators between the minimonomer droplets and the continuous phase due to the molecular interactions of initiator and monomers. V-601 was all partitioned in the continuous phase, but a part of V-65 was partitioned in the minimonomer droplets. Besides the V-501 dissolved in the continuous phase, a part of V-501 was adsorbed on the surface of minimonomer droplets. VA-061 destroyed the stability of minimonomer droplets by the formation of zwitterions with MAA.
文摘Narrow-disperse, surface-functionalized ＂living＂ polymer microspheres with uniformly cross-linked structures were prepared by two-stage precipitation copolymerization of styrene and divinylbenzene. The two-stage precipitation polymerization is composed of an initial conventional precipitation polymerization for the nucleation followed by a reverse atom transfer radical polymerization （reverse ATRP） for the controlled polymerization process. The polymerization parameters （including reaction time for the first stage, AIBN amount and monomer loading） have been studied to show significant influences on the morphologies. Moreover, narrower size distribution and an ATRP initiator-functional surface of resulting particles can be obtained by applying reverse ATRP to conventional precipitation polymerization in the second stage. Furthermore, the ＂livingness＂ of the resulting polymer microspheres was testified by their surface modification of poly[2-（dimethylamino） ethyl methacrylate] （PDMAEMA） brushes via surface-initiated ATRP （SI-ATRP）.
基金This research is financial supported by National Natural Science Foundation of China(No.20904016)Natural Science Foundation of Shandong Province(No.Y2008F30)Doctoral Foundation of Shandong Province,China (No.2007BS04036)
文摘Precipitation polymerizations of divinylbenzene（DVB） in pure supercritical carbon dioxide,and parallel runs with presence of a cosolvent were carried out.The results showed that use of acetone as the cosolvent contributed greatly to the formation of the monodisperse microspheres.PDVB microspheres,with obviously higher uniformity than reported up to date,were achieved using 6-7 mL of acetone in a reactor of 50 mL with DVB concentration of 0.4 mol/L under 16 MPa,a much lower pressure than previously reported without use of cosolvent.
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 National Natural Science Foundation of China(No.51988102)Fundamental Research Funds for the Central Universities(No.XK2020-01)。
文摘Without any type of su rfactant or dispersing agent,precipitation polymerization has great superiorities in both polymer synthesis and applications.In the present work,the polymerization of vinyl chloride(VC),n-butyl acrylate(BA),and vinyl acetate(VAc)are conducted in the precipitation polymerization system and series of their random terpolymers poly(vinyl chloride-co-n-butyl acrylate-co-vinyl acetate)(PCBV)are synthesized successfully.The effects of various polymerization conditions,including solvent polarity,temperature,initiator concentration,and monomer feed ratios on the polymerization kinetics,number-average molecular weight(M_(n)),and terpolymer composition are investigated systematically.The solvent and the monomer feed ratio are crucial factors not only for the polymer morphology,but also for the reaction kinetic.In the non-polar solvent such as n-hexane,the PCBV displays particle morphology when the composition of BA ratio lower than 10 wt%.Otherwise,the PCBV forms a uniform polymer phase and precipitates out from the mixture.In the polar solvent,e.g.,dimethyl carbonate(DMC)and ethanol,the PCBV polymer maintains a slurry state either in low or in high monomer feed ratio.Impressively,VC based ternary copolymer that obtained in n-hexane has much lower M_(n)(<20 kDa)and much higher BA units mass fraction(>40 wt%)compared with emulsion and suspension polymerization.Additionally,the terpolymer can be easily sepa rated by simple centrifugation.
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financially supported by the National Natural Science Foundation of China(No.50943028)the Program for Liaoning Excellent Talents in Universities(No.LJQ2011037)
文摘Poly（methyl methacrylate）/poly（N-isopropylacrylamide） （PMMA/PNIPAM） core-shell particles were synthesized by seeded precipitation polymerization of N-isopropylacrylamide （NIPAM） in the presence of PMMA seed particles. The anionic potassium persulfate was used as initiator, and acrylic acid as functional comonomer. It was shown that the weight ratio of the PNIPAM shell to the PMMA core can be greatly increased through continuous addition of NIPAM monomer at a relatively slow rate. PMMA/PNIPAM particles with different shell thickness were obtained by varying the amount of charged NIPAM monomers. These particles exhibited unique nonspherical core-shell morphology. PMMA core was partially coated by dense hair-like or antler-like PNIPAM shell depending on the shell thickness. The measurement of these particles＇ zeta potential at different temperatures showed that the absolute value of zeta potential unusually decreased as the particle size decreased with temperature.
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.
基金financially supported by an internal fund from Tsinghua University。
文摘The burgeoning ethylene production in the Asia-Pacific region has led to a substantial oversupply of butadiene as a byproduct,and it is highly important to develop new butadiene-based materials.Butadiene-maleic anhydride copolymer,characterized by its amphiphilic nature,shows potential applications in adhesives,emulsifiers,etc.However,the Diels-Alder(DA)reaction of butadiene and maleic anhydride competes with the polymerization,limiting the copolymer yield.In this study,the kinetics of the DA reaction and copolymerization between butadiene and maleic anhydride were examined,and the influence of various reaction conditions on the copolymer yield was investigated.We found that the DA reaction in the induction period of the radical polymerization was the critical factor in limiting copolymer yield.Therefore,we proposed the two-step method to suppress the DA reaction and achieve high-yield production(~85%)of cross-linked microspheres with controllable particle size(175-800 nm)by self-stabilized precipitation polymerization.This work enables an efficient synthesis of conjugated diolefin-maleic anhydride cross-linked microspheres,offering a novel approach to address the issue of butadiene overcapacity.
基金supported by the National Natural Science Foundation of China(52373171,52173154,52221006,22375014)the Beijing Natural Science Foundation Grant(JQ23006),and the Fundamental Research Funds for the Central Universities(ZY2404).
文摘Organic luminophores with superior solid-state luminescence are urgently required in various fields,such as lighting,display,sensing,and solar energy conversion.However,to achieve their highly efficient luminescence still remains a challenge.Herein,a newly designed Nile red derivative,Nile-DPA-VB,is successfully obtained to exhibit aggregation-induced emission characteristics with the photoluminescent quantum yield(PLQY)of 11.45%.Such PLQY could be further promoted to 53.45%when Nile-DPA-VB is polymerized undergoing precipitation polymerization process,where the confined aggregation microenvironment severely restricts the intramolecular motions of Nile-DPA-VB.Remarkably,Nile-DPA-VB is ultrasensitive to the polarity and steric effect,enabling the real-time monitoring of aggregation microenvironment evolution for precipitation polymerization.The microphase separation and dynamic hardening for the nucleation and growth processes are visually demonstrated,which contribute dominantly to the high-efficiency luminescence.Finally,by doping the as-prepared fluorescent polymeric particles into polymethyl methacrylate,functional films with high luminescence and high haze are achieved to show the potential in lighting.These findings clearly demonstrate the significant role of polymerization in constructing high-efficiency solid-state luminescent materials for practice.
基金financially supported by the Jiangsu Forestry Science and Technology Innovation and Promotion Project(No.LYKJ-Nanjing[2022]02)the Jiangsu Agricultural Science and Technology Innovation Fund(No.CX(23)3090)。
文摘Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.
基金financially supported by the National Natural Science Foundation of China(No.21802039)Hunan Provincial Natural Science Foundation of China(No.2019JJ40061)+3 种基金Scientific Research Fund of Hunan Provincial Education Department (No.18A422)the National College Students’ Innovation and Entrepreneurship Training Program Project,Hunan Province College Students’ Research Learning and Innovative Experiment Projectthe Acteristic Application Discipline of Material Science Engineering in Hunan Province(Hunan Provincial Education Department Notice(No.[2018]469)funding from Dow through the University Partnership Initiative
文摘A facile approach has been adopted for coating cross-linked polystyrene(PS) shells on the surface of Fe304 magnetic clusters using reflux-precipitation polymerization(RPP).Treating the PS shell with chlorosulfonic acid yields magnetic composite particles with acid functionality.By adjusting the amount and proportion of monomers(styrene and divinylbenzene),the obtained magnetic composite particle solid acid(MPM-5 S) exhibits a saturation magnetization value of 18 emu/g,a specific surface area of 243 m^2/g and an acid density of 2.113 mmol/g.The MPM-5 S magnetic solid acid catalyst was evaluated for esterification of oleic acid with methanol to prepare biodiesel.Under mild conditions,the conversion of oleic acid reached 91%,which was much higher than the catalytic activity of Amberlyst-15 and close to the catalytic activity of concentrated H2 SO4.The solid acid catalyst can be recovered by magnetic separation and reused three times maintaining over 95% of its initial catalytic activity.Additionally,the solid acid can be used to catalyze the dehydration of fructose to 5-hydroxymethylfurfural.
文摘A new biomimetic bulk acoustic wave sensor based on molecularly imprinted microspheres (MUM) technique was described. The sensing materials were synthesized by precipitation polymerization. By using the Scatchard analysis, the equilibrium dissociation constant K-D and the apparent maximum number Q(max) of the binding sites were calculated to be 3.70 mmol (.) L-1 and 9.11 mumol (.) g(-1), respectively. The sensor exhibited a sensitive response to the template compound (dipyridamole) in liquid phase with a detection Unfit of 2 x 10(-9) mol (.) L-1. The recoveries of the sensor were 95.1%-105.4%. Studies presented in this paper show that the stability of this sensor is excellent. The sensor has been applied successfully to the determination of dipyridamole in human urine.
