SYNTHESIS OF MONODISPERSE HOLLOW POLYMER MICROSPHERES WITH FUNCTIONAL GROUPS BY DISTILLATION PRECIPITATION POLYMERIZATION

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.

Monocrotophos Molecularly Imprinted Microspheres Prepared by Precipitation Polymerization in Acetonitrile

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.

Synthesis of Ultra-High-Molecular-Weight Polyethylene by Transition-Metal-Catalyzed Precipitation Polymerization

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.

Synthetic Features and Mechanism for the Preparation of Vinyl Chloride-co-Butyl Acrylate-co-Vinyl Acetate Terpolymer via Precipitation Polymerization

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.

Preparation of slightly crosslinked monodisperse poly(maleic anhydride-cyclohexyl vinyl ether-divinylbenzene)functional microspheres with anhydride groups via precipitation polymerization

Slightly crosslinked monodisperse poly（maleic anhydride-cyclohexyl vinyl ether-divinylbenzene） （MA-CHVE-DVB） microspheres were prepared via precipitation polymerization while using 2,2- azobisisobutyronitrile as an initiator in a mixture of methyl ethyl ketone and n-heptane without any stabilizer. The number-average diameter of the resultant poly（MA-CHVE-DVB） microspheres ranged from 0.478 to 1.386 μm with a polydispersity index of 1.00 to 1.02 that depended on the feed ratios of the MA/CHVE/DVB monomers. The introduction of one electron donor monomer cyclohexyl vinyl ether strongly affected the yield, size, and morphology of these slightly crosslinked microspheres. Quinoline- type chelating resins were obtained after combining the poly（MA-CHVE-DVB） with 8-hydroxyquinoline; the adsorption properties of these materials were measured through their ability to remove Cu^2＋ ions from water. The poly（MA-CHVE-DVB） microspheres with low degrees of crosslinking provided more effective functional groups and therefore better ion removal capabilities. These slightly crosslinked microspheres may have applications in water treatment as well as in sensing and drug delivery.

Microspheres Sensor Based on Molecularly Imprinted Polymer Synthesized by Precipitation Polymerization

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.

Narrow-disperse Highly Cross-linked “Living” Polymer Microspheres by Two-stage Precipitation Polymerization

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）.

Effects of cosolvent on formation and morphology of microspheres in precipitation polymerization of divinylbenzene in supercritical carbon dioxide

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.

Functional monodisperse microspheres fabricated by solvothermal precipitation co-polymerization

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.

Poly(methyl methacrylate)/Poly(N-isopropylacrylamide) Core-Shell Particles Prepared by Seeded Precipitation Polymerization: Unusual Morphology and Thermo-sensitivity of Zeta Potential

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.

Partition of Initiators in Quasi-static Precipitation Polymerization of AAm/MAc

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.

Phase Separation and Theta-compositions of PPES/NMP/non-solvent Systems

Poly (phthalazinone ether sulfone) (PPES) with 1:1 and 1:3 ratios of bisphenol A (BPA) unit to phthalazinone unit were selected as samples. Polymer precipitation curves for the ternary systems PPES (1:1)/NMP/ non-solvent and PPES (1:3)/NMP/non-solvent were determined by a titration method. Comparison between two sets of data is made. Non-solvents used were H2O, ethyl ether (EE), diethylene glycol (DEGC), ethyleneglycol methylether (EGME) and butanone (BO). NMP/non-solvent theta-compositions for PPES (1:1) and PPES (1:3) were also estimated. It was found that the volume ratio of non-solvent to NMP at the property mutation or worsening of PPES membrane is close to the theta-composition.

Preparation and Formation Mechanism of Porous Polyurea by Reaction of Toluene Diisocyanate with Water and Its Application as Adsorbent for Anionic Dye Removal

A novel and easy one-step protocol for preparation of a new porous material, polyurea （PPU）, is reported, which is accomplished through a precipitation polymerization of toluene diisocyanate （TDI） in mixed solvent of H20-acetone without need for surfactant and porogen. Effects of TDI concentration, mechanical stirring, solvent composition and TDI addition rate on PPU structure are studied. Surface morphology and pore structure of PPU are characterized by scanning electron microscopy and Hg intrusion. Chemical structure of the PPU polymer is investigated using NMR, XRD and FTIR. Mechanism of pore formation is discussed. The obtained PPU is used as adsorbent for anionic dyes adsorption investigation. Two anionic dyes, remazol brilliant blue R and acid fuchsine, are tested. The results indicate that the as-prepared PPU is of high performance in dye adsorption and recycled use. This study provided therefore a facile route to the preparation of a novel and attractive adsorbent candidate for removal of anionic dyes from wastewaters.

Highly stable, active and recyclable solid acid catalyst based on polymer-coated magnetic composite particles

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.

PREPARATION OF SILICA/POLY(METHACRYLIC ACID)/POLY(DIVINYLBENZENE-CO-METHACRYLIC ACID) TRI-LAYER MICROSPHERES AND THE CORRESPONDING HOLLOW POLYMER MICROSPHERES WITH MOVABLE SILICA CORE

Hollow poly（divinylbenzene-co-methacrylic acid） （P（DVB-co-MAA）） microspheres were prepared by the selective dissolution of the non-crosslinked poly（methacrylic acid） （PMAA） mid-layer in ethanol from the corresponding silica/PMAA/P（DVB-co-MAA） tri-layer hybrid microspheres, which were afforded by a three-stage reaction. Silica/PMAA core-shell hybrid microspheres were prepared by the second-stage distillation polymerization of methacrylic acid （MAA） via the capture of the oligomers and monomers with the aid of the vinyl groups on the surface of 3-（methacryloxy）propyl trimethoxysilane （MPS）-modified silica core, which was prepared by the Stober hydrolysis as the first stage reaction. The tri-layer hybrid microspheres were synthesized by the third-stage distillation precipitation copolymerization of functional MAA monomer and divinylbenzene （DVB） crosslinker in presence of silica/PMAA particles as seeds, in which the efficient hydrogen-bonding interaction between the carboxylic acid groups played as a driving force for the construction of monodisperse hybrid microspheres with tri-layer structure. The morphology and the structure of silica core, silica/PMAA core-shell particles, the tri-layer hybrid microspheres and the corresponding hollow polymer microspheres with movable silica cores were characterized by transmission electron microscopy （TEM）, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy （XPS）.

Antibacterial Nanoparticles with Universal Adhesion Function Based on Dopamine and Eugenol

In this work,dopamine methacrylamide(DMA)and eugenyl methacrylate(EMA)were used to synthesize polymeric particles of Poly(DMA-co-EMA)by free radical precipitation copolymerization.These two monomers were modified from dopamine(consisting of the catechol moieties adhering to various materials)and eugenol(with antibacterial property),respectively.The proton nuclear magnetic resonance(^(1)H NMR)and Fourier transform infrared(FT-IR)spectroscopy were applied to confirm the successful synthesis of the two monomers and copolymer.The scanning electron microscope(SEM)images showed the size and morphology of the polymer particles.The results indicated that regular particles with uniform size could be obtained with a monomer feeding ratio of 5꞉5.The results of antibacterial activity test indicated that the obtained polymer particles have an antibacterial rate over 90%to Eugenia coli.

In situ and ex situ synthesis of poly（vinyl alcohol）-Fe304 nanocomposite flame retardants

Application of flame retardants is limited because of environmental requirements. This work introduces conventional magnetic nanoparticles as a new class of nontoxic and effective flame retardant. Fe3O4 enhanced both the thermal stability and flame retardant properties of a poly（vinyl alcohol） matrix. Nanoparticles were synthesized via a simple precipitation reaction without using an inert atmosphere at room temperature. The effects of different precursors and acrylamide on the morphology of the products were investigated. Nanoparticles exhibited a ferrimagnetic behavior at room temperature. To prepare the magnetic nanocomposite, Fe3O4 nanoparticles were added to the poly（vinyl alcohol）. In the presence of a flame, the magnetic nanoparticles remained together, showed resistance to dripping and protected the polymer matrix. Dispersed nanoparticles play a role of a magnetic barrier layer, which slows product volatilization and prevents flames and oxygen from reaching the sample during decomposition of the polymer.

Reactive poly(divinyl benzene-co-maleic anhydride) nanoparticles:Preparation and characterization

Polymeric nanoparticles（NPs）have drawn great interest in the past few years due to their potential applications in the felds of biomedical and optical technologies.However,it is still a challenge to prepare functional polymeric NPs,especially for particle diameters smaller than 50 nm.In this work,we demonstrate a one-pot method to fabricate reactive poly（divinyl benzene-co-maleic anhydride）NPs（PDVBMAH NPs）through a self-stable precipitation polymerization process.The size and morphology of these PDVBMAH NPs were characterized in detail by scanning electronic microscopy,and their chemical structure was determined by IR.The results showed that these NPs were highly cross-linked and their diameter was about 30 nm with narrow distribution.Additionally,the DVB and MAH endow the NPs with reactive surface anhydride and pendant vinyl groups,and these particles could be further functionalized through reaction of these groups.A plausible pathway was proposed for the formation of PDVBMAH NPs.