Synthesis of micron-sized polymeric particles in soap-free emulsion polymerization using oil-soluble initiators and electrolytes

Soap-free emulsion polymerization of styrene using oil-soluble initiators and electrolytes was investigated to synthesize micron-sized polystyrene particles. It was clear that an oil-soluble initiator, such as AIBN, worked like a water-soluble initiator in soap-free emulsion polymerization of styrene to prepare monodispersed particles with negative charges, probably because of the polarization of the electron-attractive functional groups decomposed from the initiators and the pi electron cloud of benzene in a styrene monomer. The addition of an electrolyte enabled secondary particles to effectively promote hetero-coagulation for particle growth by reduction of an electrical double layer and prevention of self-growth. Changing the concentration and type of electrolyte enabled us to control the size up to 12 μm in soap-free emulsion polymerization of styrene using AIBN. Conventionally, organic solvents and surfactants have been used to prepare micron-sized polymeric particles, but this method enabled the synthesis of micron-sized polymeric particles in water using electrolytes without surfactants.     

Preparation of micrometer-sized polymer particles with control of initiator dissociation during soap-free emulsion polymerization

A previously proposed method of soap-free emulsion polymerization employing an amphoteric initiator, 2,2'-azobis [N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate (VA-057), was extended to synthesize micrometer-sized polystyrene particles with low polydispersity in an acidic region of pH from 3.3 to 4.6. A buffer system of CH3COOH/CH3COONa was used for the adjustment of pH, which was aimed at effective promotion of particle coagulation in early stage of the polymerization. In these experiments, CH3COOH concentration was varied from 20 to 360 mM at a CH3COONa concentration of 10 mM. Polymer particles with an average size of 1.8 microm and low polydispersity were obtained at the CH3COOH concentration of 40 mM for the concentrations of 1.1 M styrene monomer and 10 mM initiator. To more precisely control dispersion stability of particles, experiments in which pH was stepwisely changed during the polymerization were also carried out. This polymerization method could enhance the average size of particles to 2.2 microm while retaining the monodispersity of particles. Furthermore, combination of pH stepwise change and monomer addition during the polymerization could produce particles with an average size of 3.0 microm and low polydispersity.     

Size control of polystyrene nodules formed on silica particles in soap-free emulsion polymerization with amphoteric initiator

An amphoteric initiator of 2,2′-azobis[N-(2-carboxyethyl)-2-2-methylpropionamidine] (VA-057) was applied to fabrication of raspberry-shaped composite particles in soap-free emulsion polymerization of styrene in the presence of silica particles surface-modified with 3-methacryoxypropyltrimethoxysilane. In the polymerizations, pH of the solution was ranged from 7.9 to 9.9 to alter dissociation degree of ionizable groups in the initiator. Raspberry-shaped particles were obtained in a pH range of 8.0 to 9.3 followed by a tendency in which average size of polystyrene (PSt) nodules adsorbed onto the silica particles decreased with pH. This tendency was similar to that of polymer particles formed in conventional soap-free emulsion polymerization in the absence of the silica particles. An increase in silica particle concentration led to a decrease in the final size in PSt nodules. The decrease was caused by the stabilization of polymer particles fixed to the silica surface against polymer particle aggregation in water phase.     

Miniemulsion polymerization of styrene using the oil-soluble initiator AMBN

The Mettler RC1 calorimeter was used to measure the rate of polymerization of conventional emulsion, homogenized emulsion, and miniemulsion polymerizations of styrene initiated with 2,2′-azobis(2-methylbutyronitrile). It was noted that the rate of polymerization significantly increased as the surface area of the monomer droplets increased. This was taken as strong evidence that in the miniemulsion and homogenized emulsion polymerizations, the fraction of the initiator soluble in the oil phase was responsible for single radical generation. The partitioning of AMBN at 70 °C was measured by high-pressure liquid chromatography to be 134 parts in the oil : 1 part in the water. Predissolving polystyrene in the miniemulsion prior to homogenization resulted in an enhancement in the rate of polymerization, although to a lesser extent than what has been previously noted for parallel miniemulsion polymerizations initiated with potassium persulfate. It was also noted that the method of addition of the oil-soluble initiator (either predissolved in the monomer prior to homogenization or dissolved in a small separate phase of monomer and added directly to the reactor) has a measurable effect on the kinetics in the miniemulsion polymerization of styrene. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4449–4457, 1999     

Synthesis of submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene particles by seeded soap-free emulsion polymerization

Submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene(PMMA/PS) particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed particles.The obtained peanut-shaped particles showed a novel internal morphology:PS phase formed one domain which linked to the other domain having PMMA core encased by PS shell.     

Agitation requirement for synthesis of micron-sized monodisperse polymer particles in soap-free polymerization method

Single-stage polymerization recently proposed for producing micron-sized polymer particles in aqueous media by Gu, Inukai and Konno (2002) was carried out under the control of agitation with styrene monomer, an amphoteric initiator, 2,2′-azobis [N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate and a pH buffer NH₃/NH₄Cl at a monomer concentration of 1.1 kmol/m³ H₂O, an initiator concentration of 10 mol/m³ H₂O and a buffer concentration of [NH₃] = [NH₄Cl] = 10 mol/m³ H₂O. In the polymerizations, impeller speed was ranged from 300 to 500 rpm to satisfy complete dispersion of the monomer phase and not to introduce the gas phase from the free surface. Polymerization experiments under steady agitation indicated that impeller speed was an important factor for size distribution of polymer particles. An increase in impeller speed promoted particle coagulation during the polymerization to enlarge the average size of polymer particles but widen the size distribution. To produce polymer particles with narrow size distribution, stepwise reduction in impeller speed was examined in the polymerization experiments. It was demonstrated that this method was more effective than the steady agitation. The impeller speed reduction could produce highly monodisperse particles with an average size of 2 μm and a coefficient of variation of size distributions of 2.2% that was much smaller than typical monodispersity criterion of 10%.     

The free radical distribution in emulsion polymerization using oil-soluble initiators

A new approach is presented to calculate both the distribution of particles with iradicals and the average number of radicals per particle in emulsion polymerizations carried out using oil-soluble initiators. The convergence and accuracy of the approach were examined. It was found that, in agreement with previously published experimental results, the present approach predicts a kinetic behavior similar to that found for water-soluble initiators. This effect is primarily due to the desorption of initiator radicals from the polymer particles rather than the contribution of the fraction of oil-soluble initiator dissolved in the aqueous phase.     

Synthesis and properties of soap-free poly(methyl methacrylate-ethyl acrylate-methacrylic acid) latex particles prepared by seeded emulsion polymerization

In order to obtain functional polymer latex particles with clean surface and with surface carboxyl groups, P(MMA-EA) seed particles with the diameter of 335 nm were first synthesized via soap-free batch emulsion polymerization of methyl methacrylate (MMA) and ethyl acrylate (EA), and then the seeded emulsion copolymerization of MMA, EA and MAA (methacrylic acid) onto the seed particles were performed in the absence of emulsifier. Influences of ingredients and conditions on polymerization, latex particle size (D_p) and its distribution were investigated. Results showed that most of the monomers polymerized onto the seed latex particles in the second step of polymerization by using drop-wise addition method, and D_p increased from 483 nm to 829 nm with the mass ratio of core/shell monomers [C]/[S] decreased from 1:2 to 1:15. It was found that D_p decreased with the increase of MAA and initiator amounts, and the size of the latex particles became uniform with the decrease of MAA amount and with the increase of [C]/[S] value.     

Influences of the locations of monomer and initiator in the seeded polymerization systems on the morphologies of micron-sized monodispersed composite polymer particles

Three kinds of micron-sized monodispersed polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) composite particles (PS/BMA=2/1, wt. ratio) were produced by two kinds of seeded polymerizations ofn-butyl methacrylate (BMA) in the presence of about 2 m-sized monodispersed PS particles, and their morphologies were examined. One was produced by a seeded dispersion polymerization where almost monomers and initiators exist in an ethanol/water (1/1, w/w) medium. The others two were produced by seeded polymerizations utilizing the dynamic swelling method, where almost monomers exist in the PS seed particles, with 2,2-azobisisobutyronitrile initiator in the monomer-swollen particles and with 2,2-azobis [2-(2-imidazolin-2-yl)propane] initiator in an ethanol/water (1/5, w/w) medium. In the former polymerization, the produced composite particles had a core-shell structure consisting of a PS-core and a PBMA-shell, whereas in the latter two polymerizations, they had a POO (Polymeric Oil-in-Oil) structure consisting of a PS-matrix and many PBMA-domains, regardless of the location of initiator in the systems. From these results, it is concluded that the location of BMA monomer in the seeded polymerization systems with micron-sized monodispersed PS seed particles greatly affects the morphologies of produced PS/PBMA composite particles.Part CLI of the series Studies on Suspension and Emulsion     

Incorporation of nonionic emulsifier inside methacrylic polymer particles in emulsion polymerization

The incorporations of polyoxyethylene lauryl ether (Emulgen 109P) and polyoxyethylene nonylphenyl ether (Emulgen 911) nonionic emulsifiers inside poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and poly(iso-butyl methacrylate) (Pi-BMA) particles prepared by emulsifier-present emulsion polymerizations were examined. To measure the amounts of the incorporated nonionic emulsifiers, optimum compositions of 2-propanol aqueous solutions to remove the nonionic emulsifier from the particle surfaces without removal from the insides were determined. The amount of the incorporation measured by gel permeation chromatography was increased in the order of PMMA > PEMA > Pi-BMA, which accorded with the order of miscibility between each polymer and the emulsifier.     

The generation of void morphology inside soap-free P(MMA-EA-MAA) particles prepared by seeded emulsion polymerization

Monodisperse soap-free P(MMA-EA-MAA) latex particles were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and methacrylic acid (MAA), and the particles with void morphology were obtained after undergoing alkali post-treatment. Effects of treatment conditions on particle morphology were investigated. Results showed that the void particles can be obtained under the conditions of the temperature >60 degrees C, initial pH >10.0, treatment time >20 min and 2-butanone amount >2.0 ml. The particle volume and the void size increased to the maximum and then decreased with the increases of initial pH and the treatment time, and these two values increased monotonously with the treatment temperature or 2-butanone amount increased. When the treatment temperature was elevated to 90 degrees C, the treatment time was longer than 180 min, or the 2-butanone amount was more than 8.0 ml, the relatively small voids inside most of the particles combined together to form a large one. The void structure disappeared completely as the initial pH was higher than 12.0. The generation mechanism of the void morphology was discussed.     

Soap-free emulsion polymerization of aromatic vinyl monomer using AIBN

Soap-free emulsion polymerizations of aromatic vinyl monomers using 2,2′-azobis(2-methylpropionitrile) (AIBN) were investigated to clarify the origin of the negative charge of the synthesized particles. It was found that the zeta potential and size of the particles synthesized by soap-free emulsion polymerization using AIBN had a strong relationship with the pi electron cloud density in the aromatic vinyl monomer used in the polymerization. The effect of the position of the substituent atom in the phenyl ring on the synthesized particle properties was small.     

Mechanism of emulsion polymerization of styrene in soap-free systems

The formation and growth of monodisperse polystyrene latex particles in the absence of added surfactant has been studied by sampling polymerization reactions at different times and determining the surface and bulk properties of the latex. A large number of nuclei in excess of 5 × 10¹²/ml were generated during the first minute of reaction, but this fell due to coagulation until a constant number (10¹¹?10¹²/ml) was reached. The rate of polymerization per particle was then found to be proportional to the particle radius. Gel-permeation chromatography has shown that the initial particles consist mainly of material of MW 1000 with a small amount of polymer up to MW 10⁶, and the presence of this low molecular weight polymer, which in many cases can still be detected after 100% conversion, is taken as being indicative of particle formation via a micellization-type mechanism involving short-chain (MW 500) free-radical oligomers. M?_n values determined for the latex particles throughout the course of reactions show that the molecular weight increases to a maximum of about 10⁵ as the particles grow. The presence of anomalous regions within the particles has been confirmed by transmission electron microscopy, scanning electron microscopy, and gas adsorption studies. It has also been found possible to re-expose these regions within apparently homogeneous particles by stirring with styrene monomer; this is indicative of a molecular weight heterogeneity within the latex particles. The presence of sulfate, carboxyl, and hydroxyl groups upon the latex particle surfaces has been determined by conductometric titration.     

Synthesis and characterization of silica/poly (methyl methacrylate) nanocomposite latex particles through emulsion polymerization using a cationic azo initiator

Following a previous work (J. L. Luna-Xavier et al., Colloid Polym. Sci.279, 947 (2001)), silica-poly (methyl methacrylate) (PMMA) nanocomposite latex particles have been synthesized in emulsion polymerization using a cationic initiator, 2,2'-azobis (isobutyramidine) dihydrochloride (AIBA), and a nonionic polyoxyethylenic surfactant (NP30). Silica beads with diameters of 68, 230, and 340 nm, respectively, were used as the seed. Coating of the silica particles with PMMA was taking place in situ during polymerization, resulting in the formation of colloidal nanocomposites with a raspberry-like or a core-shell morphology, depending on the size and nature of the silica beads. The amount of surface polymer was quantified by means of ultracentrifugation and thermogravimetric analysis as extensively described in the first article of the series (see above reference). The influence of some determinant parameters such as the pH of the suspension, the initiator, silica, monomer, or surfactant concentration on the amount of coating polymer and on the efficiency of the coating reaction was investigated in details and discussed in light of the physicochemical properties of the seed mineral. Electrostatic attraction between the positive end groups of the macromolecules and the inorganic surface proved to be the driving force of the polymer assembly on the seed surface at high pH, while polymerization in adsorbed surfactant bilayers (so-called admicellar polymerization) appeared to be the predominant mechanism of coating at lower pH. Optimal conditions have been found to reach high encapsulation efficiencies and to obtain a regular polymer layer around silica.     

Synthesis of ZnO/polystyrene composites particles by Pickering emulsion polymerization

ZnO/polystyrene composite particles were synthesized by Pickering emulsion polymerization. ZnO nanoparticles were first prepared by reaction of zinc acetate and sodium hydroxide in ethanol medium. Then different amount of styrene monomer was emulsified in water in the presence of ZnO nanoparticles either by mechanical stirring or by sonication, followed by polymerization of styrene. Two kinds of initiators were used to start the polymerization, azobisisobutyronitrile (AIBN) and potassium persulfate (KPS). The X-ray diffraction pattern verified the crystal structure of ZnO and FT-IR spectra evidenced the existence of ZnO and polystyrene (PS) in ZnO/polystyrene composite particles. Different morphologies were observed for the composite particles when using different initiators. From TEM photographs, AIBN-initiated system produced mainly core-shell composite particles with PS as core and ZnO as shell, while KPS-initiated system showed both composite particles and pure PS particles. Two schemes of reaction mechanism were proposed to explain the morphologies accordingly. Both systems of composite particles showed good pH adjusting ability.     

Preparation of micron-sized nonspherical polystyrene/poly(styrene-<Emphasis Type="Italic">co</Emphasis>-ethyleneglycol dimethacrylate) particles by seeded soap-free emulsion polymerization

Micron-sized nonspherical polymer particles having different morphologies were synthesized by seeded soap-free emulsion polymerization of styrene(St) and ethyleneglycol dimethacrylate(EGDMA,used as a crosslinker) on spherical, linear polystyrene(PS) seed particles.The morphology of the resulting PS/poly(St-co-EGDMA) particles was dependent on the crosslinker concentration and polymerization temperature.     

具有表面活性 ATRP 引发剂的合成及应用

以4-氯甲基苯甲酸、1,10-癸二醇、顺丁烯二酸酐为主要原料,通过三步反应合成了具有阴离子表面活性的原子转移自由基聚合(ATRP)引发剂:4-(10-(4-氯甲基苯甲酰氧基)癸氧基-4-氧代-2-磺酸基丁酸二钠(3).第一步选择性酯化的分离产率为81%,第二步酯化的分离产率为64%,第三步最终产物的收率为91%.对合成...     

Synthesis of micron-sized, monodisperse polymer particles of disc-like and polyhedral shapes by seeded dispersion polymerization

Micron-sized, monodisperse polymer particles having unique disc-like and polyhedral shapes were produced by seeded dispersion polymerization of various methacrylates with 1.57 m-sized polystyrene seed particles in the presence of saturated hydrocarbon droplets in methanol/water. Such nonspherical shapes were controllable by the polymerization conditions.Part CCLX of the series Studies on Suspension and Emulsion