Effect of second monomer and initiator type, mixing method, and stabilizer content on the shape of the particles produced by seeded dispersion polymerization in the presence of saturated hydrocarbon droplets

In this work, the preparation of micron-sized polymer particles with nonspherical shapes via seeded dispersion polymerization of 2-ethylhexyl methacrylate with polystyrene seed particles in the presence of hydrocarbon droplets and evaporation of hydrocarbon after the polymerization under various polymerization conditions was discussed. The effect of second monomer and initiator type, mixing method, and stabilizer content on the shape of the obtained particles was investigated. It was observed that particles with more nonspherical shapes were obtained with increasing the alkyl chain length of ester group of the methacrylate of the second monomer which is because of increasing the absorption amounts of hydrocarbon by second polymer domains. Moreover, the experimental results showed that shape of the particles which was produced by shaking is more nonspherical than the shape of the particles which was obtained from tumbling. Furthermore, particles with different nonspherical shapes were prepared by changing the initiator type and stabilizer content.     

Preparation of nonspherical particles via dual-seeded dispersion polymerization in the presence of saturated hydrocarbon droplets

In this study, the effect of various polymerization conditions on the shape of the particles produced by dual-seeded dispersion polymerization of a second monomer with polystyrene (PS) and poly(methyl methacrylate) (PMMA) seed particles in the presence of saturated hydrocarbon droplets in a polar media was discussed. It was observed that with changing the affinity between the hydrocarbon and PS seed particles, second monomer type, polarity, and alcohol type of the medium nonspherical particles with a variety of shapes can be produced. Furthermore, we suggested that the presence of PMMA seed particles in the medium affects the distribution of the second polymer domains on the surface of the PS seed particles in addition to the absorbed amount of the hydrocarbon by PS particles and second polymer domains and the distribution of the hydrocarbon between them. Moreover, the experimental results showed that almond shell-like PS particles can be prepared under certain conditions.     

Shape of the particles produced by seeded dispersion polymerization of styrene

In this work, seeded dispersion polymerization of styrene was carried out in the presence of various types of seed particles. We found that in the case of polystyrene and poly(methyl methacrylate) seeds, the shape of the resulting particles remained spherical. For styrene/poly(nbutyl methacrylate) (PnBMA) and styrene/poly(lauryl methacrylate) seeding particles, raspberry like particles were produced along with those of occluded morphology. We studied the effects of various polymerization factors such as concentrations of a stabilizer, an initiator, and a monomer, a weight ratio of methanol to water, a type of initiator, weight ratio of styrene to Pn-BMA seed particles, and polymerization temperature on the formation of these raspberry-like particles. The experimental results showed that the increase of concentrations of the initiator and the stabilizer as well as that of methanol favors the formation of such particles by increasing their surface roughness. An increase of the temperature of polymerization had the same effect on the morphology of resulting product. We hypothesized that the nucleation and growth of specifically fine-structured polystyrene domains on the surface of the Pn-BMA particles guides the formation of non-linear morphology during seeded polymerization in colloidal solution.     

Production of micron-sized, monodispersed, multilayered composite polymer particles by multistep seeded dispersion polymerization

 Micron-sized, monodispersed, poly(methyl methacrylate) (PMMA)/polystyrene (PS)/PMMA/PS multilayered composite particles were successfully produced by three-step seeded dispersion polymerizations in methanol/water media. The first seeded dispersion polymerization was carried out with 2-μm-sized, monodispersed PMMA particles.     

Dual-seeded dispersion polymerization: Effect of different polymerization conditions on the shape of the produced particles

Dual-seeded dispersion polymerization (DSDP) of 2-ethylhexyl methacrylate with polystyrene (PS) and poly(methyl methacrylate) (PMMA) seed beads in the presence of saturated hydrocarbon droplets followed by evaporation of the hydrocarbon was studied. The effect of various polymerization conditions including initiator type and content, stabilizer type and concentration, and different hydrocarbon’s content on the shape of the obtained particles was investigated. The increase of concentration of 2,2'-azobis(isobutyronitrile) (AIBN) had no effect on the shape of the produced almond-shell-like PS particles, although it contributes in the formation of associated composite particles along with larger poly(2-ethylhexyl methacrylate) (PEHMA) beads produced by secondary nucleation. The experimental results showed that other initiators led to the formation of stable golf-ball-like PMMA particles as well as PS ones with symmetric shape. The type of stabilizer did not affect the shape of the particles. This observation suggests that unique almond-shelllike PS particles can be produced through a stabilizer-free DSDP process. The lowering of the concentration of hydrocarbons with long alkyl chains yielded stable disc-like PMMA particles. The formation of functional almond-shell-like particles by using light hydrocarbons was another interesting finding of this research.     

Synthesis of monodisperse submicron spherical poly(methylmethacrylate) particles and the molecular dynamics simulation

The molecular-dynamics method has been used to determine the conformational states of poly(methyl methacrylate) chains in a medium composed of water and a monomer (methyl methacrylate). Experimentally detected spherical particles resulting from polymerization have been found to take the form of droplet-type aggregates containing several chains, with the water and monomer concentrations in the aggregates differing from those in the dispersion medium. It has been shown that the methyl methacrylate concentration in an initial reaction mixture of about 20% is optimal for the formation of spherical droplet-type aggregates. It has been experimentally established that spherical poly(methyl methacrylate) particles with a narrow size distribution are formed at a methyl methacrylate concentration of ≈23%.     

Synthesis and characterization of magnetic and non-magnetic core-shell polyepoxide micrometer-sized particles of narrow size distribution

Core polystyrene microspheres of narrow size distribution were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2-methoxy ethanol. Uniform polyglycidyl methacrylate/polystyrene core-shell micrometer-sized particles were prepared by emulsion polymerization at 73 degrees C of glycidyl methacrylate in the presence of the core polystyrene microspheres. Core-shell particles with different properties (size, surface morphology and composition) have been prepared by changing various parameters belonging to the above seeded emulsion polymerization process, e.g., volumes of the monomer glycidyl methacrylate and the crosslinker monomer ethylene glycol dimethacrylate. Magnetic Fe(3)O(4)/polyglycidyl methacrylate/polystyrene micrometer-sized particles were prepared by coating the former core-shell particles with magnetite nanoparticles via a nucleation and growth mechanism. Characterization of the various particles has been accomplished by routine methods such as light microscopy, SEM, FTIR, BET and magnetic measurements.     

Seed Dispersion Polymerization to Micron-Size Monodisperse Polymer Particles

Abstract

Seed dispersion polymerization of methyl methacrylate (MMA) in the presence of monodisperse PMMA particles was carried out in an aqueous methanol using poly(methacrylic acid) stabilizer. The polymerization using 2. 5 μ. m-sized seed particles gave monodisperse PMMA particles in the diameter up to 4. 9 μm. The solvent composition and monomer concentration greatly affected the polymerization behavior. Under appropriate conditions, monodisperse PMMA particles in the diameter up to 8. 9 μ, m was prepared from 4. 6 μm-sized seed particles. The seed dispersion polymerization of styrene in the presence of the seed particles produced monodisperse PMMA-polystyrene particles in the micron range. The particles were supposed to have a structure consisting of PMMA-core and polystyrene-shell from ESCA analysis.     

Preparation of micron-sized, monodisperse poly(methyl methacrylate)/polystyrene composite particles having a large number of dents on their surfaces by seeded dispersion polymerization in the presence of decalin

Seeded dispersion polymerization of styrene with 1.77-µm-sized, monodisperse poly(methyl methacrylate) seed particles was carried out in a methanol/water medium (8/2, w/w) in the presence of decalin droplets. The monodisperse poly(methyl methacrylate)/polystyrene composite particles produced had a large number of dents on their surfaces. The effects of the amount of decalin in the polymerization system on the number, the diameter, and the depth of the dents on the surface of the composite particles were clarified.     

Synthesis of Bowl-like Particles by Emulsion Polymerization and Release Behavior of Solvent from the Particles

Bowl-like poly (styrene-co-glycidyl methacrylate) was synthesized by swollen seeded emulsion polymerization. The polymerization was carried out in PS seed emulsion swollen by toluene, whereby the bowl-like particles formed at last. The shape was observed by SEM. These particles became ball-like when swollen by toluene, observed by optical microscope, and the release behavior of solvent from them was examined.     

Fabrication of cage-like particles via unstable seeded dispersion polymerization: A new concept in the polymerization-induced self-assembly

The formation mechanism of hollow micron-sized polystyrene (PS) particles having numerous dents on the surface, so-called cage-like particles, obtained from seeded dispersion polymerization (SDP) of 2-ethylhexyl methacrylate (EHMA) with low molecular weight (MW) PS particles stabilized by poly(vinyl alcohol) (PVA) in the presence of hexadecane droplets was investigated. It was found that association of poly(2-ethylhexyl methacrylate) (PEHMA)/hexadecane phases which occurs due to the instability of the obtained composite particles followed by a diffusion of PS ellipsoidal particles into each other is the main process responsible for the production of such unique morphology. Time course monitoring of the SDP showed that diffusion of hexadecane and/or PS and/or PEHMA phase into PS/PEHMA/hexadecane composite particles through PS shell which happens based on Ostwald ripening is the main phenomenon which results in the formation of the dents on the surface of final particles. Moreover, the experimental results revealed that in this reaction system, the polymerization develops in a faster manner rather than the SDP employing seed particles having higher MWs. Furthermore, it was observed that particles with different surface morphologies can be produced by using different hydrocarbons. The elimination of small particles which are produced in addition to the cage-like ones via decreasing the concentration of the stabilizer was another interesting finding of this research. The acquired results showed that unstable SDP is expected to be a new concept in polymerization-induced self-assembly (PISA) which employs instability of a dispersion for self-assembly of polymeric particles, and therefore, production of polymeric unique objects.     

Poly(methyl methacrylate) dispersions in decane stabilized by a diblock copolymer

In a dispersion polymerization, the monomer is miscible with the reaction medium, while the resulting polymer is insoluble under the same conditions. The macroscopic precipitation of the polymer is prevented by a steric stabilizer. Methyl methacrylate was polymerized in decane in presence of polystyrene-block-poly(ethylene-co-propylene) and spherical dispersion particles of poly(methyl methacrylate) (PMMA) were obtained. The static light scattering yielded molar masses of particles in the range 4 × 10⁷ to 7 × 10⁹ g mol⁻¹. Dynamic light scattering provided the hydrodynamic radii from 60 to 190 nm and also information on the non-uniformity of the particles. The relations between the characteristics of the dispersion particles (concentration of components, particle mass and dimensions, molar mass of PMMA chains, surface density of stabilizing chains, etc.) were looked for. The kinetics of polymerization seems to be only little affected by the colloidal character of the system.     

Effect of monomer and hydrocarbon content and polarity of the medium on the preparation of nonspherical particles via seeded dispersion polymerization in the presence of saturated hydrocarbon droplets

In this work, the preparation of micron-sized polymer particles with nonspherical shapes via seeded dispersion polymerization of 2-ethylhexyl methacrylate (EHMA) with polystyrene (PS) seed particles in the presence of decane droplets and evaporation of decane after the polymerization under various polymerization conditions was discussed. The effect of monomer and decane content and polarity of the medium on the shape of the obtained particles was investigated. The experimental results showed that decreasing the amount of monomer and hydrocarbon volume of PEHMA/hydrocarbon domains, the particles decreased but they grew symmetrically, resulting in symmetric shapes. Furthermore, it was suggested that because of changing the solubility of the oligoradicals and hydrocarbon in the medium, the shape of the particles changed with changing the polarity of the medium. With decreasing the polarity of the medium, solubility of the oligoradicals in the medium increases and bigger polymer domains form on the surface of PS particles which can absorb higher amounts of decane. All of these can contribute to an increase in volume reduction after extraction of PEHMA/decane, resulting in various particle shapes. Further decreasing in polarity of the medium leads to an increase in the solubility of decane in the medium and decreasing the absorbed amount of decane by PS particles and PEHMA domains, resulting in lower volume reduction after evaporation of decane.     

Dispersion polymerization of methyl methacrylate in supercritical CO2 in the presence of non-fluorous random copolymers

A series of non-fluorous random copolymers, composed of 3-[tris(trimethylsilyloxy)silyl] propyl methacrylate and 2-dimethylaminoethyl methacrylate, poly(SiMA-co-DMAEMA) with different comonomer ratios were prepared and utilized as stabilizers for the free radical dispersion polymerization of methyl methacrylate (MMA) in supercritical carbon dioxide (scCO₂). It was demonstrated that the composition and concentration of the stabilizer have a dramatic effect on the morphology of resulting poly methyl methacrylate (PMMA) latex. When the copolymeric stabilizer poly(SiMA-co-DMAEMA) (71:29) was employed, free-flowing spherical PMMA particles were produced in high yield. As the concentration of stabilizer increases, the resulting size of colloidal particles decreases. In addition, the monomer concentration and initial pressure affected the particle diameter of PMMA.     

Synthesis and characteristics of snowman-like fluorescent PMMA microbeads

This paper reports the fabrication of fluorescent snowman-like poly(methyl methacrylate) (PMMA) colloidal microbeads using a two-step method. The fluorescent cross-linked PMMA seeds were first synthesized by dispersion polymerization and then swelled in a monomer solution containing the methyl methacrylate monomer, a secondary cross-linker and initiator, followed by heat-induced polymerization. Scanning electron microscopy, confocal laser scanning microscopy, and Fourier transform infrared spectroscopy confirmed the synthesis of fluorescent snowman-like particles.     

A new tool for the study of polymerization under supercritical conditions – preliminary results

Efficient stirring is needed to realize heat flow analysis with a thermally homogeneous medium. Because dispersion polymerization with supercritical fluids can be destabilized under stirring, a preliminary target has been to find a compromise between synthesis and basic reaction calorimetry requirements. This paper describes the use of poly (dimethylsiloxane) macromonomer with a molecular weight 5000 g/mol as stabilizer for the dispersion polymerization of methyl methacrylate in supercritical carbon dioxide. The effect of stirring speed and stabilizer concentration has been examined. This study has shown that poly (methyl methacrylate) can be produced at high yield and molecular weight using 10 wt% (respect to monomer) poly (dimethylsiloxane) macromonomer at stirring speeds up to 600 rpm. A polymerization enthalpy of −57.6±2 kJ/mol has been calculated being in good agreement with previously reported data. Thus, preliminary results for the heat balance using the newly developed high pressure reaction calorimeter for supercritical fluid applications have shown the important potential of reaction calorimetry to promote supercritical fluid technologies at industrial scale allowing for the determination of kinetics and thermodynamic and safety data, respectively.     

负载型原子转移自由基聚合配体的合成及应用

用丙烯酸甲酯(MA)与负载到纳米二氧化硅有机/无机杂化粒子上的三乙烯四胺(TETA)进行Michael加成反应,合成了负载型原子转移自由基聚合(ATRP)配体。将其用于甲基丙烯酸甲酯(MMA)的ATRP,结果表明,动力学曲线表现为ln[c(M0)/c(Mt)](c(M0)为单体起始浓度,c(Mt)为反应时间t时单体浓度)与时间线性相关,分子量随转化率线性增加。可以通过离心轻易将催化体系从聚合物中分离出来,回收的催化体系可再次用于MMA的ATRP,且聚合反应仍具有可控/活性的特性,克服了传统ATRP中聚合后去除含过渡金属催化体系的困难。     

核／壳结构聚丙烯酸酯塑料增韧剂的制备与结构控制

核／壳结构聚丙烯酸酯塑料增韧剂的制备与结构控制张会轩戴英杨海东＊冯之榴（吉林工学院化工系长春１３００１２）（中国科学院长春应用化学研究所１３００２２）关键词聚丙烯酸酯，增韧剂，制备，种子乳液聚合１９９６－０８－２８收稿，１９９７－０１－０６修回国家自...     

Preparation of highly monodisperse poly(methyl methacrylate) particles incorporating fluorescent rhodamine 6G for colloidal crystals

Soap-free emulsion polymerization was extended to preparation of monodisperse poly(methyl methacrylate) (PMMA) particles incorporating rhodamine 6G (R6G) fluorescent molecules. The polymerization was conducted in the presence of an anionic monomer, p-styrenesulfonate (NaSS), which improved dispersion stability of the polymer particles. NaSS concentrations was ranged up to 2 mol/m3 H2O in the polymerization at 0.5 kmol/m3 H2O methyl methacrylate (MMA) monomer and 5 mol/m3 H2O potassium persulfate (KPS) initiator for R6G concentrations from 0.1 to 10 mol/m3-polymer. At R6G concentrations lower than 1.0 mol/m3-polymer, PMMA particles were highly monodisperse and incorporated most R6G molecules. The average sizes of PMMA particles were in a rage of 160-300 nm, and decreased with the concentration of NaSS. The high monodispersity of the particles enabled the fabrication of colloidal crystals of the particles with a vertical deposition method.     

高分散性SiO2/PMMA复合材料的制备与表征——纳米SiO2在MMA中的分散

用硅烷偶联剂3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)对分散于乙醇中的纳米SiO2进行偶联改性,再通过介质置换和原位本体聚合制得SiO2/甲基丙烯酸甲酯(MMA)单体分散液和SiO2/PMMA复合材料.红外光谱分析(FTIR)和热重分析(TG)结合洗提实验考察了SiO2表面MPS的偶联率和偶联效率,透射电镜(TEM...