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.     

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.     

Preparation of novel and unique nonspherical particles with almond-shell-like shape via dual-seeded dispersion polymerization in the presence of saturated hydrocarbon droplets

In this study, the preparation of micron-sized polymer particles having a novel and unique nonspherical shape which we called almond-shell-like by dual-seeded dispersion polymerization (DSDP) of 2-ethylhexyl methacrylate (EHMA) with polystyrene (PS) and poly(methyl methacrylate) (PMMA) seed particles in the presence of decane droplets and evaporation of decane after the polymerization was discussed. The experimental results showed that mushroom-like morphology which is a precursor of the almond-shell-like shape was obtained from DSDP of EHMA. It was found that with changing the PS/PMMA seed particles' weight ratio, the size of the dents on the surface of the particles can be controlled. Furthermore, it was observed that various nonspherical particles can be produced using different methacrylic seed particles and initiators.     

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.     

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.     

Micron-sized monodispersed polymer particles produced by seeded polymerization for the dispersion of high swelling of polymer particles with a large amount of monomer

 Micron-sized monodispersed polystyrene (PS)/poly(n-butyl methacrylate) composite particles were produced as follows. First, 1.77 μm-sized monodispersed PS seed particles produced by dispersion polymerization were dispersed in ethanol/water (1/2, w/w) medium dissolving poly(vinyl alcohol) as a stabilizer. n-Butyl methacrylate (BMA) monomer dissolving benzoyl peroxide initiator was emulsified in ethanol/water (1/2, w/w) solution of sodium dodecyl sulfate as emulsifier with ultrasonic homogenizer, and the BMA monomer emulsion was mixed with the PS seed emulsion. The PS seed particles absorbed with a large amount of BMA (about 150 times weight of the seed particles) for 2 h to about 10 μm in diameter while keeping good monodispersity and BMA droplets disappeared finally. The seeded polymerization was carried out at 70 °C after a certain amount of water was added to depress the redissolving of BMA from the swollen particles into the medium by raising from room temperature to the polymerzation temperature. Received: 21 February 1996 Accepted: 4 September 1996     

Preparation of micron-size monodisperse polymer particles by seeded polymerization utilizing the dynamic monomer swelling method

Utilizing a new type of monomer swelling method, 6.1 m-size monodisperse polymer particles were prepared by seeded polymerization. 1.8 m-size monodisperse polystyrene (PS) seed particles (1.8 m in size) were prepared by dispersion polymerization in ethanol-water (80/20, v/v) medium in the presence of poly(acrylic acid) as stabilizer with 2,2-azobisisobutyronitrile as initiator. The PS seed dispersion was mixed with ethanol-water (60/40, v/v) solution dissolving styrene (S) monomer, benzoyl peroxide as initiator, and poly(vinyl alcohol) as stabilizer. By slow, continuous, dropwise addition of water with a micro feeder into the mixture, the PS particles absorbed the many S monomers, which were separated from the medium and swelled from 1.8 m to 8.4 m while keeping the monodispersity high. We named this procedure the dynamic swelling method. Then, the seeded polymerization of the absorbed S monomer was carried out in the presence of NaNO₂ as water-solube inhibitor.Part CXXII of the series Studies on Suspension and Emulsion.     

Morphology of micron-sized monodispersed composite polymer particles produced by seeded polymerization for the dispersion of highly monomer-swollen polymer particles

 Monodispersed polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) composite particles having 9.4 μm in diameter were produced by seeded polymerization for the dispersion of highly n-butyl methacrylate (BMA)-swollen PS particles, and their morphologies were examined. The highly BMA-swollen PS particles (about 150 times the weight of the PS seed particles) were prepared by mixing monodispersed 1.8 μm-sized PS seed particles and 0.7 μm sized BMA droplets prepared with an ultrasonic homogenizer in ethanol/water (1/2, w/w) medium at room temperature. After NaNO₂ aqueous solution as inhibitor was added in the dispersion, the seeded polymerization was carried out at 70 °C. In an optical microscopic observation, one or two spherical high contrast regions which consisted mainly of PS were observed inside PS/PBMA composite particles. In the PS domain, there were many fine spherical PBMA domains. Such morphologies were based on the phase separation of PS and PBMA within the homogeneous swollen particles during the seeded polymerization. Received: 04 June 1997 Accepted: 27 August 1997     

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     

Morphology of micron-sized monodispersed poly(butyl methacrylate)/polystyrene composite particles produced by seeded dispersion polymerization

In order to develop the seeded dispersion polymerization technique for the production of micron-sized monodispersed core/shell composite polymer particles the effect of polymerization temperature on the core/shell morphology was examined. Micron-sized monodispersed composite particles were produced by seeded dispersion polymerizations of styrene with about 1.4-μm-sized monodispersed poly(n-butyl methacrylate) (Pn-BMA) and poly(i-butyl methacrylate) (Pi-BMA) particles in a methanol/water (4/1, w/w) medium in the temperature range from 20 to 90 °C. The composite particles, PBMA/polystyrene (PS) (2/1, w/w), consisting of a PBMA core and a PS shell were produced with 2,2′-azobis(4-methoxy-2,4-dimethyl valeronitrile) initiator at 30 °C for Pn-BMA seed and with 2,2′-azobis(isobutyronitrile) initiator at 60 °C for Pi-BMA seed. The polymerization temperatures were a little above the glass-transition temperatures (T _g) of both Pn-BMA (20 °C) and Pi-BMA (40 °C). On the other hand, when the seeded dispersion polymerizations were carried out at much higher temperatures than the T _g of the seed polymers, composite particles having a polymeric oil-in-oil structure were produced. Received: 14 October 1998 Accepted in revised form: 2 June 1999     

Influence of the swelling state of seed polymer particles with monomer on the morphology of micron-sized monodispersed composite polymer particles produced by seeded polymerization utilizing the dynamic swelling method

 Micron-sized mono-dispersed polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) composite particles (PS/PBMA=2/1 by weight) having a heterogeneous structure in which many fine PBMA domains dispersed in a PS matrix near the particle surface were produced by seeded polymerization of n-butyl methacrylate (BMA) of which almost all had been absorbed by 1.8 μm-sized monodispersed PS seed particles utilizing the dynamic swelling method. The morphology was varied by changing the PS/BMA ratio and polymerization temperature. It was concluded that the swelling state of 2 μm-sized BMA-swollen PS particles in the seeded polymerization process is one of the important factors to control the morphology of the composite particles. Received: 27 November 1996 Accepted: 21 March 1997     

Influence of particle diameter on the morphology of micron-sized, monodispersed composite polymer particles produced by seeded polymerization for the dispersion of highly monomer-swollen polymer particles

 Micron-sized, monodispersed polystyrene (PS)/poly (n-butyl methacrylate) (PBMA) composite particles, in which the PS domain(s) were dispersed in a PBMA continuous phase, were produced by seeded polymerization for dispersions of n-butyl methacrylate (BMA) swollen PS particles in a wide range of PS/BMA ratios in the presence of NaNO₂ as a water-soluble inhibitor. Moreover, in order to change the diameter of the composite particles at same PS/BMA ratio, PS/PBMA (1/150 w/w) composite particles were produced using five kinds of PS particles in a range of diameters from 0.64 to 3.27 μm as seeds. The percentages of the PS/PBMA composite particles having double and triple and over PS domains, which were thermodynamically unstable morphologies, increased with the increase in the diameter of BMA swollen PS particles. There was a clear influence of the size of the swollen particles on the morphology of the PS/PBMA composite particles produced. Received: 30 September 1999/Accepted: 18 April 2000     

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.     

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     

Production of micron-sized, monodisperse composite polymer particles having epoxy groups by seeded dispersion polymerization

 Micron-sized, monodisperse polystyrene (PS)/glycidyl methacrylate–divinylbenzene copolymer core/shell composite particles having epoxy groups in the shells were produced by seeded dispersion copolymerization of glycidyl methacrylate and divinylbenzene in an ethanol/water medium with 1.65-μm-sized, monodisperse PS seed particles. By chemical modifications of epoxy groups with sodium hydrogensulfite and dimethylamine, composite polymer particles having sulfonate and dimethylamino groups, respectively, in the shells were prepared. Received: 13 September 2000 Accepted: 31 January 2001     

Influence of viscosity within polymerizing particle on the morphology of micron-sized,monodisperse composite polymer particles produced by seeded polymerization for the dispersion of highly monomer-swollen polymer particles

Micron-sized, monodisperse polystyrene (PS)/poly( n-butyl methacrylate) (PBMA) composite particles, in which PS domain(s) were dispersed in a PBMA continuous phase, were produced by seeded polymerization for the dispersion of highly n-butyl methacrylate (BMA)-swollen PS particles (PS/BMA=1/150, w/w) using various concentrations of benzoyl peroxide as initiator in the absence/presence of sodium nitrite (NaNO ₂) as a water-soluble inhibitor. The percentages of the composite particles having double, triple and over PS domains, which were thermodynamically unstable morphologies, increased with a rapid increase of viscosity within the polymerizing particle.     

Obtaining of monodisperse particles through soap-free and seeded polymerization, respectively, through polymerization in the presence of C60

The present study reports on methods of synthesis of self-assembling monodisperse colloidal particles, obtained for the system styrene (St)–hydroxypropyl methacrylate, through emulsion polymerization, using no surfactant. The syntheses performed have led to the conclusion that the emulsion copolymerization in the presence of fullerene is responsible both for a significant decrease of the particles size as well as for a dimensional monodispersity of the system; the latter has been achieved also through seeded polymerization. The morphology and the size distribution of particles have been explored using scanning electron microscope and dynamic light scattering.     

Preparation and thermodynamic stability of micron-sized, monodisperse composite polymer particles of disc-like shapes by seeded dispersion polymerization

Micron-sized, monodisperse composite polymer particles having "disc-like" and "polyhedral" shapes were prepared by seeded dispersion polymerization of 2-ethylhexylmethacrylate (EHMA) with 2.67-mum-sized polystyrene (PS) seed particles in methanol/water media in the presence of droplets of various saturated hydrocarbons and evaporation of the hydrocarbon after the polymerization. Such nonspherical shapes were based on the volume reduction due to the evaporation. The primary factors influencing the particle shape seemed to be the absorption rate of the hydrocarbon into the resulting PS/poly(EHMA)/hydrocarbon composite particles during the polymerization, which affected the viscosities and the volumes of the PS and poly(EHMA) phases. It was found that the morphological development during the polymerization was retarded at "hamburger-like" morphology, which is a precursor of the disc-like particle, although this morphology is a thermodynamically metastable state.     

Production of micron-sized monodispersed polymer particles by seeded polymerization for the dispersion of highly monomer-swollen particles prepared with submicron-sized polymer seed particles utilizing the dynamic swelling method

For the purpose of extending the size range of polymer seed particles used in “dynamic swelling method” (DSM), first it was verified theoretically that the submicron-sized polymer particles produced by emulsion polymerization can also absorb a large amount of monomer by DSM in both equilibrium and kinetic control states. Next, on the basis of the theoretical results, experimentally about 2.6 μm-sized styrene-swollen polystyrene (PS) particles were prepared utilizing DSM in the presence of 0.64 μm-sized monodispersed PS seed particles produced by emulsifier-free emulsion polymerization. Moreover, 2.5 μm-sized monodispersed PS particles were produced by the addition of cupric chloride as a water-soluble inhibitor to depress the by-production of submicron-sized PS particles in the seeded polymerization at 30°C with 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) initiator. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2513–2519, 1998