Morphology of micron-sized polystyrene particles crosslinked with urethane acrylate

The morphology of micron-sized polystyrene particles crosslinked with a urethane acrylate crosslinker was studied with different concentrations of urethane acrylate and medium solvency by means of simple dispersion polymerization. The urethane acrylate employed as a crosslinker showed an excellent effect on maintaining the monodispersity of the polystyrene particles at a moderate crosslinker concentration (to about 5 wt%) in terms of the monomer-swellable surface of primary particles. By enhancing the medium solvency, the amount of urethane acrylate incorporated was increased, while the monodispersity of the final particles was maintained. It was believed that the increase in solvency on adding xylene to ethanol solution helped the diffusion of the styrene monomers into the primary particles. At high concentration of urethane acrylate, however, nonspherical particles, ellipsoidal or egg-like singlets and asymmetric doublets, were observed. The increased crosslinking density seemed to repel the styrene monomers during particle growth. Received: 30 June 1998 Accepted in revised form: 9 September 1998     

Production of micron-sized monodispersed core/shell polymethyl methacrylate/polystyrene particles by seeded dispersion polymerization

 Micron-sized monodispersed polymethyl methacrylate (PMMA)/polystyrene (PS) (PMMA/PS=2/1, wt ratio) composite particles consisting of PMMA-core and PS-shell were successfully produced by seeded dispersion polymerization of styrene in a methanol/water medium in the presence of about 2 μm-sized monodispersed PMMA particles. From the view point of thermodynamic equilibrium, such a morphology is difficult to form by usual seeded polymerization in a polar medium such as water. It is concluded that seeded dispersion polymerization in which almost all monomers and initiators exist in the medium has an advantage to produce core/shell polymer particles in which polymer layers accumulate in their order of the production regardless of the hydrophobicity of polymers, because of high viscosity in polymerizing particles. Received: 9 December 1996 Accepted: 26 February 1997     

Preparation and characterization of micron-sized polystyrene/polysiloxane core/shell particles

A procedure has been developed to coat micron-sized polystyrene (PS) spheres with a smooth layer of polysiloxane by a sol–gel process of methyl trimethoxylsilane (MTMS) without using silane coupling agents. The thickness of the shells can be easily varied with different polystyrene seeds and methyl trimethoxysilane feed ratio. When we used PS particles with diameters of 2.09 μm prepared by conventional dispersion polymerization as seeds, the thickness of the polysiloxane shells can be varied from 0.11 to 0.21 μm. The particle size, size distribution, thermal decomposition, and solvent resistance were investigated by scanning electron microscope (SEM), transmission electron microscope (TEM), size analyzer, and TG, respectively.     

Production of micron-sized monodispersed cross-linked polymer particles having hollow structure

4 μm-sized monodispersed cross-linked polymer particles having hollow structure were produced as follows. First, 1.7 μm-sized monodispersed polystyrene (PS) seed particles produced by dispersion polymerization were dispersed in ethanol/water (7/3, w/w) solution in which divinylbenzene (DVB), benzoyl peroxide (BPO), poly(vinyl alcohol), and toluene was dissolved. The PS seed particles were swollen with DVB, toluene and BPO maintaining high monodispersity throughout the dynamic swelling process where water was slowly added continuously. And then, the seeded polymerization of the (toluene/DVB)-swollen PS particles was carried out.     

Production of micron-sized, monodisperse, transformable rugby-ball-like-shaped polymer particles

Micron-sized, monodisperse, “rugby-ball-like” polymer particles were produced by seeded polymerization for the dispersion of (divinylbenzene/vinylbiphenyl/xylene)-swollen polystyrene particles prepared by utilizing the dynamic swelling method which the authors proposed in 1991. The shape of the composite polymer particle was reversibly transformed between a rugby-ball-like shape and a spherical one by absorbing/releasing toluene. Received: 24 January 2001/Accepted: 18 April 2001     

Production of micron-sized, monodispersed, multihollow polystyrene/poly(3,5-xylidine) composite particles by chemical oxidative seeded polymerization

 Micron-sized, monodispersed polystyrene/poly(3,5-xylidine) composite polymer particles were produced by chemical oxidative seeded polymerization of 3,5-xylidine with 1.37-μm-sized, monodispersed polystyrene seed particles. The chemical oxidative seeded polymerization was conducted in an aqueous medium at 25 °C in the presence of poly(vinyl alcohol) as a stabilizer using ammonium persulfate as an oxidant. The composite particles had a multihollow structure. Received: 30 June 1999/Accepted in revised form: 21 October 1999     

Monodisperse micron-sized crosslinked polystyrene particles. IV. Effect of network structure on polymerization procedure

Monodisperse micron-sized polystyrene particles crosslinked using urethane acrylate were produced by dispersion polymerization in ethanol solution and the effect of the crosslinked network structure on the polymerization procedure was studied. The influences of the concentrations of the initiator and urethane acrylate on the particle diameter (D _n), the particle number density (N _p), and the polymerization rate (R _p) were found to obey the approximate relationships D _n ∝ [initiator]^0.43 [urethane acrylate]^0.05, N _p ∝ [initiator]^−1.30 [urethane acrylate]^0.19, and R _p ∝ [initiator]^{0.24 ± 0.02}. The power-law dependence of D _n and N _p on the initiator concentration showed a similar trend to that of linear polystyrene reported in the literature. Especially, it was found that urethane acrylate does not have a serious effect on D _n and N _p of the particles produced. The dependence of R _p on the initiator concentration was observed to be higher than that of linear polystyrene, suggesting that there is still competition between heterogeneous polymerization and solution polymerization because of the crosslinked network structure of the primary particle. Received: 1 April 1999 Accepted in revised form: 29 June 1999     

Monodisperse micron-sized cross-linked polystyrene particles. VI. Understanding of nucleated particle formation and particle growth

 The procedure of nucleated particle formation and particle growth in dispersion polymerization was studied with the intention of understanding the production of monodisperse polystyrene particles cross-linked with urethane acrylate (UA). The time required for the formation of primary particles was determined exactly from the turbidity measurement of the reaction mixture with the polymerization time. It could be found that differing from conventional divinyl cross-linkers, such as divinylbenzene, UA had a boundary concentration where the association and coagulation of preformed nuclei with other oligomers and/or nuclei effectively took place until the primary particle formed. Similarly to linear polystyrene particles, the particle number density of the primary particles cross-linked with UA remained constant to the final particles. This observation verifies the suggestion that the primary particles cross-linked with UA readily absorbed the monomers from the medium during the stage of particle growth. Received: 31 August 1999 Accepted: 7 January 2000     

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     

Production of micron-sized monodispersed composite polymer particles by seeded polymerization utilizing the dynamic swelling method

 In order to develop the seeded polymerization technique utilizing the dynamic swelling method (DSM) proposed by authors for the production of micron-sized mono-dispersed “composite” polymer particles consisting of two kinds of polymers, the seeded polymerization for the dispersion of ethyl methacry-late (EMA)-swollen PS particles prepared utilizing DSM was carried out. Monodispersed PS/poly(ethyl methacrylate) (PEMA) composite particles having 7 μm in diameter were produced by the addition of NaCl to lower the solubility of EMA in medium and by the addition of CuCl₂ as a water-soluble inhibitor to depress the by-production of submicron-sized PEMA particles. Received: 16 July 1996 Accepted: 10 October 1996     

Production of micron-sized monodispersed core/shell composite polymer particles by seeded dispersion polymerization

 The effect of the weight ratio of seed polymer/monomer on the morphology of the poly(methyl methacrylate) (PMMA)/polystyrene (PS) monodispersed composite particles produced by batch seeded dispersion polymerization of styrene with 1.64-μm-sized monodispersed PMMA seed particles in a methanol/water medium (4/1 w/w) was examined. In the PMMA/PS weight ratios of 3/1 and 2/1, the composite particles had a clear morphology consisting of a PMMA core and a PS shell. In the ratio of 1/1, a lot of small PS domains were observed in the PMMA core though the PS shell was still formed. By stepwise addition of styrene monomer, the formation of the small PS domain was depressed and complete core/shell morphology was formed. Absorption/release treatments of toluene into/from the PMMA/PS (1/1 w/w) composite particles resulted in a drastic morphological change from the core/shell structure to a multi- layered one. Received: 2 February 1999 Accepted in revised form: 7 April     

Preparation of micron-sized composite polymer particles containing hydrophilic 2-hydroxyethyl methacrylate and their biomedical applications

Micron-sized polystyrene or PS particles were first prepared by dispersion polymerization. Then a series of polystyrene/poly(styrene-2-hydroxyethyl methacrylate) or PS/P(S-HEMA) composite polymer particles was prepared by seeded copolymerization using different amounts of 2-hydroxyethyl methacrylate (HEMA) at the constant core/shell ratio of 1/0.5. The produced PS seed and composite polymer particles were characterized by transmission electron microscopy. Adsorption behaviors of some biologically active macromolecules were studied under similar conditions. In each case the magnitude of adsorption on composite polymer particles decreased with the increase in HEMA content in the recipe, which means that the hydrophobic interaction between the surface of the particles and biomolecules decreased. The specific activities of trypsin aqueous solution and adsorbed trypsin on PS seed and composite polymer particles prepared with different HEMA contents were also measured and compared. The activity of adsorbed trypsin on composite polymer particles improved significantly with the incorporation of hydrophilic HEMA.     

Colloidal characterization of micron-sized rod-like magnetite particles

Rod-like magnetite particles have been prepared following a precipitation procedure in the presence of an external magnetic field. These particles have been characterized and results compared to those obtained for spheres which were synthesized following the same recipe but in the absence of a magnetic field. Both spheres and rod-like particles have a saturation magnetization of 475 kA/m, an isoelectric point at approximately pH 6.6, and a magnetite inverse spinel structure. DLVO theory qualitatively predicts the results obtained regarding the stability of the magnetite dispersions.     

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.     

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     

Scanning white-light interferometry as a novel technique to quantify the surface roughness of micron-sized particles for inhalation

A novel approach of measuring the surface roughness of spherical and flat micron-sized drug particles using scanning white-light interferometry was applied to investigate the surface morphology of micron-sized active pharmaceutical ingredients (APIs) and excipient particles used for inhalation aerosols. Bovine serum albumin (BSA) and alpha-lactose monohydrate particles were chosen as model API and excipient particles, respectively. Both BSA and lactose particles were prepared with different degrees of surface corrugation using either controlled spray drying (four samples of BSA) or decantation (two samples of lactose). Particle size distributions were characterized by laser diffraction, and particles were imaged by scanning electron microscopy (SEM). Surface roughness of the BSA and lactose particles was quantified by white-light optical profilometry using vertical scanning interferometry (VSI) at full resolution using a 50x objective lens with 2.0x and 0.5x fields of view for BSA and lactose, respectively. Data were analyzed using Vision software (version 32, WYKO), and surface roughness values are expressed as root-mean-square roughness ( Rrms). Furthermore, data were compared to topographical measurements made using conventional atomic force microscopy. Analysis of the optical profilometry data showed significant variation in BSA roughness ranging from 18.58 +/- 3.80 nm to 110.90 +/- 13.16 nm for the smoothest and roughest BSA particles, respectively, and from 81.20 +/- 15.90 nm to 229.20 +/- 68.20 nm for decanted and normal lactose, respectively. The Rrms values were in good agreement with the AFM-derived values. The particle morphology was similar to SEM and AFM images. In conclusion, scanning white-light interferometry provides a useful complementary tool for rapid evaluation of surface morphology and roughness in particles used for dry powder inhalation formulation.     

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     

Preparation of micron-sized aromatic polyamide particles using ultrasonic irradiation

Aromatic polyamide particles were prepared by reacting p-phthalyl chloride and 4,4′-diaminodiphenyl ether in an acetone solution with a high water content, using a precipitation polymerization method with ultrasonic irradiation. The average particle diameter was ca. 712 nm, and the particles were porous and spherical with a narrow size distribution. They showed a high degree of crystallinity and excellent thermal stability. The morphology and the thermal decomposition temperature of the submicron particles were found to depend strongly on the volume of water added to the reaction system. In this polymerization method, the addition of water was essential for the formation of spherical particles. The simultaneous mixing process resulted in the formation of particles with a narrow size distribution, and the use of ultrasonic irradiation was effective in reducing particle size.     

Shear-induced assembly of graphene oxide particles into stripes near surface

We report the shear-induced assembly of graphene oxide (GO) particles into periodic stripe-like patterns near the surface. These stripe-like patterns, which have an average periodic length of 100–250 μm, are aligned in a wavy manner along the normal to the flow direction. The self-assembled GO structures are investigated at different depths using three different analysis methods, namely, reflective microscopy observations of the photonic-crystalline GO dispersion, polarized optical microscopy, and fluorescence confocal laser scanning microscopy. The surface microstructures observed in reflection mode are different from the shear-induced band structures formed in bulk thermotropic liquid crystals and liquid crystal polymers, in terms of the shape and scale of the stripes. Further, there is also a difference in terms of the dependence of the stripe width on the shear rate. The observations suggest that the stripes are formed because of a competition between the stable surface-field-induced planar alignment of the GO particles near the surface and their relatively unstable shear-induced vertical alignment in the bulk. The findings of this study should advance our understanding of GO assembly under shear stress. Further, the proposed method is a novel one for inducing the assembly of GO particles into microstructures shaped as thread-like stripes.     

Accumulation of monomolecular polystyrene particles from a water surface onto a substrate

Monomolecular particles of polystyrene (M_w/M_n = 1.04, M_w = 3.84 ? 10⁶) formed by spreading of a dilute solution in benzene over a water surface were successfully accumulated onto a hydrophobic substrate by the horizontal lifting method. The accumulation was quantitative (up to 66 layers) to give a multilayer film. The substrates used were silicon single crystals, quartz coated with an iron(III) stearate monolayer, and poly(methylmethacrylate) plates. The film contained voids amounting to 20-30 vol%. The surface structure observed by transmission electron microscopy clearly showed a multilayer, particle structure. These facts indicate that the molecules exist as monomolecular particles in the film. The film should be a suitable material to study properties of polymeric monomolecules in a very unusual state as compared with the ordinary solid.