Highly monodisperse crosslinked polystyrene microparticles by dispersion polymerization

 Highly monodisperse polystyrene microparticles cross-linked with urethane acrylates were produced by dispersion polymerization in ethanol solution in the presence of 2,2′-azobis (isobutyronitrile) initiator, polyvinylpyrrolidone stabilizer, and Aerosol–OT costabilizer. Different from conventional crosslinkers, the urethane acrylates employed as a crosslinker showed an excellent effect on maintaining the monodispersity of polystyrene microparticles even in the moderate crosslinker concentration. This was believed that the urethane acrylate helped forming the monomer-swellable surface of primary particles, because of its structurally long tetramethylene oxide groups in its molecule. However, at high concentration of the urethane acrylate, the rough surface and the coagulum of particles were observed, which was attributed to the seriously decreased solubility of the monomer mixtures in ethanol solution. The solubility of the mixtures of styrene monomer and urethane acrylate in the media had a serious effect on the average particle size and morphology of the final particles. This could be confirmed by the measurement of cloud points and fractional conversions. Received: 21 February 1997 Accepted: 25 May 1998     

Poly(methyl methacrylate) hollow particles by water-in-oil-in-water emulsion polymerization

Poly(methyl methacrylate) particles having hollow structures were produced by water-in-oil-in-water (W/O/W) emulsion polymerization where sorbitan monooleate (Span80) was used as a primary surfactant and sodium laurylsulfate and Glucopen (APG, polypeptide derivative) were used as secondary surfactants. Urethane acrylate having a molecular structure with a hard segment in the molecular backbone, a long soft segment in the middle, and vinyl groups at both ends was employed as a reactive viscosity enhancer. At low concentration of urethane acrylate, only a few particles contained a void in the polymer phase. However, as the concentration of urethane acrylate increased, the number of the particles containing the void increased. This was because urethane acrylate increased the viscosity of the monomer mixture and helped to form the stable W/O/W emulsion droplets, which possibly restricted droplet coalescence during emulsion polymerization. Moreover, at high concentration of urethane acrylate (above 7 wt%), multi-hollow-structured particles were obtained. It is believed that the increase in the lyophilicity of the monomer mixture caused by urethane acrylate led to stronger interfacial activity of the primary surfactant (Span80) and finally resulted in many internal aqueous droplets. Received: 31 July 1998 Accepted: 13 October 1998     

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     

Highly monodisperse crosslinked polymethylmethacrylate microparticles by dispersion polymerization

Highly monodisperse polymethylmethacrylate (PMMA) microparticles crosslinked with carboxylic group-containing urethane acrylates (CUA) were produced by simple dispersion polymerization in methanol solution. In contrast to conventional crosslinkers, the CUA employed as a crosslinker was excellent for maintaining the monodispersity of PMMA microparticles even at moderate crosslinker concentrations (to about 5 wt%). It was believed that the CUA helped form the monomer-swellable surface of primary particles, because of the structurally long tetramethylene oxide groups in the molecule. Carboxylic groups in the molecular backbone resulted in larger primary particles by increasing the solubility of the monomer mixture in the medium. Owing to these larger primary particles, the crosslinked PMMA particles showed lower polymerization rates than the linear ones during particle growth. However, at high CUA concentrations (about 10 wt%), bimodal distributions were observed. This was attributed to the high crosslinking density of the primary particle surfaces. Therefore, monomer diffusion toward the polymer phase was restricted, resulting in more favorable secondary nucleation in the medium. Received: 12 May 1998 Accepted: 19 August 1998     

Monodisperse micron-sized macroporous poly(styrene-co-divinylbenzene) particles by seeded polymerization

Macroporous poly(styrene-co-divinylbenzene) particles were produced in a micron-size range by two-stage swelling and continuous polymerization. The molecular weight of the polystyrene seed particles was controlled by incorporating a urethane acrylate. It was found that the porosity of the particles produced by the seeded polymerization was dependent on the molecular weight of the seed polymer. As the molecular weight of the polystyrene seed increased, the porous particles produced became macroporous. Interestingly, the high molecular weight of the polystyrene seed had a negligible influence on the change of porosity of the seeded polymerized particles. It is believed that the viscosity of the swollen droplet phase remained pretty high with the change in composition because the polystyrene seed copolymerized with urethane cacrylate had many side chains. Received: 16 December 1999 Accepted: 9 August 2000     

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.     

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     

Synthesis and characterization of new flame-retardant microspheres by dispersion polymerization of pentabromobenzyl acrylate

New flame-retardant nano/micro particles of sizes ranging between 0.06 ± 0.01 and 1.70 ± 0.23 μm were formed by dispersion polymerization of the pentabromobenzyl acrylate monomer (PBBA) in methyl ethyl ketone as a continuous phase. The effect of various polymerization parameters, e.g., monomer concentration, initiator type and concentration, stabilizer concentration and crosslinker monomer concentration, on the size, size distribution and polymerization yield of the produced poly(pentabromobenzyl acrylate) particles has been elucidated. Poly(pentabromobenzyl acrylate)/polystyrene (PPBBA/PS) nano/micro blends of the contents of different PPBBA particles were prepared by mixing the PPBBA particles with a PS solution in methylene chloride, followed by evaporation of the methylene chloride from the mixture. The thermal stability of these blends was also studied.     

Control of particle size in dispersion polymerization of methyl methacrylate

Poly(methyl methacrylate) (PMMA) particles ranging in diameter from 2 to 10 μm were prepared by dispersion polymerization. The effects of various polymerization parameters on the size and monodispersity were systematically investigated. The particle size was found to increase with increasing polymerization temperature, concentration and decomposition rate of the initiator, and solvency of the dispersion medium. It also increased with increasing concentration and molecular weight of the polymeric stabilizer, poly(vinyl pyrrolidone) (PVP). As the monomer concentration was increased from 5 to 20 wt %, a minimum was found in the particle size at a monomer concentration of 10 wt %. A costabilizer was found to be necessary for preparing monodisperse particles at stabilizer concentrations below 2 wt %. A recycling experiment showed that the consumption of PVP was quite small in each cycle and the residual materials in this system could be reused readily. © 1993 John Wiley & Sons, Inc.     

Monodisperse Crosslinked Microsphere Polymer Particles by Dispersion Copolymerization of Glycidyl Methacrylate and Divinylbenzene

Monodisperse polyglycidyl methacrylate (PGMA) microsphere particles crosslinked with divinylbenzene crosslinker were prepared by single-stage dispersion copolymerization in ethanol medium. 1 wt% of DVB was successfully incorporated due to the costabilizing effect of GMA as a surface-active monomer. This behavior may indicate that the fast formation of stable primary particle leads to monodispersity. The average particle sizes and the particle size distributions increased with the DVB crosslinker concentration. The effects of two different variables (initiator concentration, crosslinker concentration) on the rate of dispersion copolymerization have been investigated. With the initiator concentration, the polymerization procedure mainly depended on the dual natures of general dispersion polymerization, in the crosslinked state. Up to 1 wt% DVB, the particle growth was controlled by the monomer diffusion from the continuous phase into the particle phase.     

Dispersion copolymerization of styrene and butyl acrylate in polar solvents

Monodisperse copolymer particles from 1.1 to 2.6 μm in diameter were obtained by unseeded batch dispersion copolymerization of styrene and butyl acrylate in an ethanol–water medium. A two-level factorial design using bottle polymerizations was initially carried out including the following variables: stabilizer concentration, initiator concentration, polarity of the dispersion medium, initial monomer concentration, and temperature. Once the region of experimental conditions in which monodisperse latexes can be prepared was identified, further effort was devoted to analyze the effect of other variables. It was found that the temperature at which nucleation occurs and the evolution of the temperature after the onset of nucleation were critical to obtain monodisperse particles. The particle size increased with increasing initial monomer concentration and ethanol–water weight ratio, and decreasing stabilizer concentration. A minimum quantity of emulsifier was necessary to avoid coalescence of particles and to obtain monodisperse particles. © 1996 John Wiley & Sons, Inc.     

Emulsifier-free emulsion polymerization of the comonomer system styrene/tetrahydrofurfuryl metacrylate

 The emulsifier-free emulsion copolymerization of styrene and tetrahydrofurfuryl methacrylate (TMA) in aqueous phase is described. Monodisperse latex particles with diameters from about 280 to 620 nm are obtained consisting of a hydro-phobic polystyrene core and a hydrophilic poly-TMA shell. The influence of a variation of TMA, styrene and initiator (potassium persulfate) concentration in the original emulsion on particle size, molecular weight and composition of the copolymer is described. The concentration of TMA and initiator affects the number of primary particles but not the size of the final particles, whereas the styrene concentration strongly influences the particle diameter, a large size being favored by a high styrene concentration. The molecular weights of the polymers are between 6.2×10⁴ and 7.0×10⁵ g/mole. Size exclusion chromatography of polymer solutions in tetra-hydrofuran shows that high molecular weights are especially found in large particles, which are preferentially formed in emulsions with a high concentration of styrene. ¹H-NMR spectroscopy of the polymer shows that only about 50% of the initial TMA concentration are polymerized in the particles. Thus the copolymers prepared at increasing styrene concentration and constant initiator concentration of the emulsion show an increasing polystyrene content and are formed in particles of increasing size. Received: 4 June 1997 Accepted: 19 August 1997     

Synthesis and characterization of micrometer‐sized particles of narrow size distribution with chloromethyl functionality on the basis of single‐step swelling of uniform polystyrene template microspheres

Polystyrene template microspheres of 1.4 ± 0.1 μm were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2‐methoxy ethanol. These template particles were then swelled at room temperature in a single step with emulsion that was prepared in sodium dodecyl sulfate aqueous solution from a swelling solvent (dibutyl phthalate) containing the initiator (benzoyl peroxide) and monomer(s) (chlormethylstyrene, divinylbenzene, or ethylene dimethacrylate). Composite uniform particles composed of the template polystyrene and noncrosslinked or crosslinked polychloromethylstyrene were prepared by polymerizing the monomer(s) within the swelled particles at 73 °C. Crosslinked uniform polychloromethylstyrene particles of higher surface area were formed by dissolving the template polystyrene polymer of the composite particles. The influence of various reaction parameters, such as dibuthyl phthalate concentration, chloromethylstyrene concentration, crosslinker type and concentration, and so forth on the molecular weight, size, size distribution, shape, morphology, surface area, and decomposition temperature of the particles was investigated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1342–1352, 2002     

交联剂加入方式对聚苯乙烯微球形貌和分散性能的影响

以醇水混合液为分散介质,偶氮二异丁腈为引发剂,聚乙烯吡咯烷酮为稳定剂,二乙烯基苯为交联剂,采用分散聚合法一步制备了粒径约为1μm的单分散交联聚苯乙烯微球;采用扫描电镜和激光粒度仪等分析微球表面形貌及粒径分布,研究了滴加交联剂开始时间、交联剂浓度、引发剂浓度等对微球形貌和分散性能的影响.结果表明,在实验进行4h时加入交联剂,且交联剂滴加持续时间为2h的条件下,可制得平均粒径为1μm左右的交联聚苯乙烯微球,其具有较好的单分散性和球形度,且表面光滑.     

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 of micron-size polystyrene particles in supercritical carbon dioxide

The dispersion polymerization of styrene in supercritical CO₂ utilizing poly(1,1-dihydroperfluorooctyl acrylate) (p-FOA) as a polymeric stabilizer was investigated as well as poly(1,1-dihydroperfluorooctyl methacrylate) (p-FOMA). The resulting high yield (>85%) of spherical and relatively uniform polystyrene (PS) particles with micron-size range (2.9–9.6 µm) was formed for 40 h at 370 bar using various amounts of p-FOA and p-FOMA as a stabilizer with good stability until the end of the reaction. The particle diameter was shown to be dependent on the weight percent of added stabilizer. Previously, we reported that p-FOA was not effective for the dispersion polymerization of styrene as a stabilizer. Here, we find that p-FOA can indeed be an effective stabilizer for the dispersion polymerization of styrene in supercritical CO₂, but the pressure necessary to achieve good stability is higher than pressure used by us previously. This study suggests the possibility that fluorinated acrylic homopolymers are effective for the dispersion polymerization of various kinds of monomers as a stabilizer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2429–2437, 1999     

Synthesis of di‐ and triblock copolymers of styrene and butyl acrylate by controlled atom transfer radical polymerization

Di‐ and triblock copolymers of styrene and butyl acrylate with controlled molar masses (M_n up to ≈ 10⁵) were sequentially prepared by radical atom transfer polymerization in a homogeneous medium using chlorine end capped polymers as initiators and the copper^(I) chloride/bipyridine complex as catalyst, in the presence of dimethylformamide. Random poly(styrene‐co‐butyl acrylate) was synthesized and the cross‐over reactions between Cl end capped polystyrene and poly(butyl acrylate) to the opposite monomers were examined.     

Synthesis of highly crosslinked monodisperse polymer particles: Effect of reaction parameters on the size and size distribution

Monodisperse polystyrene particles crosslinked with different concentrations of divinylbenzene were synthesized in the 3.2–9.1 μm size range by dispersion polymerization in an isopropyl alcohol/toluene mixed‐dispersion medium with poly(N‐vinylpyrrolidone) as a steric stabilizer and 2,2′‐azobisisobutyronitrile as a radical initiator. The effects of the reaction parameters such as the crosslinking agent concentration, media solvency (controlled by varying the amount of toluene addition), the initiator concentration, and the stabilizer concentration on the particle size and size distribution were investigated with reference particles with a monodisperse size distribution and crosslinked by 1.5 wt % divinylbenzene. The appropriate increase in media solvency was a prerequisite for preparing crosslinked particles without coagulated and/or odd‐shaped particles. The investigation of the effects of the polymerization parameters also shows that only specific sets of conditions produce particles with a monodisperse size distribution. The glass‐transition temperatures of the particles increased with increasing divinylbenzene concentration. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4368–4377, 2002     

Poly(2‐hydroxyethyl methacrylate‐co‐N,O‐dimethacryloylhydroxylamine) particles by dispersion polymerization

Poly(2‐hydroxyethyl methacrylate‐co‐N,O‐dimethacryloylhydroxylamine) particles were prepared by dispersion polymerization in toluene/2‐methylpropan‐1‐ol medium using cellulose acetate butyrate and dibenzoyl peroxide (BPO) as a steric stabilizer and initiator, respectively. The particle size was reduced with decreasing solvency of the reaction medium (more nuclei were generated) because the critical chain length of the precipitated oligomers decreased with an increasing toluene content, which is a poorer solvent for the polymer than 2‐methylpropan‐1‐ol. There is an optimum initiator concentration (2 wt % BPO relative to monomers) for producing low‐polydispersity particles under given conditions. Additionally, discrete spherical particles were obtained at a low monomer concentration and/or higher polymerization temperature. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1625–1632, 2002     

Dispersion polymerization in polar solvents

The effect of the nitrogen purge, monomer purification, type of agitation, and presence of costabilizer on the particle size distribution (PSD) was investigated in the dispersion po-lymerization of styrene in ethanol and in the dispersion copolymerization of styrene and butyl acrylate in a water–ethanol mixture. Purging with nitrogen and, to a lesser extent, monomer purification, were of paramount importance to achieve monodispersity. The type of agitation had a week effect on the PSD, whereas the presence of costabilizer had no effect on the PSD. © 1995 John Wiley & Sons, Inc.