Electron microscopic observation of uniform macroporous particles. I. effect of seed latex type and diluent

Uniform and macroporous polymer particles in the size range of 5–21 μm were prepared by a multistep seeded polymerization method. The uniform polystyrene particles in the size range of 1.9–7.5 μm were used as the seed particles in the preparation of macroporous beads. The seed particles with different sizes and molecular weights were produced by dispersion polymerization, by changing the type of dispersion medium and the initiator concentration. In the synthesis of macroporous particles, a two‐step swelling procedure was employed. The seed latexes were first swollen by a low molecular‐weight organic agent (i.e., dibutyl phthalate, DBP), then by a divinylbenzene–ethylvinylbenzene isomer mixture including an oil phase soluble initiator (i.e., benzoyl peroxide). The porous structure in the final beads was achieved by the polymerization of the monomer phase within the swollen seed particles including a mixture of linear polystyrene and DBP. The initiator concentration in the repolymerization step, the seed latex type (i.e., the diameter and the molecular weight of seed latex), DBP/seed latex, and the monomer/seed latex ratios were changed to achieve uniform polymer beads with different average sizes and pore structures. The average size, the size distribution, and the surface morphology of final beads were analyzed by Scanning Electron Microscopy. The internal structure of the beads were analyzed by Transmission Electron Microscopy. The results indicated that the average size of the final particles increased with increasing the seed latex diameter, DBP/seed latex, and monomer/seed latex ratios. The average pore size decreased with decreasing the molecular weight of the seed latex and increasing the DBP/seed latex and monomer/seed latex ratios. These tendencies were explained by the viscosity change of the porogen solution used in the repolymerization step. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2271–2290, 1999     

Synthesis of greater than 10‐μm‐sized,monodispersed polymer particles by one‐step seeded polymerization for highly monomer‐swollen polymer particles prepared utilizing the dynamic swelling method

The thermodynamic simulation under the kinetic control state indicates that 1.77‐µm‐sized monodispersed polystyrene (PS) particles can absorb 500 times the amount of the styrene monomer with keeping the monodispersity by the “dynamic swelling method” (DSM) which the authors proposed in 1991. Actually, about 14.1‐µm‐sized monodispersed styrene‐swollen PS particles in which PS seed particles absorbed 500 times the amount of styrene monomer were successfully prepared utilizing DSM. By one‐step seeded polymerization for the dispersion of the swollen particles at 30°C for 48 h with the 2,2′‐azobis(4‐methoxy‐2,4‐dimethyl valeronitrile) initiator, 13.1‐µm‐sized monodispersed PS particles were produced. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 278–285, 1999     

羧基聚苯乙烯微球的单分散性制备及表征

文章通过分散聚合法,以苯乙烯（St）为聚合单体,聚乙烯吡咯烷酮（PVP）为稳定剂,偶氮二异丁腈（AIBN）为引发剂,乙醇和水作为分散介质,合成微米级聚苯乙烯微球,并以此微球为种子,利用种子修饰法进一步合成羧基聚苯乙烯微球,并对合成的羧基微球单分散性、表面形貌及表面羧基密度进行表征。结果表明,在合成的聚苯乙烯微球表面成功连接上羧基基团,微球具有较高的羧基密度,并且保持良好的单分散性,适合下一步在其表面进行化学与生物活化以制备液相芯片的敏感元件。     

Investigation for surface morphology and mechanical property variations of single polymer particles

Monodisperse polymer particles were prepared via one‐step seeded polymerization using polystyrene, poly(methyl methacrylate), or styrene/methyl methacrylate copolymer [poly(ST‐co‐MMA)] as seed particles and 1,6‐hexanedioldiacrylate or divinylbenzene as crosslinking monomer. For the study, the effects of the combination of seed polymer and crosslinking monomer, the ratio of the absorbed monomer to the seed polymer particles (swelling ratio: S/R), and the seeded polymerization rate on the variation of surface morphology and mechanical properties of polymer particles, such as recovery rate, K‐values, breaking strength, and breaking displacement were investigated by using microcompression test. It was observed that the surface morphology could be controlled by changing polymerization rate or combination of seed polymer and crosslinking monomer, and it had a great influence on mechanical properties, especially the breaking strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2350–2360, 2007     

Monodisperse‐porous poly(styrene‐co‐divinylbenzene) beads providing high column efficiency in reversed phase HPLC

A multistage polymerization protocol, the so‐called “modified seeded polymerization,” was developed for the production of monodisperse‐porous poly(styrene‐co‐divinylbenzene) providing high column efficiency as a packing material in reversed phase high performance liquid chromatography (RPLC). In the first stage of the multistage production, uniform polystyrene seed particles, produced by dispersion polymerization, were swollen by an organic agent (i.e., the diluent) and then by a monomer mixture containing styrene and divinylbenzene. The final porous particles were obtained in the monodisperse form by the polymerization of monomer mixture in the seed particles. By the use of a small size seed latex with low molecular weight and by the selection of the appropriate diluent, relatively small monodisperse‐porous particles with suitable pore structure could be achieved. In the reversed phase separation of alkylbenzenes, under isocratic conditions, theoretical plate numbers up to 40,000 plates/m were achieved by using 5.2 μm porous particles, obtained by a toluene‐dibutyl phthalate mixture as the diluent. No significant decrease in the resolution power was observed by the fourfold increase in the mobile phase flow rate. The column efficiency and the resolution observed with 5.2 μm monodisperse‐porous particles were significantly higher with respect to the currently available polymer based packing materials used in the reversed phase HPLC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1430–1438, 2005     

Preparation of micron‐size monodispersed PS/P(St/MAA) microspheres by seeded dispersion polymerization

Uniform polystyrene (PSt) particles with the size of 1.9 μm were first prepared via dispersion polymerization, and then used as the seeds in a second‐stage dispersion copolymerization of styrene (St) and methacrylic acid (MAA) to produce carboxyl‐carrying microspheres. The PSt seed particles were swollen by monomer mixture of St and MAA, including an oil‐soluble initiator 2,2′‐azobisiso‐butyronitrile (AIBN), before polymerization. Finally, uniform PS/P(St/MAA) (polydispersity index, PDI = 1.02) microspheres with the size of 2.2 μm were obtained. The average particle size and size distribution of the final microspheres were investigated. MAA contents between 54 and 97 mg/g were detected from the PS/P(St/MAA) particles produced under different conditions. Dispersion medium has great influence on the kinetics of polymerization, due to its effect on the partitioning of monomers, solvents, and initiator in the particle phase, probably as well as on the conformation of the dispersion agent on the surface of the particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3586–3591, 2006     

Functional,uniform, and macroporous latex particles: Preparation,electron microscopic characterization,and nonspecific protein adsorption properties

A series of uniform, macroporous particles with different surface chemistries were prepared with different acrylic comonomers [methyl methacrylate (MMA), butyl methacrylate (BMA), epoxypropyl methacrylate (EPMA), 2‐hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA)] with styrene–divinylbenzene (S–DVB) in a multistep seeded polymerization. In the synthesis, uniform polystyrene seed particles 6.2 μm in size were swollen first with a low molecular weight organic agent and then with a monomer phase including an S–DVB mixture and a relatively polar acrylic monomer. Final macroporous particles approximately 10 μm in size were obtained by the repolymerization of the monomer phase in the swollen seed particles. Surface and bulk morphologies were investigated with scanning and transmission electron microscopy, respectively. Although highly porous particles could be achieved with relatively hydrophobic monomers such as styrene, BMA, MMA, and EPMA, the use of hydrophilic monomers such as HEMA and MAA led to the synthesis of uniform particles with lower macroporosity. A comparison of Fourier transform infrared and Fourier transform infrared/diffuse reflectance spectroscopy spectra indicated that the concentration of polar acrylic monomer on the surface was higher than in the bulk structure. The nonspecific protein adsorption behavior of uniform, macroporous particles was investigated with albumin as a model protein. The highest nonspecific albumin adsorption was observed with plain poly(styrene‐co‐divinylbenzene) [poly(S–DVB)] particles. The particles produced with MMA and EPMA also exhibited albumin adsorption capacities very close to that of plain poly(S–DVB). Reasonably low nonspecific albumin adsorption was observed with the particles produced in the presence of MAA, HEMA, and BMA. Poly(S–DVB) particles functionalized with poly(vinyl alcohol) provided nearly zero nonspecific albumin adsorption. For nonspecific albumin binding onto the particles via a physical adsorption mechanism, desorption ratios higher than 80% could be achieved. The desorption ratio with the EPMA‐carrying particles was only 5% because the albumin adsorption onto EPMA‐carrying particles occurred predominantly with covalent‐bond formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 414–429, 2002; DOI 10.1002/app.10412     

Chromatographic performance of monodisperse–macroporous particles produced by “modified seeded polymerization.” I: Effect of monomer/seed latex ratio

In this study, the monodisperse–macroporous particles produced by a relatively new polymerization protocol, the so‐called, “modified seeded polymerization,” were used as column‐packing material in the reversed phase chromatography (RPC) of proteins. The particles were synthesized in the form of styrene‐divinylbenzene copolymer approximately 7.5 μm in size. In the first stage of the synthesis, the monodisperse polystyrene particles 4.4 μm in size were obtained by dispersion polymerization and used as the “seed latex.” The seed particles were swollen by a low‐molecular‐weight organic agent and then by a monomer mixture. The monodisperse–macroporous particles were obtained by the polymerization of monomer mixture in the seed particles. In the proposed polymerization protocol, the number of successive swelling stages was reduced with respect to the present techniques by the use of sufficiently large particles with an appropriate average molecular weight as the seed latex. A series of particles with different porosity properties was obtained by varying the monomer/seed latex ratio. The separation behavior of HPLC columns including the produced particles as packing material was investigated in the RPC mode using a protein mixture including albumin, lysozyme, cytochrome c, and ribonuclease A. The chromatograms were obtained with different flow rates under an acetonitrile–water gradient. The theoretical plate number increased and chromatograms with higher resolutions were obtained with the particles produced by using a lower monomer/seed latex ratio. The separation ability of the column could be protected over a wide range of flow rates (i.e., 0.5–3 mL/min) with most of the materials tested. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 607–618, 2004     

聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子的制备

由种子乳液聚合法制备了聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子。以过硫酸钾(KPS)为引发剂,辛基酚聚氧乙烯醚(OP-10)为乳化剂,合成了聚苯乙烯(PS)种子核;连续滴加甲基丙烯酸甲酯(MMA),在核表面富集MMA,制备了粒径范围在0.16~0.67μm的核-壳粒子;当单体苯乙烯与甲基丙烯酸甲酯(St/MMA)的比为30∶70(质量比)时,所得粒径在0.18μm,粒径分布为0.012。差示扫描量热(DSC)研究显示,复合粒子的玻璃化转变温度(Tg)为97.2℃,峰形单一,表现出良好的热性能。     

2‐Hydroxyethylmethacrylate carrying uniform porous particles: preparation and electron microscopy

Uniform macroporous particles carrying hydroxyl groups have been obtained in the size range 3–11.5 µm by seeded polymerization. For this purpose, uniform polystyrene particles in the size range 1.9–6.2 µm were used as seeds. The seed particles were successively swollen by dibutyl phthalate (DBP) and a monomer mixture comprising styrene, 2‐hydroxyethylmethacrylate (HEMA) and a crosslinker. Two different crosslinkers, divinylbenzene (DVB) and ethylene glycol dimethacrylate (EGDMA), were tested. Size distribution properties together with bulk and surface structures of the particles have been characterized by both scanning and transmission electron microscopy. While EGDMA provides uniform particles with a non‐porous surface, DVB produces uniform particles having a highly porous surface and interior. The comparison of FTIR and FTIR‐DRS spectra shows that the HEMA concentration is higher on the particle surface than within the particle interior. Seed latex size and monomer/seed latex ratios are identified as the most important variables affecting the final particles. Different seed latexes have been tried; the result is that highly macroporous particles with a sponge‐like pore structure both on the surface and in the particle interior have been obtained by use of the seed latex with the largest particles and the lowest molecular weight. An increase in the HEMA feed concentration leads to final particles with a non‐porous surface and a crater‐like porosity in the particle interior. The average pore size significantly decreases with increasing DBP/seed latex and monomer/seed latex ratios. © 2001 Society of Chemical Industry     

Highly crosslinked micron‐sized,monodispersed polystyrene particles by batch dispersion polymerization,Part 1: Batch,delayed addition,and seeded batch processes

The seeded batch dispersion polymerization with or without monomer absorption was compared with the batch polymerization and delayed addition by batch polymerization, to prepare the highly crosslinked, monodispersed polystyrene (PS) particles. The seeded batch polymerization was carried out under the variation of styrene (in second stage)/styrene (in PS seed) (St/St) ratio, divinylbenzene (DVB) concentration, and polymerization temperature using 1.9‐μm monodispersed PS seed particles. The experimental results imply that the seeded batch process is more efficient method that could avoid the sensitive particle nucleation step in the presence of the crosslinker than the batch and delayed addition processes. Without monomer absorption, 2.3‐μm uniform crosslinked PS particles with 7 wt % of the DVB were prepared in 1/1 (St/St) ratio. In comparison, with the monomer absorption, monodispersed and smooth‐surfaced PS particles containing 20 wt % of the DVB were formed. A total of 5% weight loss of the crosslinked PS particles determined by TGA occurred from 353.8 to 374.8°C, and the degree of swellability in toluene decreased from 150 to 104.5% with increasing the DVB concentration from 5 to 20 wt % because of the increase of the crosslink density of the particles. The seeded polymerization, especially through monomer absorption procedure, is a novel way to obtain highly crosslinked, monodispersed PS particles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigation for surface morphology variation of monodisperse polymer particle

Monodisperse polymer particles composed of polystyrene (PS) and poly(1,6‐hexanedioldiacrylate) were prepared via one‐step seeded polymerization using PS as seed particles. For the study, the effects of the molecular weight of seed polymer particles, the ratio of the absorbed hexanediol dimethacrylate (HDDA) to the seed polymer particles (swelling ratio), and the seeded polymerization rate on the surface morphology of poly(St‐HDDA) particles were investigated. It was observed that the crater‐shaped defect was at the surface of poly(St‐HDDA) particles, independent of the molecular weight of seed polymer, and swelling ratio. But its surface morphology could be controlled by changing the rate of the seeded polymerization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2385–2394, 2007     

Electron microscopic observation of uniform macroporous particles. II. Effect of DVB concentration

The electron microscopic observation of uniform and macroporous poly(styrene‐co‐divinylbenzene) particles prepared by a two‐step seeded polymerization method was performed. In the synthesis of uniform macroporous particles, the uniform polystyrene latices produced by a dispersion polymerization method with two different sizes and average molecular weights were utilized as the seed particles. The seed particles were first swollen with dibutylphthalate and then with a monomer phase, including styrene and divinylbenzene. The macroporous structure of the final particles was achieved by using a porogen mixture consisting of dibutylphthalate and linear polystyrene. The linear polystyrene part of the porogen solution was directly obtained from the seed latex. The macroporous particles with different diameters and porosities were produced by changing the divinylbenzene concentration between 25 and 100% in the repolymerization step. The effect of divinylbenzene concentration on the size and the surface morphology of the final particles were investigated by scanning electron microscopy. The internal structure of the final particles was analyzed by transmission electron microscopy. The results indicated that the average size of the final particles increased with the increasing divinylbenzene concentration. The increase in the DVB concentration also led to an increase in the average pore size. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2291–2302, 1999     

Preparation and modification of monodisperse hydrogel microspheres

Monodisperse hydrogel microspheres were prepared by precipitation polymerization of acrylamide and comonomers in ethanol and propan-2-ol and their mixtures. The size of the microspheres varied from 0.2 to 1.3 μm as a function of the solubility parameter of the dispersants. The applicability of the three-component solubility parameter approach by Paine was examined. Seeded polymerization of styrene using the seed microspheres mentioned above yielded unique composite microspheres whose surface property changed gradually with the content of styrene.     

种子聚合法制备PS/PAA核壳微球的研究

设计制备了以疏水性聚苯乙烯(PS)为核、以亲水性聚丙烯酸(PAA)为壳的PS/PAA核壳结构复合微球。首先利用无皂乳液聚合法制备了亚微米级的PS微球,再以其为种子,利用种子无皂乳液聚合法制备PS/PAA核壳微球。在种子聚合阶段,选用AIBN当引发剂,经过红外光谱(IR)表征,表明当使用油溶性引发剂偶氮二异丁腈(AIBN),使其最终形成PS/PAA核壳结构微球。这种方法解决了亲水性较强的单体在以水为介质时在PS微球溶于少量的苯乙烯(St),并在引发聚合之前经过充分的吸附溶胀,可使亲水性单体AAc在PS种子微球表面聚合生成壳层,解决表面不容易直接聚合生成壳层的问题。     

Monosize polystyrene latices carrying functional groups on their surfaces

In this study, monosized polystyrene (PS) latices were prepared by dispersion polymerization of styrene in isopropanol-water media using poly(acrylic acid) (PAA) as a steric stabilizer and 2,2′-azobisizobutyronitrile (AIBN) as an initiator. The effects of initiator and stabilizer concentrations, alcohol/water and monomer/dispersion medium ratio on the polymerization kinetics, and the size and monodispersity of PS latices were experimented with in a stirred reactor system. Monosize PS beads in the size range of 1.0–3.0 μm were obtained. The PS latex obtained in the first step having a diameter of 2.3 μm were used as the seed latex, and styrene/acrylate monomers, acrylic acid (AA), 2-hydroxyethyl methacrylate (HEMA), and dimethylaminoethyl methacrylate (DMAEMA) were copolymerized onto the PS latex particles. The incorporation of functional groups to the surface and bulk structure of PS was confirmed by IR, FTIR, XPS, and zeta potential measurements. © 1994 John Wiley & Sons, Inc.     

Size control of polystyrene beads by multistage seeded emulsion polymerization

Micron‐sized monodisperse crosslinked polystyrene (PS) beads have been prepared by a multistage emulsion polymerization using styrene monomer, divinylbenzene crosslinking agent, and potassium persulfate initiator in the absence of emulsifier. In the first stage of the reaction, the lower the reaction temperature, the larger the bead size obtained. In the later stages of the reaction, the particle size is increased with the initiator concentration and monomer content. Particle nucleation of the preexisting polymer seed of 0.7–0.8 μm in diameter is prepared at 60°C, then the monodisperse crosslinked PS beads > 2 μm are synthesized up to the third stage of the reaction. As the particle size grows, the number of free radicals in the growing particles increases, and the conversion of the next stage is continuously increased. The reaction mechanism is suggested that the continuous polymerization be conducted due to the diffusion of monomer into the preexisting particles to induce spherical beads in the later stages of the reaction. Otherwise, phase separation or the formation of protrusion by the capture of free radicals will be taking place. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2259–2269, 1999     

Mechanism and grafting reactions in seeded emulsion polymerization with emulsified monomer feeding

The seeded emulsion polymerization of styrene with emulsified monomer feeding was performed by polyethyl acrylate (PEA) latex as seed emulsion. It was shown that the grafting reactions occurred between two components on the composite latex particles. The loci of seeded polymerization were studied by the kinetics of grafting reaction. The highest grafting efficiency in the initial period of seeded emulsion polymerization supported the fact that the surfaces of PEA particles are the sites of polymerization of styrene. The grafting efficiency decreased with increasing monomer‐to‐polymer ratio and initiator concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1495–1499, 1999     

Syntheses of acrylate core/shell imbiber beads by seeded suspension copolymerization and one‐stage copolymerization for solvent absorption–desorption

Seeded suspension copolymerization or a one‐stage copolymerization was used to synthesize acrylate core/shell imbiber beads. A two‐stage polymerization technique was used for seeded suspension polymerization. The seed particles for poly(methyl acrylate) or poly(2‐ethylhexyl acrylate) were synthesized first in a mixed solvent of toluene/isooctane containing the ethylene glycol dimethacrylate (EGDMA) crosslinking agent. These beads were swollen in styrene‐EGDMA‐BPO (benzoyl peroxide) and then polymerized in the aqueous phase to produce the polystyrene (PS) shell. The one‐stage copolymerization was carried out in toluene/isooctane containing methyl methacrylate (MMA), styrene (St), EGDMA, and BPO at 75°C for 10 h to give a core/shell copolymer of St‐MMA morphology. The appearance of core/shell imbiber beads prepared from these two techniques varied from monomer to monomer. This article describes the preparation, characterization, and application of the core/shell beads for organic solvent absorption/desorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 670–682, 2002     

Synthesis and properties of amphiphilic nonspherical SPS/PS composite particles by multi-step seeded swelling polymerization

Amphiphilic nonspherical particles have asymmetric surface physical and chemical properties. Such a unique structure makes them suitable for applications in many areas, such as chemical and biological sensors, colloidal surfactants, self-assembly, building blocks of complex superstructures, and materials engineering. In this study, amphiphilic sulfonated polystyrene/polystyrene (SPS/PS) composite particles with controllable morphologies are synthesized by combining modified treatment and multistage seeded swelling polymerization. Core-shell SPS particles were first obtained by modifying cross-linked PS particles with concentrated sulfuric acid, and the surface of SPS particles was a hydrophilic sulfonated polystyrene layer. With further twice seeded swelling polymerization, new hydrophobic PS oil phase sprouted on the strong hydrophilic surface even without any surfactant assistance in aqueous media. The morphologies of these SPS/PS composite particles could be adjusted by changing the crosslinking density of the seed microspheres, the sulfonation temperature and the swelling ratio of monomer/seed. These polymer composite particles can be used as solid surfactants.