Chromatographic performance of monodisperse macroporous particles produced by modified seeded polymerization. II. The effect of the diluent/seed‐latex ratio

Poly(styrene‐co‐divinylbenzene)‐based monodisperse macroporous particles were obtained by a modified seeded polymerization technique. The monodisperse polystyrene particles, obtained by dispersion polymerization in sufficiently large sizes and with suitable average molecular weights, were directly used as the seed latex in the production of macroporous particles. Therefore, the number of swelling and polymerization stages in the multistage production was reduced. In the first stage, the seed particles were swollen with a diluent, dibutyl phthalate (DBP), and then with a monomer phase including styrene, divinylbenzene, and, as an initiator, benzoyl peroxide. The monodisperse macroporous particles were obtained by the repolymerization of the monomer mixture in the seed particles. The particles, having different porosity characteristics, were synthesized through variations in the dibutyl phthalate/seed‐latex (DBP/SL) ratio. Selected macroporous particle samples were slurry‐packed into stainless steel high‐performance liquid chromatography columns (300 mm long × 7.8‐mm i.d.). The separation of the protein mixture by these columns in the reversed‐phase chromatography (RPC) mode was investigated. Liquid chromatograms with high resolutions were obtained under an acetonitrile/water gradient over a wide range of flow rates (i.e., 0.5–3 mL/min), especially for the particles produced with a monomer/seed‐latex (M/SL) ratio of 3.0 mL/g. In the RPC experiments, the particles produced with an M/SL ratio of 3.0 mL/g and DBP/SL ratios of 1.0 and 1.5 mL/g exhibited better chromatographic performance than the other samples. The maximum theoretical plate number was 3500 for the particles produced with the M/SL ratio of 3.0 mL/g and DBP/SL ratio of 1.5 mL/g with albumin as the analyte. The size exclusion chromatography (SEC) calibration curves and the back‐pressure/flow‐rate relationships of the produced columns were also determined. The particles obtained with an M/SL ratio of 3.0 mL/g and a DBP/SL ratio of 1.5 mL/g exhibited the best performance in SEC applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3685–3696, 2004     

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     

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     

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     

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     

中空聚合物微球的制备——种子及核乳胶粒的制备

为了制得具有中空结构的聚合物微球,首先以十二烷基苯磺酸钠(SDBS)为乳化剂,在其用量低于CMC的条件下,进行甲基丙烯酸甲酯(MMA)、甲基丙烯酸(MAA)和丙烯酸丁酯(BA)的乳液聚合,制备了带羧基的种子乳胶粒.然后采用MMA、MAA和二乙烯基苯为单体进行种子乳液聚合,制备了轻度交联的带羧基的核乳胶粒.该核乳胶粒经过核-壳乳液聚合和适当的碱处理工艺就可成为具有中空结构的聚合物微球.采用粒度仪测定了乳胶粒的直径及其分布,采用TEM对乳胶粒结构形态进行了表征.研究了种子及核乳胶粒制备过程中单体加料方式、乳化剂用量及羧基单体种类等因素对聚合稳定性、乳胶粒直径及其分布以及最终的中空聚合物微球结构形态的影响,确定了制备种子及核乳胶粒的最佳工艺条件.在制备种子阶段,SDBS用量为单体总量的0.5%,采用一次性加入单体的进料工艺;在核乳胶粒制备阶段,以MAA为羧基单体,所有单体采用"饥饿式"加料,半连续补加乳化剂并使乳化剂用量为核单体总量的0.15%时可保持聚合稳定性并保证无新乳胶粒生成.     

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     

Preparation and characterization of imidazole‐functionalized microspheres

The preparation of imidazole‐functionalized latex microspheres by a two‐stage emulsion copolymerization process and their characterization are reported on. Emulsifier‐free emulsion copolymerization of styrene (St) and 1‐vinyl imidazole (VIMZ) exhibited bimodal particle size distributions caused by secondary homogeneous nucleation process. However, secondary nucleation can be avoided by using cetyltrimethylammonium bromide (CTAB) as a stabilizer at a concentration below its cmc (critical micelle concentration). This would result in the formation of monodisperse latex particles. The final particle size diameter depended on the concentration of CTAB as well as the amount of VIMZ. To control the amount of the functional imidazole groups on the latex particle surfaces, independent of the latex diameters, without secondary nucleation of particles, the seeded emulsion copolymerization of styrene and VIMZ was explored as a second‐stage polymerization at different concentrations and ratios of monomers in the presence of the previously prepared monodisperse poly(styrene‐co‐1‐vinyl imidazole) seed latex particles. The concentration of imidazole functional groups on the surface of the latex particles could also be varied through the rearrangement of hydrophilic imidazole groups by varying the second‐stage monomer addition process such as the utilization of monomer‐swollen seed particles or a shot addition of monomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 120:5753–5762, 2006     

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     

Modified emulsifier‐free emulsion polymerization of butyl methacrylate with ionic or/and nonionic comonomers

A modified emulsifier‐free emulsion polymerization of butyl methacrylate (BMA) with ionic or/and nonionic comonomers was successfully used to prepare nanosized poly(butyl methacrylate) (PBMA) latices with high polymer contents. After seeding particles were generated in an initial emulsion system, consisting of a portion of BMA, water, ionic comonomer [sodium styrenesulfonate (NaSS)] or nonionic comonomer [2‐hydroxyethyl methacrylate (HEMA)] and potassium persulfate, most of the BMA monomer or the mixture of BMA and HEMA was added dropwise to the polymerizing emulsion over a period of 6–12 h. Stable latices with high PBMA contents up to 27% were obtained. It was found that the latex particle sizes (2R_h) were largely reduced (34 nm) by the continuous addition of monomer(s) compared to those (107 nm) obtained by the batch polymerization method. The effect of comonomer concentration on the particle size, the number of PBMA particles/mL of latex (N_d), and the molar mass (M_w) of copolymer during the polymerization were discussed. The surface compositions of latex particles were analyzed by X‐ray photoelectron spectroscopy, indicating that the surface of latex particles was significantly enriched in NaSS or/and HEMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3080–3087, 2004     

Preparation of monodispersed hollow polymer particles by seeded emulsion polymerization under low emulsifier conditions

In a low emulsifier system, the MMA‐BA‐MAA copolymer emulsions were prepared as seed latices and the seeded emulsion polymerization of MMA‐MAA‐DVB was consequently carried out to prepare carboxylated core particles. The hydrophobic shell was then synthesized onto the core using styrene, acrylonitrile, and divinylbenzene as comonomers. The hollow latex particles were obtained by alkalization treatment of the core‐shell latex particles. The effects of the feeding rate of monomer mixture, contents of emulsifier SDBS and crosslinking agent DVB, and ratio of the monomers during the core stage and shell stage on the morphology and volume expansion of the latex particles were investigated. The results show that the monodispersed hollow latex particles with large size can be obtained when the feeding rate is 0.1 g/min, SDBS content is 0.15 and 0.2 wt % during the core stage and shell stage, respectively, DVB contents are 1% during the preparation of shell copolymers, and the monomer ratio of the core particle to shell layer is 1 : 8. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1505–1510, 2005     

Surface modification of monodisperse‐crosslinked polymeric microspheres using a redox initiation system

The surface modification of monodisperse‐crosslinked polymeric microspheres was carried out by introducing hydroxyl groups on the surface and utilizing the redox initiation system. The emulsions of the second monomer mixture were swollen into the monodisperse PS seed particles. The hydroxyl groups were introduced by hydrolysis of the acetate groups on the surface of microspheres. Ceric ammonium sulfate in sulfuric acid solution was employed to graft the acrylic monomer onto the polymeric microspheres. The surface characteristics of the surface‐modified particles were confirmed by FTIR, SEM, and TGA measurements. From the FE‐TEM image, a uniform coating layer was confirmed on the surface of microsphere. In DSC analysis, only an exothermal peak appeared when high content of DVB was used in the seeded polymerization, while, T_gs emerged after hydrolysis and graft polymerization using the low content of DVB in the second monomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1349–1356, 2006     

Synthesis of well‐defined,functionalized polymer latex particles through semicontinuous emulsion polymerization processes

The design of a semicontinuous emulsion polymerization process, primarily based on theoretical calculations, has been carried out with the objective of achieving overall independent control over the latex particle size, the monodispersity in the particle size distribution, the homogeneous copolymer composition, the concentration of functional groups (e.g., carboxyl groups), and the glass‐transition temperature with n‐butyl methacrylate/n‐butyl acrylate/methacrylic acid as a model system. The surfactant coverage on the latex particles is very important for maintaining a constant particle number throughout the feed process, and this results in the formation of monodisperse latex particles. A model has been set up to calculate the surfactant coverage from the monomer feed rate, surfactant feed rate, desired solid content, and particle size. This model also leads to an equation correlating the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture. This equation can be used to determine the maximum polymerization rate, only below or at which monomer‐starved conditions can be achieved. The maximum polymerization rate provides guidance for selecting the monomer feed rate in the semicontinuous emulsion polymerization process. The glass‐transition temperature of the resulting carboxylated poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) copolymer can be adjusted through variations in the compositions of the copolymers with the linear Pochan equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 30–41, 2003     

Monodisperse core/shell latex particles containing carboxylic acid groups and their optimum acid content for pore generation

Monodisperse seeded latex particles with a core–shell morphology were prepared by copolymerizing, via dropwise addition, styrene (St)–methyl methacrylate (MMA)–acrylic acid (AA) or St–MMA–methacrylic acid (MAA) onto monodisperse seed latex particles of P(St–MMA). The seeded particles thus prepared were subjected to an alkali/acid treatment in order to generate pores in the particles. For the same carboxylic acid content, the volume expansion of the particles due to pore generation was higher in the particles containing AA than in those containing MAA. The size of the pores increased with increasing AA content. However, a maximum particle volume expansion of about 50% was observed for the particles containing 8 mol % AA in the monomer mixture employed in the second stage, and an explanation for this optimum is suggested. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1455–1460, 1999     

Polymeric particles prepared with fluorinated surfmer

Fluoro-containing particles have been obtained by miniemulsion polymerization of styrene and n-butyl methacrylate in presence of fluorinated monomer mono-fluoroalkyl maleate (MFM) which acts as a surfmer providing efficient stability to obtained dispersion and functionalization of particle surface with fluoro-groups. Increase of the MFM concentration in reaction mixture reduces the particle size and dispersions with narrower particle size distribution can be obtained. Blends of fluorinated latexes with styrene-butadiene copolymer latex were examined with regard to formation of low free energy surfaces. It has been shown that blends containing MFM-functionalized polymeric particles possess more hydrophobic surfaces then similar latex films, where particles prepared by polymerization of expensive fluorinated monomer have been applied.     

Study on synthesis and morphology control of poly(4‐vinylpyridine‐co‐butyl acrylate)/poly(styrene‐co‐butyl acrylate) composite microspheres

Monodispersed crosslinked cationic poly(4‐vinylpyridine‐co‐butyl acrylate) [P(4VP‐BA)] seed latexes were prepared by soapless emulsion polymerization, using 2,2′‐azobismethyl(propionamidine)dihydrochloride (V₅₀) as an initiator and divinylbenzene (DVB) or ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The optimum condition to obtain monodispersed stable latex was investigated. It was found that the colloidal stability of the P4VP latex can be improved by adding an adequate amount of BA (BA/4VP = 1/4, w/w), and adopting a semicontinuous monomer feed mode. Subsequently, poly(4‐vinylpyridine‐co‐butyl acrylate)/Poly(styrene‐co‐butyl acrylate) [P(4VP‐BA)/P(ST‐BA)] composite microspheres were synthesized by seeded polymerization, using the above latex as a seed and a mixture of ST and BA as the second‐stage monomers. The effects of the type of crosslinker, the degree of crosslinking, and the initiators (AIBN and V₅₀) on the morphology of final composite particles are discussed in detail. It was found that P(4VP‐BA)/P(ST‐BA) composite microspheres were always surrounded by a PST‐rich shell when V₅₀ was used as initiator, while sandwich‐like or popcorn‐like composite particles were produced when AIBN was employed. This is because the polarity of the polymer chains with AIBN fragments is lower than for the polymer with V₅₀ fragments, hence leading to higher interfacial tension between the second‐stage PST‐rich polymer and the aqueous phase, and between PST‐rich polymer and P4VP‐rich seed polymer. As a result, the seed cannot be engulfed by the PST‐rich polymer. Furthermore, the decrease of T_g of the second‐stage polymer promoted phase separation between the seeds and the PST‐rich polymer: sandwich‐like particles formed more preferably than popcorn‐like particles. It is important knowledge that various morphologies different from PST‐rich core/P4VP‐rich shell morphology, can be obtained only by changing the initiator, considering P4VP is much more hydrophilic than PST. The zeta potential of composite particles initiated by AIBN in seeded polymerization shifted from a positive to a negative charge. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1190–1203, 2002     

Control of pore generation and pore size in nanoparticles of poly(styrene‐methyl methacrylate‐acrylic acid)

Seeded emulsion polymerization of styrene‐methyl methacrylate‐acrylic acid onto seed latexes of monodisperse particles of poly(styrene‐methyl methacrylate) was conducted with or without divinyl benzene as a crosslinking agent. Experiments revealed that almost no new particles were formed during the second stage of polymerization, and that the seeded latex particles obtained were almost monodisperse. An alkali‐acid treatment was then applied to the seeded latex particles swollen in 2‐butanone. Experimental results indicated that: (1) for uncrosslinked particles, an optimum volume expansion of >50% is reached for a ratio of the swelling agent, 2‐butanone, to polymer (methyl‐ethyl‐ketone/polymer by weight) between 2.0 and 2.9; the volume expansion is much lower outside the above range. (2) For crosslinked particles, the particle volume expansion follows the same pattern, but with smaller values. (3) pH plays an important role in pore generation and volume expansion. Pore generation is optimized by decreasing pH to a value as low as 1.5 during acid treatment, and by keeping pH in the optimum range between 11.98 and 12.20 during alkali treatment. Based on the above observations, a discussion regarding the mechanism of pore generation and particle expansion is provided. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 419–426, 1999     

Preparation of normal‐phase HPLC stationary phase based on monodisperse hydrophilic polymeric beads and their application

The monodisperse, 5.0 μm hydrophilic macroporous poly(glycidymethacrylate‐co‐ethylenedimethacrylate) beads were first prepared based on monosized linear poly(glycidylmethacrylate) beads as seed by using a single‐step swelling and polymerization method. The seed beads prepared by dispersion polymerization exhibited good absorption of the monomer phase. The pore size distribution of the beads was evaluated by mercury instrusion method. The surface area was calculated from the BET isotherms of nitrogen adsorption and desorption. The beads were modified to be a normal‐phase liquid chromatographic (NPLC) stationary phase for high performance liquid chromatography (HPLC) in the following steps. First, the beads were completely hydrolyzed. Second, hydrolyzed particles were reacted with epichlorihydrin followed by another hydrolysis of the newly introduced epoxide groups. The retention properties of the NPLC stationary phase were easily modulated by changes in the composition of the mobile phase. The performance of theses beads was demonstrated with the separation of a variety of polar compounds. The satisfactory results were obtained. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of polysiloxane–polyacrylates composite latices and their film properties

Gamma‐ray induced seeded emulsion polymerization of methyl methacrylate and butyl acrylate was carried out in the presence of a polymerizable polysiloxane seed latex, obtained by ring‐opening copolymerization of octamethyl cyclotetrasiloxane (D₄) and tetramethyl tetravinyl cyclotetrasiloxane (VD₄), catalyzed by dodecylbenzene sulfonic acid (DBSA). A series of polysiloxane seed latices with different molecular weights, vinyl contents and particle sizes was used. The conversion–time curve showed that the polymerization rate was accelerated significantly by the seed latex. The obtained composite latices also showed good storage stability, mechanical stability and high electrolyte resistance ability. By using transmission electron microscopy (TEM), the morphology of the composite latex particles was found to display a quite uniform fine structure. The graft polymerization reactions between the polymerizable polysiloxane and the acrylates were confirmed by Fourier‐transform infrared spectroscopy (FT‐IR) and the graft efficiencies were also studied. The influence of seed content, molecular weight, vinyl content of the polysiloxane and seed latex particles size on the mechanical performance, water absorption ratio, surface properties and transparency of the latex films was also investigated. It was found that the seed content and particles size greatly affect the mechanical performance, water absorption ratio and transparency of the latex films. Copyright © 2005 Society of Chemical Industry     

Novel method of preparation of a charged mosaic membrane by using dipole‐like microspheres. II. Preparation of dumbbell/egg‐like microspheres

The dumbbell‐like/egglike microspheres of poly(4‐vinylpyridine/n‐butyl acrylate)/polystyrene [P(4VP/nBA)/PS] were prepared by soap‐free seed emulsion polymerization. The effects of various polymerization parameters, such as the amount of ethyl acetate (EA) in the continuous phase, swelling time, degree of crosslinking of seed polymer, polymerization temperature, and compatibility of seed polymer and the secondary polymer, and so forth, on the formation of dumbbell‐like/egglike morphology were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that secondary particles could be eliminated either by drastically increasing the number of seed particles or by stripping EA from the seed latex by dialysis and evaporation under a vacuum. Swelling the seed particle with the secondary monomer was essential for the preparation of egglike microspheres. For the localization of PS domains on one side of the egglike particle, the most effective factors were to elevate the polymerization temperature up to 90°C and simultaneously to lower the compatibility of the polymer on the seed particle surface with the phase of PS, while using the uncrosslinked seed latex. Crosslinking the seed latex was not suitable for localizing the PS domains in the seed particle, especially when the degree of crosslinking exceeded 0.5 wt % of EGDMA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2002–2017, 2001