Seeded Polymerization Technique Research Articles

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

AbstractPoly(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

Direct coating of gold nanoparticles with silica by a seeded polymerization technique

Gold nanoparticles prepared through a conventional citrate-reduction method were directly coated with silica by means of a seeded polymerization technique based on the Stöber method. The method required no surface modification. The addition of tetraethylorthosilicate and water prior to ammonia was found to be critical to obtain a proper coating. The silica shell thickness was varied from 30 to 90 nm for TEOS concentrations of 0.0005–0.02 M at 10.9 M of water and 0.4 M of ammonia. The optical spectra of the core–shell gold–silica composite particles agreed with predictions of Mie theory.

Synthesis and characterization of surface-cyanofunctionalized poly ( N -isopropylacrylamide) latexes

A series of P[N-isopropylacrylamide (NIPAM)] latexes with different contents of cyano groups were successfully prepared by either seeded or shot-growth polymerizations of an aqueous solution containing acrylonitrile (AN) onto a seed P[NIPAM] latex, respectively, and further characterized by FT-IR, 1H-NMR, elemental analysis, as well as by quasielastic light scattering (QELS) and scanning electron microscopy (SEM). All prepared surface-cyanofunctionalized P[NIPAM] latexes exhibited the same range of lower critical solution temperature (LCST) as a pure P[NIPAM] latex. The shot polymerization process proved more efficient at yielding cyano derivatized latexes than the seeded polymerization technique. The amount of incorporated cyano groups onto the particles was determined with a good correlation both by 1H-NMR and elemental analysis. The higher the amount of initially introduced AN monomer in the reaction mixture, the more cyano groups were incorporated onto the particles. The surface of the particles with high content of cyano groups appeared quite rough by SEM in comparison with that of the pure P[NIPAM] particles.

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.

Independent control of mechanical and chemical properties of monodispersed polystyrene–divinyl benzene microspheres by two‐step polymerization

AbstractMonodispersed polystyrene (PS) latices of the particle size ranging between 4 and 10 μm were prepared by a conventional dispersion polymerization technique using poly‐(acrylamide) as a stabilizer. Styrene containing 2–20% of divinyl benzene (DVB) was subsequently polymerized on the surface of the latex by a seeded polymerization technique for the purpose of modifying the thermo‐mechanical and chemical properties of the microspheres. The softening temperature during hot pressing and the resistance against the dissolution on swelling in toluene or methyl ethyl ketone increased with increasing amount of DVB. The state of seeded polymerized particles was revealed to depend more on the total amount than the composition of the monomer added. By using the present technique, it is possible to prepare chemically stable, monodispersed microspheres with their diameters and softening temperature varying from 4.5 to 12 μm and from 106 to 126°C, respectively, with a free combination by choosing the appropriate dispersion polymerization condition and the amount of DVB during subsequent seeded polymerization.

Glycidyl methacrylate-styrene copolymer latex particles for immunologic agglutination tests

New latex particles for immunologie agglutination reaction were prepared by a seeded polymerization technique for the emulsifier-free copolymerization of styréne and glycidyl methacrylate. The surface of the latex particles was presumed to be dotted with hydrophilic domains, giving stability to the particles. The remaining areas, to which many antigens or antibodies were strongly adsorbed, were hydrophobic. Various groups of the glycidyl methacrylate-styrene latex particles were coated with human immunoglobulin G, and immunologie agglutinating potencies were compared by the box-titration method. Immunologie reactivities of the latex particles decreased with an increase of glycidyl methacrylate content at concentrations of 1 mol% or higher. Latex particles containing 0.5 to 0.75 mol% GMA caused strong immunologie agglutination besides showing good stability, indicating the availability of these latex particles. Glycidyl methacrylate-free polystyrene latex particles caused non-specific agglutination, while the immunologie agglutinating ability of glycidyl methacrylate-styrene latex particles, prepared by the unseeded polymerization technique was weak.

An experimental study of ideal and nonideal behavior in styrene emulsion polymerization

AbstractAn experimental investigation was conducted to relate the average number of radicals per particle, n̄ to the dimensionless parameter α, as suggested by Stockmayer. Seed emulsion polymerizations of polystyrene were run over a wide range of particle sizes and initiator levels in the 50−70°C temperature range. The seed polymerization technique removed the question of particle formation behavior and allowed a straightforward determination of n̄. Alpha was varied more than three orders of magnitude and resulted in measured values of n̄ in the range 0.5−1.3. These data are in good agreement with Stockmayer's relationship as long as the value of the termination rate constant is taken at the monomer/polymer ratios found in emulsion polymerization. For polystyrene at a monomer/polymer ratio of 60/40 this value is an order of magnitude lower than that found for infinitely dilute polystyrene solutions.