SYNOPSISRelatively uniform polymeric microspheres, the coefficients of variation being close to lo%, were obtained by the BPO-initiated suspension polymerization of styrenic monomers. Unlike the conventional stirred-tank system, a particular microporous glass membrane ( SPG ) provided uniform monomer droplets continuously when monomer was allowed to permeate through the micropores. The monomer droplets were suspended in an aqueous solution containing the stabilizing agents, transferred to a stirred vessel, and polymerized. Up to 10 pm spheres, of a far narrower size distribution than those obtained by conventional microsuspension polymerization spheres, were obtained. The initial droplet size and distribution were retained with the successful suppression of secondary particle nucleation by the addition of hydroquinone in the aueous phase. Crosslinked polystyrene spheres were also synthesized in the presence of various low-molecular-weight diluents. While a good solvent, toluene, was not so effective; poor solvents, n-hexane and n-heptane, easily yielded the microporous structure, the specific surface area being as high as 160 m2/g.

SYNOPSISApplication of the particulate microporous glass membrane (SPG) was extended to the synthesis of fairly monodisperse poly(methy1 methacrylate) (PMMA) microspheres. Hydrophilic monomers have been believed to yield polymer particles of a broad size distribution when the SPG technique was employed. This difficulty was overcome by adopting the droplet swelling technique. The primary uniform emulsion composed of a mixture of hydrophobic diluent (and/or monomer), cosurfactant, and initiator was prepared with an SPG membrane and was allowed to absorb MMA (and diluent) under the principle of the degradative diffusion process from droplets in the secondary emulsion. The coefficient of variation of PMMA spheres was around 10%. Porous PMMA spheres possessing up to 185 m2/g of specific surface area were obtained as well as one-eyed spheres and smooth and solid spheres. 0

Fairly uniform porous microspheres of poly(styrene) (PS) and poly(methy1 methacrylate) (PMMA) were synthesized using a particular microporous glass membrane (SPG). Average diameters of these spheres are from 2.5 to 38 ym with the coefficient of variation (CV) around 10%. A maximum specific surface area of 370 mzlg was achieved. Uniform dispersion of MMA droplets was successfully prepared only when the swelling process reported by Higuchi and Misra was adopted. Two potential applications, one as a packing material for column chromatography, and the other as a can-ier of enzyme immobilization, were demonstrated.

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Fairly uniform spheres of crosslinked polystyrene (PS) and polymethyl methacrylate (PMMA), prepared by a particular emulsification process using SPG (Shirasu Porous Glass) membranes and subsequent suspension polymerization, were applied for immobilizing carriers of Glucoamylase (GluA). A mixture of monomers, solvents, and oil-soluble initiator was allowed to permeate through the micropores of SPG, suspended in an aqueous solution of poly(vinyl alcohol), and polymerized while retaining the narrow size distribution during polymerization. A small amount of acrylic acid or glycidyl methacrylate (GMA) was incorporated for the immobilization of GluA via covalent bonding. Although GluA has been regarded as being difficult to retain its activity after the immobilization process, a porous structure of the carriers definitely favored the immobilization, and a maximum 55% relative activity (RA) was obtained by the physical adsorption to PMMA spheres. The reaction of epoxide in GMA with 6aminocaproic acid provided a spacer arm for the carboxyl group. An improvement of activity was expected by the incorporation of the spacer arms; however, barely noticeable activity was observed for PMMA carriers either by the physical adsorption or by the covalent bonding. A slight improvement was observed for PS carriers with spacers compared to the carriers without them. The diffusion process of oligosaccharides in the porous carriers seemed to retard the rate of hydrolysis in the case of largest carriers, 60 mm PS-DVB-AA spheres. The activity of immobilized GluA was retained during a long storage period of more than 150 days, some of them even increasing gradually, while the activity of native GluA dropped to zero after 100 days.