Seed particle polymerization

Core-shell polymerization is a seed particle polymerization variation of emulsion polymerization. The seed particles are suspended in the continuous phase. The pre-polymerization mixture of monomer, cross-linker, template and initiator is added to the particle suspension as an emulsion prepared in the continuous phase. The mixture is stirred until the polymerization has completed. The addition of pre-polymerization mixture is repeated several times until the spheres reach the desired size range. The beads formed are composed of a core (i.e. the seed particle) and a shell ofMIP [98, 99],... 

Only particles of linear or very slightly cross-linked <0.6%) polymers may be produced by dispersion polymerization. Obviously, dispersion polymerization may be used for the production of monosized seed particles, which, after transfer to aqueous conditions, are used for the production of different cross-linked and macroporous particles by the activated swelling and polymerization method. 

Two different methods have been used for the incorporation of the activating ogliomer (or monomer) in the seed particles. The first method involves the application of a small organic chemical, such as chloroundecane or dibutyl phthalate, which is incorporated into the particles in the first swelling step. In the second method, an ogliomer compound is formed by polymerization of monomers that are absorbed inside the seed particles. 

Sheu and coworkers [111] produced polysty-rene-polydivinylbenzene latex interpenetrating polymer networks by the seeded emulsion polymerization of styrene-divinylbenzene in the crosslinked uniform polystyrene particles. In this study, a series of uniform polystyrene latexes with different sizes between 0.6 and 8.1... 

The uniform polymeric microspheres in submicron-or micron-size range can also be prepared as seed particles by the soapless emulsion or dispersion polymerization of a hydrophobic monomer like styrene. The uniform seed particles are swollen with the organic phase including functional comonomer, monomer, and oil-soluble initiator at a low temperature in an aqueous... 

In another study, uniform composite polymethyl-methacrylate/polystyrene (PMMA/PS) composite particles in the size range of 1-10 fim were prepared by the seeded emulsion polymerization of styrene [121]. The PMMA seed particles were initially prepared by the dispersion polymerization of MMA by using AIBN as the initiator. In this polymerization, poly(7V-vinyl pyrolli-done) and methyl tricaprylyl ammonium chloride were used as the stabilizer and the costabilizer, respectively, in the methanol medium. Seed particles were swollen with styrene monomer in a medium comprised of seed particles, styrene, water, poly(7V-vinyl pyrollidone), Polywet KX-3 and aeorosol MA emulsifiers, sodium bicarbonate, hydroquinone inhibitor, and azobis(2-methylbu-... 

PS/PHEM A particles in micron-size range were also obtained by applying the single-stage soapless emulsion copolymerization method [124]. But, this method provided copolymer particles with an anomalous shape with an uneven surface. PS or PHEMA particles prepared by emulsifier-free emulsion polymerization were also used as seed particles with the respective comonomer to achieve uniform PS/PHEMA or PHEMA/PS composite particles. PS/PHEMA and PHEMA/PS particles in the form of excellent spheres were successfully produced 1 iLitm in size in the same study. 

Preparation of uniform seed particles Soapless emulsion polymerization is usually preferred for the preparation of uniform seed particles since this technique provides emulsifier-free, larger, and highly uniform micropheres relative to those that can be obtained by the conventional emulsion recipes including emulsifiers and various additives. The size of uniform seed particles with the soapless emulsion procedure is in the range of 0.6-1.2 tm depending on the polymerization conditions [75,108]. 

A research group in Lehigh University has extensively studied the synthesis and characterization of uniform macroporous styrene-divinylbenzene copolymer particles [125,126]. In their studies, uniform porous polymer particles were prepared via seeded emulsion polymerization in which linear polymer (polystyrene seed) or a mixture of linear polymer and solvent were used as inert diluents [125]. The average pore diameter was on the order of 1000 A with pore volumes up to... 

Mass transfer of monomer from the suspended drops through the aqueous phase to the seeded particles continues throughout the polymerization. 

There are many variations on this theme. Fed-batch and continuous emulsion polymerizations are common. Continuous polymerization in a CSTR is dynamically unstable when free emulsifier is present. Oscillations with periods of several hours will result, but these can be avoided by feeding the CSTR with seed particles made in a batch or tubular reactor. 

It was apparent that the dense adsorption layer of HPC which was formed on the silica particles at the LCST plays a part in the preparation of new composite polymer latices, i.e. polystyrene latices with silica particles in the core. Figures 10 and 11 show the electron micrographs of the final silica-polystyrene composite which resulted from seeded emulsion polymerization using as seed bare silica particles, and HPC-coated silica particles,respectively. As may be seen from Fig.10, when the bare particles of silica were used in the seeded emulsion polymerization, there was no tendency for encapsulation of silica particles, and indeed new polymer particles were formed in the aqueous phase. On the other hand, encapsulation of the seed particles proceeded preferentially when the HPC-coated silica particles were used as the seed and fairly monodisperse composite latices including silica particles were generated. This indicated that the dense adsorption layer of HPC formed at the LCST plays a role as a binder between the silica surface and the styrene molecules. 

Seeded dispersion polymerization was extensively investigated for radical systems [17]. Much less is known about seeded dispersion polymerizations with propagation on ionic and/or pseudoionic active centers. Awan et al. reported seeded ionic polymerization of styrene, which at certain conditions produced particles with narrow diameter size dispersity [18,19]. We presented the first data on the seeded ring-opening polymerization with constant number of microspheres. 

Hayashi et al., 1989], involving the addition of monomer and initiator to a previously prepared emulsion of polymer particles, is especially useful for this purpose since it allows the variation of certain reaction parameters while holding N constant. Thus, h in seeded styrene polymerization drops from 0.5 to 0.2 when the initiator concentration decreases from 10-2 to 1CT5 M. At sufficiently low Ru the rate of radical absorption is not sufficiently high to counterbalance the rate of desorption. One also observes that above a particular initiation rate ([I] = lO-2 M in this case), the system maintains case 2 behavior with h constant at 0.5 and Rp independent of Ri. A change in Ri simply results in an increased rate of alternation of activity and inactivity in each polymer particle. Similar experiments show that h drops below 0.5 for styrene when the particle size becomes sufficiently small. The extent of radical desorption increases with decreasing particle size since the travel distance for radical diffusion from a particle decreases. 

The already mentioned definition of seeded polymerization is in the broad sense of the word. Seeded polymerization in the narrow sense is polymerization after swelling the seed particle with monomer. Figure 12.2.4 shows what the seeded polymerization can form. Making larger particles is one of popular uses of seeded polymerization, but it does not belong to surface modification. Therefore, making larger particles is not discussed here. 

Seeded polymerization using a slight amount of monomer leads to the surface modification without changing particle size. The resulting particles are a kind of core-shell particles or, more exactly, core-skin particles (Fig. 12.2.4C). Seeded polymerization of sugar-units-containing styrene derivative on polystyrene seed particle was carried out to obtain latex particles covered with sugar units (17). A necessary condition for this is that the monomer is more hydrophilic than the seed polymer. If not, the monomer permeates into the seed particle and only a small fraction remains on the... 

A reactive surfactant shown next (RS) was used as a comonomer in a seeded polymerization. RS was easily adsorbed on seed particles due to their amphiphilicity. If dialkyl fumarate was preabsorbed in the particle, the polymerization proceeded quickly and resulted in the formation of skin layer of RS-fumarate copolymer. Because the vinyl group in RS is an allyl type, RS in aqueous phase hardly polymerizes and no water-soluble homopolymer was formed. The active ester group of RS on the skin layer was used for the preparation of functional microspheres (18). 

After monomer molecules permeate into seed particles, subsequent polymerization often results in phase separation because different kinds of polymers have little... 

St and divinylbenzene (DVB) were polymerized in a dispersion of acryl-amide-methacrylic acid-methylenebisacrylamide terpolymer particles (25). Fine polystyrene particles were formed in/on each seed terpolymer particle. The former was smaller by about one-twentieth than the latter. The distribution of polystyrene particles depended on the cross-link density. Different amounts of St and DVB were charged in the seeded polymerization, and the resulting composite particles were used for protein adsorption measurement to assess the hydrophobicity of the particle surface. The adsorbed amount was almost proportional to the amount of St and DVB charged. In contrast, cells were less stimulated by the 5% St-containing particle than by the 0% St-containing one, that is, the seed particle. This phenomenon is attributed to selective protein adsorption on the 5% St-containing particle (26). 

If this composition, M0, is allowed to polymerize to a low conversion as a seed particle, a polymer of composition, Pt, is formed. If an additional monomer is now added gradually at the same rate as the polymer is formed, a monomer composition, Mo, is maintained and only a polymer of composition, Pt, is formed. 

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