Suspension droplets

Suspension polymerization of water-insoluble monomers (e.g., styrene and divinylbenzene) involves the formation of an oil droplet suspension of the monomer in water with direct conversions of individual monomer droplets into the corresponding polymer beads. Preparation of beaded polymers from water-soluble monomers (e.g., acrylamide) is similar, except that an aqueous solution of monomers is dispersed in oil to form a water-in-oil (w/o) droplet suspension. Subsequent polymerization of the monomer droplets produces the corresponding swollen hydrophilic polyacrylamide beads. These processes are often referred to as inverse suspension polymerization. 

The most important feature of o/w suspension polymerization is the formation of an oil droplet suspension of the monomer in the water and the maintenance of the individual droplets throughout the polymerization process. Droplet formation in an oil-in-water mixture is accomplished and controlled by two major factors mechanical stirring and the volume ratio of the monomer phase to water. The stirring speed is a key factor in controlling the size of oil droplets and the final size of the polymers. The stirring speed usually needs to be over... 

Tryggvason, G., FernAndez, A., Lu, J., The effect of electrostatic forces on droplet suspensions, in Proceedings of the Second M.I.T. Conference on Computatkmal Fluid and Solid Mechanics, Jime 17-20 2003, M.I.T, Cambridge, MA, Elsevier,... 

Droplet suspensions (gas-liquid, two-component system) Since the inertia of a liquid suspended in the gas phase is higher than the inertia of the gas, the time for the displacement of liquid under the pressure waves should be considered. Temkin (1966) proposed a model to account for the response of suspension with pressure and temperature changes by considering the suspensions to move with the pressure waves according to the Stokes s law. The oscillatory state equation is thereby approximated by a steady-state equation with the oscillatory terms neglected, which is valid if the ratio of the relaxation time to the wave period is small, or... 

This expression shows the difference of sonic velocity c in a particle suspension from that in the air, co as a function of the mass fraction of suspension, Xs, the relaxation times, jd and t and the frequency, w. These equations show that the acoustic velocity in a droplet suspension is a strong function of frequency and... 

Babick et.al. [261] compare sound spectroscopic determination of particle size distributions of sub-micron emulsions with dynamic light scattering and laser diffraction using olive oil in water droplet suspensions at volume concentrations from 1% to 60%. 

Multiphase processing is an important area in every shape or form that is manufactured from polymers. Micron thickness extruded layer structures in polymer films and sub-micron droplet suspensions in mouldings all play a crucial role in product enhancement. These microstructures generally originate or are influenced by their process history. 

Suspensions and Solutions. The particle-size range for the separation of suspended solids from fluids is diagrammed in Figure 19.1. As noted, the solid particulate sizes vary from the macro to the ionic, thereby entering the domain of true solutions. The fluid is usually a liquid, but there are of course solid and liquid (or droplet) suspensions occurring in a gaseous phase. 

In mass polymerization bulk monomer is converted to polymers. In solution polymerization the reaction is completed in the presence of a solvent. In suspension, dispersed mass, pearl or granular polymerization the monomer, containing dissolved initiator, is polymerized while dispersed in the form of fine droplets in a second non-reactive liquid (usually water). In emulsion polymerization an aqueous emulsion of the monomer in the presence of a water-soluble initiator Is converted to a polymer latex (colloidal dispersion of polymer in water). 

Although it is hard to draw a sharp distinction, emulsions and foams are somewhat different from systems normally referred to as colloidal. Thus, whereas ordinary cream is an oil-in-water emulsion, the very fine aqueous suspension of oil droplets that results from the condensation of oily steam is essentially colloidal and is called an oil hydrosol. In this case the oil occupies only a small fraction of the volume of the system, and the particles of oil are small enough that their natural sedimentation rate is so slow that even small thermal convection currents suffice to keep them suspended for a cream, on the other hand, as also is the case for foams, the inner phase constitutes a sizable fraction of the total volume, and the system consists of a network of interfaces that are prevented from collapsing or coalescing by virtue of adsorbed films or electrical repulsions. 

Apart from chemical composition, an important variable in the description of emulsions is the volume fraction, outer phase. For spherical droplets, of radius a, the volume fraction is given by the number density, n, times the spherical volume, 0 = Ava nl2>. It is easy to show that the maximum packing fraction of spheres is 0 = 0.74 (see Problem XIV-2). Many physical properties of emulsions can be characterized by their volume fraction. The viscosity of a dilute suspension of rigid spheres is an example where the Einstein limiting law is [2]... 

An aerosol is a suspension of either a solid or a liquid in a gas. Fog, for example, is a suspension of small liquid water droplets in air, and smoke is a suspension of small solid particulates in combustion gases. In both cases the liquid or solid particulates must be small enough to remain suspended in the gas for an extended time. Solid aerosol particulates, which are the focus of this problem, usually have micrometer or submicrometer diameters. Over time, solid particulates settle out from the gas, falling to the Earth s surface as dry deposition. 

In a suspension polymerisation monomer is suspended in water as 0.1—5-mm droplets, stabilised by protective coUoids or suspending agents. Polymerisation is initiated by a monomer-soluble initiator and takes place within the monomer droplets. The water serves as both the dispersion medium and a heat-transfer agent. Particle sise is controlled primarily by the rate of agitation and the concentration and type of suspending aids. The polymer is obtained as small beads about 0.1—5 mm in diameter, which are isolated by filtration or centrifugation. 

Suitable protective coUoids for the preparation of acryhc suspension polymers include ceUulose derivatives, polyacrylate salts, starch, poly(vinyl alcohol), gelatin, talc, clay, and clay derivatives (95). These materials are added to prevent the monomer droplets from coalescing during polymerisation (110). Thickeners such as glycerol, glycols, polyglycols, and inorganic salts ate also often added to improve the quahty of acryhc suspension polymers (95). 

Because the polymerization occurs totally within the monomer droplets without any substantial transfer of materials between individual droplets or between the droplets and the aqueous phase, the course of the polymerization is expected to be similar to bulk polymerization. Accounts of the quantitative aspects of the suspension polymerization of methyl methacrylate generally support this model (95,111,112). Developments in suspension polymerization, including acryUc suspension polymers, have been reviewed (113,114). 

Suspension Polymerization. In this process the organic reaction mass is dispersed in the form of droplets 0.01—1 mm in diameter in a continuous aqueous phase. Each droplet is a tiny bulk reactor. Heat is readily transferred from the droplets to the water, which has a large heat capacity and a low viscosity, faciUtating heat removal through a cooling jacket. 

In the suspension methods, agglomerate formation occurs by hardening of feed droplets into soHd particles, by layering of soHds deposited from the feed onto existing nuclei, and by adhesion of small particles into aggregates as binding soHds from the dispersed feed are deposited. The product size achievable in these methods is usually limited to ca 5 mm and is often much smaller (see Drying). 

Divinylbenzene copolymers with styrene are produced extensively as supports for the active sites of ion-exchange resins and in biochemical synthesis. About 1—10 wt % divinylbenzene is used, depending on the required rigidity of the cross-linked gel, and the polymerization is carried out as a suspension of the monomer-phase droplets in water, usually as a batch process. Several studies have been reported on the reaction kinetics (200,201). 

Emulsion Polymerization. Emulsion and suspension reactions are doubly heterogeneous the polymer is insoluble in the monomer and both are insoluble in water. Suspension reactions are similar in behavior to slurry reactors. Oil-soluble initiators are used, so the monomer—polymer droplet is like a small mass reaction. Emulsion polymerizations are more complex. Because the monomer is insoluble in the polymer particle, the simple Smith-Ewart theory does not apply (34). 

In the suspension polymerization of PVC, droplets of monomer 30—150 p.m in diameter are dispersed in water by agitation. A thin membrane is formed at the water—monomer interface by dispersants such as poly(vinyl alcohol) or methyl cellulose. This membrane, isolated by dissolving the PVC in tetrahydrofuran and measured at 0.01—0.02-p.m thick, has been found to be a graft copolymer of polyvinyl chloride and poly(vinyl alcohol) (4,5). Early in the polymerization, particles of PVC deposit onto the membrane from both the monomer and the water sides, forming a skin 0.5—5-p.m thick that can be observed on grains sectioned after polymerization (4,6). Primary particles, 1 p.m in diameter, deposit onto the membrane from the monomer side (Pig. 1), whereas water-phase polymer, 0.1 p.m in diameter, deposits onto the skin from the water side of the membrane (Pig. 2) (4). These domain-sized water-phase particles may be one source of the observed domain stmcture (7). 

Polymerization Kinetics of Mass and Suspension PVC. The polymerization kinetics of mass and suspension PVC are considered together because a droplet of monomer in suspension polymerization can be considered to be a mass polymerization in a very tiny reactor. During polymerization, the polymer precipitates from the monomer when the chain size reaches 10—20 monomer units. The precipitated polymer remains swollen with monomer, but has a reduced radical termination rate. This leads to a higher concentration of radicals in the polymer gel and an increased polymerization rate at higher polymerization conversion. 

Suspension Polymerization. Suspension polymerization is carried out in small droplets of monomer suspended in water. The monomer is first finely dispersed in water by vigorous agitation. Suspension stabiUzers act to minimize coalescence of droplets by forming a coating at the monomer—water interface. The hydrophobic—hydrophilic properties of the suspension stabiLizers ate key to resin properties and grain agglomeration (89). 

---