Aqueous soap emulsion

Hot emulsion polymerization uses typical emulsion recipes containing potassium peroxydisulfate (free radical generator) and dodecyl mercaptan (chain transfer agent) in an aqueous soap emulsion at a reaction temperature of 50 C. 

Polymerisation in emulsion, in which the monomer is (a) dispersed in monomer droplets stabilized by an adsorbed layer of soap molecules (Fryling and Harrington, 1944, Kolthoff and Dale, 1945, Price and Adams, 1945, Siggia et ah, 1945, Vinograd etal, 1944) (b) solubilised in the soap micelles (Harkins, 1945, McBain, 1942, McBain and Soldate, 1944) which exist in an aqueous soap solution of sufficient concentration and (c) molecularly dissolved in the water. The amount of polymer formed in the droplets, in the micelles, and in solution will depend upon the way in which the monomer and catalyst are distributed in the three existing phases the monomer phase, the soap micelle phase, and the water phase - and possibly also upon the accessibility and reactivity of the monomer in these three phases. In certain aqueous soap emulsions, such as styrene, dichlorostyrene, or isoprene, the amount of molecularly dissolved monomer is small and, therefore, the reaction will occur preponderantly either in the monomer droplets or in the soap micelles. If the polymer formation occurs preponderantly in the micellar phase, one is inclined to speak of a typical emulsion polymerisation. If, however, polymerisation takes place to a considerable extent both in the monomer droplets and the soap micelles, the case is intermediate between suspension and emulsion polymerisation. There also exist emulsion... 

Fisher Scientific) was emulsified into aqueous soap solutions of 0.25 w% each of sodium laurate and sodium oleate prepared from sodium hydroxide, lauric acid (Aldrich Gold Label) and oleic acid (Fisher Purified). Coarse emulsions were used for microscopy (as in Figure 2), but fine emulsions (with droplet sizes of about 0.2 microns), used for determination of middle phase film thicknesses, were made by ultrasonication with a cell disruptor. 

In this method, it is very frequently most difficult to obtain a distinct separation of other and aqueous soap solution—an intermediate layer of emulsion remaining even after prolonged standing, and various expedients have been recommended to overcome this, such as addition of alcohol (when petroleum ether is used), glycerine, more ether, water, or caustic potash solution, or by rotatory agitation. 

Emulsion polymerization—adding an initiator (such as potassium persulfate) to the emulsion of water-insoluble monomers (such as styrene) in aqueous soap solution... 

Rosin sizing usually involves the addition of dilute aqueous solutions or dispersions of rosin soap size and alum to a pulp slurry (44—46). Although beater addition of either coreactant is permissable, addition of both before final pulp refining is unwise because subsequently exposed ceUulose surfaces may not be properly sized. The size and alum should be added sufficiendy eady to provide uniform distribution in the slurry, and adequate time for the formation and retention of aluminum resinates, commonly referred to as size precipitate. Free rosin emulsion sizes, however, do not react to a significant degree with alum in the pulp slurry, and addition of a cationic starch or resin is recommended to maximize retention of size to fiber. Subsequent reaction with aluminum occurs principally in the machine drier sections (47). 

Emulsion Polymerization. When the U.S. supply of natural mbber from the Far East was cut off in World War II, the emulsion polymerization process was developed to produce synthetic mbber. In this complex process, the organic monomer is emulsified with soap in an aqueous continuous phase. Because of the much smaller (<0.1 jira) dispersed particles than in suspension polymerization and the stabilizing action of the soap, a proper emulsion is stable, so agitation is not as critical. In classical emulsion polymerization, a water-soluble initiator is used. This, together with the small particle size, gives rise to very different kinetics (6,21—23). 

Commercial chloroprene polymerization is most often carried out in aqueous emulsion using an anionic soap system. This technique provides a relatively concentrated polymerization mass having low viscosity and good transfer of the heat of polymerization. A water-soluble redox catalyst is normally used to provide high reaction rate at relatively low polymerization temperatures. 

After only a small percentage of the monomer has been converted to polymer (in the presence of emulsifier), the initially low surface tension of the aqueous emulsion rises rather abruptly, indicating a decrease in the soap concentration in the aqueous phase of the emulsion. The soap concentration is then too low to maintain micelles, which may therefore be abandoned as a locus for further polymerization beyond this point. As additional evidence of the depletion of soap in the aqueous phase, monomer droplets are no longer stable, and upon discontinuing agitation a supernatant monomer layer is readily formed. 

Heat the oil phase and water phase to about 65° C. Add the oil phase slowly to the aqueous phase with stirring to form a crude emulsion. Cool to about 50°C and homogenize. Cool with agitation until congealed. Note In this classic preparation, the stearic acid reacts with the alkaline borate to form the emulsifying stearate soap. VIII. Paste (zinc oxide paste, USP) Zinc oxide 25%... 

The anhydrous petrolatum base may be made more miscible with water through the use of an anhydrous liquid lanolin derivative. Drugs can be incorporated into such a base in aqueous solution if desired. Poly-oxyl 40 stearate and polyethylene glycol 300 are used in an anti-infective ointment to solubilize the active principle in the base so that the ointment can be sterilized by aseptic filtration. The cosmetic-type bases, such as the oil-in-water (o/w) emulsion bases popular in dermatology, should not be used in the eye, nor should liquid emulsions, owing to the ocular irritation produced by the soaps and surfactants used to form the emulsion. 

Many rubber compounds have a tendency to stick in the mould cavity after vulcanisation and require some type of mould release agent. The substances used are surface-active materials such as detergents, soaps, wetting agents, silicone emulsions, aqueous dispersions of talc, mica and fatty acids, applied by spray or brush. Alternatively, dry types based on polytetrafluoroethylene or polyethylene, usually carried in a solvent, can be aerosol applied. An alternative is the addition of an incompatible material to the rubber compound which will bleed to the rubber surface during vulcanisation. 

Monomers may be polymerized using a water-soluble initiator while dispersed, by agitation, in a concentrated soap solution. In this emulsion system initiation occurs in the aqueous phase and propagation occurs in the soap micelles. Since the growing macroradicals are not terminated until a new free radical enters the micelle, high molecular weight products are rapidly obtained. The rate of polymerization and DP is proportional to the number of activated micelles. 

The emulsion was then allowed to separate and it was found on analysis of the soap content of the aqueous lower layer and the concentrated emulsion in the upper layer that the emulsion had abstracted soap from the solution. Owing to the fact that the fatty acids are soluble in the oil the hydrolysis of the soaps and the subsequent removal of the fatty acid in the oil phase had to be eliminated by the addition of caustic soda. In this way the true quantity of soap at the oil-water interface could be determined. Some of the results, obtained are tabulated below. 

This phenomenon of self-emulsification was first observed by Johannes Gad in 1878 when he gently layered a solution of lauric acid on top of an aqueous alkaline solution, thereby making a soap in situ but also forming an emulsion without the aid of external agitation. A laboratory curiosity for the next 50 or so years, the principle became recognized as being valuable for the formulation of herbicides and insecticides such as DDT. The concentrate could be reconstituted with ditch water and sprayed without the need to carry water to the site. 

POLYMERIZATION (Emulsion). Since an aqueous system provides a medium for dissipation of the heat from exothermic addition polymerization processes, many commercial elastomers and vinyl polymers are produced by the emulsion process. This two-phase (warer-hydrophobic monomer) system employs soap or other emulsifiers to reduce the interfacial tension and disperse the monomers in the water phase. Aliphatic alcohols may be used as surface tension regulators,... 

In emulsion polymerization the organic monomer is emulsified with soap in an aqueous continuous phase. 

The mechanism of emulsion polymerisation is complex. The basic theory is that originally proposed by Harkins21. Monomer is distributed throughout the emulsion system (a) as stabilised emulsion droplets, (b) dissolved to a small extent in the aqueous phase and (c) solubilised in soap micelles (see page 89). The micellar environment appears to be the most favourable for the initiation of polymerisation. The emulsion droplets of monomer appear to act mainly as reservoirs to supply material to the polymerisation sites by diffusion through the aqueous phase. As the micelles grow, they adsorb free emulsifier from solution, and eventually from the surface of the emulsion droplets. The emulsifier thus serves to stabilise the polymer particles. This theory accounts for the observation that the rate of polymerisation and the number of polymer particles finally produced depend largely on the emulsifier concentration, and that the number of polymer particles may far exceed the number of monomer droplets initially present. 

Surfactants are a class of amphipathic compounds that includes soaps, detergents, and emulsifiers. With the use of surfactants, hydrophobic compounds can be suspended in aqueous solution by forming micelles (see Fig. 2-7). A micelle has a hydrophobic core consisting of the hydrophobic compound and the hydrophobic tails of the surfactant the hydrophilic heads of the surfactant cover the surface of the micelle. A suspension of micelles is called an emulsion. The more hydrophilic the head group of the surfactant, the more powerful it is—that is, the greater its capacity to emulsify hydrophobic material. 

Anionic surfactants are negatively charged in an aqueous solution (i.e., -COO-, -OSOj), and widely used because of their cost and performance. Sodium lauryl sulfate, the main component of which is sodium dodecyl sulfate, is highly soluble in water and commonly used to form oil-in-water (O/W) emulsions. Reacting an alkali hydroxide with a fatty acid (e.g., oleic acid) can produce alkali metal soaps (e.g., sodium oleate). Careful attention must be paid to the pH of the dispersion medium and the presence of multivalent metals (see Section 4.2.5). Alkali earth metal soaps (e.g., calcium oleate) produce stable water-in-oil (W/O) emulsions because of their low water solubility and are produced by reacting oleic acid with calcium hydroxide. Triethanolamine stearate produces stable O/W emulsions in situ by reacting triethanolamine in aqueous solution with melted stearic acid at approximately 65°C (e.g., vanishing cream). 

Aqueous suspensions comprise a wide range of adhesives. These will contain as additives the various soaps, surfactants, and wetting agents necessary to stabilize the emulsion or latex. Additives are also incorporated into aqueous formulations to provide system stability under repeated freeze-thaw cycles during storage. 

The most widely accepted theories of emulsion polymerization (5, ) point out that new latex particles are generated only as long as soap In excess of the particle surface adsorption requirements is present In the system. After sufficient particle surface area has developed to adsorb the soap in the aqueous... 

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