Emulsions and suspensions

Several polymerization techniques are in widespread usage. Our discussion is biased in favor of methods that reveal additional aspects of addition polymerization and not on the relative importance of the methods in industrial practice. We shall discuss four polymerization techniques bulk, solution, suspension, and emulsion polymerization. 

The fourth and most interesting of the polymerization techniques we shall consider is called emulsion polymerization. It is important to distinguish between suspension and emulsion polymerization, since there is a superficial resemblance between the two and their terminology has potential for confusion A suspension of oil drops in water is called an emulsion. Water-insoluble monomers are used in the emulsion process also, and the polymerization is carried out in the presence of water however, the following significant differences also exist ... 

Suspension- and emulsion-polymerized PVDF exhibit dissimilar behavior in solutions. The suspension resin type is readily soluble in many solvents even in good solvents, solutions of the emulsion resin type contain fractions of microgel, which contain more head-to-head chain defects than the soluble fraction of the resin (116). Concentrated solutions (15 wt %) and melt rheology of various PVDF types also display different behavior (132). The Mark-Houwink relation (rj = KM°-) for PVDF in A/-methylpyrrohdinone (NMP) containing 0.1 molar LiBr at 85°C, for the suspension (115) and emulsion... 

Eor the preparation of suspensions and emulsions, coUoid mills and homogenizers, respectively, are used. Ultrasonic mills that utilize vibrating reeds in restricted chambers to reduce the particle size of the dispersed ingredients can also be employed (see Colloids Ultrasonics). 

HomopolymeriZation. The free-radical polymeri2ation of VDC has been carried out by solution, slurry, suspension, and emulsion methods. 

Polymerization Processes. Vinyl acetate has been polymerized industrially by bulk, solution, suspension, and emulsion processes (34). Perhaps 90% of the material identified as poly(vinyl acetate) or copolymers that are predominantly vinyl acetate are made by emulsion techniques. Detailed information is in patent and scientific Hterature and in procedures available in the brochures from monomer producing companies (15,34). 

Chain transfer to monomer and to other small molecules leads to lower molecular weight products, but when polymerisation occurs ia the relative absence of monomer and other transfer agents, such as solvents, chain transfer to polymer becomes more important. As a result, toward the end of batch-suspension or batch-emulsion polymerisation reactions, branched polymer chains tend to form. In suspension and emulsion processes where monomer is fed continuously, the products tend to be more branched than when polymerisations are carried out ia the presence of a plentiful supply of monomer. 

Acrylate esters can be polymerised in a variety of ways. Among these is ionic polymerisation, which although possible (6—9), has not found industrial apphcation, and practically all commercial acryUc elastomers are produced by free-radical polymerisation. Of the four methods available, ie, bulk, solution, suspension, and emulsion polymerisation, only aqueous suspension and emulsion polymerisation are used to produce the ACMs present in the market. Bulk polymerisation of acrylate monomers is hasardous because it does not allow efficient heat exchange, requited by the extremely exothermic reaction. 

The viscosity of a fluid arises from the internal friction of the fluid, and it manifests itself externally as the resistance of the fluid to flow. With respect to viscosity there are two broad classes of fluids Newtonian and non-Newtonian. Newtonian fluids have a constant viscosity regardless of strain rate. Low-molecular-weight pure liquids are examples of Newtonian fluids. Non-Newtonian fluids do not have a constant viscosity and will either thicken or thin when strain is applied. Polymers, colloidal suspensions, and emulsions are examples of non-Newtonian fluids [1]. To date, researchers have treated ionic liquids as Newtonian fluids, and no data indicating that there are non-Newtonian ionic liquids have so far been published. However, no research effort has yet been specifically directed towards investigation of potential non-Newtonian behavior in these systems. 

Chain reactions are used to prepare a variety of high molar mass polymers of commericial importance and in practice may take one of four forms, namely bulk, solution, suspension, and emulsion methods. These four methods are described in the sections that follow, together with the loop modification which has become of commercial importance recently in producing latexes by emulsion polymerisation for the paint industry. 

Solutions, colloidal suspensions and emulsions, pumpable solids suspensions, pastes and sludges. 

Disperse systems can be classified in various ways. Classification based on the physical state of the two constituent phases is presented in Table 1. The dispersed phase and the dispersion medium can be either solids, liquids, or gases. Pharmaceutically most important are suspensions, emulsions, and aerosols. (Suspensions and emulsions are described in detail in Secs. IV and V pharmaceutical aerosols are treated in Chapter 14.) A suspension is a solid/liquid dispersion, e.g., a solid drug that is dispersed within a liquid that is a poor solvent for the drug. An emulsion is a li-quid/liquid dispersion in which the two phases are either completely immiscible or saturated with each other. In the case of aerosols, either a liquid (e.g., drug solution) or a solid (e.g., fine drug particles) is dispersed within a gaseous phase. There is no disperse system in which both phases are gases. 

Sec. VI.) Dispersions containing larger dispersed phases, usually 10-50 pm in size, are referred to as coarse dispersions, which include most pharmaceutical suspensions and emulsions. 

An interface is defined as a boundary between two phases. The solid/liquid and the liquid/liquid interfaces are of primary interest in suspensions and emulsion, respectively. Other types of interfaces such as liquid/gas (foams) or solid/gas interfaces also play a major role in certain pharmaceutical dosage forms, e.g., aerosols. 

Aqueous products that are at greatest risk from microbial spoilage include solutions, suspensions, and emulsions for repeated oral, parenteral, or external use and include critical products such as multidose injections and eye drops. Unpreserved products without adequate antimicrobial efficacy should not be presented in containers intended for use on more than one occasion unless justified. When antimicrobial preservatives are used, their efficacy has to be demonstrated using the Ph Eur test for antimicrobial preservative efficacy. Factors to be taken into account in designing a preserved product include the nature of the preservative, its concentration in the product, the... 

Suspension and emulsion polymerization processes are very similar in that they both require an interface. The main difference is where the reaction takes place, on the skin of the suspended droplet or in the center of the micelle. 

Polystyrene is unusual among commodity polymers in that we can prepare it in a variety of forms by a diversity of polymerization methods in several types of reaction vessel. j Polystyrene may be atactic, isotactic, or syndiotactic. Polymerization methods include free radical, cationic, anionic, and coordination catalysis. Manufacturing processes include bulk, solution, suspension, and emulsion polymerization. We manufacture random copolymers ... 

Why are suspension and emulsion polymerization processes the primary methods by which polyvinyl chloride is manufactured How are these processes carried out ... 

Power law relaxation is no guarantee for a gel point. It should be noted that, besides materials near LST, there exist materials which show the very simple power law relaxation behavior over quite extended time windows. Such behavior has been termed self-similar or scale invariant since it is the same at any time scale of observation (within the given time window). Self-similar relaxation has been associated with self-similar structures on the molecular and super-molecular level and, for suspensions and emulsions, on particulate level. Such self-similar relaxation is only found over a finite range of relaxation times, i.e. between a lower and an upper cut-off, and 2U. The exponent may adopt negative or positive values, however, with different consequences and... 

Population Balance Approach. The use of mass and energy balances alone to model polymer reactors is inadequate to describe many cases of interest. Examples are suspension and emulsion polymerizations where drop size or particle distribution may be of interest. In such cases, an accounting for the change in number of droplets or particles of a given size range is often required. This is an example of a population balance. 

A distinction is drawn between bulk, suspension and emulsion PVC on the basis of different polymerization methods. 

Manufacturing Processes. The three manufacturing processes already mentioned (continuous mass polymerization, batch suspension and emulsion polymerization) continued to compete with each other after 1945. Whereas the third one gradually decreased in importance, the other two were given preference in... 

Polymers may be made by four different experimental techniques bulk, solution, suspension, and emulsion processes. They are somewhat self-explanatory. In bulk polymerization only the monomers and a small amount of catalyst is present. No separation processes are necessary and the only impurity in the final product is monomer. But heat transfer is a problem as the polymer becomes viscous. In solution polymerization the solvent dissipates the heat better, but it must be removed later and care must be used in choosing the proper solvent so it does not act as a chain transfer agent. In suspension polymerization the monomer and catalyst are suspended as droplets in a continuous phase such as water by continuous agitation. Finally, emulsion polymerization uses an emulsifying agent such as soap, which forms micelles where the polymerization takes place. 

Thickening agent for various suspension and emulsion systems packaging film, wet-strength adhesive Automotive safety glass as the interlayer... 

The principle free radical polymerization techniques are bulk, solution, suspension, and emulsion. Tables 6.5 and 6.6 briefly describe these techniques. 

Monomer and initiator must be soluble in the liquid and the solvent must have the desired chain-transfer characteristics, boiling point (above the temperature necessary to carry out the polymerization and low enough to allow for ready removal if the polymer is recovered by solvent evaporation). The presence of the solvent assists in heat removal and control (as it also does for suspension and emulsion polymerization systems). Polymer yield per reaction volume is lower than for bulk reactions. Also, solvent recovery and removal (from the polymer) is necessary. Many free radical and ionic polymerizations are carried out utilizing solution polymerization including water-soluble polymers prepared in aqueous solution (namely poly(acrylic acid), polyacrylamide, and poly(A-vinylpyrrolidinone). Polystyrene, poly(methyl methacrylate), poly(vinyl chloride), and polybutadiene are prepared from organic solution polymerizations. 

Vinyl monomers can be polymerized using solution, bulk, suspension, and emulsion techniques. Each has its own characteristic strengths and weaknesses. 

Heterogeneous polymerization is used extensively to control the thermal and viscosity problems. There are three types of heterogeneous polymerization precipitation, suspension, and emulsion. Emulsion polymerization is discussed in Chap. 4. Precipitation polymerizations begin... 

Suspension and emulsion techniques provide additional means for modifying the properties of the resulting polymers, for example ... 

CONDITIONS OF STABILITY IN SUSPENSIONS AND EMULSIONS The following experimental values were obtained by Porter ... 

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